CN116018559A

CN116018559A - Photosensitive transfer material and method for producing resin pattern

Info

Publication number: CN116018559A
Application number: CN202180055455.1A
Authority: CN
Inventors: 有富隆志
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2020-08-27
Filing date: 2021-08-26
Publication date: 2023-04-25
Also published as: WO2022045255A1; JPWO2022045255A1

Abstract

The present invention provides a photosensitive transfer material and application thereof, the photosensitive transfer material comprising: a temporary support having a 1 st surface and a 2 nd surface located on the opposite side of the 1 st surface; and a photosensitive resin layer located on the 2 nd surface of the temporary support, wherein the L value of the 2 nd surface of the temporary support measured by SCE method is 1.5 or less.

Description

Photosensitive transfer material and method for producing resin pattern

Technical Field

The present invention relates to a photosensitive transfer material and a method for producing a resin pattern.

Background

In display devices (for example, organic Electroluminescence (EL) display devices and liquid crystal display devices) including a touch panel such as a capacitive input device, the touch panel includes a conductive pattern. The conductive pattern is used as a sensor of a visual recognition portion, an edge wiring, or a lead wiring, for example. Examples of the method for producing the pattern such as the conductive pattern and the resin pattern include a method using a photosensitive transfer material. As a method for producing a resin pattern using a photosensitive transfer material, a method including the following steps is widely used: a step of providing a photosensitive resin layer and a temporary support on a substrate using a photosensitive transfer material; a step of exposing the photosensitive resin layer to light in a pattern through the temporary support; and a step of developing the exposed photosensitive resin layer (for example, japanese patent application laid-open No. 2017-156735).

Disclosure of Invention

Technical problem to be solved by the invention

In a method for producing a resin pattern using a photosensitive transfer material, improvement in linearity of the resin pattern is required. Further, the linearity of the resin pattern also affects, for example, the linearity of the circuit wiring formed using the resin pattern.

An object of an embodiment of the present invention is to provide a photosensitive transfer material for forming a resin pattern having high linearity.

Another object of another embodiment of the present invention is to provide a method for manufacturing a resin pattern capable of having high linearity.

Means for solving the technical problems

The present invention includes the following means.

<1> a photosensitive transfer material, comprising:

a temporary support having a 1 st surface and a 2 nd surface located on the opposite side of the 1 st surface; a kind of electronic device with high-pressure air-conditioning system

A photosensitive resin layer located on the 2 nd surface of the temporary support,

l of the 2 nd surface of the temporary support measured by SCE method ^* The value is 1.5 or less.

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

the temporary support has a thickness of 16 μm or less.

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

l of the 1 st surface of the temporary support measured by SCE method ^* The value is 0.6 or more.

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

l of the 1 st surface of the temporary support measured by SCE method ^* The value is 2.0 or less.

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

the thickness of the photosensitive resin layer is 1-10 μm.

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

the temporary support includes a particle-containing layer and a base material disposed as the outermost layer of the temporary support in this order in the stacking direction of the photosensitive resin layers from the temporary support.

<7> a photosensitive transfer material, comprising:

the temporary support is a polyester film composed of 2 or more layers, and at least one surface layer does not contain particles.

<8> the photosensitive transfer material according to <7>, wherein,

the surface layer on the 2 nd surface side of the temporary support contains no particles.

<9> the photosensitive transfer material according to <7> or <8>, wherein,

The surface layer on the 1 st surface side of the temporary support contains no particles.

<10> the photosensitive transfer material according to any one of <7> to <9>, wherein,

<11> the photosensitive transfer material according to any one of <7> to <10>, wherein,

<12> the photosensitive transfer material according to any one of <7> to <11>, wherein,

the arithmetic average roughness Ra of the 1 st surface of the temporary support is 1nm to 50nm.

<13> the photosensitive transfer material according to any one of <7> to <12>, wherein,

the surface layer has a phase separation structure.

<14> the photosensitive transfer material according to any one of <7> to <13>, wherein,

the surface layer contains a polyester resin having an alicyclic structure.

<15> the photosensitive transfer material according to <14>, wherein,

the alicyclic structure is cyclohexane ring.

<16> the photosensitive transfer material according to <14> or <15>, wherein,

the surface layer contains a copolymerized polyethylene terephthalate containing isophthalic acid as a copolymerization component.

<17> a method for producing a resin pattern using the photosensitive transfer material according to any one of <1> to <16>, the method comprising:

a step of preparing a substrate;

a step of bringing the photosensitive transfer material into contact with the substrate, and disposing the photosensitive resin layer and the temporary support in this order on the substrate;

a step of exposing the photosensitive resin layer to a pattern; a kind of electronic device with high-pressure air-conditioning system

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

Effects of the invention

According to an embodiment of the present invention, there is provided a photosensitive transfer material for forming a resin pattern having high linearity.

According to another embodiment of the present invention, there is provided a method for manufacturing a resin pattern having high linearity.

Drawings

Fig. 1 is a schematic side view showing a layer structure of the photosensitive transfer material according to the present invention.

Fig. 2 is a schematic side view showing another layer structure of the photosensitive transfer material according to the present invention.

Fig. 3 is a schematic side view showing another layer structure of the photosensitive transfer material according to the present invention.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited by the following embodiments. The following embodiments may be appropriately modified within the scope of the object of the present invention.

In the case where the embodiments of the present invention are described with reference to the drawings, the description of the constituent elements and symbols repeated in the drawings may be omitted. The constituent elements denoted by the same reference numerals in the drawings refer to the same constituent elements. The ratio of the dimensions in the drawings does not necessarily represent the ratio of the actual dimensions.

In the present invention, the numerical range indicated by the term "to" means a range in which the numerical values before and after the term "to" are included as a lower limit value and an upper limit value, respectively. In the numerical ranges described in stages in the present invention, the upper limit or the lower limit described in any numerical range may be substituted for the upper limit or the lower limit of the numerical range described in other stages. In addition, in the numerical ranges described in the present invention, the upper limit value or the lower limit value described in any numerical range may be substituted for the values shown in the embodiments.

In the present invention, the term "process" includes not only an independent process but also a process which cannot be clearly distinguished from other processes, as long as the intended purpose of the process can be achieved.

In the present invention, "mass%" and "mass%" have the same meaning, and "part by mass" have the same meaning.

In the present invention, when a plurality of substances corresponding to a certain component are present in a composition, unless otherwise specified, the amount of the above component in the composition refers to the total amount of the plurality of the above substances present in the composition.

In the present invention, a combination of 2 or more preferred modes is a more preferred mode.

In the present invention, ordinal words (for example, "1 st" and "2 nd") are terms used to distinguish a plurality of constituent elements, and do not limit the number of constituent elements or the merits of the constituent elements.

In the present invention, the unsubstituted and substituted groups (atomic groups) include groups having a substituent and groups having no substituent. For example, the label of "alkyl" includes an alkyl group having a substituent (a substituted alkyl group) and an alkyl group having no substituent (an unsubstituted alkyl group).

In the present invention, the chemical structural formula is sometimes represented by a simplified structural formula in which a hydrogen atom is omitted.

In the present invention, "(meth) acrylic" means acrylic acid or methacrylic acid.

In the present invention, "(meth) acrylate" means an acrylate or a methacrylate.

In the present invention, "(meth) acryl" means acryl or methacryl.

In the present invention, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using a particle beam such as an electron beam and an ion beam. Examples of the light used for exposure include an open spectrum of a mercury lamp, extreme ultraviolet rays and extreme ultraviolet rays (EUV (Extreme ultraviolet lithography) light) typified by excimer laser, and active rays (active energy rays) such as X-rays.

In the present invention, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are molecular weights converted by detecting a compound in Tetrahydrofuran (THF) by a differential refractometer and using polystyrene as a standard substance by using a gel permeation chromatography (GPC: gel Permeation Chromatography) analysis apparatus using columns of TSKgel GMHxL (Tosoh Corporation), TSKgel G4000HxL (Tosoh Corporation) and TSKgel G2000HxL (Tosoh Corporation).

In the present invention, unless otherwise specified, the refractive index is a value measured at a wavelength of 550nm using an ellipsometer.

In the present invention, the term "solid component" refers to a component that removes a solvent from the total components of an object.

< photosensitive transfer Material >

The photosensitive transfer material according to the first embodiment of the present invention includes: a temporary support having a 1 st surface and a 2 nd surface located on the opposite side of the 1 st surface; and a photosensitive resin layer located on the 2 nd side of the temporary support, wherein L of the 2 nd side of the temporary support is measured by a SCE (Specular Component Exclude: except for specular reflection light; the same applies hereinafter) ^* The value is 1.5 or less. According to the first embodiment described above, a photosensitive transfer material is provided in which a resin pattern having high linearity is formed.

The reason for estimation expressed by the above effects will be described below. In the method for producing a resin pattern using a photosensitive transfer material, one of factors affecting the linearity of the resin pattern is, for example, the smoothness of the surface of a temporary support. The temporary support having low surface smoothness increases surface diffusion at the temporary supportIs used for the light quantity of the light source. In exposure of the photosensitive resin layer through the temporary support, an increase in light diffused on the surface of the temporary support causes a decrease in the linearity of the resin pattern. On the other hand, in the photosensitive transfer material according to the first embodiment of the present invention, L of the 2 nd surface of the temporary support measured by SCE method ^* The value is 1.5 or less. In the photosensitive transfer material, the 2 nd surface of the temporary support faces the photosensitive resin layer. L as determined by the SCE method ^* The value is L, which is determined by removing specular reflection light and from diffuse reflection light ^* a ^* b ^* L of color system ^* . "L of 2 nd surface of temporary support measured by SCE method ^* The characteristic of a value of 1.5 or less indicates that the amount of diffuse light generated on the 2 nd surface of the temporary support is small, in other words, the 2 nd surface of the temporary support has high smoothness. The temporary support having the above-described characteristics reduces diffusion of light passing through the temporary support during exposure of the photosensitive resin layer through the temporary support. Therefore, according to the first embodiment of the present invention, there is provided a photosensitive transfer material for forming a resin pattern having high linearity.

The photosensitive transfer material according to the second embodiment of the present invention includes a temporary support having a 1 st surface and a 2 nd surface located on the opposite side of the 1 st surface, and a photosensitive resin layer located on the 2 nd surface of the temporary support, wherein the temporary support is a polyester film composed of 2 or more layers, and at least one surface layer (i.e., at least one of a layer disposed as the outermost layer on the 1 st surface side and a layer disposed as the outermost layer on the 2 nd surface side) does not contain particles.

Even in the second embodiment described above, a photosensitive transfer material is provided in which a resin pattern having high linearity is formed.

In the present invention, the description of both the first embodiment and the second embodiment is considered when the photosensitive transfer material according to the present invention or the photosensitive transfer material is not specifically defined but simply referred to as "photosensitive transfer material according to the present invention".

Temporary support

The photosensitive transfer material according to the present invention includes a temporary support having a 1 st surface and a 2 nd surface on a side opposite to the 1 st surface. In the photosensitive transfer material, the temporary support supports at least the photosensitive resin layer. In the photosensitive transfer material, the temporary support is a member that can be peeled from an adjacent layer (for example, a photosensitive resin layer). In the photosensitive transfer material, the 2 nd surface of the temporary support faces the photosensitive resin layer.

< temporary support in photosensitive transfer Material according to first embodiment of the invention >

Hereinafter, a temporary support (hereinafter, also referred to as temporary support (1)) in the photosensitive transfer material according to the first embodiment of the present invention will be described.

In the photosensitive transfer material according to the first embodiment of the present invention, L of the 2 nd surface of the temporary support measured by SCE method ^* The value (hereinafter, sometimes referred to as "L of the 2 nd plane ^* Value). ) Is 1.5 or less. L through the 2 nd side ^* The value is 1.5 or less, and light diffusion during exposure of the photosensitive resin layer through the temporary support (1) is reduced. As a result, a resin pattern having high linearity is formed. L of the 2 nd surface of the temporary support (1) from the viewpoint of linearity of the resin pattern ^* The value is preferably 1.2 or less, more preferably 1.0 or less, and particularly preferably 0.7 or less. L of the 2 nd surface of the temporary support (1) ^* The value may be 0.5 or less or 0.2 or less. L of the 2 nd surface of the temporary support (1) ^* The lower limit of the value is not limited. L of the 2 nd surface of the temporary support (1) ^* The value may be 0.1 or more.

In the present invention, L of the 2 nd side ^* The values were determined by the following method. The temporary support is peeled off from the photosensitive transfer material. L at 10 total was measured at 3CM intervals along the width direction of the 2 nd surface of the temporary support using a spectrocolorimeter (e.g., CM-700d, konica Minolta, inc.) ^* Values. As a light source of the spectrocolorimeter, a D65 light source was used. For L at 10 points measured by SCE method ^* Arithmetic averaging of the values, using the obtained value as L of object plane based on SCE method ^* Values.

In the photosensitive transfer material according to the first embodiment of the present invention, L of the 1 st surface of the temporary support measured by SCE method ^* The value (hereinafter, sometimes referred to as "L of the 1 st plane ^* Value). ) And is not limited. As described above, L was measured by the SCE method ^* The value represents smoothness. L of the 1 st plane ^* The greater the value, the lower the smoothness of the 1 st surface of the temporary support (1) becomes, and the conveyability of the temporary support (1) and the photosensitive transfer material is improved. On the other hand, L of the 1 st plane ^* The smaller the value, the higher the smoothness of the 1 st surface of the temporary support (1) becomes, improving the linearity of the resin pattern. L of the 1 st surface of the temporary support (1) from the viewpoint of conveyability ^* The value is preferably 0.1 or more, more preferably 0.6 or more. L of the 1 st surface of the temporary support (1) from the viewpoint of linearity of the resin pattern ^* The value is preferably 2.5 or less, more preferably 2.0 or less, further preferably 1.5 or less, particularly preferably 1.0 or less. L of the 1 st surface of the temporary support (1) ^* The value may be 0.8 or less. L of the 1 st plane ^* Value by L according to plane 2 ^* The method of measuring the value is carried out.

L of the 2 nd surface from the viewpoint of linearity and conveyability of the resin pattern ^* Value and L of the 1 st surface in the temporary support (1) ^* Ratio of values ([ L of 2 nd side ] ^* Value of]L of 1 st face ^* Value of]) Preferably 2 or less, more preferably 1.5 or less, further preferably 1 or less, and particularly preferably 0.8 or less. L of the 2 nd side ^* Value and L of 1 st face ^* The ratio of values may be 0.7, 0.5 or less or 0.3 or less. L of the 2 nd side ^* Value and L of 1 st face ^* The lower limit of the ratio of values is not limited. L of the 2 nd side ^* Value and L of 1 st face ^* The ratio of values may be 0.1 or more, 0.2 or more, or 0.3 or more. L of the 2 nd surface from the viewpoint of linearity and conveyability of the resin pattern ^* Value and L of 1 st face ^* The ratio of the values is preferably from 0.1 to 2, more preferably from 0.2 to 1.1, particularly preferably from 0.2 to 0.9.

L of the 2 nd side ^* Value of L of 1 st face ^* The value is for example determined by the surface shape of the temporary support (1)And (5) row adjustment. As a reduction in L ^* Examples of the method of the value include a method of reducing the amount of particles contained in the temporary support (1), a method of reducing the size of particles, a method of increasing the coating thickness of the particle-containing layer with respect to the size of particles, and a method of improving the uniformity of the thickness unevenness of the temporary support (1). As an increase L ^* Examples of the method of the value include a method of increasing the amount of particles contained in the temporary support (1), a method of increasing the size of particles, and a method of reducing the coating thickness of the particle-containing layer with respect to the size of particles. In order to improve uniformity of thickness unevenness of the temporary support, it is useful to increase the stretching temperature at the time of longitudinal stretching.

The temporary support (1) preferably has light transmittance. In the present invention, "having light transmittance" means that the transmittance at the wavelength used for pattern exposure is 50% or more. The transmittance of the temporary support (1) at the wavelength used in pattern exposure (more preferably, at 365 nm) is preferably 60% or more, and more preferably 70% or more, from the viewpoint of improving the exposure sensitivity of the photosensitive resin layer. The transmittance is a ratio of the intensity of light (emitted light) passing through the object to the intensity of light (incident light) perpendicularly incident to the main surface of the object. The transmittance was measured using a known spectroscope (e.g., "MCPD Series", OTSUKA ELECTRONICS co., LTD).

The thickness of the temporary support (1) is not limited. The thickness of the temporary support (1) can be determined by the material from the viewpoints of the strength as the support, the flexibility required for bonding to the substrate, and the light transmittance required for exposure. The thickness of the temporary support (1) is preferably 100 μm or less, more preferably 50 μm or less, further preferably 20 μm or less, and particularly preferably 16 μm or less, from the viewpoints of ease of handling and versatility. The thickness of the temporary support (1) is preferably 5 μm or more, more preferably 10 μm or more, from the viewpoint of ease of handling and versatility.

The thickness of the temporary support was measured by the following method. A cross section along the thickness direction of the temporary support (direction perpendicular to the main surface of the temporary support) was observed using a scanning electron microscope. The thickness of the temporary support was measured at 10 from the observation image, and the measured values were arithmetically averaged. The obtained value is used as the thickness of the temporary support.

The layer structure of the temporary support (1) is not limited. The temporary support (1) may be a temporary support having a single-layer structure or a temporary support having a multi-layer structure. The layer structure of the temporary support (1) will be described below. However, the layer structure of the temporary support (1) is not limited to the layer structure shown below.

Examples of the temporary support (1) having a single-layer structure include a glass substrate, a resin film, and paper. From the viewpoints of strength, flexibility, and light transmittance, the resin film is preferable. Examples of the resin film include polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among the above, a PET film is preferable, and a biaxially stretched PET film is more preferable. Examples of the method for producing the resin film include extrusion molding.

Examples of the temporary support (1) having a multilayer structure include a substrate and a particle-containing layer. The temporary support (1) having a multilayer structure may contain a layer (e.g., an adhesive layer) other than the above-described particle-containing layer.

From the viewpoint of conveyability, the temporary support (1) preferably includes a particle-containing layer (hereinafter, sometimes referred to as "particle-containing layer 1") and a base material disposed as outermost layers of the temporary support in the stacking direction from the temporary support toward the photosensitive resin layer. In other words, the temporary support (1) preferably includes a substrate and a particle-containing layer (1 st particle-containing layer) disposed as an outermost layer on the 1 st surface side of the temporary support (1) in this order. The surface of the 1 st particle-containing layer contains the 1 st surface of the temporary support (1).

The temporary support (1) may include a substrate and a particle-containing layer (hereinafter, sometimes referred to as "particle-containing layer 2") disposed as an outermost layer of the temporary support in this order in the stacking direction from the temporary support toward the photosensitive resin layer. In other words, the temporary support (1) may include a substrate and a particle-containing layer (particle-containing layer 2) disposed as an outermost layer on the 2 nd surface side of the temporary support in this order. The surface of the 2 nd particle-containing layer contains the 2 nd surface of the temporary support (1).

The temporary support (1) may comprise a plurality of particle-containing layers. For example, the temporary support (1) may include a layer containing the 1 st particles, a base material, and a layer containing the 2 nd particles in this order in the stacking direction from the temporary support toward the photosensitive resin layer.

Examples of the base material include a glass substrate, a resin film, and paper. The substrate is preferably a resin film, more preferably a polyethylene terephthalate (PET) film, and particularly preferably a biaxially stretched PET film. Examples of the resin film include the resin films described above. Examples of the method for producing the resin film include extrusion molding.

Examples of the particles in the particle-containing layer include inorganic particles and organic particles. Examples of the inorganic particles include particles containing an inorganic oxide. Examples of the inorganic oxide include silicon oxide (silica), titanium oxide (titania), zirconium oxide (zirconia), magnesium oxide (magnesa), and aluminum oxide (alumina). Examples of the organic particles include particles containing a polymer. Examples of the polymer include acrylic resin, polyester, polyurethane, polycarbonate, polyolefin and polystyrene. From the viewpoint of the abrasion resistance of the particles, the particles are preferably inorganic particles, more preferably particles containing an inorganic oxide, further preferably particles containing at least 1 selected from the group consisting of silicon oxide, titanium oxide, zirconium oxide, magnesium oxide and aluminum oxide, and particularly preferably particles containing silicon oxide.

The particle diameter of the particles in the particle-containing layer is not limited. The average particle diameter of the particles is preferably 1 μm or less, more preferably 300nm or less, further preferably 100nm or less, and particularly preferably 80nm or less, from the viewpoint of linearity of the resin pattern. From the viewpoint of transport properties, the average particle diameter of the particles is preferably 5nm or more, more preferably 20nm or more, and particularly preferably 40nm or more. The average particle diameter of the particles is preferably 5nm to 1. Mu.m, more preferably 20nm to 300nm, and particularly preferably 40nm to 100nm from the viewpoints of linearity and transport property of the resin pattern. In the present invention, the average particle diameter of the particles is measured by the following method. The particle diameters of 15 particles were measured using a Transmission Electron Microscope (TEM). The "particle diameter" is the maximum value of a straight line connecting 2 points on the contour line of the particle in a plan view. The arithmetic average of the measured values was used as the average particle diameter of the particles.

The shape of the particles in the particle-containing layer is not limited. Examples of the shape of the particles in plan view include circular, elliptical, polygonal, and irregular shapes.

The particle-containing layer may contain a binder. Examples of the binder include polymers. Examples of the polymer include acrylic resins, polyurethanes, polyolefins, styrene-butadiene polymers, polyesters, polyvinyl chloride and polyvinylidene chloride.

The thickness of the particle-containing layer is not limited. From the viewpoint of transport properties, the thickness of the particle-containing layer (except for particles exposed on the surface of the particle-containing layer. Hereinafter, the same applies in this stage) is preferably 3 μm or less, more preferably 2 μm or less. Further, from the viewpoint of uniform presence of particles, the thickness of the particle-containing layer is preferably 5nm or more, more preferably 20nm or more. The thickness of the particle-containing layer is measured by a method according to the method for measuring the thickness of the temporary support.

The method for producing the particle-containing layer is not limited. The particle-containing layer is formed, for example, by coating a particle-containing layer-forming composition on a substrate and drying the coated particle-containing layer-forming composition. In the above method, the composition for forming a particle-containing layer may be coated on an unstretched film, a uniaxially stretched film or a biaxially stretched film. The unstretched film or the uniaxially stretched film coated with the composition for forming a particle-containing layer may be further stretched. The particle-containing layer may be formed together with the substrate by, for example, coextrusion.

The film used as the temporary support (1) is preferably free from deformations (e.g., wrinkles), scratches, and defects.

From the viewpoints of pattern formability at the time of pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the number of particles, impurities, defects and precipitates contained in the temporary support (1) is small. Particle, impurity and defect number of 2 μm or more diameter Preferably 50/10 mm ² Hereinafter, more preferably 10 pieces/10 mm ² Hereinafter, it is more preferably 3/10 mm ² Hereinafter, it is particularly preferably 0/10 mm ² 。

Preferable modes of the temporary support (1) 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 these publications are incorporated by reference into the present specification.

Examples of the temporary support (1) include a biaxially stretched polyethylene terephthalate film having a film thickness of 16. Mu.m, a biaxially stretched polyethylene terephthalate film having a film thickness of 12. Mu.m, and a biaxially stretched polyethylene terephthalate film having a film thickness of 9. Mu.m.

< temporary support in photosensitive transfer Material according to the second embodiment of the invention >

Hereinafter, a temporary support (hereinafter, also referred to as temporary support (2)) in the photosensitive transfer material according to the second embodiment of the present invention will be described.

In the photosensitive transfer material according to the second embodiment of the present invention, the temporary support is a polyester film composed of 2 or more layers, and at least one surface layer may not contain particles.

Here, the term "the surface layer contains no particles" means that the surface layer is observed by a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM) and the average number of particles present when 10 viewing angles are confirmed at a magnification of 5,000 times is 0.5 particles/mm ² The following is given. That is, when confirmed by the above method, the average number of particles present is 0.5 particles/mm ² Hereinafter, the term "surface layer contains no particles".

The above observation method is described in further detail.

The polyester resin was removed from the polyester film as the surface layer of the temporary support by a plasma low-temperature ashing treatment to expose the particles. As the treatment conditions, conditions were selected under which the polyester resin was ashed but the particles were not extremely damaged. The sample after the treatment was observed at a magnification of 5000 times using a scanning electron microscope (SEM, for example, hitachi, ltd.s-4000 type), and a particle image was read into an image analyzer (NIRECO CORPORATION LUZEX _ap) to confirm the presence or absence of particles and the number of particles.

In addition, when the particles were significantly damaged by the plasma low-temperature ashing treatment, the cross section of the temporary support was observed at 5000 times using a transmission electron microscope (TEM, for example, hitachi, ltd.h-600 type), and the presence or absence of the particles and the number of particles were confirmed.

When observed by SEM and TEM, the average number of particles present at 10 viewing angles was 0.5 particles/mm when confirmed at a magnification of 5,000 times ² Hereinafter, it is determined that the surface layer of the observation target does not contain particles.

If the temporary support (2) is a polyester film composed of 2 layers, one of the 2 layers becomes a surface layer on the 1 st side (i.e., a layer disposed as the outermost layer on the 1 st side), and the other layer becomes a surface layer on the 2 nd side (i.e., a layer disposed as the outermost layer on the 2 nd side). If the temporary support (2) is a polyester film composed of 3 or more layers, it is composed of a surface layer on the 1 st side (i.e., a layer disposed as the outermost layer on the 1 st side), a surface layer on the 2 nd side (i.e., a layer disposed as the outermost layer on the 2 nd side), and 1 or 2 or more intermediate layers sandwiched between these 2 surface layers.

The temporary support (2) is a temporary support in which at least one surface layer of the 2 surface layers does not contain particles.

In addition, from the viewpoint of reducing diffusion of light during exposure of the photosensitive resin layer via the temporary support and forming a resin pattern having high linearity, it is preferable that the surface layer on the 2 nd surface side of the temporary support (2) contains no particles. The surface layer on the 2 nd surface side of the temporary support (2) does not contain particles, so that scattering of light by the particles can be suppressed.

In addition, from the viewpoints of patterning property at the time of pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the surface layer on the 1 st surface side of the temporary support (2) contains no particles.

L of the 2 nd surface of the temporary support (2) measured by the SCE method from the viewpoint of straightness of the resin pattern ^* The value is preferably 1.5 or less, more preferably 1.2 or less, further preferably 1.0 or less, and particularly preferably 0.7 or less. L of the 2 nd surface of the temporary support (2) ^* The lower limit of the value is not limited, and may be, for example, 0.1 or more.

On the other hand, L of the 1 st surface of the temporary support (2) measured by SCE method ^* The value is preferably 2.0 or less, more preferably 1.5 or less, further preferably 1.0 or less, and particularly preferably 0.8 or less. L of the 1 st surface of the temporary support (2) ^* The lower limit of the value is not limited, and may be, for example, 0.1 or more, preferably 0.6 or more.

From the viewpoint of conveyability, the arithmetic average roughness Ra of the 1 st surface of the temporary support (2) is preferably 1nm to 50nm, more preferably 1nm to 40nm.

The arithmetic average roughness Ra of the 1 st surface in the temporary support (2) is determined by the method according to JIS B0601: the measurement was carried out by the method of 1994. Specifically, the measurement can be performed by the same method as the arithmetic average roughness Ra of the surface of the protective film described later.

The film may be a film composed of 2 or more layers constituting the temporary support (2), and the resin constituting the film may be a film composed mainly of a polyester resin. The term "resin constituting the film contains a polyester resin as a main component" means that at least 70 mol% or more of the resin constituting the film is a polyester resin.

The polyester resin constituting the polyester film is obtained by polymerization of a monomer containing a dicarboxylic acid, a diol, and an ester-forming derivative thereof as constituent components. Specific examples of the polyester resin constituting the film include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polyhexamethylene terephthalate, polyhexamethylene naphthalate, copolymers thereof, and the like, and polyethylene terephthalate is particularly preferred.

As the dicarboxylic acid component (including dicarboxylic acids and ester-forming derivatives thereof) which is a monomer for obtaining the polyester resin, aromatic dicarboxylic acids are preferably used.

Examples of the aromatic dicarboxylic acid include terephthalic acid, 2, 6-naphthalene dicarboxylic acid, isophthalic acid, and the like, and terephthalic acid is particularly preferred.

The dicarboxylic acid component may be used in an amount of 1 or 2 or more. For example, 2 or more kinds of aromatic dicarboxylic acids may be used in combination, or an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid may be used in combination.

Examples of the diol component (including diols and ester-forming derivatives thereof) which is a monomer for obtaining polyesters include ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, and neopentyl glycol, and ethylene glycol is particularly preferred.

The diol component may be used in an amount of 1 or 2 or more.

The polyester resin constituting the polyester film can be produced by a conventionally known method. Examples of the method include a method of removing the remaining diol component by directly esterifying the dicarboxylic acid component with the diol component and then heating the reaction product under reduced pressure and performing polycondensation, and a method of using a dialkyl ester of a dicarboxylic acid as the dicarboxylic acid component and performing transesterification with the diol component and then performing polycondensation in the same manner as described above. In this case, conventionally known alkali metal, alkaline earth metal, manganese, cobalt, zinc, antimony, germanium, titanium compounds and the like can be used as a reaction catalyst, if necessary.

The intrinsic viscosity of the polyester resin constituting the polyester film is preferably 0.5dl/g to 0.8dl/g, more preferably 0.55dl/g to 0.70dl/g.

The temporary support (2) preferably has a phase separation structure in the surface layer containing no particles. That is, the surface layer preferably contains no particles and has a phase separation structure (specifically, may be an island structure). The surface layer forms surface irregularities derived from a phase separation structure by not containing particles but having a phase separation structure (e.g., a sea-island structure). Specifically, a film having a surface layer with a phase separation structure is biaxially stretched to generate easily stretchable regions and hardly stretchable regions derived from the phase separation structure, for example, and the stretching is uneven to form minute surface irregularities.

In order to form a phase separation structure in the surface layer as described above, the surface layer preferably contains a polyester resin having an alicyclic structure. That is, the surface layer is formed into a phase separation structure (for example, a sea-island structure) by a polyester resin containing a main polyester resin (for example, a polyester resin having an aromatic ring structure) and a polyester resin having an alicyclic structure different from the compatibility of the main polyester resin.

The alicyclic structure in the polyester resin having the above alicyclic structure may preferably be a cyclopropane ring, a cyclobutane ring, a cyclopentane ring or a cyclohexane ring, and particularly preferably a cyclohexane ring. The polyester resin having an alicyclic structure is obtained by polycondensation reaction of, for example, dimethyl terephthalate as a dicarboxylic acid component, 1, 3-cyclopropanediol, 1, 3-cyclobutanediol, 1, 3-cyclopentanediol, 1, 4-cyclohexanedimethanol, etc., as a diol component, in the presence of 200ppm of butyltin tris (2-ethylhexanoate).

The content of the polyester resin having an alicyclic structure is preferably 3 to 10 mass% relative to the total mass of the surface layer from the viewpoints of the formability of surface irregularities, the occurrence of coating defects in the composition for forming a photosensitive resin layer, and the like.

The temporary support (2) preferably contains a polyester resin having an alicyclic structure in the surface layer and a copolymerized polyethylene terephthalate containing isophthalic acid as a copolymerization component.

Here, the copolymerized polyethylene terephthalate using isophthalic acid as a copolymerization component means a polyester resin which contains ethylene glycol as a most diol component, terephthalic acid as a most dicarboxylic acid component, and isophthalic acid as a dicarboxylic acid component. The copolymerization ratio of isophthalic acid is preferably in the range of 0.1 to 49 mol%, more preferably 0.5 to 40 mol%, based on the entire dicarboxylic acid component. When the surface layer contains a copolymerized polyethylene terephthalate containing an isophthalic acid component as a copolymerization component, it is preferable in terms of film formability because it is different from a polyester resin having an alicyclic structure in terms of stretchability, and therefore it is preferable in terms of easiness in forming surface irregularities.

The content of the copolymerized polyethylene terephthalate containing isophthalic acid as a copolymerization component is not particularly limited, and is preferably 10 to 20% by mass based on the total mass of the constituent surface layer.

The thickness of the surface layer is preferably 0.5 μm to 2.5 μm, more preferably 0.6 μm to 2.0 μm, from the viewpoint of linearity and transportation of the resin pattern.

The thickness of the temporary support (2) is preferably 50 μm or less, more preferably 40 μm or less. The lower limit of the thickness of the temporary support is, for example, 5 μm or more.

(layer structure)

In the temporary support (2), as the layer structure of the polyester film composed of 2 layers, there may be mentioned a layer (skin layer)/B layer (skin layer), and as the layer structure of the polyester film composed of 3 layers, there may be mentioned a layer/B layer (intermediate layer)/a layer, a layer/B layer (intermediate layer)/C layer (skin layer). Examples of the polyester film having 4 or more layers include a film having a laminated structure in the intermediate layer.

In the case where the layer a is a surface layer containing no particles, the layer B (surface layer), the layer B (intermediate layer), and the layer C (surface layer) may be polyester films, respectively, and may contain particles within a range not impairing the object of the present invention, but may be a layer (polyester film) containing no particles as in the case of the layer a. In the case where the layer B (surface layer), the layer B (intermediate layer), or the layer C (surface layer) is a layer containing particles, the particles may be organic particles or inorganic particles. Examples of the organic particles include particles of polyimide resins, olefin or modified olefin resins, crosslinked polystyrene resins, silicone resins, and the like. Examples of the inorganic particles include particles such as silica, calcium carbonate, aggregated alumina, aluminum silicate, mica, clay, talc, and barium sulfate.

The particles are preferably particles in which the surface of the particles is modified with a surfactant or the like to improve affinity with the polyester resin. The particles are preferably particles having a nearly spherical shape and a small difference in refractive index from the polyester resin, and examples thereof include colloidal silica and organic particles, and particularly preferably silicone resin particles and crosslinked polystyrene resin particles. Among them, the crosslinked polystyrene resin particles composed of a styrene-divinylbenzene copolymer adjusted by emulsion polymerization preferably have a particle shape close to true sphere and a uniform particle size distribution, and thus can realize uniform protrusion formation.

The temporary support (2) is preferably as follows: the polyester film having 3 or more layers, wherein the two surface layers contain no particles and contain a polyester resin having an alicyclic structure, and the thickness is 0.5-2.5 [ mu ] m, and the arithmetic average roughness Ra of the 1 st surface side is 1-50 nm or less.

The method for manufacturing the temporary support (2) will be described below.

The polyester film having 2 or more layers as the temporary support (2) may be produced by melt film formation by a coextrusion method. In the case of obtaining a layer (polyester film) containing particles, there is a method of dispersing particles in ethylene glycol as a glycol component to prepare a slurry, for example, after high-precision filtration of coarse particles, adding the ethylene glycol slurry in an arbitrary stage before completion of polyester polymerization. In the case of adding particles, for example, the hydrosol or the alcohol sol obtained in the synthesis of the particles may be directly added without drying the same. Further, a method of mixing the aqueous slurry of particles with polyester particles and then supplying the mixture to a vent-type twin-screw kneading extruder to contain the particles in the polyester film may be used.

The particles containing particles and the particles containing no particles prepared for each layer are mixed as necessary, and then supplied to a known extruder for melt lamination. As the extruder, a single-shaft or double-shaft extruder can be used. In order to omit the step of drying the pellets, a vent type extruder in which a vacuum line is provided in the extruder may be used. In addition, in the formation of the layer B having the largest extrusion amount, a so-called tandem extruder having a function of melting the pellets and a function of keeping the melted pellets at a constant temperature may be used.

The melt melted by the extruder and extruded was filtered through a filter. For example, a high-precision filter that collects 95% or more of impurities having a diameter of 5 μm or more can be used as the filter. Then, the film was extruded from a slit-shaped slit die into a sheet, and cooled and solidified on a casting roll to prepare an unstretched film. That is, a plurality of extruders and a plurality of layers of manifold or hinge blocks (for example, a hinge block having a rectangular junction) are used to laminate, a sheet is extruded from a die, and cooled on a casting roll to produce an unstretched film. In this case, a static mixer and a gear pump are preferably provided in the flow path of the melt.

The temporary support (2) is preferably a biaxially stretched film.

The stretching method may be simultaneous biaxial stretching or sequential biaxial stretching. In the case of the sequential stretching, the stretching temperature in the stretching in the first longitudinal direction is preferably 90 to 130 ℃, more preferably 100 to 125 ℃, from the viewpoint of suppressing breakage of the film and suppressing thermal damage. In addition, from the viewpoint of preventing uneven stretching and scratches, stretching is preferably performed in a classification of 2 or more.

From the viewpoints of suppressing stretching unevenness and suppressing breakage of the film, the stretching ratio is preferably 3 to 4.5 times (preferably 3.5 to 4.3 times) in the longitudinal direction and 3.2 to 5 times (preferably 4.0 to 4.6 times) in the width direction. After the stretching, the heat setting is preferably performed at 200 to 230 ℃ (preferably 210 to 230 ℃) for 0.5 to 20 seconds (preferably 1 to 15 seconds) from the viewpoint of obtaining a specific heat shrinkage rate or the like as desired. Further, after the thermosetting state, a relaxation treatment of 0.1% to 7.0% is preferably performed in the length and/or width direction.

Hereinafter, the description will be made of both the temporary support (1) and the temporary support (2) in the case of simply called "temporary support", unless otherwise specified.

Photosensitive resin layer

The photosensitive transfer material according to the present invention includes a photosensitive resin layer on the 2 nd surface of a temporary support. The photosensitive resin layer is preferably a negative type photosensitive resin layer in which the solubility of the exposed portion in a developer is reduced by exposure and the non-exposed portion is removed by development. However, the photosensitive resin layer is not limited to the negative type photosensitive resin layer. The photosensitive resin layer may be a positive type photosensitive resin layer in which the solubility of the exposed portion in a developer is improved by exposure and the exposed portion is removed by development.

The photosensitive resin layer preferably contains a polymer a, a polymerizable compound B, and a photopolymerization initiator. The photosensitive resin layer preferably contains 10 to 90 mass% of the polymer a, 5 to 70 mass% of the polymerizable compound B, and 0.01 to 20 mass% of the photopolymerization initiator, based on the total solid content mass of the photosensitive resin layer. The components of the photosensitive resin layer will be described below.

(Polymer A)

Examples of the polymer a include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamides, polyesters, polyamide resins, epoxy resins, polyacetals, polyhydroxystyrenes, polyimide resins, polybenzoxazoles, polysiloxanes, polyethylenimines, polyallylamines, and polyalkylene glycols. Polymer a is preferably an alkali soluble polymer. The alkali-soluble polymer compound contains a polymer compound that is easily dissolved in an alkali substance. In the present invention, "alkali solubility" means a property of having a solubility of 0.1g or more in an aqueous solution (100 g) containing 1 mass% sodium carbonate at 22 ℃.

The acid value of the polymer a is preferably 220mgKOH/g or less, more preferably less than 200mgKOH/g, and particularly 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 limited. The acid value of the polymer A is preferably 60mgKOH/g or more, more preferably 120mgKOH/g or more, still more preferably 150mgKOH/g or more, particularly preferably 170mgKOH/g or more, from the viewpoint of more excellent developability. The acid value of the polymer a may be adjusted by using the type of the structural unit constituting the polymer a and the content of the structural unit containing an acid group.

In the present invention, the "acid value" is the mass (mg) of potassium hydroxide required for neutralizing 1g of the sample. The unit of acid value is represented by mgKOH/g. The acid value can be calculated, for example, from the average content of acid groups in the compound.

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 of the polymer a is more preferably 100,000 or less, still more preferably 80,000 or less, and particularly preferably 70,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film (for example, edge meltability and chipping property), the weight average molecular weight is preferably set to 5,000 or more. The weight average molecular weight of the polymer a 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 a degree to which the photosensitive resin layer easily protrudes from the end surface of the roller in the photosensitive transfer material wound in a roller shape. The chipping property is the degree to which chips are easily scattered when the unexposed film is cut by a dicing machine. For example, if the generated chip is transferred to a mask used at the time of exposure, the chip becomes a cause of defective products. The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, particularly preferably 1.0 to 3.0. In the present invention, the dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight). In the present invention, the weight average molecular weight and the number average molecular weight are values measured by gel permeation chromatography.

The glass transition temperature (Tg) of the polymer A is preferably 30℃or more and 135℃or less. When the Tg of the polymer a is 135 ℃ or lower, deterioration of line width thickness and resolution at the time of focus position shift at the time of exposure can be suppressed. The Tg of the polymer A is more preferably 130℃or lower, still more preferably 120℃or lower, particularly preferably 110℃or lower. The Tg of the polymer A is 30℃or higher, whereby edge melting resistance can be improved. 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.

From the viewpoint of suppressing deterioration of line width thickness or resolution at the time of focus position shift at the time of exposure, polymer a preferably contains a structural unit having an aromatic hydrocarbon group. The polymer a may contain 1 or 2 or more structural units having an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content of the structural unit 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, relative to the total mass of the polymer a. The upper limit of the content of the structural unit having an aromatic hydrocarbon group in the polymer a is not limited. The content of the structural unit having an aromatic hydrocarbon group in the polymer a is preferably 95 mass% or less, more preferably 85 mass% or less. When the photosensitive resin layer contains a plurality of polymers a, the content of the structural units having an aromatic hydrocarbon group is determined as a weight average value. When the photosensitive resin layer contains a plurality of polymers a, the content of the structural units having an aromatic hydrocarbon group is determined as a weight average value.

The structural unit having an aromatic hydrocarbon group is introduced using a monomer having an aromatic hydrocarbon group. Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, t-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Among the above, monomers having an aralkyl group or styrene are preferable. In the case where the structural unit having an aromatic hydrocarbon group in the polymer a is a structural unit derived from styrene, the content of the structural unit derived from styrene is preferably 20 to 80 mass%, more preferably 25 to 70 mass%, and particularly preferably 30 to 60 mass% relative to the total mass of the polymer a.

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

Examples of the monomer having a phenylalkyl group include ethyl (meth) acrylate.

Examples of the monomer having a benzyl group include (meth) acrylic acid esters having a benzyl group (e.g., benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, and the like) and vinyl monomers having a benzyl group (e.g., vinylbenzyl chloride and vinylbenzyl alcohol). Among the above, benzyl (meth) acrylate is preferable. When the structural unit having an aromatic hydrocarbon group in the polymer a is a structural unit derived from benzyl (meth) acrylate, the content of the structural unit derived from benzyl (meth) acrylate 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, relative to the total mass of the polymer a.

The polymer a containing a structural unit having an aromatic hydrocarbon group preferably contains at least 1 selected from the group consisting of a structural unit derived from a first monomer and a structural unit derived from a second monomer, and a structural unit having an aromatic hydrocarbon group.

The polymer a containing no structural unit having an aromatic hydrocarbon group preferably contains a structural unit derived from a first monomer, more preferably contains a structural unit derived from a first monomer and a structural unit derived from a second monomer.

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 the above, (meth) acrylic acid is preferable. The polymer a may contain 1 or 2 or more structural units derived from the first monomer alone. The content of the first monomer in the polymer a is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and particularly preferably 15 to 35% by mass, relative to the total mass of the polymer a.

The second monomer is a monomer that is non-acidic and has at least 1 polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth) acrylic esters (for example, 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, 2-ethylhexyl (meth) acrylate, and esters of vinyl alcohol (for example, vinyl acetate) and (meth) acrylonitrile. Among the above, 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 particularly preferably 20 to 45% by mass, relative to the total mass of the polymer a.

From the viewpoint of suppressing deterioration of line width thickness or resolution at the time of focus position shift at the time of exposure, the polymer a preferably contains at least 1 selected from the group consisting of a structural unit derived from a monomer having an aralkyl group and a structural unit derived from styrene. Preferable specific examples of the polymer a include copolymers of methacrylic acid, benzyl methacrylate and styrene, and copolymers of methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene.

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

The polymer a may have a branched structure or an alicyclic structure in a side chain. For example, a branched structure or an 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 alicyclic structure in the side chain of the polymer A may be a single ring or multiple rings.

Also, the polymer a may have a linear structure on a side chain.

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

Specific examples of the monomer having a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Further, specific examples of the monomer having a group having an alicyclic structure in a side chain include (meth) acrylic esters having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Examples of the monomer having a group having an alicyclic structure in a side chain 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-ethyladamantyl (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, 5-methyl-1-adamantyl (meth) acrylate, 1-octahydro-indene (meth) acrylate, 1-methyl (meth) acrylate, 1-octahydro) acrylate, and the like Tricyclodecane (meth) acrylate, 3-hydroxy-2, 6-trimethyl-bicyclo [3.1.1] heptyl (meth) acrylate, 3, 7-trimethyl-4-hydroxy-bicyclo [4.1.0] heptyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate. Among the above, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthol and tricyclodecane (meth) acrylate are preferable, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, mono-2-adamantyl (meth) acrylate and tricyclodecane (meth) acrylate are more preferable.

The photosensitive resin layer may contain 1 or 2 or more kinds of polymers a. When 2 or more polymers a are used, it is preferable to use 2 polymers a containing structural units having an aromatic hydrocarbon group or to use a polymer a containing structural units having an aromatic hydrocarbon group in combination with a polymer a not containing structural units having an aromatic hydrocarbon group. In the latter case, the proportion of the polymer a containing the structural unit 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 particularly preferably 90% by mass or more, relative to the total mass of the polymer a.

The content of the polymer a in the photosensitive resin layer is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, based on the total mass of the photosensitive resin layer. From the viewpoint of controlling the development time, the content of the polymer a is preferably 90 mass% or less. From the viewpoint of improving the edge melting resistance, the content of the polymer a is preferably 10 mass% or more.

The synthesis of polymer a is preferably carried out by: to a solution of the monomer diluted with a solvent (for example, acetone, methyl ethyl ketone, and isopropyl alcohol), a radical polymerization initiator (for example, benzoyl peroxide, and azoisobutyronitrile) is added in an appropriate amount, and the mixture is heated and stirred. A part of the mixture may be added dropwise to the reaction solution and synthesized. After the completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As the synthesis apparatus, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

(polymerizable Compound B)

The polymerizable compound B is a compound having a polymerizable group. In the present invention, the "polymerizable compound" refers to a compound which is polymerized by receiving the action of a polymerization initiator and which is different from the above-mentioned polymer a.

The polymerizable group is not limited as long as it is a group involved in polymerization reaction, and examples thereof include an ethylenically unsaturated group (for example, vinyl group, acryl group, methacryl group, styryl group, and maleimide group) and a cationically polymerizable group (for example, epoxy group and oxetanyl group). The polymerizable group is preferably an ethylenically unsaturated group, more preferably an acryl group or a methacryl group.

In terms of more excellent photosensitivity of the photosensitive resin layer, the polymerizable compound B is preferably a compound having at least 1 ethylenically unsaturated group (i.e., an ethylenically unsaturated compound), more preferably a compound having 2 or more ethylenically unsaturated groups in one molecule (i.e., a polyfunctional ethylenically unsaturated compound). In addition, the number of the ethylenically unsaturated groups contained in the ethylenically unsaturated compound of one molecule is preferably 6 or less, more preferably 3 or less, and particularly preferably 2 or less, in terms of more excellent resolution and releasability. The ethylenically unsaturated compound is preferably a (meth) acrylate compound having a (meth) acryloyl group.

In terms of more excellent balance of photosensitivity, resolution and releasability of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound having 2 or 3 ethylenically unsaturated groups in one molecule (i.e., a 2-functional or 3-functional ethylenically unsaturated compound), more preferably a compound having 2 ethylenically unsaturated groups in one molecule (i.e., a 2-functional ethylenically unsaturated compound). From the viewpoint of excellent releasability, the content of the 2-functional ethylenically unsaturated compound in the photosensitive resin layer is preferably 60 mass% or more, more preferably more than 70 mass%, and particularly preferably 90 mass% or more, relative to the total mass of the polymerizable compound B. The upper limit of the content of the 2-functional ethylenically unsaturated compound is not limited. The content of the 2-functional ethylenically unsaturated compound in the photosensitive resin layer may be 100 mass% with respect to the total mass of the polymerizable compound B. That is, all of the polymerizable compounds B contained in the photosensitive resin layer may be 2-functional ethylenically unsaturated compounds.

The photosensitive resin layer preferably contains an aromatic ring and a polymerizable compound B1 having 2 ethylenically unsaturated groups. The polymerizable compound B1 is a compound (i.e., a 2-functional ethylenically unsaturated compound) contained in the above-described polymerizable compound B, the compound having 2 ethylenically unsaturated groups in one molecule.

Examples of the aromatic ring include an aromatic hydrocarbon ring (for example, benzene ring, naphthalene ring, and anthracene ring), an aromatic heterocyclic ring (for example, thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring), and condensed rings thereof. The aromatic ring is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring. The aromatic ring may have a substituent. The polymerizable compound B1 may have 2 or more aromatic rings.

The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving resolution by suppressing swelling of the 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). The bisphenol structure is preferably a bisphenol a structure. Examples of the polymerizable 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. Each ethylenically unsaturated group may be directly bonded to the terminal of the bisphenol structure, or may be bonded via 1 or more alkyleneoxy groups. The alkyleneoxy group is preferably ethyleneoxy or propyleneoxy, more preferably ethyleneoxy. The number of alkyleneoxy groups added to the bisphenol structure is not limited. The number of alkyleneoxy groups added to the bisphenol structure is preferably 4 to 16, more preferably 6 to 14 per 1 molecule. The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A2016-224162. The contents of the above publications are incorporated into the present specification by reference.

The polymerizable compound B1 is preferably a 2-functional ethylenically unsaturated compound having a bisphenol a structure, and more preferably 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane. Examples of 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane include 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324, M, hitachi Chemical co., ltd.), 2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane, 2-bis (4- (methacryloxypentethoxy) phenyl) propane (BPE-500, shin-Nakamura Chemical co., ltd.), 2-bis (4- (methacryloxydodecyoxytetrapropoxy) phenyl) propane (FA-3200 MY, hitachi Chemical co., ltd.), 2-bis (4- (methacryloxypentaethoxy) phenyl) propane (BPE-1300, shin-Nakamura Chemical co., ltd.), 2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-83, shin-ltd., ltd.10, and (NK-62, ltd.) and (NK-62, di-62, and (ltd.) acrylic acid ESTERs.

The polymerizable compound B1 may be, for example, a compound represented by the following formula (I).

[ chemical formula 1]

In the formula (I), R ₁ R is R ₂ Each independently represents a hydrogen atom or a methyl group, A represents C ₂ H ₄ B represents C ₃ H ₆ ，n ₁ N is as follows ₃ Each independently represents an integer of 1 to 39, n ₁ +n ₃ Is an integer of 2 to 40, n ₂ N is as follows ₄ Each independently represents an integer of 0 to 29, 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. In the case of blocks, - (A-O) -can be on the diphenyl side, - (B-0) -can be on the diphenyl sideAnd (3) sides. n is n ₁ +n ₂ +n ₃ +n ₄ Preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 12. n is n 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 photosensitive resin layer may contain 1 or 2 or more kinds of polymerizable compounds B1.

From the viewpoint of more excellent resolution, the content of the polymerizable compound B1 in the photosensitive resin layer is preferably 10 mass% or more, more preferably 20 mass% or more, relative to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 70 mass% or less, more preferably 60 mass% or less, from the viewpoints of transferability and edge melting resistance.

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

The photosensitive resin layer may contain a polymerizable compound B other than the polymerizable compound B1. Examples of the polymerizable compound B other than the polymerizable compound B1 include monofunctional ethylenically unsaturated compounds (i.e., compounds having 1 ethylenically unsaturated group in one molecule), 2-functional ethylenically unsaturated compounds having no aromatic ring (i.e., compounds having no aromatic ring and having 2 ethylenically unsaturated groups in one molecule), and 3-functional or more ethylenically unsaturated compounds (i.e., compounds having 3 or more ethylenically unsaturated groups in one molecule).

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

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

Examples of alkylene glycol di (meth) acrylates include tricyclodecane dimethanol diacrylate (A-DCP, shin-Nakamura Chemical Co., ltd.), tricyclodecane dimethanol dimethacrylate (DCP, shin-Nakamura Chemical Co., ltd.), 1, 9-nonanediol diacrylate (A-NOD-N, shin-Nakamura Chemical Co., ltd.), 1, 6-hexanediol diacrylate (A-HD-N, shin-Nakamura Chemical Co., ltd.), ethylene glycol dimethacrylate, 1, 10-decanediol 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 commercial products of urethane di (meth) acrylate 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 (meth) acrylate compounds having a dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate and glycerol tri (meth) acrylate skeleton.

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.

Examples of the alkylene oxide modified products of the ethylenically unsaturated compounds having 3 or more functions include caprolactone-modified (meth) acrylate compounds (for example, KAYARAD DPCA-20 (Nippon Kayaku co., ltd.) and a-9300-1CL (Shin-Nakamura Chemical co., ltd.), alkylene oxide-modified (meth) acrylate compounds (KAYARAD RP-1040 (Nippon Kayaku co., ltd.), ATM-35E (Shin-Nakamura Chemical co., ltd.), a-9300 (Shin-Nakamura Chemical co., ltd.), and ebryl 135 (DAICEL-ALLNEX ltd.)), ethoxylated glycerol triacrylates (for example, a-GLY-9E (Shin-Nakamura Chemical co., ltd.)), aroix TO-2349 (toseico., ltd.), ARONIX-520 (toagenix co., ltd.)), and aroeix-510.

From the viewpoint of the processing liquid resistance such as development, the photosensitive resin layer preferably contains polymerizable compounds B1 and 3 or more functional ethylenically unsaturated compounds, and more preferably contains polymerizable compounds B1 and 2 or more 3 or more functional ethylenically unsaturated compounds. The mass ratio of the polymerizable compound B1 to the ethylenically unsaturated compound having 3 or more functions (total mass of the polymerizable compounds B1: total mass of the ethylenically unsaturated compounds having 3 or more functions) is preferably 1:1 to 5:1, more preferably 1.2:1 to 4:1, and particularly preferably 1.5:1 to 3:1.

As the polymerizable compound B other than the polymerizable compound B1, the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 can be used.

The photosensitive resin layer may contain 1 or 2 or more kinds of polymerizable compounds B.

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

The molecular weight of the polymerizable compound B is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200. The molecular weight of the polymerizable compound B having a molecular weight distribution is represented by a weight average molecular weight (Mw).

From the viewpoints of resolution and linearity, the ratio Mm/Mb of the content Mm of the ethylenically unsaturated compound to the content Mb of the polymer a in the photosensitive resin layer is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 to 0.9. The ethylenically unsaturated compound in the photosensitive resin layer preferably contains a (meth) acrylic compound, more preferably contains a (meth) acrylate compound, from the viewpoints of curability and resolution. From the viewpoints of curability, resolution, and linearity, the ethylenically unsaturated compound in the 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 compounds contained in the photosensitive resin layer.

(photopolymerization initiator)

The photopolymerization initiator is a compound that starts polymerization of the polymerizable compound upon receiving active light (for example, ultraviolet rays, visible rays, and X rays).

The kind of photopolymerization initiator is not limited. The photopolymerization initiator according to the present invention includes a known photopolymerization initiator. Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and a photo radical polymerization initiator is preferable.

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

From the viewpoints of photosensitivity, visibility of an exposed portion, visibility of a non-exposed portion, and resolution, the photosensitive resin layer preferably contains at least 1 selected from 2,4, 5-triarylimidazole dimer and derivatives thereof as a photo radical polymerization initiator. 2,4, 5-triarylimidazole dimers and derivatives thereof 2 of the 2,4, 5-triarylimidazole structures may be the same or different. Examples of the derivative of the 2,4, 5-triarylimidazole dimer include a 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-chlorophenyl) -4, 5-di (methoxyphenyl) imidazole dimer, a 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer and a 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer.

Examples of the photo radical polymerization initiator include those described in paragraphs 0031 to 0042 of JP 2011-95716 and in paragraphs 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 and anisole (p, p' -dimethoxybenzyl).

Examples of commercial products of the photo radical polymerization initiator include TAZ-110 (trade name: midori Kagaku Co., ltd.), benzophenone, TAZ-111 (trade name: midori Kagaku Co., ltd.), 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE OXE01, BASF Co., ltd.), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetoxime) (trade name: IRGACURE OXE02, BASF Co., IRGACURE OXE03 (BASF Co., ltd.), IRGACURE OXE04 (BASF Co., ltd.), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (trade name: omni 379EG, IGM Resins B.V.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- (4-methylbenzoyl) -2-morpholinopropane-1- (Om-1-hydroxy-1, om-3-yl) propanone (trade name: omGACURE OXE03 (BASF Co., IRGACURE OX Co., ltd.), IRGACURE OX 04 (BASF Co., ltd.), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (trade name: omni 379EG, IGM resin B.V.), 2-methyl-1- (4-methylbenzoyl) propane-2- [ hydroxy ] ketone (Om-4- (L-methyl-4-methyl-1- (L-methyl) hydroxy) ketone (L, L-2-methyl) ketone (L, L-methyl) ketone (L) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: omnirad 369, IGM Resins b.v.), 2-hydroxy-2-methyl-1-phenylpropane-1-one (trade name: omnirad 1173, IGM Resins b.v.), 1-hydroxycyclohexyl phenyl ketone (trade name: omnirad 184, IGM Resins b.v.), 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: omnirad 651, IGM Resins b.v.), 2,4, 6-trimethylbenzil-diphenyl phosphine oxide (trade name: omnirad TPO H, IGM Resins b.v.), bis (2, 4, 6-trimethylbenzil) phenylphosphine oxide (trade name: omnirad 819, IGM Resins b.v.), photopolymerization initiators of oxime esters (trade name: lunar 6, DKSH MANAGEMENT ltd, trade name), 2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenylbisimidazole (trade name: 2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer, trade name: B-for 4, bisphenol-c-2- (2-chlorophenyl) -4, 5' -diphenyl sulfide, 4- [ 3, 37, 4-diphenyl sulfide, 4- [ 3-chlorophenyl ] -2- (2-chlorophenyl) -4, 35, 3- [ diphenyl sulfide ],37, 1-diphenyl sulfide, 2-dione-2- (O-benzoyloxime) (trade name: TR-PBG-305, CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS co., ltd.), 1, 2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furylcarbonyl) -9H-carbazol-3-yl ] -,2- (O-acetyloxime) (trade name: TR-PBG-326, CHANGZHOU TRONLY NEW ELE CTRONIC MATERIALS co., ltd.), 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) octanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1, 2-dione-2- (O-benzoyloxime) (trade name: TR-PBG-391, CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS 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 that generates an acid in response to an active light having a wavelength of 300nm or more (preferably a wavelength of 300nm to 450 nm). The photo-cation polymerization initiator which does not directly react with 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 reacts with 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 which generates an acid having a pKa of 4 or less, more preferably a photo-cation polymerization initiator which generates an acid having a pKa of 3 or less, and particularly preferably a photo-cation polymerization initiator which generates an acid having a pKa of 2 or less. The lower limit of pKa is not limited. The pKa of the acid generated from the photo-cationic polymerization initiator is 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 (for example, diaryliodonium salts and triarylsulfonium salts) and quaternary ammonium salts. As the ionic photo-cation polymerization initiator, the ionic photo-cation polymerization initiator described in 0114 to 0133 of JP-A2014-85643 can be used. Examples of the nonionic photo-cationic polymerization initiator include trichloromethyl s-triazines, diazomethane compounds, imide sulfonate compounds and oxime sulfonate compounds. Examples of the trichloromethyl-s-triazines, diazomethane compounds and imide sulfonate compounds include those described in paragraphs 0083 to 0088 of JP-A2011-221494. Further, as the oxime sulfonate compound, the compounds described in paragraphs 0084 to 0088 of International publication No. 2018/179640 can be used.

The photosensitive resin layer preferably contains a photo radical polymerization initiator, more preferably contains at least one selected from the group consisting of 2,4, 5-triarylimidazole dimer and derivatives thereof.

The photosensitive resin layer may contain 1 or 2 or more photopolymerization initiators.

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

(pigment)

From the viewpoints of visibility of an exposed portion, visibility of a non-exposed portion, pattern visibility after development, and resolution, the photosensitive resin layer preferably contains a dye (hereinafter, sometimes referred to as "dye N") 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. The photosensitive resin layer contains the dye N, so that adhesion of a layer (for example, a temporary support) adjacent to the photosensitive resin layer is improved, and resolution is improved.

In the present invention, the term "change in maximum absorption wavelength by an acid, a base or a radical" used in relation to a dye includes (1) a manner in which a dye in a colored state is decolorized by an acid, a base or a radical, (2) a manner in which a dye in a decolorized state is developed by an acid, a base or a radical, and (3) a manner in which a dye in a developed state becomes a developed state of other hues. For example, the dye N may be a compound that develops color by changing from a decolored state by exposure or a compound that is decolored by changing from a decolored state by exposure. The dye N may be a dye that changes its state of color development or decoloration by the action of an acid, an alkali or a radical generated in the photosensitive resin layer by exposure. The dye N may be a dye whose state (e.g., pH) in the photosensitive resin layer changes by an acid, an alkali, or a radical, and whose state changes in color or decoloration. The dye N may be a dye which changes its color development or decoloration state by directly receiving an acid, an alkali or a radical without exposure.

From the viewpoints of visibility of the exposed portion and visibility of the non-exposed portion, the dye N is preferably a dye that develops color by an acid, a base, or a radical.

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

The dye N is preferably a dye that changes by the maximum absorption wavelength of radicals, and more preferably a dye that develops by radicals, from the viewpoints of visibility of an exposed portion, visibility of a non-exposed portion, pattern visibility after development, and resolution.

Examples of the coloring mechanism of the dye N in the present invention include a system in which 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 from a photo radical polymerization initiator, a photo cation polymerization initiator (photoacid generator), or a photobase generator contained in the photosensitive resin layer.

From the viewpoints of visibility of the exposed portion and visibility of 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 550 to 700nm, and still more preferably 550 to 650nm. The number of maximum absorption wavelengths in the wavelength range of 400 to 780nm at the time of color development may be 1 or 2 or more. When the number of maximum absorption wavelengths in the wavelength range of 400 to 780nm at the time of color development is 2 or more, the maximum absorption wavelength having the highest absorbance among the 2 or more maximum absorption wavelengths may be 450nm or more.

The maximum absorption wavelength of the dye N was measured by the following method. In the atmospheric environment, a transmission spectrum of a solution containing pigment N (liquid temperature: 25 ℃) was measured in a wavelength range of 400nm to 780nm using a spectrophotometer (for example, UV3100, shimadzu Corporation), and the intensity of the detection light was extremely small. As the maximum absorption wavelength, a wavelength at which the intensity of light becomes extremely small is used.

Examples of the coloring matter that is colored or decolored by exposure include leuco coloring matter.

Examples of the coloring matter to be decolorized by exposure to light include leuco coloring matter, diarylmethane coloring matter, oxazine coloring matter, xanthene coloring matter, iminonaphthoquinone coloring matter, azomethine coloring matter and anthraquinone coloring matter.

The pigment N is preferably a leuco pigment from the viewpoints of visibility of the exposed portion and visibility of the non-exposed portion.

Examples of the leuco dye include leuco dyes having a triarylmethane skeleton (triarylmethane-based dyes), leuco dyes having a spiropyran skeleton (spiropyran-based dyes), leuco dyes having a fluoran skeleton (fluoran-based dyes), leuco dyes having a diarylmethane skeleton (diarylmethane-based dyes), leuco dyes having a rhodamine lactam skeleton (rhodamine lactam-based dyes), leuco dyes having an indolyl phthalide skeleton (indolyl phthalide-based dyes), and leuco dyes having a leuco golden amine skeleton (leuco golden amine-based dyes). Among the above, triarylmethane-based pigments or fluoran-based pigments are preferable, and leuco pigments (triphenylmethane-based pigments) or fluoran-based pigments having a triphenylmethane skeleton are more preferable.

The leuco dye preferably has a lactone ring, a sunnes ring or a sultone ring from the viewpoint of visibility of an exposed portion and a non-exposed portion. The lactone ring, the sunset ring, or the sultone ring in the leuco dye reacts with a radical generated by a photo radical polymerization initiator or an acid generated by a photo cation polymerization initiator, thereby changing the leuco dye to a closed-loop state to decolorize it or changing the leuco dye to an open-loop state to develop it. The leuco dye is preferably a compound having a lactone ring, a sunnes ring or a sultone ring, and the lactone ring, the sunnes ring or the sultone ring is developed by free radical or acid ring opening, more preferably a compound having a lactone ring, and the lactone ring is developed by free radical or acid ring opening.

Specific examples of the leuco dye include p, p', p "-hexamethyltriphenylmethane (colorless crystal violet), pergascript Blue SRB (Novartis International AG), crystal violet lactone, malachite green lactone, benzoyl leuco methylene blue, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) amino fluoran, 2-anilino-3-methyl-6- (N-ethyl-p-formyldiamino) fluoran, 3, 6-dimethoxyfluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluoran, 3- (N, N-diethylamino) -6-methyl-7-fluoran, 3- (N, N-diethylamino) -6-methyl-7-chlorofluoran, 3- (N, N-diethylamino) -6-methyl-7-N- (N, N-dibenzylamino) -6-methyl-7-phenylfluoran, 3- (N, N-diethylamino) -6-methyl-7-phenylfluoran, n-diethylamino) -7-chlorofluoran, 3- (N, N-diethylamino) -7-benzylaminofluoran, 3- (N, N-diethylamino) -7, 8-benzofluoran, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluoran, 3- (N, N-dibutylamino) -6-methyl-7-phenylfluoran, 3-hydropyridyl-6-methyl-7-anilinofluoran, 3-pyrrolo-6-methyl-7-anilinofluoran, 3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3-bis (1-N-butyl-2-methylindol-3-yl) phthalide, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphenylphthalide, 3- (4-diethyl-amino-6-methyl-7-anilino-4-phenylphthalide, 3- (1-ethyl-2-methylindol-3-yl) phthalide, 3-bis (1-N-methyl-2-methylindol-3-yl) phthalide, 9' - [9H ] xantham-3-one.

Examples of the dye N include dyes. Examples of dyes include brilliant Green, ethyl violet, methyl Green, crystal violet, vinylred, methyl violet 2B, quinolizine Red, rose Red, formylyellow, thiomorpholine, xylenol Blue, methyl orange, para-methylred, congo Red, benzopurin 4B, alpha-naphthalene Red, naphthalene Blue 2B, naphthalene Blue a, methyl violet, malachite Green, hydroquinone, victoria pure Blue-alkyl naphthalene sulfonate, victoria pure Blue BOH (Hodogaya Chemical co., LTD.), oil Blue #603 (ORIENT CHEMICAL INDUSTRIES co., LTD), oil Pink # 312 (oriant CHEMICAL INDUSTRIESCO., LTD), oil Red 5B (ORIENT CHEMICAL INDUSTRIES co., LTD), oil Scarlet #308 (ORIENT CHEMICAL INDUSTRIES co., LTD), oil Red OG (ORIENTCHEMICAL INDUSTRIES co., LTD), oil Red RR (ORIENT CHEMICAL INDUSTRIES co., LTD), oil 97502 (ORIENT CHEMICAL INDUSTRIES co, LTD), 69 (Hodogaya Chemical co., LTD), oil Pink (p-cresol), 4-hydroxy-4-ethyl amino-4-imino-4-methyl-4-N-imino-4-nitro-N-phenyl-imino-4-ethyl-imino-N-methyl-4-N-nitro-4-imino-N-nitro-4-nitro-N-phenyl-4-imino-4-N-imino-4-ethyl-N-4-nitro-N-imino-4-N-nitro-4-N-imino-N-4, p-nitro-N-4-nitro-N-imino-N-butyl amine 1-phenyl-3-methyl-4-p-diethylaminophenylimine-5-pyrazolone and 1-beta-naphthyl-4-p-diethylaminophenylimine-5-pyrazolone.

Pigment N is preferably leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-alkyl naphthalene sulfonate.

The photosensitive resin layer may contain 1 or 2 or more pigments N.

The content of the dye N is preferably 0.1 mass% or more, more preferably 0.1 mass% to 10 mass%, even more preferably 0.1 mass% to 5 mass%, and particularly preferably 0.1 mass% to 1 mass% relative to the total mass of the photosensitive resin layer, from the viewpoints of visibility of an exposed portion, visibility of a non-exposed portion, pattern visibility after development, and resolution. The content of the dye N is the content of the dye N when all of the dye N contained in the photosensitive resin layer is in a color development state. Hereinafter, a method of quantifying a dye by using a dye developed by a radical as an example will be described. A solution was prepared in which pigment (0.001 g) was dissolved in methyl ethyl ketone (100 mL) and 0.01g was dissolved in methyl ethyl ketone (100 mL). A photo radical polymerization initiator (Irgacure OXE01, BASF JAPAN LTD.) was added to each solution, and then 365nm light was irradiated to generate radicals, thereby bringing all the pigments into a developed state. The absorbance of each solution was measured under atmospheric conditions using a spectrophotometer (manufactured by UV3100, shimadzu Corporation) at a liquid temperature of 25 ℃. Next, absorbance of the solution in which all the pigments were developed was measured by the same method as described above except that the photosensitive resin layer (3 g) was dissolved in methyl ethyl ketone instead of the pigments. The amount of the pigment contained in the photosensitive resin layer was calculated from the absorbance of the solution containing the photosensitive resin layer based on the calibration curve.

(surfactant)

From the viewpoint of uniformity of thickness, the photosensitive resin layer preferably contains a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (Non-ionic) surfactants, and amphoteric surfactants. The surfactant is preferably a nonionic surfactant. The surfactant is preferably a fluorine-based surfactant or a silicone-based surfactant.

As the commercial products of the fluorine-based surfactant, there may be mentioned, for example, megaface (for example, 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-578-2, MFS-579, MFS-586, MFS-628, MFS-631, MFS-603, R-41-LM, R-01, R-40, RS-43, RS-6, RS-DS, F-53, R-94, and the like), coruor-72, and the like, FC430, FC431, FC171, sumitomo 3M Limited), surflon (e.g., S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393 and KH-40, AGC Inc.), polyFox (e.g., PF636, PF656, PF6320 and PF6520, PF7002, OMNOVA Solutions Inc.), ftergent (e.g., 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G), 710LA, 710FS, 730LM, 650AC, 681 and 683, neos Corporation), U-120E (Uni-chem co., ltd.).

As the fluorine-based surfactant, an acrylic compound having a molecular structure containing a functional group containing a fluorine atom, in which a functional group portion containing a fluorine atom is broken and the fluorine atom volatilizes when heat is applied, may be used. As the above-mentioned fluorine-based surfactant, there may be mentioned the Megaface DS series of DIC CORPORATION (Japanese chemical industry report (year 2016, month 2, day 22), japanese industrial news (year 2016, month 2, month 23), and Megaface DS-21, for example.

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 can also be used.

As the fluorine-based surfactant, a block polymer may be used.

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

As the fluorine-based surfactant, a fluorine-containing polymer having a group containing an ethylenically unsaturated bond in a side chain can also be used. As the above-mentioned commercial products of the fluorine-based surfactant, megaface (for example, RS-101, RS-102, RS-718K and RS-72-K, DIC CORPORATION) can be mentioned.

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

Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates (for example, glycerin ethoxylate) and propoxylates (for example, glycerin propoxylate) thereof. Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, pluronic (for example, L10, L31, L61, L62, 10R5, 17R2 and 25R2, hydroopaat WE 3323, BASF), tetronic (for example, 304, 701, 704, 901, 904 and 150R1, BASF), solsperse20000 (The Lubrizol Corporation), NCW-101 (FUJIFILM Wako Pure Chemical Corporation), NCW-1001 (FUJIFILM Wako Pure Chemical Corporation), NCW-1002 (FUJIFILM Wako Pure Chemical Corporation), piomin (for example, D-1105, D-6112-W and D-6315, taketo Oil & Fat co., l.), OLF [ NE E1010 (Nissin Chemical, ltd.) and Suyn (for example, 400, ltd.) and (for example, 400, ltd.) are included.

Examples of the silicone surfactant include linear polymers composed of siloxane bonds, and modified siloxane polymers in which an organic group is introduced into a side chain or a terminal.

Examples of the surfactant include DOWSIL8032 ADDITIVE, toray SILICONE DC PA, toray SILICONE SH PA, toray SILICONE DC PA, and Toray SIL [ CONE SH21PA, toray SILICONE SH28PA, toray SILICONE SH PA, toray SILICONE SH30PA, and Toray SILICONE SH8400 (Dow Corning Toray Co., ltd.).

Examples of the surfactant include EXP.S-309-2, EXP.S-315, EXP.S-503-2 and EXP.S-505-2 (DIC CORPORATION).

Examples of the surfactant include X-22-4952, X-22-4272, X-22-6266, KF-351A, K354-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002 (Shin-Etsu Chemical Co., ltd.).

Examples of the surfactant include KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, and KP-652 (Shin-Etsu Chemical Co., ltd.).

Examples of the surfactant include F-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (Momentive performance Materials Inc.).

Examples of the surfactant include BYK307, BYK323, and BYK330 (BYK Co,. LTD).

Examples of the surfactant include BYK300, BYK306, BYK310, BYK320, BYK325, BYK313, BYK315N, BYK, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (BYK Co,. LTD).

The photosensitive resin layer may contain 1 or 2 or more 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 thermally crosslinkable compounds, radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, sensitizers, plasticizers, heterocyclic compounds, and solvents. The photosensitive resin layer may contain 1 or 2 or more additives.

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 an ethylenically unsaturated 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, in the case where the polymer a and/or the ethylenically unsaturated compound has at least one of the hydroxyl group and the carboxyl group, the hydrophilicity of the film formed is reduced, and the function when the film obtained by curing the photosensitive resin layer is used as a protective film tends to be enhanced.

The blocked isocyanate compound means a "compound having a structure in which an isocyanate group of an isocyanate is protected (so-called mask) 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 using a differential scanning calorimeter and analyzed by DSC (Differential scanning calorimetry: differential scanning calorimeter)".

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 diesters (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. ] having a structure represented by-C (=N-OH) -, in the molecule.

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

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 isocyanurating hexamethylene diisocyanate to protect it.

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 of easier setting of the dissociation temperature in a preferable range and easier reduction of development residues than a compound having no oxime structure.

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 commercial products of the blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, karenz (registered trademark) MOI-BP, etc. (the above is made by SHOWA DENKO K.K.), and blocked Duranate series (for example, 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 2]

The thermally crosslinkable compound may be used alone or in combination of 1 or 2 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.

Examples of the radical polymerization inhibitor include thermal polymerization inhibitors described in paragraph 0018 of Japanese patent No. 4502784. The radical polymerization inhibitor is preferably phenothiazine, phenoxazine or 4-methoxyphenol. Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride salt, aluminum nitrosophenyl hydroxylamine salt and diphenylnitrosoamine. In order not to impair the sensitivity of the photosensitive resin layer, it is preferable to use an aluminum nitrosophenyl hydroxylamine salt as a radical polymerization inhibitor.

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

Examples of carboxybenzotriazoles include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole. Examples of the commercial products of carboxybenzotriazoles include CBT-1 (JOHOKU CHEMICAL CO., LTD.).

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

The kind of sensitizer is not limited. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2, 4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

From the viewpoints of an improvement in sensitivity to light sources and an improvement in curing speed based on the balance between polymerization speed and chain transfer, the content of the sensitizer when the photosensitive resin layer contains the sensitizer is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass%, relative to the total mass of the photosensitive resin layer.

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

Examples of the solvent include solvents described in the following "method for forming a photosensitive resin layer". For example, when a photosensitive resin layer is formed using a composition for forming a photosensitive resin layer containing a solvent, the solvent may remain in the photosensitive resin layer.

The photosensitive resin layer may further contain at least 1 selected from the group consisting of metal oxide particles, antioxidants, dispersants, acid breeder agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, tackifiers, crosslinking agents, organic and inorganic deposition inhibitors.

The additives contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of Japanese unexamined patent publication No. 2014-85643. The contents of the above publications are incorporated into the present specification by reference.

(impurity)

The photosensitive resin layer may contain impurities. Examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Since halide ions, sodium ions and potassium ions are easily mixed as impurities, the content of halide ions, sodium ions and potassium ions is preferably within the following range.

The content of impurities in the photosensitive resin layer is preferably 80ppm or less, more preferably 10ppm or less, and particularly preferably 2ppm or less, relative to the total mass of the photosensitive resin layer. The content of impurities in the photosensitive resin layer may be 1ppb or more or 0.1ppm or more with respect to the total mass of the photosensitive resin layer. As a method for setting the impurity content to be within the above range, a method for selecting a raw material having a small impurity content, preventing the mixing of impurities at the time of forming the photosensitive resin layer, and cleaning the photosensitive resin layer is used. The impurities are quantified by a known method such as ICP (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 the above-mentioned compound in the photosensitive resin layer is preferably 100ppm or less, more preferably 20ppm or less, and particularly preferably 4ppm or less, relative to the total mass of the photosensitive resin layer. The content of the above-mentioned compound in the photosensitive resin layer may be 10ppb or more or 100ppb or more with respect to the total mass of the photosensitive resin layer. The content of the compound is adjusted by the same method as the method for adjusting the content of the impurity. The above-mentioned compounds are then quantified by a known assay.

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

(residual monomer)

The photosensitive resin layer may contain a residual monomer, for example, a residual monomer corresponding to each structural unit of the polymer a.

From the viewpoints of pattern formability 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 polymer a. The lower limit of the content of the residual monomer is not particularly limited, but is preferably 1 mass ppm or more, more preferably 10 mass ppm or more, relative to the total mass of the polymer a.

From the viewpoints of pattern formability and reliability, the content of the residual monomer corresponding to each structural unit of the polymer a 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 of the content of the residual monomer corresponding to each structural unit of the polymer a is not particularly limited, but is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, with respect to the total mass of the photosensitive resin layer.

The residual monomer amount of the monomer in synthesizing the polymer a by the polymer reaction is also preferably within the above range. For example, in the case of synthesizing the polymer a 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.

(thickness)

The thickness of the photosensitive resin layer is not limited. The thickness of the photosensitive resin layer is determined, for example, in the range of 0.1 μm to 100 μm. The thickness of the photosensitive resin layer is preferably 50 μm or less, more preferably 30 μm or less, and particularly preferably 20 μm or less from the viewpoints of developability and resolution. The thickness of the photosensitive resin layer is preferably 10 μm or less, more preferably 5 μm or less. The thickness of the photosensitive resin layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, and particularly preferably 0.5 μm or more, from the viewpoint of the processing liquid resistance of the developer or the like. The thickness of the photosensitive resin layer is preferably 0.5 μm to 10 μm, more preferably 0.5 μm to 5 μm. The thickness of the photosensitive resin layer is preferably 1 μm to 10 μm, particularly preferably 0.5 μm to 4 μm. The thickness of the photosensitive resin layer is measured by a method according to a method for measuring the thickness of the temporary support.

(transmittance)

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

(method for Forming photosensitive resin layer)

The method for forming the photosensitive resin layer is not limited as long as it is a method capable of forming a layer containing the above components. The photosensitive resin layer is formed, for example, by: a photosensitive resin layer-forming composition is prepared, applied to the 2 nd surface of the temporary support, and the applied photosensitive resin layer-forming composition is dried.

Examples of the composition for forming a photosensitive resin layer include a composition containing a polymer a, a polymerizable compound B, and a photopolymerization initiator. In order to adjust the viscosity of the photosensitive resin layer-forming composition and to facilitate formation of the photosensitive resin layer, the photosensitive resin layer-forming composition preferably contains a solvent.

The solvent is not limited as long as it is a solvent capable of dissolving or dispersing the components of the photosensitive resin layer. Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents, amide solvents, and lactone solvents.

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.

The solvent may be any solvent described in paragraphs 0092 to 0094 of Japanese patent application laid-open No. 2018/179640 or in paragraph 0014 of Japanese patent application laid-open No. 2018-177889. The contents of these publications are incorporated by reference into the present specification.

The photosensitive resin layer-forming composition may contain 1 or 2 or more solvents. The photosensitive resin layer-forming composition preferably contains at least 1 selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, more preferably contains at least 1 selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, and at least 1 selected from the group consisting of ketone solvents and cyclic ether solvents, and particularly preferably contains at least 1 selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, ketone solvents, and cyclic ether solvents.

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

The method for producing the composition for forming a photosensitive resin layer is not limited. The photosensitive resin layer-forming composition is prepared, for example, as follows: a solution in which each component is dissolved in a solvent is prepared in advance, and the obtained solution is mixed in a predetermined ratio. Before forming the photosensitive resin layer, the photosensitive resin layer-forming composition is preferably filtered using a filter having a pore diameter of 0.2 μm to 30 μm.

Examples of the method for applying the composition for forming a photosensitive resin layer include slit coating, spin coating, curtain coating, and inkjet coating.

Thermoplastic resin layer

The photosensitive transfer material according to the present invention may contain a thermoplastic resin layer. The photosensitive transfer material includes the thermoplastic resin layer, so that the following property of the photosensitive transfer material to the substrate is improved and air bubbles are prevented from being mixed between the photosensitive transfer material and the substrate during the bonding of the photosensitive transfer material to the substrate. Further, the photosensitive transfer material includes a thermoplastic resin layer, so that adhesion between the layers is improved. The photosensitive transfer material according to the present invention preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer. The thermoplastic resin layer is described in, for example, paragraphs 0189 to 0193 of JP-A-2014-85643. The contents of the above publications are incorporated into the present specification by reference.

(alkali-soluble resin)

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, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethylenimines, polyallylamines, and polyalkylene glycols.

The alkali-soluble resin is preferably an acrylic resin from the viewpoints of developability and adhesion to the adjacent layer. Here, the acrylic resin means a resin containing at least 1 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. From the viewpoints of developability and adhesion to an adjacent layer, the alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth) acrylic acid.

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

The alkali-soluble resin preferably contains an acid group. Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group, and a phosphonate group. The acid group is preferably a carboxyl group.

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 acid value of the alkali-soluble resin is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less.

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 in the polymer described in paragraph 0025 of JP 2011-95716, carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the polymers described in paragraphs 0033 to 0052 of JP 2010-237589, and carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the binder polymers described in paragraphs 0053 to 0068 of JP 2016-224162.

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 acrylic resin.

The alkali-soluble resin may contain a reactive group. 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 10,000 ～ 100,000, and particularly preferably 20,000 ～ 50,000.

The thermoplastic resin layer may contain 1 or 2 or more alkali-soluble resins.

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

(pigment)

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

From the viewpoints of visibility of the exposed portion, visibility of the 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.

The thermoplastic resin layer may contain 1 or 2 or more pigments B.

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%, still 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 dye B herein refers to the content of the dye when all of the dye B contained in the thermoplastic resin layer is in a color development state. Hereinafter, a method of quantifying a dye by using a dye developed by a radical as an example will be described. A solution in which pigment B (0.001 g) was dissolved in methyl ethyl ketone (100 mL) and a solution in which pigment B (0.01 g) was dissolved in methyl ethyl ketone (100 mL) were prepared. A photo radical polymerization initiator (Irgacure OXE01, BASF JAPAN LTD.) was added to each solution, and then 365nm light was irradiated to generate radicals, thereby bringing all the pigments into a developed state. In the atmospheric environment, absorbance of each solution at 25℃was measured using a spectrophotometer (UV 3100, shimadzu Corporation), and a calibration curve was prepared. Next, absorbance of the solution in which the pigment was completely 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 pigment. The amount of pigment contained in the thermoplastic resin layer is calculated from the absorbance of the solution containing the thermoplastic resin layer according to the calibration curve.

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

(Compounds which generate acids, bases or free radicals by means of light)

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 photoacid generators, photobase generators, and photo radical polymerization initiators (photo radical generators). Among the above, photoacid generators are preferred.

From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. The photo-acid generator may be a photo-cation polymerization initiator described in the item of the "photosensitive resin layer". The preferable mode of the photoacid generator is the same as the preferable mode of the photo cation polymerization initiator described in the item of the "photosensitive resin layer" described above, except for the following matters. From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least 1 selected from the group consisting of onium salt compounds and oxime sulfonate compounds. The photoacid generator preferably contains an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion. Specific examples of the preferred photoacid generator are shown below.

[ chemical formula 3]

The thermoplastic resin layer may contain a photobase generator. Examples of the photobase generator include 2-nitrobenzyl cyclohexyl carbamate, triphenylmethanol, O-carbamoyl hydroxylamine, 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 (triphenylmethyl borate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2, 6-dimethyl-3, 5-diacetyl-4- (2-nitrophenyl) -1, 4-dihydropyridine and 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 described in the item of the "photosensitive resin layer" may be exemplified by photo radical polymerization initiators. The preferred mode of the photo radical polymerization initiator is the same as that described in the item of the "photosensitive resin layer" above.

The thermoplastic resin layer may contain 1 or 2 or more kinds of compound C.

The content of the compound C in the thermoplastic resin layer 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.

(plasticizer)

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

The molecular weight of the plasticizer, which is the weight average molecular weight (Mw) in the case where the plasticizer has a molecular weight distribution, is preferably smaller than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.

Examples of the plasticizer include compounds which are compatible with alkali-soluble resins and which exhibit plasticity. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound containing an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer more preferably has a polyethoxy structure or a polypropoxy structure.

The plasticizer preferably contains a (meth) acrylate compound from the viewpoints of resolution and storage stability. From the viewpoints of compatibility, resolution, and adhesion to an adjacent 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 item of the "polymerizable compound B". When the thermoplastic resin layer of the photosensitive transfer material is in contact with the photosensitive resin layer, the thermoplastic resin layer and the photosensitive resin layer preferably contain the same (meth) acrylate compound. The thermoplastic resin layer and the photosensitive resin layer contain the same (meth) acrylate compound, thereby suppressing the diffusion of components between the layers and improving the storage stability.

From the viewpoint of adhesion to the adjacent layer, the (meth) acrylate compound used as the plasticizer preferably does not polymerize even in the exposed portion after exposure.

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

The (meth) acrylate compound used as the plasticizer is also preferably a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound.

The thermoplastic resin layer may contain 1 or 2 or more plasticizers.

The content of the plasticizer in the thermoplastic resin layer 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 to adjacent layers, and developability.

(surfactant)

From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. Examples of the surfactant include the surfactants described in the item of the "photosensitive resin layer". The preferred mode of the surfactant is the same as that described in the item of the "photosensitive resin layer" above.

The thermoplastic resin layer may contain 1 or 2 or more surfactants.

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

(sensitizer)

The thermoplastic resin layer may contain a sensitizer. Examples of the sensitizer include the sensitizer described in the item of "photosensitive resin layer".

The thermoplastic resin layer may contain 1 or 2 or more kinds of sensitizers.

From the viewpoints of improving the sensitivity to light sources and visibility of exposed portions and non-exposed portions, the content of the sensitizer is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass%, relative to the total mass of the thermoplastic resin layer.

(additive)

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

(thickness)

The thickness of the thermoplastic resin layer is not limited. From the viewpoint of adhesion to the adjacent layer, the thickness of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more. From the viewpoints of developability and resolution, the 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. The thickness of the thermoplastic resin layer is measured by a method according to a method for measuring the thickness of the temporary support.

(method for Forming thermoplastic resin layer)

The method for forming the thermoplastic resin layer is not limited as long as the layer containing the above components can be formed. The thermoplastic resin layer is formed, for example, by: a thermoplastic resin layer-forming composition is prepared, the thermoplastic resin layer-forming composition is applied to an object (for example, a photosensitive resin layer), and the applied thermoplastic resin layer-forming composition is dried.

In order to adjust the viscosity of the thermoplastic resin layer-forming composition to facilitate formation of the thermoplastic resin layer, the thermoplastic resin layer-forming composition preferably contains a solvent. The solvent is not limited as long as it is a solvent capable of dissolving or dispersing the components of the thermoplastic resin layer. The solvent may be the solvent described in the item of the "photosensitive resin layer". The preferred mode of the solvent is the same as that described in the item of the "photosensitive resin layer" described above.

The thermoplastic resin layer-forming composition may contain 1 or 2 or more solvents.

The content of the solvent in the thermoplastic resin layer-forming composition is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the thermoplastic resin layer-forming composition.

The composition for forming a thermoplastic resin layer is prepared, for example, by a method according to the method for preparing the composition for forming a photosensitive resin layer. The thermoplastic resin layer-forming composition is applied, for example, by a method according to the application method of the photosensitive resin layer-forming composition.

Intermediate layer

The photosensitive transfer material according to the present invention preferably includes an intermediate layer between the photosensitive resin layer and the thermoplastic resin layer. By including the intermediate layer in the photosensitive transfer material, mixing of components generated between layers during formation of the photosensitive transfer material or storage of the photosensitive transfer material can be suppressed. The intermediate layer is preferably a water-soluble layer from the viewpoint of suppressing mixing of components generated between the development property and the formation of the photosensitive transfer material or between the storage intermediate layers of the photosensitive transfer material. In the present invention, "water-soluble" means a property of 0.1g or more in water (100 g) having a pH of 7.0 at a liquid temperature of 22 ℃.

Examples of the intermediate layer include an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in JP-A-5-72724. The oxygen barrier layer is preferable in terms of improving sensitivity at the time of exposure, reducing time load of an exposure machine, and improving productivity. The oxygen barrier layer is preferably an oxygen barrier layer which exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (1 mass% aqueous sodium carbonate solution, liquid temperature: 22 ℃).

The intermediate layer preferably contains a resin. Examples of the resin include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, and polyamide resins. The resin may be a homopolymer or a copolymer. The resin is preferably a water-soluble resin.

The intermediate layer preferably contains polyvinyl alcohol, more preferably polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of suppressing the formation of oxygen-blocking and photosensitive transfer materials or the mixing of components generated between the intermediate layers in the storage of the photosensitive transfer materials.

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

The intermediate layer may contain 1 or 2 or more resins.

From the viewpoint of suppressing the mixing of components occurring between the oxygen barrier property and the formation of the photosensitive transfer material or between the storage layers of the photosensitive transfer material, the content of the resin in the intermediate layer is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass, relative to the total mass of the intermediate layer.

The intermediate layer may contain additives such as surfactants as needed. Examples of the surfactant include the surfactants described in the item of the "photosensitive resin layer". The preferred mode of the surfactant is the same as that described in the item of the "photosensitive resin layer" above.

The thickness of the intermediate layer is not limited. The thickness of the intermediate layer is preferably 0.1 μm to 5. Mu.m, more preferably 0.5 μm to 3. Mu.m. If the thickness of the intermediate layer is within the above range, the oxygen barrier property is not reduced, and the mixture of components generated between the formation of the photosensitive transfer material and the storage intermediate layer of the photosensitive transfer material can be suppressed, and the increase in the removal time of the intermediate layer in the developing step can be suppressed. The thickness of the intermediate layer is measured by a method according to the method of measuring the thickness of the temporary support.

The method of forming the intermediate layer is not limited. The intermediate layer is formed, for example, by: an intermediate layer forming composition containing a resin and an optional additive is prepared, the intermediate layer forming composition is applied to the surface of the thermoplastic resin layer or the photosensitive resin layer, and the applied intermediate layer forming composition is dried.

In order to adjust the viscosity of the intermediate layer-forming composition to facilitate formation of the intermediate layer, the intermediate layer-forming 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 1 selected from 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 glycerol. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol or ethanol.

Protective film

The photosensitive transfer material according to the present invention preferably contains a protective film. The photosensitive transfer material according to the present invention preferably includes a temporary support, a photosensitive resin layer, and a protective film in this order. The protective film is preferably the outermost layer of the photosensitive transfer material.

Examples of the protective film include a resin film and paper. From the viewpoints of strength and flexibility, a resin film is preferable. Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among the above, a polyethylene film, a polypropylene film or a polyethylene terephthalate film is preferable.

The thickness of the protective film is not limited. The thickness of the protective film is preferably 5 μm to 100. Mu.m, more preferably 10 μm to 50. Mu.m. The thickness of the protective film is measured by a method according to a method for measuring the thickness of the temporary support.

From the viewpoint of further excellent resolution, the arithmetic average roughness Ra of the surface of the photosensitive resin layer side of the protective film (hereinafter, sometimes simply referred to as "surface of the protective film") is preferably 0.3 μm or less, more preferably 0.1 μm or less, and particularly preferably 0.05 μm or less. The arithmetic average roughness Ra of the surface of the protective film is in the above range, and is considered to improve the uniformity of the thicknesses of the photosensitive resin layer and the resin pattern formed. The lower limit of the arithmetic average roughness Ra of the protective film is preferably 0.001 μm or more.

The arithmetic average roughness Ra of the surface of the protective film was measured by the following method. The surface profile of the protective film was obtained using a three-dimensional optical analyzer (New View7300, zygo company) under the following conditions. As the measurement and analysis software, microscope Application of MetroPro ver8.3.2 was used. Next, the Surface Map screen is displayed using the analysis software described above, and the histogram number is obtained in the Surface Map screen. An arithmetic average roughness Ra is calculated from the obtained histogram numbers. In the measurement of the arithmetic average roughness Ra of the surface of the protective film contained in the photosensitive transfer material, the protective film may be peeled off from the photosensitive transfer material, and the arithmetic average roughness Ra of the surface of the protective film may be measured.

Relation between temporary support, photosensitive resin layer and protective film

The photosensitive transfer material according to the present invention is preferably as follows:

the elongation at break at 120 ℃ of the cured film obtained by curing the photosensitive resin layer is 15% or more,

the surface of the temporary support on the photosensitive resin layer side has an arithmetic average roughness Ra of 50nm or less,

the surface of the protective film on the photosensitive resin layer side has an arithmetic average roughness Ra of 150nm or less.

The photosensitive transfer material according to the present invention preferably satisfies the following formula (B1).

X Y < 1,500: (R1)

In the above formula (R1), X represents a value (%) of elongation at break at 120 ℃ of a cured film obtained by curing the photosensitive resin layer, and Y represents a value (nm) of arithmetic average roughness Ra of the surface of the temporary support on the photosensitive resin layer side.

X Y is more preferably 750 or less.

The elongation at break at 120℃is preferably 2 times or more greater than the elongation at break at 23℃of the cured film obtained by curing the photosensitive resin layer.

Using a mercury lamp with an ultra-high pressure of 120mJ/cm ² After curing the photosensitive resin layer having a thickness of 20 μm by exposure to light, the resultant was irradiated with a high-pressure mercury lamp at 400mJ/cm ² The cured film after exposure and heating at 145℃for 30 minutes was further subjected to additional exposure, and elongation at break was measured by a tensile test.

The photosensitive transfer material according to the present invention preferably satisfies the following formula (R2).

Y is less than or equal to Z: (R2)

In the above formula (R2), Y represents the value (nm) of the arithmetic average roughness Ra of the surface of the temporary support on the photosensitive resin layer side, and Z represents the value (nm) of the arithmetic average roughness Ra of the surface of the protective film on the photosensitive resin layer side.

Other layers

The photosensitive transfer material according to the present invention may contain a layer other than the above-described layer (hereinafter referred to as "other layer" in this paragraph). Examples of the other layer include a contrast enhancement layer (also referred to as a refractive index adjustment layer). 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 by reference into the present specification.

Method for producing photosensitive transfer Material

The method for producing the photosensitive transfer material according to the present invention is not limited. The photosensitive transfer material is manufactured, for example, by the method of forming each layer described above. Hereinafter, a method for producing the photosensitive transfer material will be described with reference to fig. 1 and 2. Fig. 1 is a schematic diagram showing the structure of a photosensitive transfer material according to the present invention. Fig. 2 is a schematic diagram showing a structure of a photosensitive transfer material according to another embodiment of the present invention. Fig. 3 is a schematic diagram showing a structure of a photosensitive transfer material according to another embodiment of the present invention.

The photosensitive transfer material 100 shown in fig. 1 includes a temporary support 10, a photosensitive resin layer 20, and a protective film 30 in this order. The photosensitive transfer material 100 is manufactured by, for example, the following method. A temporary support 10 having a 2 nd surface 10b is prepared on the 1 st surface 10a and the opposite side to the 1 st surface 10 a. L of the 2 nd surface 10b of the temporary support 10 measured by SCE method ^* The value is 1.5 or less. The photosensitive resin layer-forming composition is applied to the 2 nd surface 10b of the temporary support 10, and the applied photosensitive resin layer-forming composition is dried to form the photosensitive resin layer 20. A protective film 30 is disposed on the photosensitive resin layer 20. The photosensitive transfer material 100 manufactured by the above method is wound up, whereby the photosensitive transfer material 100 in the form of a roll can be manufactured and stored. The photosensitive transfer material 100 in roll form is used for bonding to a substrate, for example, by a roll-to-roll method.

The photosensitive transfer material 110 shown in fig. 2 includes a temporary support 11, a photosensitive resin layer 20, and a protective film 30 in this order. The temporary support 11 includes a particle-containing layer 11-1 and a base material 11-2 in this order in the stacking direction from the temporary support 11 toward the photosensitive resin layer 20. In the temporary support 11, the particle-containing layer 11-1 is disposed as the outermost layer on the 1 st surface 11a side of the temporary support 11. In the temporary support 11, the base material 11-2 is disposed as the outermost layer on the 2 nd surface 11b side of the temporary support 11. The photosensitive transfer material 110 is manufactured by the same method as the method for manufacturing the photosensitive transfer material 100 described above, except that the temporary support 11 is prepared instead of the temporary support 10, for example.

The photosensitive transfer material 120 shown in fig. 3 includes, in order, a temporary support 10, a thermoplastic resin layer 40, an intermediate layer 50, a photosensitive resin layer 20, and a protective film 30. As a method for producing the photosensitive transfer material 120, for example, a method of sequentially forming the thermoplastic resin layer 40, the intermediate layer 50, the photosensitive resin layer 20, and the protective film 30 on the 2 nd surface 10b of the temporary support according to the above-described method is mentioned.

The method for producing the photosensitive transfer material according to the present invention is not limited to the above method. For example, instead of forming each layer on the protective film as a temporary support, a photosensitive transfer material can be manufactured.

Application of photosensitive transfer Material

The photosensitive transfer material according to the present invention is preferably used for various applications required for precision micro-processing by photolithography, for example. For example, after patterning the photosensitive resin layer, the photosensitive resin layer or a cured product thereof may be etched as a coating or electroformed mainly by electroplating. The cured product obtained by patterning can be used as a permanent film. The cured product obtained by patterning can be used as, for example, a wiring protective film having an interlayer insulating film, a wiring protective film, or an index matching layer. The photosensitive transfer material according to the present invention is preferably used in a method for forming wiring in a semiconductor package, a printed board, or a sensor board, for example. The photosensitive transfer material according to the present invention is preferably used in a method for forming a conductive film such as a touch panel, an electromagnetic shield material, and a thin film heater, for example. The photosensitive transfer material according to the present invention is preferably used in, for example, a liquid crystal sealing material, a micromachine, and a method for forming a structure in a microelectronic region.

The photosensitive transfer material according to the present invention can be used as a photosensitive transfer material for a wiring protective film, for example. The layer structure of the photosensitive transfer material preferably used as the photosensitive transfer material for the wiring protective film is, for example, the following (1) and (2).

(1) Temporary support, photosensitive resin layer, refractive index adjustment layer, and protective film

(2) Temporary support/photosensitive resin layer/protective film

The following describes the constituent elements of a photosensitive transfer material that is preferably used as a photosensitive transfer material for a wiring protective film. However, the constituent elements of the photosensitive transfer material preferably used as the photosensitive transfer material for the wiring protective film are not limited to those shown below.

(temporary support)

The temporary support may be, for example, a temporary support described in the above item "temporary support". The preferred mode of the temporary support is the same as the preferred mode of the temporary support described in the above item of "temporary support".

(protective film)

Examples of the protective film include the protective film described in the above "protective film". The preferred mode of the protective film is the same as the preferred mode of the protective film described in the above item of "protective film".

(photosensitive resin layer)

Alkali-soluble resins

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

Examples of the alkali-soluble resin include (meth) acrylic resins, styrene resins, epoxy resins, amide epoxy resins, alkanol resins, phenolic resins, ester resins, urethane resins, epoxy acrylate resins obtained by the reaction of an epoxy resin with (meth) acrylic acid, and acid-modified epoxy acrylate resins obtained by the reaction of an epoxy acrylate resin with an acid anhydride.

As one of preferable modes of the alkali-soluble resin, a (meth) acrylic resin is given in terms of excellent alkali developability and film formability.

In addition, in the present specification, (meth) acrylic resin means a resin having a structural unit derived from a (meth) acrylic compound. The content of the structural unit derived from the (meth) acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, with respect to all the structural units of the (meth) acrylic resin.

The (meth) acrylic resin may be composed of only structural units derived from the (meth) acrylic compound, or may have structural units derived from a polymerizable monomer other than the (meth) acrylic compound. That is, the upper limit of the content of the structural unit derived from the (meth) acrylic compound is 100 mass% or less with respect to all the structural units of the (meth) acrylic resin.

Examples of the (meth) acrylic compound include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, and (meth) acrylonitrile.

Examples of the (meth) acrylic acid ester include alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-trifluoroethyl (meth) acrylate, and 2, 3-tetrafluoropropyl (meth) acrylate, and alkyl (meth) acrylates are preferable.

Examples of the (meth) acrylamide include acrylamide such as diacetone acrylamide.

Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates having an alkyl group having 1 to 12 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and dodecyl (meth) acrylate.

The (meth) acrylic acid ester is preferably an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms, and more preferably methyl (meth) acrylate or ethyl (meth) acrylate.

The (meth) acrylic resin may have structural units other than those derived from the (meth) acrylic compound.

The polymerizable monomer forming the structural unit is not particularly limited as long as it is a compound other than a (meth) acrylic compound copolymerizable with the (meth) acrylic compound, and examples thereof include styrene, vinyl toluene, and α -methylstyrene, and other styrene compounds that may have a substituent at the α -position or the aromatic ring, vinyl alcohol esters such as acrylonitrile and vinyl n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, and maleic acid monoesters such as fumaric acid, cinnamic acid, α -cyanocinnamic acid, itaconic acid, and crotonic acid.

These polymerizable monomers may be used in an amount of 1 or 2 or more in combination.

Further, from the viewpoint of improving the alkali developability, the (meth) acrylic resin preferably contains a structural unit having an acid group. Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group, and a phosphonate group.

Among them, the (meth) acrylic resin more preferably contains a structural unit having a carboxyl group, and further preferably has a structural unit derived from the above (meth) acrylic acid.

In terms of excellent developability, the content of the structural unit having an acid group (preferably, structural unit derived from (meth) acrylic acid) in the (meth) acrylic resin is preferably 10 mass% or more with respect to the total mass of the (meth) acrylic resin. The upper limit is not particularly limited, but is preferably 50 mass% or less, more preferably 40 mass% or less, in view of excellent alkali resistance.

Further, the (meth) acrylic resin more preferably has a structural unit derived from the above alkyl (meth) acrylate.

The content of the structural unit derived from the alkyl (meth) acrylate in the (meth) acrylic resin is preferably 50 to 90% by mass, more preferably 60 to 90% by mass, and still more preferably 65 to 90% by mass, relative to all the structural units of the (meth) acrylic resin.

The (meth) acrylic resin is preferably a resin having both a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester, and more preferably a resin composed of only a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester.

The (meth) acrylic resin is also preferably an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate.

From the viewpoint of resolution, the (meth) acrylic resin preferably has at least 1 selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from alkyl methacrylate, and preferably has both a structural unit derived from methacrylic acid and a structural unit derived from alkyl methacrylate.

From the viewpoint of resolution, the total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate in the (meth) acrylic resin is preferably 40 mass% or more, more preferably 60 mass% or more, with respect to all the structural units of the (meth) acrylic resin. The upper limit is not particularly limited, and may be 100 mass% or less, preferably 80 mass% or less.

Also, from the viewpoint of resolution, the (meth) acrylic resin preferably has at least 1 selected from the group consisting of structural units derived from methacrylic acid and structural units derived from alkyl methacrylate, and at least 1 selected from the group consisting of structural units derived from acrylic acid and structural units derived from alkyl acrylate.

From the viewpoint of resolution, the total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate is preferably 60/40 to 80/20 in terms of mass ratio to the total content of the structural units derived from acrylic acid and the structural units derived from alkyl acrylate.

In terms of excellent developability of the photosensitive resin layer after transfer, the (meth) acrylic resin preferably has an ester group at the end.

The terminal part of the (meth) acrylic resin is composed of a part derived from a polymerization initiator used for synthesis. The (meth) acrylic resin having an ester group at the end can be synthesized by using a polymerization initiator that generates a radical having an ester group.

In addition, from the viewpoint of developability, the alkali-soluble resin is preferably, for example, an alkali-soluble resin having an acid value of 60mgKOH/g or more.

Further, from the viewpoint of easy formation of a firm film by heat crosslinking with the crosslinking component, the alkali-soluble resin is, for example, more preferably a resin having a carboxyl group with an acid value of 60mgKOH/g or more (so-called carboxyl group-containing resin), and further preferably a (meth) acrylic resin having a carboxyl group with an acid value of 60mgKOH/g or more (so-called carboxyl group-containing (meth) acrylic resin).

If the alkali-soluble resin is a resin having a carboxyl group, for example, the three-dimensional crosslink density can be increased by adding a thermally crosslinkable compound such as a blocked isocyanate compound and thermally crosslinking. Further, if the carboxyl group of the resin having a carboxyl group is dehydrated and rendered hydrophobic, the wet heat resistance can be improved.

The (meth) acrylic resin having an acid value of 60mgKOH/g or more and containing a carboxyl group is not particularly limited as long as the above-mentioned acid value condition is satisfied, and can be appropriately selected from known (meth) acrylic resins.

For example, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more from among the polymers described in paragraph 0025 of JP 2011-095716, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more from among the polymers described in paragraphs 0033 to 0052 of JP 2010-237589, and the like can be preferably used.

As another preferable mode of the alkali-soluble resin, a styrene-acrylic acid copolymer is exemplified. In the present specification, the styrene-acrylic acid copolymer means a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic acid compound, and the total content of the structural unit derived from the styrene compound and the structural unit derived from the (meth) acrylic acid compound is preferably 30 mass% or more, more preferably 50 mass% or more, with respect to all the structural units of the copolymer.

The content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 5% by mass to 80% by mass based on the total structural units of the copolymer.

The content of the structural unit derived from the (meth) acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass to 95% by mass based on the total structural units of the copolymer.

From the viewpoint of moisture permeability and strength of the obtained cured film, the alkali-soluble resin preferably has an aromatic ring structure, and more preferably contains a structural unit having an aromatic ring structure.

Examples of the monomer forming the structural unit having an aromatic ring structure include styrene compounds such as styrene, t-butoxystyrene, methyl styrene and α -methyl styrene, benzyl (meth) acrylate, and the like.

Among them, a styrene compound is preferable, and styrene is more preferable.

Further, from the viewpoint of the moisture permeability and strength of the obtained cured film, the alkali-soluble resin more preferably has a structural unit (structural unit derived from styrene) represented by the following formula (S).

[ chemical formula 4]

In the case where the alkali-soluble resin contains a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass, relative to all the structural units of the alkali-soluble resin, from the viewpoints of moisture permeability and strength of the obtained cured film.

From the viewpoint of the moisture permeability and strength of the obtained cured film, the content of the structural unit having an aromatic ring structure in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 60 mol% with respect to all the structural units of the alkali-soluble resin.

Further, from the viewpoint of the moisture permeability and strength of the obtained cured film, the content of the structural unit represented by the above formula (S) in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, still more preferably 20 to 60 mol%, and particularly preferably 20 to 50 mol% with respect to all the structural units of the alkali-soluble resin.

In the present specification, when the content of the "structural unit" is defined in a molar ratio, the meaning of the "structural unit" and the "monomer unit" is the same. In the present specification, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

The alkali-soluble resin preferably has an aliphatic hydrocarbon ring structure from the viewpoints of development residue inhibition, strength of the obtained cured film, and adhesiveness of the obtained uncured film. That is, the alkali-soluble resin preferably contains a structural unit having an aliphatic hydrocarbon ring structure. Among them, the alkali-soluble resin more preferably has a ring structure in which an aliphatic hydrocarbon ring having 2 or more rings is condensed.

Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having the aliphatic hydrocarbon ring structure include tricyclodecane ring, cyclohexane ring, cyclopentane ring, norbornane ring and isobornane ring.

Among them, from the viewpoints of development residue inhibition, strength of the obtained cured film, and adhesion of the obtained uncured film, a ring in which an aliphatic hydrocarbon ring of 2 or more rings is condensed is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo [ 5.2.1.0) ^2，6 ]Decane ring).

Examples of the monomer forming the structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.

The alkali-soluble resin preferably has a structural unit represented by the following formula (Cy), more preferably a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy), from the viewpoints of development residue inhibition, strength of the obtained cured film, and adhesiveness of the obtained uncured film.

[ chemical formula 5]

R in formula (Cy) ^M Represents a hydrogen atom or a methyl group, R ^Cy A monovalent group having an aliphatic hydrocarbon ring structure.

R in formula (Cy) ^M Preferably methyl.

R in formula (Cy) is from the viewpoints of development residue inhibition, strength of the obtained cured film and adhesiveness of the obtained uncured film ^Cy The monovalent group is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and still more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.

R of formula (Cy) ^Cy The aliphatic hydrocarbon ring structure may have a single ring structure or a polycyclic structure.

And R of formula (Cy) from the viewpoints of development residue inhibition, strength of the obtained cured film and adhesiveness of the obtained uncured film ^Cy The aliphatic hydrocarbon ring structure in (a) is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure or an isobornane ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and still more preferably a tetrahydrodicyclopentadiene ring structure.

In addition, in the case of the optical fiber,r of formula (Cy) from the viewpoints of development residue inhibition, strength of the obtained cured film and adhesiveness of the obtained uncured film ^Cy The aliphatic hydrocarbon ring structure in (a) is preferably a ring structure in which an aliphatic hydrocarbon ring having 2 or more rings is condensed, and more preferably a ring in which an aliphatic hydrocarbon ring having 2 to 4 rings is condensed.

In addition, from the viewpoints of development residue inhibition, strength of the obtained cured film, and adhesion of the obtained uncured film, R in formula (Cy) ^Cy The group in which an oxygen atom of-C (=0) 0-in the formula (Cy) is directly bonded to the aliphatic hydrocarbon ring structure, that is, an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentyl group, and still more preferably a dicyclopentyl group.

The alkali-soluble resin may contain 1 structural unit having an aliphatic hydrocarbon ring structure alone or 2 or more.

In the case where the alkali-soluble resin contains a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, still more preferably 20 to 70% by mass relative to all the structural units of the alkali-soluble resin from the viewpoints of development residue inhibition, strength of the obtained cured film, and adhesiveness of the obtained uncured film.

Further, from the viewpoints of the development residue inhibition property, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, the content of the structural unit having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol% with respect to all the structural units of the alkali-soluble resin.

Further, from the viewpoints of the development residue inhibition property, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, the content of the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, still more preferably 20 to 50 mol% with respect to all the structural units of the alkali-soluble resin.

In the case where the alkali-soluble resin contains a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 40 to 75% by mass relative to all the structural units of the alkali-soluble resin from the viewpoints of development residue inhibition, strength of the obtained cured film, and adhesiveness of the obtained uncured film.

Further, from the viewpoints of the development residue inhibition property, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 40 to 60 mol% with respect to all the structural units of the alkali-soluble resin.

Further, from the viewpoints of the present development residue inhibition property, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 40 to 60 mol% with respect to all the structural units of the alkali-soluble resin.

Further, from the viewpoints of the development residue inhibition property, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the alkali-soluble resin preferably satisfy the relationship shown by the following formula (SCy), more preferably satisfy the following formula (SCy-1), and even more preferably satisfy the following formula (SCy-2).

nS/(nS+ nCy) is less than or equal to 0.2 and less than or equal to 0.8: (SCy)

nS/(nS+ nCy) is less than or equal to 0.30 and less than or equal to 0.75: (SCy-1)

nS/(nS+ nCy) is less than or equal to 0.40 and less than or equal to 0.70: (SCy-2)

The alkali-soluble resin preferably contains a structural unit having an acid group from the viewpoints of developability and adhesion to a substrate.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxyl group is preferable.

The structural unit having the acid group is preferably a structural unit derived from (meth) acrylic acid shown below, and more preferably a structural unit derived from methacrylic acid.

[ chemical formula 6]

The alkali-soluble resin may contain 1 structural unit having an acid group alone or 2 or more.

In the case where the alkali-soluble resin contains a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass relative to the total structural units of the alkali-soluble resin from the viewpoints of developability and adhesion to a substrate.

Further, from the viewpoints of developability and adhesion to a substrate, the content of the structural unit having an acid group in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol% with respect to all the structural units of the alkali-soluble resin.

In addition, from the viewpoints of developability and adhesion to a substrate, the content of the structural unit derived from (meth) acrylic acid in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol% with respect to all the structural units of the alkali-soluble resin.

From the viewpoints of curability and strength of the obtained cured film, the alkali-soluble resin preferably has a reactive group, and more preferably contains a structural unit having a reactive group.

The reactive group is preferably a radical polymerizable group, and more preferably an ethylenically unsaturated group. Also, when the alkali-soluble resin has an ethylenically unsaturated group, the alkali-soluble resin preferably contains a structural unit having an ethylenically unsaturated group in a side chain.

In the present specification, "main chain" means a relatively longest bonding chain among molecules of a polymer compound constituting a resin, and "side chain" means an atomic group branched from the main chain.

As the ethylenically unsaturated group, an allyl group or a (meth) acryloxy group is more preferable.

Examples of the structural unit having a reactive group include the structural units shown below, but are not limited thereto.

[ chemical formula 7]

The alkali-soluble resin may contain 1 kind of structural unit having a reactive group alone or 2 or more kinds of structural units.

In the case where the alkali-soluble resin contains a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, still more preferably 20 to 40% by mass, relative to all the structural units of the alkali-soluble resin, from the viewpoints of curability and strength of the resulting cured film.

From the viewpoints of curability and strength of the resulting cured film, the content of the structural unit having a reactive group in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol% based on all the structural units of the alkali-soluble resin.

As a method for introducing a reactive group into an alkali-soluble resin, the following method can be mentioned: an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, a carboxylic anhydride, and the like are reacted with a functional group such as a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group (acetoacetyl group), a sulfo group, and the like.

As a preferred example of the method for introducing the reactive group into the alkali-soluble resin, there is a method in which a polymer having a carboxyl group is synthesized by polymerization, and then glycidyl (meth) acrylate is reacted with a part of the carboxyl group of the obtained resin by a polymer reaction to introduce a (meth) acryloyloxy group into the polymer. By this method, an alkali-soluble resin having a (meth) acryloyloxy group in a side chain can be obtained.

The polymerization reaction is preferably carried out at a temperature of 70 to 100 ℃, more preferably at a temperature of 80 to 90 ℃. As the polymerization initiator used in the above polymerization reaction, azo-based initiators are preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation are more preferable. The polymer reaction is preferably carried out at a temperature of 80℃to 110 ℃. In the above-mentioned polymer reaction, a catalyst such as an ammonium salt is preferably used.

In view of the more excellent effect in the present invention, the alkali-soluble resin is preferably a resin shown below. The content ratios (a to d) of the respective structural units shown below, the weight average molecular weight Mw, and the like can be appropriately changed according to the purpose.

[ chemical formula 8]

In the resin, it is preferable that a is 20 to 60% by mass, b is 10 to 50% by mass, c is 5.0 to 25% by mass, and d is 10 to 50% by mass.

[ chemical formula 9]

[ chemical formula 10]

In the resin, it is preferable that a is 30 to 65% by mass, b is 1.0 to 20% by mass, c is 5.0 to 25% by mass, and d is 10 to 50% by mass.

[ chemical formula 11]

In the resin, a is preferably 1.0 to 20% by mass, b is preferably 20 to 60% by mass, c is preferably 5.0 to 25% by mass, and d is preferably 10 to 50% by mass.

Also, the alkali-soluble resin may contain a polymer containing a structural unit having a carboxylic anhydride structure (hereinafter, also referred to as "polymer X").

The carboxylic anhydride structure may be any of a chain carboxylic anhydride structure and a cyclic carboxylic anhydride structure, but is preferably a cyclic carboxylic anhydride structure.

The ring of the cyclic carboxylic acid anhydride structure is preferably a 5-to 7-membered ring, more preferably a 5-or 6-membered ring, and still more preferably a 5-membered ring.

The structural unit having a carboxylic anhydride structure is preferably a structural unit in which a 2-valent group obtained by removing 2 hydrogen atoms from the compound represented by the following formula P-1 is contained in the main chain, or a 1-valent group obtained by removing 1 hydrogen atom from the compound represented by the following formula P-1 is bonded directly to the main chain or via a 2-valent linking group.

[ chemical formula 12]

In the formula P-1, R ^A1a Represents a substituent, n ^1a R is a number of ^A1a May be the same or different, Z ^1a Represents a group of valence 2 forming a ring comprising-C (=o) -O-C (=o) -n ^1a And represents an integer of 0 or more.

As R ^A1a Examples of the substituent include alkyl groups.

As Z ^1a The alkylene group having 2 to 4 carbon atoms is preferable, the alkylene group having 2 or 3 carbon atoms is more preferable, and the alkylene group having 2 carbon atoms is still more preferable.

n ^1a And represents an integer of 0 or more. At Z ^1a In the case of an alkylene group having 2 to 4 carbon atoms, n ^1a Preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.

At n ^1a When an integer of 2 or more is represented, a plurality of R's are present ^A1a May be the same or different. And there are a plurality of R ^A1a May bond to each other to form a ring, but are preferably bonded to each other without forming a ring.

The structural unit having a carboxylic anhydride structure is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic anhydride, still more preferably a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride, particularly preferably a structural unit derived from maleic anhydride or itaconic anhydride, and most preferably a structural unit derived from maleic anhydride.

Specific examples of the structural unit having a carboxylic anhydride structure are given below, but the structural unit having a carboxylic anhydride structure is not limited to these specific examples. In the following structural units, rx represents a hydrogen atom, a methyl group, or CH ₂ OH groups or CF ₃ The radical, me, represents methyl.

[ chemical formula 13]

[ chemical formula 14]

The number of structural units having a carboxylic anhydride structure in the polymer X may be 1 or 2 or more.

The total content of the structural units having the carboxylic anhydride structure is preferably 0 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, and still more preferably 10 mol% to 35 mol% with respect to all the structural units of the polymer X.

The photosensitive resin layer may contain only 1 polymer X or 2 or more.

When the photosensitive resin layer contains the polymer X, the content of the polymer X is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, still more preferably 0.5 to 20% by mass, and still more preferably 1 to 20% by mass, based on the total mass of the photosensitive resin layer, from the viewpoints of resolution and developability.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 ～ 50,000, and particularly preferably 20,000 ～ 30,000, from the viewpoint of improving resolution and developability.

The acid value of the alkali-soluble resin is preferably 10mgKOH/g to 200mgKOH/g, more preferably 60mgKOH/g to 200mgKOH/g, still more preferably 60mgKOH/g to 150mgKOH/g, particularly preferably 60mgKOH/g to 110mgKOH/g.

The acid value of the alkali-soluble resin was as defined in JIS K0070: 1992.

The dispersibility (weight average molecular weight/number average molecular weight) of the alkali-soluble resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0, from the viewpoint of developability.

The photosensitive resin layer may contain only 1 alkali-soluble resin or 2 or more kinds of alkali-soluble resins.

The content of the alkali-soluble resin is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass, based on the total mass of the photosensitive resin layer, from the viewpoints of photosensitivity, resolution, and developability.

Polymerizable compound

The photosensitive resin layer may contain a polymerizable compound.

The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group, and a radical polymerizable group is preferable.

The polymerizable compound preferably includes a polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as "ethylenically unsaturated compound").

As the ethylenically unsaturated group, (meth) acryloyloxy is preferred.

In addition, the ethylenically unsaturated compound in the present specification is a compound other than the binder polymer described above, and preferably has a molecular weight of less than 5,000.

The preferred mode of the ethylenically unsaturated compound is the same as that of the ethylenically unsaturated compound described in the above item of the "photosensitive resin layer".

As a preferred embodiment of the ethylenically unsaturated compound, a compound represented by the following formula (M) (also simply referred to as "compound M") is given.

Q ² -R ¹ -Q ¹ : (M)

Q in formula (M) ¹ Q and Q ² Each independently represents (meth) acryloyloxy, R ¹ Represents a divalent linking group having a chain structure.

Q in formula (M) ¹ Q and Q ² In (a), from the viewpoint of synthesis easiness, Q ¹ Q and Q ² Preferably the same groups.

And, from the viewpoint of reactivity, Q in the formula (M) ¹ Q and Q ² Preference is given to acryloyloxy.

R as formula (M) ¹ From the viewpoints of development residue inhibition, rust resistance, and bending resistance of the obtained cured film, alkylene and alkyleneoxy alkylene (-L) are preferable ¹ -O-L ¹ (-) or polyalkoxyalkylene (- (L) ¹ -O) _P -L ¹ (-), more preferably a carbon atomThe hydrocarbon group or the polyalkylene oxide alkylene group having 2 to 20 carbon atoms is more preferably an alkylene group having 4 to 20 carbon atoms, and particularly preferably a linear alkylene group having 6 to 18 carbon atoms.

The hydrocarbon group is not particularly limited as long as at least a part thereof has a chain structure, and may be, for example, a branched, cyclic or linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, or a combination thereof, preferably an alkylene group or a group formed by combining 2 or more alkylene groups and 1 or more arylene groups, more preferably an alkylene group, and further preferably a linear alkylene group.

In addition, the L ¹ Each independently represents an alkylene group, preferably ethylene, propylene or butylene, more preferably ethylene or 1, 2-propylene.

p represents an integer of 2 or more, preferably an integer of 2 to 10.

From the viewpoints of development residue inhibition, rust resistance, and bending resistance of the obtained cured film, the connection Q in the compound M ¹ And Q is equal to ² The number of atoms of the shortest connecting chain is preferably 3 to 50, more preferably 4 to 40, still more preferably 6 to 20, particularly preferably 8 to 12.

In the present specification, "connection Q ¹ And Q is equal to ² The atomic number "of the shortest connecting chain between them means that the chain will be linked to Q ¹ R of (2) ¹ To atoms in (A) connected to Q ² R of (2) ¹ The shortest number of atoms to be connected.

Specific examples of the compound M include 1, 3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 7-pentanediol di (meth) acrylate, 1, 8-octanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol/propylene glycol) di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate. The above ester monomers can also be used as mixtures.

Among the above compounds, at least 1 compound selected from the group consisting of 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate is preferable, at least 1 compound selected from the group consisting of 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate and 1, 10-decanediol di (meth) acrylate is more preferable, and at least 1 compound selected from the group consisting of 1, 9-nonanediol di (meth) acrylate and 1, 10-decanediol di (meth) acrylate is more preferable from the viewpoints of development residue inhibition, rust resistance and bending resistance of the obtained cured film.

Further, as one of preferable modes of the ethylenically unsaturated compound, an ethylenically unsaturated compound having 2 or more functions is exemplified.

In the present specification, "an ethylenically unsaturated compound having 2 or more functions" means a compound having 2 or more ethylenically unsaturated groups in one molecule.

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

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

The 2-functional ethylenically unsaturated compound is not particularly limited, and may be appropriately selected from known compounds.

Examples of the 2-functional ethylenically unsaturated compound other than the above compound M include tricyclodecanedimethanol di (meth) acrylate and 1, 4-cyclohexanediol di (meth) acrylate.

Examples of commercial products of 2-functional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK ESTER A-DCP, shin-Nakamura Chemical Co., ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK ESTER DCP, shin-Nakamura Chemical Co., ltd.), 1, 9-nonanediol diacrylate (trade name: NK ESTER A-NOD-N, shin-Nakamura Chemical Co., ltd.), and 1, 6-hexanediol diacrylate (trade name: NK ESTER A-HD-N, shin-Nakamura Chemical Co., ltd.).

The ethylenically unsaturated compound having 3 or more functions is not particularly limited, and may be appropriately selected from known compounds.

Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth) acrylate compounds (Nippon Kayaku Co., ltd., manufactured by KAYARAD (registered trademark) DPCA-20, shin-Nakamura Chemical Co., ltd., manufactured by A-9300-1CL, etc.), alkylene oxide-modified compounds of (meth) acrylate compounds (Nippon Kayaku Co., ltd., manufactured by KAYARAD (registered trademark) RP-1040, shin-Nakamura Chemical Co., ltd., manufactured by ATM-35E, A-9300, EBRYL (registered trademark) 135, etc.), ethoxylated glycerol triacrylate (Shin-Nak amura Chemical Co., manufactured by Ltd., manufactured by ESTER A-GLY-9E, etc.).

As the ethylenically unsaturated compound, urethane (meth) acrylate compounds can be mentioned.

Examples of urethane (meth) acrylates include urethane di (meth) acrylates, such as propylene oxide modified urethane di (meth) acrylates and ethylene oxide and propylene oxide modified urethane di (meth) acrylates.

Further, as the urethane (meth) acrylate, urethane (meth) acrylates having 3 or more functions can be mentioned. The lower limit of the number of functional groups is more preferably 6 or more, and still more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of urethane (meth) acrylates having 3 or more functions include 8UX-015A (manufactured by Taisei Fine chemical Co., ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., ltd.), UA-1 100H (manufactured by Shin-Nakamura Chemica ] Co., ltd.), kyoeisha Chemical Co., manufactured by Ltd.), AH-600 (trade name) manufactured by Ltd., and UA-306H, UA-306T, UA-306I, UA-510H and UX-5000 (both manufactured by Nippon Kayaku Co., ltd.).

As a preferred embodiment of the ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group is mentioned.

Examples of the acid group include a phosphate group, a sulfo group and a carboxyl group.

Among these, a carboxyl group is preferable as the acid group.

Examples of the ethylenically unsaturated compound having an acid group include 3 to 4 functional ethylenically unsaturated compounds having an acid group [ ethylenically unsaturated compounds having a carboxyl group introduced into pentaerythritol tri-and tetra-acrylate (PETA) skeleton (acid value: 80mgKOH/g to 120 mgKOH/g) ] and 5 to 6 functional ethylenically unsaturated compounds having an acid group (ethylenically unsaturated compounds having a carboxyl group introduced into dipentaerythritol penta-and hexaacrylate (DPHA) skeleton [ acid value: 25mgKOH/g to 70 mgKOH/g) ].

These ethylenically unsaturated compounds having 3 or more functions of an acid group may be used in combination with the 2-functional ethylenically unsaturated compound having an acid group, if necessary.

The ethylenically unsaturated compound having an acid group is preferably at least 1 selected from ethylenically unsaturated compounds having 2 or more functions of a carboxyl group and carboxylic anhydrides thereof.

If the ethylenically unsaturated compound having an acid group is at least 1 selected from the group consisting of ethylenically unsaturated compounds having 2 or more functions of a carboxyl group and carboxylic anhydrides thereof, the developability and film strength are further improved.

The ethylenically unsaturated compound having 2 or more functions of carboxyl group is not particularly limited, and can be appropriately selected from known compounds.

Examples of the ethylenically unsaturated compound having a carboxyl group and having 2 or more functions include ARONIX (registered trademark) TO-2349 (TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-520 (TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-510 (TOAGOSEI CO., LTD.), and the like.

As the ethylenically unsaturated compound having an acid group, a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of Japanese unexamined patent publication No. 2004-239942, the contents of which are incorporated herein by reference, is preferable.

Examples of the ethylenically unsaturated compound include compounds obtained by reacting an α, β -unsaturated carboxylic acid with a polyhydric alcohol, compounds obtained by reacting an α, β -unsaturated carboxylic acid with a glycidyl group-containing compound, urethane monomers such as (meth) acrylate compounds having urethane bonds, phthalic acid compounds such as γ -chloro- β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxyethyl- β ' - (meth) acryloyloxyethyl-phthalate and β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, and alkyl (meth) acrylates.

These may be used singly or in combination of 2 or more.

Examples of the compound obtained by reacting an α, β -unsaturated carboxylic acid with a polyhydric alcohol include bisphenol a (meth) acrylate compounds such as 2, 2-bis (4- ((meth) acryloxypolyethoxy) phenyl) propane, 2-bis (4- ((meth) acryloxypolypropoxy) phenyl) propane, 2-bis (4- ((meth) acryloxypolyethoxy polypropoxy) phenyl) propane, polyethylene glycol di (meth) acrylate having an ethylene oxide group number of 2 to 14, polypropylene glycol di (meth) acrylate having an ethylene oxide group number of 2 to 14, polyethylene glycol di (meth) acrylate having an ethylene oxide group number of 2 to 14 and an ethylene oxide group number of 2 to 14, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxy tri (meth) acrylate, trimethylolpropane triethoxy tri (meth) acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, trimethylolpropane (meth) acrylate, tetramethyl) tetraethoxymethane (meth) acrylate, trimethylolpropane (meth) acrylate, tetramethyl) and tetramethyl (meth) acrylate Dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Among them, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, or di (trimethylolpropane) tetraacrylate is more preferable.

Examples of the ethylenically unsaturated compound include caprolactone-modified compounds (for example, KAYARAD (registered trademark) DPCA-20, shin-Nakamura Chemical co, ltd. A-9300-1CL, etc. manufactured by Nippon Kayaku co., ltd. Manufactured by Nippon Kayaku co., etc., shin-Nakamura Chemical co., ltd. Manufactured by Shin-E, A-9300, EBECRYL (registered trademark) 135, etc. manufactured by DAICEL-ALLNEX ltd. Manufactured by Nippon Kayaku co., etc.), ethoxylated glycerol triacrylate (Shin-Nakamura Chemical co., a-GLY-9E, etc.), and the like.

As the ethylenically unsaturated compound, an ethylenically unsaturated compound containing an ester bond is also preferable from the viewpoint of excellent developability.

The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as the ester bond is contained in the molecule, but from the viewpoint of excellent curability and developability, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, or di (trimethylolpropane) tetraacrylate is more preferable.

From the viewpoint of imparting reliability, the ethylenically unsaturated compound is preferably an ethylenically unsaturated compound containing an aliphatic group having 6 to 20 carbon atoms and the ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure.

Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate.

As a preferred embodiment of the ethylenically unsaturated compound, there is mentioned an ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure (preferably a 2-functional ethylenically unsaturated compound).

The above-mentioned ethylenically unsaturated compound is preferably an ethylenically unsaturated compound having a 2-or more aliphatic hydrocarbon ring-condensed ring structure (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure), more preferably a 2-functional ethylenically unsaturated compound having a 2-or more aliphatic hydrocarbon ring-condensed ring structure, and still more preferably tricyclodecane dimethanol di (meth) acrylate.

The aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure or an isobornane structure from the viewpoints of moisture permeability and bending resistance of the obtained cured film and adhesiveness of the obtained uncured film.

The molecular weight of the olefinically unsaturated compound is preferably from 200 to 3,000, more preferably from 250 to 2,600, even more preferably from 280 to 2,200, particularly preferably from 300 to 2,200.

The ratio of the content of the ethylenically unsaturated compound having a molecular weight of 300 or less in the ethylenically unsaturated compound contained in the photosensitive resin layer is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less, relative to the content of all the ethylenically unsaturated compounds contained in the photosensitive resin layer.

As one of preferable embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains an ethylenically unsaturated compound having 2 or more functions, more preferably contains an ethylenically unsaturated compound having 3 or more functions, and further preferably contains an ethylenically unsaturated compound having 3 or 4 functions.

Further, as one of preferable embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an alkali-soluble resin containing a structural unit having an aliphatic hydrocarbon ring.

Further, as one of preferable embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group, more preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and even more preferably contains succinic acid modified products of 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and dipentaerythritol pentaacrylate.

Further, as one of preferable embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound represented by the formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, more preferably contains a compound represented by the formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

In addition, as one of preferable embodiments of the photosensitive resin layer, from the viewpoints of development residue inhibition and rust prevention, the photosensitive resin layer preferably contains a 2-functional ethylenically unsaturated compound (preferably a 2-functional (meth) acrylate compound) and a 3-functional or more ethylenically unsaturated compound (preferably a 3-functional or more (meth) acrylate compound).

The mass ratio of the 2-functional ethylenically unsaturated compound to the content of the 3-functional or more ethylenically unsaturated compound is preferably 10:90 to 90:10, more preferably 30:70 to 70:30.

The content of the 2-functional ethylenically unsaturated compound is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, relative to the total amount of all ethylenically unsaturated compounds.

The content of the 2-functional ethylenically unsaturated compound in the photosensitive resin layer is preferably 10 to 60% by mass, more preferably 15 to 40% by mass, relative to the total mass of the photosensitive resin layer.

In addition, as one of preferable embodiments of the photosensitive resin layer, from the viewpoint of rust resistance, the photosensitive resin layer preferably contains the compound M and a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure.

In addition, as one of preferable embodiments of the photosensitive resin layer, from the viewpoints of substrate adhesion, development residue inhibition property, and rust inhibitive property, the photosensitive resin layer preferably contains a compound M and an ethylenically unsaturated compound having an acid group, more preferably contains a compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, further preferably contains a compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a 3-functional ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group, and particularly preferably contains a compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a 3-functional ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth) acrylate compound.

Further, as one of preferable embodiments of the photosensitive resin layer, from the viewpoints of substrate adhesion, development residue inhibition property, and rust resistance, the photosensitive resin layer preferably contains 1, 9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, further preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

The photosensitive resin layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.

The content of the 2-functional or more ethylenically unsaturated compound in the ethylenically unsaturated compound is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass, based on the total content of all the ethylenically unsaturated compounds contained in the photosensitive resin layer.

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

The content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 1 to 70% by mass, more preferably 5 to 70% by mass, still more preferably 5 to 60% by mass, and particularly preferably 5 to 50% by mass, relative to the total mass of the photosensitive resin layer.

Polymerization initiator-

The photosensitive resin layer may contain a polymerization initiator.

As the polymerization initiator, a photopolymerization initiator is preferable.

The preferred mode of the photopolymerization initiator is the same as that described in the item of the "photosensitive resin layer".

The polymerization initiator may be used alone or in combination of 2 or more.

The content of the polymerization initiator is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and still more preferably 1.0 mass% or more, relative to the total mass of the photosensitive resin layer. The upper limit is preferably 10 mass% or less, more preferably 5 mass% or less, based on the total mass of the photosensitive resin layer.

Heterocyclic compounds

The photosensitive resin layer may contain a heterocyclic compound.

The heterocycle of the heterocyclic compound may be a single ring or a plurality of rings.

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 1 atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, more preferably has a nitrogen atom.

Examples of the heterocyclic compound include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodamine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds.

Among the above, as the heterocyclic compound, at least 1 compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodamine compound, a thiazole compound, a benzimidazole compound and a benzoxazole compound is preferable, and at least 1 compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound and a benzoxazole compound is more preferable.

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

[ chemical formula 15]

[ chemical formula 16]

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

[ chemical formula 17]

[ chemical formula 18]

As thiadiazole compounds, the following compounds can be exemplified.

[ chemical formula 19]

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

[ chemical formula 20]

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

[ chemical formula 21]

/>

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

[ chemical formula 22]

As benzothiazole compounds, the following compounds can be exemplified.

[ chemical formula 23]

As benzimidazole compounds, the following compounds can be exemplified.

[ chemical formula 24]

[ chemical formula 25]

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

[ chemical formula 26]

The heterocyclic compound may be used alone or in combination of 2 or more.

When the photosensitive resin layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0% by mass, more preferably 0.10 to 10.0% by mass, still more preferably 0.30 to 8.0% by mass, and particularly preferably 0.50 to 5.0% by mass, relative to the total mass of the photosensitive resin layer.

Aliphatic thiol compounds

The photosensitive resin layer may contain an aliphatic thiol compound.

When the photosensitive resin layer contains an aliphatic thiol compound, the aliphatic thiol compound reacts with an ethylenically unsaturated compound, whereby curing shrinkage of the formed film is suppressed and stress is relaxed.

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) is preferable.

Among the above, the aliphatic thiol compound is more preferably a polyfunctional aliphatic thiol compound from the viewpoint of adhesion of the formed pattern (particularly adhesion after exposure).

In the present specification, the "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having 2 or more thiol groups (also referred to as "mercapto groups") in the molecule.

As the polyfunctional aliphatic thiol compound, a low molecular compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, still more preferably 150 to 1,000.

The number of functional groups of the polyfunctional aliphatic thiol compound is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, from the viewpoint of adhesion of the pattern to be formed.

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-ethane dithiol, 1, 3-propane dithiol, 1, 6-hexamethylenedithiol, 2' - (ethylenedithiol), succinic acid bis (3-mercaptoethyl) disulfide, and mesoethyl (3-mercapto) disulfide ether.

Among the above, at least 1 compound selected from trimethylolpropane tris (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane and 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione is preferable as the polyfunctional aliphatic thiol compound.

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.

The photosensitive resin layer may contain 1 kind of aliphatic thiol compound alone or 2 or more kinds of aliphatic thiol compounds.

When the photosensitive resin layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5% by mass to 50% by mass, still more preferably 5% by mass to 30% by mass, and particularly preferably 8% by mass to 20% by mass, relative to the total mass of the photosensitive resin layer.

Thermally 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.

Examples of the thermally crosslinkable compound include the thermally crosslinkable compound described in the above-mentioned "photosensitive resin layer".

The heat-crosslinkable compound may be used alone or in combination of 1 or more than 2.

Surfactant-containing compositions

The photosensitive resin layer may contain a surfactant.

Examples of the surfactant include the surfactants described in the item of the "photosensitive resin layer".

The surfactant may be used alone or in combination of 2 or more.

When the photosensitive resin layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and even more preferably 0.05 to 0.80% by mass, based on the total mass of the photosensitive resin layer.

Radical polymerization inhibitors

The photosensitive resin layer may contain a radical inhibitor.

Examples of the radical polymerization inhibitor include the radical polymerization inhibitor described in the above "photosensitive resin layer".

The radical polymerization inhibitor may be used alone or in combination of at least 2 kinds.

When the photosensitive resin layer contains a radical inhibitor, the content of the radical 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. When the content is 0.01 mass% or more, the storage stability of the photosensitive resin layer is more excellent. On the other hand, when the content is 3 mass% or less, the maintenance of sensitivity and the suppression of discoloration of the dye are more excellent.

Hydrogen donating compounds

The photosensitive resin layer may contain a hydrogen-donating compound.

The hydrogen-donating compound has the effect of further improving the sensitivity of the photopolymerization initiator to active light, suppressing inhibition of polymerization of the polymerizable compound by oxygen, and the like.

Examples of the hydrogen-donating compound include amine-based compounds and amino acid compounds.

Examples of the amines include compounds described in, for example, japanese patent application laid-open No. 9-134692, japanese patent application laid-open No. 59-138205, japanese patent application laid-open No. 60-084305, japanese patent application laid-open No. 62-018537, japanese patent application laid-open No. 64-033104, and Research Disclosure 33825, and Japanese patent application laid-open No. 44-020189, japanese patent application laid-open No. 51-082102, and Japanese patent application laid-open No. Journal of Polymer Society-3173 (1972). More specifically, 4' -bis (diethylamino) benzophenone, tris (4-dimethylaminophenyl) methane (alias: colorless crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline may be mentioned.

Among them, from the viewpoints of sensitivity, curing speed and curability, at least 1 selected from the group consisting of 4,4' -bis (diethylamino) benzophenone and tris (4-dimethylaminophenyl) methane is preferable as the amine.

Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

Among them, N-phenylglycine is preferred as the amino acid compound from the viewpoints of sensitivity, curing speed and curability.

Examples of the hydrogen-donating compound include an organometallic compound (tributyltin acetate, etc.) described in JP-B-48-042965, a hydrogen donor described in JP-B-55-034414, and a sulfur compound (trithiane, etc.) described in JP-A-6-308727.

The hydrogen-donating compound may be used alone or in combination of 1 or more than 2.

When the photosensitive resin layer contains a hydrogen-donating compound, the content of the hydrogen-donating compound is preferably 0.01 to 10.0 mass%, more preferably 0.01 to 8.0 mass%, and even more preferably 0.03 to 5.0 mass% relative to the total mass of the photosensitive resin layer, from the viewpoint of improving the curing rate by balancing the polymerization growth rate and chain transfer.

Impurity-

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

Examples of the impurities include the impurities described in the above-mentioned "photosensitive resin layer".

Residual monomers-

The photosensitive resin layer may contain residual monomers corresponding to the respective structural units of the polymer a.

Examples of the residual monomer corresponding to each structural unit of the polymer a in the photosensitive resin layer include residual monomers corresponding to each structural unit of the polymer a described in the above "photosensitive resin layer".

Other ingredients-

The photosensitive resin layer may contain components other than the components described above (hereinafter, also referred to as "other components"). Examples of the other component include a colorant, an antioxidant, and particles (for example, metal oxide particles). Further, as other components, other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706 may be mentioned.

As the particles, metal oxide particles are preferable.

The metal in the metal oxide particles also includes metalloids such as B, si, ge, as, sb and Te.

For example, from the viewpoint of transparency of the cured film, the average primary particle diameter of the particles is preferably 1nm to 200nm, more preferably 3nm to 80nm.

The average primary particle diameter of the particles was calculated by measuring the particle diameters of any 200 particles using an electron microscope and arithmetically averaging the measurement results. In addition, when the shape of the particles is not spherical, the longest side is defined as the particle diameter.

When the photosensitive resin layer contains particles, the photosensitive resin layer may contain only 1 kind of particles having different metal types, sizes, and the like, or may contain 2 or more kinds of particles.

Preferably, the photosensitive resin layer contains no particles, or when the photosensitive resin layer contains particles, the content of particles exceeds 0 mass% and 35 mass% or less relative to the total mass of the photosensitive resin layer, more preferably contains no particles, or the content of particles exceeds 0 mass% and 10 mass% or less relative to the total mass of the photosensitive resin layer, still more preferably contains no particles, or the content of particles exceeds 0 mass% and 5 mass% or less relative to the total mass of the photosensitive resin layer, still more preferably contains no particles, or the content of particles exceeds 0 mass% and 1 mass% or less relative to the total mass of the photosensitive resin layer, and particularly preferably contains no particles.

The photosensitive resin layer may contain a colorant (pigment, dye, etc.), but from the viewpoint of transparency, for example, it is preferable that the colorant is substantially not contained.

In the case where the photosensitive resin layer contains a colorant, the content of the colorant is preferably less than 1 mass%, more preferably less than 0.1 mass%, relative to the total mass of the photosensitive resin layer.

Examples of the antioxidant include 3-pyrazolidinones such as 1-phenyl-3-pyrazolidinone (referred to as "phenanthridinone"), 1-phenyl-4, 4-dimethyl-3-pyrazolidinone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone and chlorohydroquinone; para-methyl aminophenol, para-hydroxyphenylglycine, and para-phenylenediamine.

Among them, 3-pyrazolidinone is preferable, and 1-phenyl-3-pyrazolidinone is more preferable, from the viewpoint of storage stability and curability.

When the photosensitive resin layer contains an antioxidant, the content of the antioxidant is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, and still more preferably 0.01 mass% or more, based on the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 1 mass% or less.

Thickness of photosensitive resin layer

The thickness (layer thickness) of the photosensitive resin layer is not particularly limited, but is preferably 30 μm or less, more preferably 20 μm or less, further preferably 15 μm or less, particularly preferably 10 μm or less, and most preferably 5.0 μm or less from the viewpoints of developability and resolution. As a lower limit, the film obtained by curing the photosensitive resin layer is preferably 0.60 μm or more, more preferably 1.5 μm or more, in view of excellent strength.

Refractive index of photosensitive resin layer

The refractive index of the photosensitive resin layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.

Color of photosensitive resin layer

The photosensitive resin layer is preferably colorless. Specifically, total reflection (incidence angle 8 °, light source: D-65 (2 ° view)) is observed in CIE1976 (L) ^* ，a ^* ，b ^* ) L in color space ^* The value is preferably from 10 to 90, a ^* The value is preferably from-1.0 to 1.0, b ^* The value is preferably-1.0 to 1.0.

The pattern (cured film of the photosensitive resin layer) obtained by curing the photosensitive resin layer is preferably colorless.

Specifically, total reflection (incidence angle 8 °, light source: D-65 (2 ° view)) is observed in CIE1976 (L) ^* ，a ^* ，b ^* ) L of a pattern in color space ^* The value is preferably 10 to 90, a of the pattern ^* The value is preferably-1.0 to 1.0, b of the pattern ^* The value is preferably-1.0 to 1.0.

Moisture permeability of photosensitive resin layer

From the viewpoint of rust resistance, the layer thickness of the pattern (cured film of the photosensitive resin layer) obtained by curing the photosensitive resin layer was 40. Mu.mThe moisture permeability of (C) is preferably 500 g/(m) ² 24 hr) or less, more preferably 300 g/(m) ² 24 hr) or less, more preferably 100 g/(m) ² 24 hr) or less.

In addition, in the cured film obtained by curing the photosensitive resin layer, the exposure amount was 300mJ/cm by using i-rays ² After exposing the photosensitive resin layer to light, the film was subjected to post baking at 145℃for 30 minutes to measure the moisture permeability.

(refractive index adjusting layer)

The photosensitive transfer material preferably has a refractive index adjustment layer.

As the refractive index adjustment layer, a known refractive index adjustment layer can be applied. Examples of the material contained in the refractive index adjustment layer include alkali-soluble resins, ethylenically unsaturated compounds, metal salts, and particles.

The method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a resin and particles, and a method of using a complex of a metal salt and a resin.

Examples of the alkali-soluble resin and the ethylenically unsaturated compound include those described in the above item of "photosensitive resin layer".

Examples of the particles include metal oxide particles and metal particles.

The type of the metal oxide particles is not particularly limited, and known metal oxide particles can be used. The metal in the metal oxide particles also includes metalloids such as B, si, ge, as, sb and Te.

As the metal oxide particles, specifically, selection is preferableZirconium self-oxide particles (ZrO ₂ Particles, nb ₂ O ₅ Particles, titanium oxide particles (TiO ₂ Particles), silica particles (SiO ₂ Particles) and their composite particles.

Among these, the metal oxide particles are more preferably at least 1 selected from the group consisting of zirconia particles and titania particles, for example, from the viewpoint of easy adjustment of refractive index.

Examples of the commercial products of the metal oxide particles include calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F04), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F74), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F75), calcined zirconia particles (manufactured by CIK NanoTekCorporation, product name: ZRPGM15WT% -F76), zirconia particles (manufactured by Nanouse OZ-S30M, nissan Chemical Industries, ltd.) and zirconia particles (manufactured by Nanouse OZ-S30K, nissan Chemical Industries, ltd.).

The particles may be used alone or in combination of 2 or more.

The content of the particles in the refractive index adjustment layer is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 40 to 85% by mass, relative to the total mass of the refractive index adjustment layer.

When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 40 to 85% by mass, relative to the total mass of the refractive index adjustment layer.

The refractive index of the refractive index adjustment layer is preferably higher than that of the photosensitive resin layer.

The refractive index of the refractive index adjustment layer is preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and particularly preferably 1.65 or more. The upper limit of the refractive index adjustment layer is preferably 2.10 or less, more preferably 1.85 or less, and particularly preferably 1.78 or less.

The thickness of the refractive index adjusting layer is preferably 50nm to 500nm, more preferably 55nm to 110nm, and still more preferably 60nm to 100nm.

The refractive index adjustment layer is formed using, for example, a refractive index adjustment layer. The composition for forming a refractive index adjustment layer preferably contains various components for forming a refractive index adjustment layer and a solvent as described above. In the composition for forming a refractive index adjustment layer, the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the refractive index adjustment layer.

The solvent is not particularly limited as long as it can dissolve or disperse the component contained in the refractive index adjusting layer, and is preferably at least 1 selected from 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 glycerol, preferably alcohols having 1 to 3 carbon atoms, and more preferably methanol or ethanol.

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

The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

The method for forming the refractive index adjusting layer is not particularly limited as long as the layer containing the above-described components can be formed, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, and the like).

(relationship of temporary support, photosensitive resin layer and protective film)

In the photosensitive transfer material preferably used as the photosensitive transfer material for the wiring protective film, the above-described relationship among the temporary support, the photosensitive resin layer, and the protective film is preferably satisfied.

< method for producing resin Pattern >

The method for producing a resin pattern according to an embodiment of the present invention is a method for producing a resin pattern using the photosensitive transfer material according to the present invention. According to an embodiment of the present invention, there is provided a method for manufacturing a resin pattern having high linearity. The method for producing a resin pattern according to an embodiment of the present invention preferably includes: a step of preparing a substrate (hereinafter, sometimes referred to as a "preparation step"); a step of bringing the photosensitive transfer material into contact with the substrate, and disposing a photosensitive resin layer and a temporary support on the substrate in this order (hereinafter, sometimes referred to as a "bonding step"); a step of performing pattern exposure (hereinafter, sometimes referred to as an "exposure step") on the photosensitive resin layer; and a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter, sometimes referred to as a "developing step").

Preparation Process

In the preparation step, a substrate is prepared. The kind of the substrate is not limited. The substrate is preferably a substrate comprising a conductive layer. The substrate is preferably a substrate including a base material and a conductive layer on the base material, and more preferably a substrate including a base material and a conductive layer in contact with the base material. The conductive layer may be disposed on a single side of the substrate. The conductive layers may be disposed on both sides of the substrate, respectively. The substrate may comprise layers other than the conductive layer.

Examples of the substrate include glass, silicon, and a resin film. The substrate is preferably transparent. In the present invention, "transparent" means that the transmittance at a wavelength of 400nm to 700nm is 80% or more. The refractive index of the substrate is preferably 1.50 to 1.52.

Examples of the transparent Glass include tempered Glass represented by gorella Glass of Corning Incorporated co. As the transparent glass, materials used in japanese patent application laid-open publication nos. 2010-86684 and 2010-152809 and 2010-257492 can also be used.

The resin film is preferably a resin film having little optical distortion or high transparency. Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, and cycloolefin polymer.

In the method for producing a resin pattern using the roll-to-roll method, the base material is preferably a resin film.

Examples of the conductive layer include a conductive layer used for a normal circuit wiring and a touch panel wiring. The conductive layer is preferably a wiring corresponding to an electrode pattern or a peripheral extraction portion of a sensor for a visible portion of the capacitive touch panel.

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

Examples of the component of the conductive layer include a metal and a conductive metal oxide. Examples of the metal include Al, zn, cu, fe, ni, cr, mo, ag and Au. Examples of the conductive metal Oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide ), and SiO2. In the present invention, "conductive" means that the volume resistivity is less than 1X 10 ⁶ Properties of Ω cm. The volume resistivity of the conductive metal oxide is preferably less than 1×10 ⁴ Ωcm。

In the case of manufacturing a resin pattern using a substrate including a plurality of conductive layers, it is preferable that at least 1 conductive layer of the plurality of conductive layers contains a conductive metal oxide.

The substrate may contain 1 or more than 2 conductive layers. In the case where the substrate includes 2 or more conductive layers, the substrate preferably includes 2 or more conductive layers formed of materials different from each other.

A preferred form of conductive layer is described, for example, in paragraph 0141 of international publication No. 2018/155193, which is incorporated herein by reference.

As the substrate including the conductive layer, a substrate having at least one of a transparent electrode and routing wiring is preferable. The substrate described above can be preferably used as a substrate for a touch panel. The transparent electrode can preferably function as an electrode for a touch panel. The transparent electrode is preferably formed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), and a metal thin wire such as a metal mesh and a metal nanowire. The fine metal wire may be a fine wire of silver, copper, or the like. Among them, silver conductive materials such as silver mesh and silver nanowire are preferable.

As a material of the 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 composed 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.

Lamination Process

In the bonding step, the photosensitive transfer material is brought into contact with a substrate, and a photosensitive resin layer and a temporary support are sequentially disposed on the substrate.

The photosensitive transfer material is as described in the above item "photosensitive transfer material". The preferred embodiment of the photosensitive transfer material used in the bonding step is the same as that described in the item of "photosensitive transfer material".

In the bonding step, the photosensitive resin layer and the temporary support disposed on the substrate are the photosensitive resin layer and the temporary support contained in the photosensitive transfer material, respectively. That is, the layer structure of the laminate obtained by the bonding step changes according to the layer structure of the photosensitive transfer material. For example, in the bonding step, when the photosensitive transfer material including the temporary support, the thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer in this order is brought into contact with the substrate, the photosensitive resin layer, the intermediate layer, the thermoplastic resin layer, and the temporary support are sequentially disposed on the substrate. When the photosensitive transfer material contains a protective film, the protective film is removed from the photosensitive transfer material, and then the photosensitive transfer material is brought into contact with the substrate.

In the bonding step, the photosensitive transfer material is preferably brought into contact with the substrate and pressure-bonded to the substrate. For example, it is preferable to press the photosensitive transfer material against the substrate by bringing the photosensitive transfer material into contact with the substrate and applying pressure and heat to the substrate and the photosensitive transfer material using a device such as a roller.

In the method of bringing the photosensitive transfer material into contact with the substrate (including a method of pressing the photosensitive transfer material against the substrate), for example, a known transfer method or a known lamination method is used. In the method of bringing the photosensitive transfer material into contact with the substrate, for example, a laminator, a vacuum laminator, or an automatic cutting laminator capable of further improving productivity is used.

Exposure process

In the exposure step, the photosensitive resin layer is subjected to pattern exposure. The arrangement and size of the pattern in the pattern exposure are not limited. At least a part of the pattern (preferably a part corresponding to the electrode pattern or the lead-out wiring 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.

Examples of the light source in the exposure step include a light source that irradiates light (e.g., 365nm or 405 nm) of a wavelength capable of exposing the photosensitive resin layer. Examples of the light source include an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode ).

The exposure is preferably 5mJ/cm ² ～300mJ/cm ² More preferably 10mJ/cm ² ～200mJ/cm ² 。

In the exposure step, the photosensitive resin layer may be subjected to pattern exposure after the temporary support is peeled off. In the exposure step, the temporary support may be peeled off after pattern exposure of the photosensitive resin layer via the temporary support.

In the exposure system using a photomask, when the temporary support is peeled off before pattern exposure, the photosensitive resin layer may be exposed by bringing the photomask into contact with the photosensitive resin layer, or the photosensitive resin layer may be exposed by bringing the photomask close to the photosensitive resin layer without bringing the photomask into contact with the photosensitive resin layer. In the exposure system using a photomask, in the case of exposing the photosensitive resin layer through the temporary support, the photosensitive resin layer may be exposed by bringing the photomask into contact with the temporary support, or the photosensitive resin layer may be exposed by bringing the photomask close to the temporary support without bringing the photomask into contact with the temporary support. In order to prevent contamination of the photomask due to contact between the photosensitive resin layer and the photomask and to avoid an influence on exposure due to impurities adhering to the photomask, it is preferable to pattern-expose the photosensitive resin layer via a temporary support.

The exposure method is not limited. Examples of the exposure method include a contact exposure method and a noncontact exposure method. As the contact exposure method, for example, a method of pattern-exposing the photosensitive resin layer using a photomask is mentioned. Examples of the non-contact exposure method include a proximity (proximity) exposure method, a projection exposure method using a lens system or a mirror system, and a direct exposure method using an exposure laser. In the projection exposure system using a lens system or a mirror system, an exposure machine having a Numerical Aperture (NA) of an appropriate lens can be used according to the required resolution and depth of focus. In the direct exposure method, the drawing may be performed directly on the photosensitive layer, or the reduction projection exposure may be performed on the photosensitive layer via a lens. The exposure may be performed under atmospheric pressure, reduced pressure, or vacuum. The exposure can be performed by inserting a liquid such as water between the light source and the photosensitive resin layer.

Development Process

In the development step, the exposed photosensitive resin layer is developed to form a resin pattern. When the photosensitive resin layer is a negative photosensitive resin layer, the non-exposed portion of the photosensitive resin layer is removed, and the exposed portion of the photosensitive resin layer forms a resin pattern. When the photosensitive resin layer is a positive photosensitive resin layer, the exposed portion of the photosensitive resin layer is removed, and the non-exposed portion of the photosensitive resin layer is formed into a resin pattern. In the bonding step, the thermoplastic resin layer and the intermediate layer disposed on the substrate are removed together with the removed photosensitive resin layer. The thermoplastic resin layer and the intermediate layer can be removed by dissolving or dispersing the developer.

The development is performed, for example, using a developer. The developer is not limited as long as it is a developer of the photosensitive resin layer to be removed. As the developer, a known developer is used. Examples of the developer include a developer described in JP-A-5-72724. The developer is preferably an aqueous alkali developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05mol/L to 5 mol/L. The developer may contain a water-soluble organic solvent and/or a surfactant. The developer described in paragraph 0194 of International publication No. 2015/093271 is also preferable.

The liquid Wen Bingmo of the developer is limited. The liquid temperature of the developer is preferably 20 to 40 ℃.

The development method is not limited. The development method may be, for example, puddle development, shower development, spin development, or dip development. The shower development is a method of removing the photosensitive resin layer to be subjected to the exposure by spraying a developing solution onto the photosensitive resin layer after the exposure.

After the development step, the cleaning agent is sprayed, and the development residue is preferably removed while wiping with a brush.

The resin pattern obtained through the above-described process may be used as a permanent film or an etched protective film.

Roll-to-roll method

The method for producing the resin pattern is preferably performed in a roll-to-roll manner. The roll-to-roll method is the following: the method includes a step of unwinding a substrate or a laminate including a substrate before any step included in the method for producing a resin pattern (sometimes referred to as an "unwinding step") and a step of winding a substrate or a laminate including a substrate after any step (hereinafter sometimes referred to as a "winding step"), and at least any step (preferably all steps) is performed while carrying the substrate or the laminate including the substrate. As the unwinding method in the unwinding step and the winding method in the winding step, for example, a known method suitable for the roll-to-roll system is used.

< method for producing Circuit Wiring >

The method for manufacturing a circuit wiring according to an embodiment of the present invention is a method for manufacturing a circuit wiring using the photosensitive transfer material according to the present invention. According to an embodiment of the present invention, a method for manufacturing a circuit wiring having high linearity is provided. The method for manufacturing a circuit wiring according to an embodiment of the present invention preferably includes: a step of preparing a substrate including a conductive layer (hereinafter, sometimes referred to as a "preparation step"); a step of bringing the photosensitive transfer material into contact with the substrate, and disposing a photosensitive resin layer and a temporary support on the substrate in this order (hereinafter, sometimes referred to as a "bonding step"); a step of performing pattern exposure (hereinafter, sometimes referred to as an "exposure step") on the photosensitive resin layer; a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter, sometimes referred to as a "developing step"); and a step of forming a circuit wiring by etching the conductive layer not covered with the resin pattern (hereinafter, sometimes referred to as an "etching step").

Preparation Process

In the preparation step, a substrate including a conductive layer is prepared. The substrate including the conductive layer is as described in the item of the above "method for manufacturing a resin pattern". The preferred embodiment of the substrate including the conductive layer is the same as the preferred embodiment of the substrate including the conductive layer described in the item of the "method for manufacturing a resin pattern" described above.

Lamination Process

In the bonding step, the photosensitive transfer material is brought into contact with a substrate, and a photosensitive resin layer and a temporary support are sequentially disposed on the substrate. The bonding step is as described in the above item "method for producing a resin pattern". The preferred mode of the bonding step is the same as the preferred mode of the bonding step described in the item of the "method for producing a resin pattern" described above.

Exposure process

In the exposure step, the photosensitive resin layer is subjected to pattern exposure. The exposure step is as described in the above item "method for producing a resin pattern". The preferred mode of the exposure step is the same as the preferred mode of the exposure step described in the item of the "method for producing a resin pattern" described above.

Development Process

In the development step, the exposed photosensitive resin layer is developed to form a resin pattern. The development step is as described in the above item "method for producing a resin pattern". The preferred mode of the developing process is the same as the preferred mode of the developing process described in the item of the "method for producing a resin pattern" described above.

Etching Process

In the etching step, the conductive layer not covered with the resin pattern is subjected to etching treatment to form a circuit wiring. In the etching step, the resin pattern functions as a protective film for the conductive layer. In the etching step, the conductive layer not covered with the resin pattern is removed by etching treatment, and the conductive layer covered with the resin pattern forms a circuit wiring.

As a method of etching treatment, for example, a known method is used. Examples of the method of the etching treatment include the method described in paragraphs 0209 to 0210 of Japanese patent application laid-open No. 2017-120435, the method described in paragraphs 0048 to 0054 of Japanese patent application laid-open No. 2010-152155, and wet etching and dry etching (e.g., plasma etching) in which the etching solution is immersed.

The etching liquid used in the wet etching method may be appropriately selected from an acidic etching liquid and an alkaline etching liquid according to the etching object. Examples of the acidic etching solution include aqueous solutions containing at least 1 acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid. The acidic etching solution may be, for example, an aqueous solution containing the above-mentioned acidic component and at least 1 salt selected from the group consisting of ferric chloride, ammonium fluoride and potassium permanganate. The acidic component may be a component obtained by combining a plurality of acidic components. Examples of the alkaline etching liquid include aqueous solutions containing at least 1 alkali component selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines and salts of organic amines (for example, tetramethylammonium hydroxide). As the alkaline etching liquid, for example, an aqueous solution containing the above-mentioned alkali component and a salt (for example, potassium permanganate) is also mentioned. The alkali component may be a component obtained by combining a plurality of alkali components.

Removal Process

The method for manufacturing a circuit wiring according to an embodiment of the present invention preferably includes a step of removing the remaining resin pattern after the etching step.

As a method for removing the resin pattern, for example, a method for removing the resin pattern using a chemical treatment is mentioned. A method of removing the resin pattern using a removing liquid is preferable. Examples of the method for removing the resin pattern using the removing liquid include a method in which the substrate containing the resin pattern is immersed in the removing liquid under stirring at a liquid temperature of 30 to 80 ℃ (preferably 50 to 80 ℃) for 1 to 30 minutes.

Examples of the removing liquid include removing liquids containing an inorganic base component or an organic base component and at least 1 selected from the group consisting of water, dimethyl sulfoxide and N-methylpyrrolidone. 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 remaining resin pattern may be removed by a known method such as a spraying method, and a spin-on immersion method.

Other procedures

The method for manufacturing a circuit wiring according to an embodiment of the present invention may include other steps in addition to the above steps. Examples of the other steps include the following steps. The exposure step, the development step, and other steps which can be applied to the method for manufacturing a circuit wiring according to an embodiment of the present invention are described in paragraphs 0035 to 0051 of japanese unexamined patent publication No. 2006-23696. The contents described in the above publications are incorporated into the present specification by reference.

(step of reducing reflectance of visible ray)

The method for manufacturing a circuit wiring according to an embodiment of the present invention may include a step of performing a process of reducing the reflectance of a part or all of the plurality of conductive layers of the substrate. As the treatment for reducing the reflectance of visible light, for example, an oxidation treatment is given. For example, when the conductive layer contains copper, copper is oxidized to form copper oxide, and the conductive layer is blackened, whereby the visible ray reflectance of the conductive layer 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. The contents described in these publications are incorporated into the present specification by reference.

(step of forming an insulating film and step of forming a novel conductive layer on the surface of the insulating film)

The method for manufacturing a circuit wiring according to an embodiment of the present invention preferably includes a step of forming an insulating film on a surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film. Through the above steps, the second electrode pattern insulated from the first electrode pattern can be formed. As a method for forming the insulating film, for example, a known method for forming a permanent film is given. An insulating film having a desired pattern can be formed by photolithography using an insulating photosensitive material. As a method for forming a new conductive layer on the surface of the insulating film, for example, a new conductive layer having a desired pattern can be formed by photolithography using a photosensitive material having conductivity.

In the method for manufacturing a circuit wiring according to an embodiment of the present invention, it is also preferable that a circuit is formed sequentially or simultaneously with the conductive layers formed on both surfaces of the base material using a pair of substrates each having a plurality of conductive layers on both surfaces of the base material. According to the above method, the first conductive pattern can be formed on one surface of the substrate, and the second conductive pattern can be formed on the other surface of the substrate. The conductive pattern described above is used, for example, as a circuit wiring for a touch panel. The conductive pattern as described above is preferably formed in a roll-to-roll manner.

Roll-to-roll method

The method for manufacturing a circuit wiring according to an embodiment of the present invention is preferably performed in a roll-to-roll manner. The roll-to-roll method is as described in the above item of "method for producing a resin pattern".

Use of Circuit Wiring

The circuit wiring obtained by the method for manufacturing a circuit wiring according to an embodiment of the present invention is applicable to various devices. Examples of the device including the circuit wiring include an input device, preferably a touch panel, and more preferably a capacitive touch panel. The input device is applicable to a display device such as an organic EL display device or a liquid crystal display device.

< method for manufacturing touch Panel >

A method for manufacturing a touch panel according to an embodiment of the present invention is a method for manufacturing a touch panel using the photosensitive transfer material according to the present invention. The method for manufacturing a touch panel according to an embodiment of the present invention preferably includes the method for manufacturing a circuit wiring according to an embodiment of the present invention. That is, the method for manufacturing a touch panel according to an embodiment of the present invention preferably includes the preparation step, the exposure step, the development step, and the etching step described in the above-described item "method for manufacturing a circuit wiring". Through the above steps, for example, a wiring for a touch panel is formed. Examples of patterns of a photomask used for manufacturing a wiring for a touch panel include pattern a and pattern B described in japanese patent application laid-open publication No. 2019-204070. The method for manufacturing a touch panel according to an embodiment of the present invention may further include other steps described in the above-described item "method for manufacturing a circuit wiring". In order to form the constituent elements of the touch panel other than the wiring, a known method for manufacturing the touch panel is referred to.

Examples of the detection method of the touch panel include a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among the above, the electrostatic capacitance system is preferable.

Examples of the Touch panel type include an embedded type (for example, the structure described in fig. 5, 6, 7 and 8 of japanese patent application laid-open No. 2012-517051), a so-called external type (for example, the structure described in fig. 19 of japanese patent application laid-open No. 2013-168125 and the structure described in fig. 1 and 5 of japanese patent application laid-open No. 2012-89102), an OGS (One Glass Solution: monolithic glass) type, a TOL (Touch-on-Lens) type (for example, the structure described in fig. 2 of japanese patent application laid-open No. 2013-54727), various types of external type (so-called GG, g1.g2, GFF, GF1 and G1F), and other structures (for example, the structure described in fig. 6 of japanese patent application laid-open No. 2013-164871).

Examples

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples. The contents (e.g., materials, use amounts, proportions, processing contents, and processing steps) of the embodiments shown below may be appropriately changed within the scope of the object of the present invention.

< preparation of composition 1 for Forming particle-containing layer >

The mixture obtained by mixing the components shown below was filtered using a 6 μm filter (F20, mahle Filter Systems Japan corp.) and membrane deaeration was performed using 2×6Radial Flow Super Phobic (Polypore co., ltd.). The particle-containing layer forming composition 1 was obtained by the above steps.

Acrylic polymer (AS-563A, DAICEL MIRAIZU LTD., solid content: 27.5 mass%): 167 parts by mass

Nonionic surfactant (NAROACTY CL95, sanyo Chemical Industries, ltd., solid content: 100 mass%): 0.7 part by mass

Anionic surfactant (RAPISOL A-90, NOF CORPORATION, aqueous dilution with a solid content of 1% by mass): 114.4 parts by mass

Bacillush wax dispersion (Cellulose 524, CHUKYO YUSHI CO., LTD., solid content: 30% by mass): 7 parts by mass

Carbodiimide Compound (CARBODILITE V-02-L2, nisshinbo Chemical Inc., diluted with water having a solid content of 10% by mass): 20.9 parts by mass

Matting agent (Snowtex XL, nissan Chemical Corporation, solid content: 40% by mass, average particle size: 50 nm): 2.8 parts by mass

Water: 690.2 parts by mass

< preparation of composition 2 for Forming particle-containing layer >

Except that the amount of matting agent added was 3.6 parts by mass, a composition 2 for forming a particle-containing layer was obtained in the same manner as the preparation method of the composition 1 for forming a particle-containing layer.

< preparation of composition 3 for Forming particle-containing layer >

The mixture obtained by mixing the components shown below was filtered using a 6 μm filter (F20, mahle Filter Systems Japan corp.) and membrane deaeration was performed using 2×6Radial Flow Super Phobic (Polypore co., ltd.). The particle-containing layer forming composition 3 was obtained by the above steps.

Anionic surfactant (RAPISOLA-90, NOF CORPORATION, aqueous dilution with a solid content of 1% by mass): 55.7 parts by mass

Matting agent (AEROSIL OX50, NIPPON AEROSIL co., ltd., solid content: 10 mass%, water dispersion, median diameter: 0.2 μm): 3.5 parts by mass

Water: 743 parts by mass

< preparation of composition 4 for Forming particle-containing layer >

Except that the amount of matting agent added was 6.0 parts by mass, a composition 4 for forming a particle-containing layer was obtained in the same manner as the preparation method of the composition 1 for forming a particle-containing layer.

< production of temporary support 1 >

The temporary support 1 is manufactured by the following method.

(extrusion molding)

Particles of polyethylene terephthalate (PET) produced using the citric acid chelate organic titanium complex described in japanese patent No. 5575671 as a superposition catalyst are dried, and the water content of the particles is set to 50ppm or less. The dried pellets were charged into a hopper of a single-shaft kneading extruder having a diameter of 30mm, and melted at 280 ℃. After passing the melt through a filter (pore size: 2 μm), it was extruded from a die to a cooling roll at 25℃to obtain an unstretched film. In the above method, the melt is brought into close contact with the cooling roll by an electrostatic application method.

(stretching and coating)

The cured, unstretched film was subjected to successive biaxial stretching by the following method, whereby a particle-containing layer having a thickness of 40nm was formed on a polyethylene terephthalate film having a thickness of 16. Mu.m.

(a) Stretching in the longitudinal direction

The unstretched film was stretched in the machine direction (transport direction) by passing it between 2 pairs of nip rolls having different peripheral speeds. The conditions of longitudinal stretching are shown below.

Preheating temperature: 75 DEG C

Stretching temperature: 100 DEG C

Stretch ratio: 3.4 times

Drawing speed: 1,300%/second

(b) Coating

The composition 1 for forming a particle-containing layer was applied to one side of the longitudinally stretched film using a bar coater so that the thickness after film formation became 40nm.

(c) Transverse stretching

The film coated with the composition 1 for forming a particle-containing layer was transversely stretched using a tenter under the following conditions.

Preheating temperature: 110 DEG C

Stretching temperature: 120 DEG C

Stretch ratio: 4.2 times

Drawing speed: 50%/second

(Heat setting and thermal relaxation)

The biaxially stretched film stretched in the machine direction and the transverse direction was heat-set under the following conditions.

Heat setting temperature: 227 DEG C

Heat setting time: for 6 seconds

After heat setting, the tenter width was reduced and the biaxially stretched film was thermally relaxed under the following conditions.

Thermal relaxation temperature: 190 DEG C

Thermal relaxation rate: 4%

(coiling)

After heat setting and thermal relaxation, both ends of the film were trimmed, and after extrusion processing (knurling) was performed at 10mm width on the ends of the film, the film was wound up at a tension of 40 kg/m. The width of the film was 1.5m, and the roll length of the film was 6 and 300m. The resulting film roll was set as a temporary support 1.

The temporary support 1 comprises, in order, a polyethylene terephthalate film (substrate) and a particle-containing layer. The haze of the temporary support 1 was 0.2%. Haze was measured as total haze using a haze meter (NIPPON DENSHOKU INDUSTRIES co., ltd., NDH 2000). The heat shrinkage rate based on heating at 150 ℃ for 30 minutes was 1.0% on the MD (conveying direction, machine Direction) side and 0.2% on the TD (direction orthogonal to the conveying direction on the face of the film, transverse Direction) side. The thickness of the particle-containing layer was 40nm as measured from a section TEM photograph. The average particle diameter of the particles contained in the particle-containing layer measured by the above method was 50nm using a Transmission Electron Microscope (TEM) type HT-7700 manufactured by Hitachi High-Technologies Corporation.

< production of temporary supports 2 to 11 >

A temporary support was obtained by the same method as the method for producing the temporary support 1, except that the types of the composition for forming a particle-containing layer and the arrangement of the particle-containing layer were appropriately changed according to the following table.

TABLE 1

In the above table, the temporary support having a column of "2 nd side" indicating the type of the composition for forming a particle-containing layer contains a particle-containing layer disposed as the outermost layer on the 2 nd side of the temporary support. In the above table, the temporary support having a column of "1 st surface" indicating the type of the composition for forming a particle-containing layer contains a particle-containing layer disposed as the outermost layer on the 1 st surface side of the temporary support.

< preparation of composition 1 for Forming photosensitive resin layer >

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

TABLE 2

< preparation of composition 2 for Forming photosensitive resin layer >

The solvent and the following components were mixed to prepare a photosensitive resin layer-forming composition 2.

TABLE 3

< preparation of composition 1 for Forming thermoplastic resin layer >

The solvent and the following components were mixed to prepare a thermoplastic resin layer-forming composition 1.

TABLE 4

The following shows the meaning of abbreviations described in the above tables.

A-2: benzyl methacrylate/methacrylic acid/acrylic acid copolymer (75 mass%/10 mass%/15 mass%, weight average molecular weight: 30,000, tg:75 ℃, acid value: 186 mgKOH/g)

B-1: the following structural compound (pigment developed by acid)

[ chemical formula 27]

C-1: the compounds having the structures shown below (photoacid generators, compounds described in paragraph 0227 of JP-A2013-47765, and methods described in paragraph 0227 were synthesized.)

[ chemical formula 28]

D-3: NK ESTER A-DCP (tricyclodecane dimethanol diacrylate, shin-Nakamura Chemical Co., ltd.)

D-4:8UK-015A (multifunctional urethane acrylate Compound, taisei Fine Chemical Co., ltd.)

D-5: aromix TO-2349 (multifunctional acrylate compound having carboxyl group, toagoseico., ltd.)

E-1: megaface F-552 (fluoro surfactant, DIC CORPORATION)

F-1: phenothiazine (FUJIFILM Wako Pure Chemical Corporation)

F-2: CBT-1 (carboxybenzotriazole, JOHOKU CHEMICAL CO., LTD.)

< preparation of composition 1 for Forming Water-soluble resin layer >

The following components were mixed to prepare a water-soluble resin layer-forming composition 1.

Ion-exchanged water: 38.12 parts by mass

Methanol (MITSUBISHI GAS CHEMICAL compass, inc.): 57.17 parts by mass

KURARAY co, ltd.poval 4-88LA (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 (fluoro surfactant, DIC Corporation): 0.0035 parts by mass

Example 1 ]

The photosensitive resin layer-forming composition 1 was applied to the 2 nd surface of the temporary support 1 using a slit nozzle. The applied composition 1 for forming a photosensitive resin layer was dried at 100℃for 120 seconds to form a photosensitive resin layer having a thickness of 5. Mu.m. The photosensitive transfer material obtained by the above steps contains a temporary support and a photosensitive resin layer in this order.

< examples 2 to 14 and comparative example 1>

A photosensitive transfer material was obtained by the same procedure as that described in example 1, except that the types of temporary supports and the thicknesses of the photosensitive resin layers were appropriately changed as described in table 5.

Example 15 ]

The thermoplastic resin layer-forming composition 1 was applied to the 2 nd surface of the temporary support 1 using a slit-shaped nozzle. The coated thermoplastic resin layer-forming composition 1 was dried at 100℃for 120 seconds to form a thermoplastic resin layer having a thickness of 2. Mu.m.

The water-soluble resin layer-forming composition 1 was applied onto the thermoplastic resin layer using a slit nozzle. The coated water-soluble resin layer-forming composition 1 was dried at 120℃for 120 seconds to form a water-soluble resin layer having a thickness of 1. Mu.m. The water-soluble resin layer is an intermediate layer.

The photosensitive resin layer-forming composition 2 was applied onto the water-soluble resin layer using a slit nozzle. The applied composition 2 for forming a photosensitive resin layer was dried at 100℃for 120 seconds to form a photosensitive resin layer having a thickness of 2. Mu.m.

The photosensitive transfer material obtained by the above steps contains a temporary support, a thermoplastic resin layer, a water-soluble resin layer, and a photosensitive resin layer in this order.

After the temporary support was peeled off from the photosensitive transfer material, the L of the 1 st surface of the temporary support was measured by the following method ^* Value and L of 2 nd side ^* Values. L was measured at 10 total points along the width direction of the target surface at 3CM intervals using a spectrocolorimeter (CM-700 d, konica Minolta, inc.) ^* Values. Specific measurement conditions are shown below. For L at 10 points measured by SCE method ^* The values are arithmetically averaged. L using the obtained value as object plane based on SCE method ^* Values. The measurement results are shown in table 5.

Light source: d65 light source

Mode: SCI+SCE mode

Diameter measurement: 8mm phi

< minimum resolution linewidth and linearity >

A copper layer having a thickness of 200nm was formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by sputtering, thereby producing a PET substrate with a copper layer. The photosensitive transfer material and the copper layer-carrying PET substrate were bonded by a roll-to-roll method using a vacuum laminator (MCK co., ltd., roll temperature: 110 ℃, line pressure: 1.0MPa, line speed: 0.5 m/min). The laminate obtained contains at least a PET film, a copper layer, a photosensitive resin layer, and a temporary support in this order. The obtained laminate was defoamed under pressure at 0.6MPa and 60℃for 0.5 hours using an autoclave apparatus. The photosensitive resin layer was exposed to light through a line-space pattern mask (Duty ratio: 1, line width was changed stepwise from 1 μm to 20 μm every 1 μm) without peeling off the temporary support using an ultra-high pressure mercury lamp. Development is performed after the temporary support is peeled off. For development, a 1.0 mass% aqueous sodium carbonate solution at 25 ℃ was used and development by spraying was performed for 30 seconds. By the above method, an exposure amount (hereinafter, referred to as "reference exposure amount") of a line width of the resin pattern corresponding to the space pattern and 20 μm line of the mask was determined to be exactly 20 μm. Next, a resin pattern was formed by the same method as the above method except that the photosensitive resin layer was exposed to the reference exposure amount. The resin pattern was observed using a Scanning Electron Microscope (SEM). The minimum value of the line width of the resin pattern without peeling of the resin pattern and without residue in the space portion of the resin pattern is adopted as the minimum resolution line width. The measurement results are shown in the following table. The smaller the minimum resolution line width, the better the resolution.

Next, a resin pattern having a line width of 10 μm was observed with a Scanning Electron Microscope (SEM), and a maximum value-minimum value of the line width (hereinafter, referred to as "variation value of the line width") was measured in a range of 100 μm in length. The linearity of the resin pattern was evaluated based on the line width fluctuation value according to the following criteria. The evaluation results are shown in table 5.

A: the variation of the line width is less than 0.4 μm.

B: the variation of the line width is more than 0.4 μm and less than 0.7 μm.

C: the variation of the line width is more than 0.7 μm and less than 1.0 μm.

D: the variation of the line width is 1.0 μm or more and less than 1.5 μm.

E: the variation of the line width is more than 1.5 mu m.

< transport Property >

A copper layer having a thickness of 200nm was formed on a polyethylene terephthalate film (PET film) having a thickness of 100 μm by sputtering, thereby producing a PET substrate with a copper layer. The photosensitive transfer material and the copper-layer-attached PET substrate were bonded by a roll-to-roll method using a vacuum laminator (MCK co., ltd., roll temperature: 120 ℃, line pressure: 1.0MPa, line speed: 0.5 m/min). The layer structure of the obtained laminate was a PET film/copper layer/photosensitive resin layer/temporary support. The temporary support of the laminate was visually observed, and the occurrence of wrinkles was evaluated according to the following criteria. The evaluation results are shown in table 5.

A: no wrinkles were confirmed at all.

B: strong wrinkles (for example, wrinkles having a width of 10 μm to 100 μm) were confirmed to be visually recognized.

TABLE 5

Table 5 shows that the straightness of the resin patterns in examples 1 to 15 is superior to that of the resin pattern in comparative example 1.

< preparation of composition for Forming photosensitive resin layer >

Compositions A-1 to A-10 for forming a photosensitive resin layer having compositions shown in the following tables were prepared.

TABLE 6

TABLE 7

(Compound B)

The structure of compound B is shown below.

[ chemical formula 29]

(Compound C)

The structure of compound C is shown below.

[ chemical formula 30]

(preparation of P-1 solution)

As the P-1 solution, a solution of 36.3% by mass of a solid content of the polymer P-1 having the following structure (solvent: propylene glycol monomethyl ether acetate) was used. The polymer P-1 is an alkali-soluble resin. In the polymer P-1, the lower right numerical value of each structural unit represents the content ratio (mol%) of each structural unit. The P-1 solution was prepared by the polymerization step and the addition step described below.

Polymerization procedure-

Propylene glycol monomethyl ether acetate (SANWA KAGAKU SANGYO CO., LTD., product name PGM-Ac) (60 g), propylene glycol monomethyl ether (SANWA KAGAKU SANGYOCO., LTD., product name PGM) (240 g) were introduced into a 2000mL flask. The obtained liquid was heated to 90℃while stirring at a stirring speed of 250rpm (round per minute; the same applies hereinafter).

As a preparation of the dropping liquid (1), the dropping liquid (1) was obtained by mixing methacrylic acid (107.1 g), methyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name MMA) (5.46 g) and cyclohexyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name CHMA) (231.42 g) and diluting with PGM-Ac (60 g).

As preparation of the dropping liquid (2), the dropping liquid (2) was obtained by dissolving dimethyl 2,2' -azobis (2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Corporation, trade name V-601) (9.637 g) in PGM-Ac (136.56 g).

The dropwise addition solution (1) and the dropwise addition solution (2) were simultaneously added dropwise over 3 hours to the above-mentioned 2000mL flask (specifically, a 2000mL flask containing a liquid heated to 90 ℃).

Next, the vessel of the dropping liquid (1) was purged with PGM-Ac (12 g), and the purged liquid was dropped into the above-mentioned 2000mL flask. Next, the vessel of the dropping liquid (2) was purged with PGM-Ac (6 g), and the purged liquid was dropped into the above-mentioned 2000mL flask. In these dropwise addition, the reaction solution in the 2000mL flask was kept at 90℃and stirred at a stirring speed of 250 rpm. Further, as a post reaction, stirring was carried out at 90℃for 1 hour.

V-601 (2.401 g) was added to the reaction solution after the post-reaction as the 1 st additional addition of the initiator. Further, the vessel of V-601 was purged with PGM-Ac (6 g), and the purging liquid was introduced into the reaction solution. Then, the mixture was stirred at 90℃for 1 hour.

Next, V-601 (2.401 g) was added to the reaction solution as the 2 nd additional addition of the initiator. Further, the vessel of V-601 was purged with PGM-Ac (6 g), and the purging liquid was introduced into the reaction solution. Then, the mixture was stirred at 90℃for 1 hour.

Next, V-601 (2.401 g) was added to the reaction solution as the 3 rd additional addition of the initiator. Further, the vessel of V-601 was purged with PGM-Ac (6 g), and the purging liquid was introduced into the reaction solution. Then, the mixture was stirred at 90℃for 3 hours.

Addition procedure-

After stirring at 90℃for 3 hours, PGM-Ac (178.66 g) was introduced into the reaction solution. Subsequently, tetraethylammonium bromide (manufactured by FUJIFILM Wako Pure Chemical Corporation) (1.8 g) and hydroquinone monomethyl ether (manufactured by FUJIFILM Wako Pure Chemical Corporation) (0.8 g) were added to the reaction solution. Further, each vessel was purged with PGM-Ac (6 g), and the purging liquid was introduced into the reaction solution. Then, the temperature of the reaction solution was raised to 100 ℃.

Then, glycidyl methacrylate (manufactured by NOF CORPORATION, trade name BLEMEER G) (76.03G) was added dropwise to the reaction solution over 1 hour. The container of blemmerg was purged with PGM-Ac (6 g) and the purge was introduced into the reaction solution. Then, as an addition reaction, stirring was carried out at 100℃for 6 hours.

Then, the reaction solution was cooled and filtered through a mesh filter (100 mesh) for dust removal to obtain a solution (1158 g) of polymer P-1 (solid content: 36.3 mass%). The weight average molecular weight of the obtained polymer P-1 was 27000, the number average molecular weight was 15000, and the acid value was 95mgKOH/g. The structure of the polymer P-1 is shown below. Wherein the molar ratio of the repeating units is 51.5:2:26.5:20 in this order from the repeating unit on the left.

[ chemical formula 31]

(preparation of P-2 solution)

A36.5% by mass solution of polymer P-2 as a P-2 solution was prepared in the following manner. The polymer P-2 is an alkali-soluble resin. Propylene glycol monomethyl ether 82.4g was charged to the flask and heated to 90℃under a nitrogen stream. To this liquid, a solution prepared by dissolving 38.4g of styrene, 30.1g of dicyclopentanyl methacrylate, 34.0g of methacrylic acid in 20g of propylene glycol monomethyl ether and a solution prepared by dissolving 5.4g of a polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) in 43.6g of propylene glycol monomethyl ether acetate were simultaneously added dropwise over 3 hours. After the completion of the dropwise addition, 0.75g of V-601 was added 3 times every 1 hour. Then, it was allowed to react for 3 hours. Then, 58.4g of propylene glycol monomethyl ether acetate and 11.7g of propylene glycol monomethyl ether were diluted. The reaction solution was warmed to 100℃under an air flow, and 0.53g of tetraethylammonium bromide and 0.26g of p-methoxyphenol were added. To this was added dropwise 25.5g of glycidyl methacrylate (BLEMEER GH manufactured by NOF Corporation) over a period of 20 minutes. This was allowed to react at 100℃for 7 hours to give a solution of polymer P-2. The solid content concentration of the obtained solution was 36.5 mass%. Regarding the polymer P-2, the weight average molecular weight in terms of standard polystyrene in GPC was 17000, the dispersity was 2.4, and the acid value was 95mgKOH/g. The residual monomer amount as determined by gas chromatography was less than 0.1 mass% in any of the monomers with respect to the solid content of the polymer P-2. The structure of the polymer P-2 is shown below. Wherein the molar ratio of the repeating units is 41.0:15.2:23.9:19.9 in this order from the repeating units on the left.

[ chemical formula 32]

(preparation of P-3 solution)

A36.2% by mass solution of polymer P-3 as a P-3 solution was prepared in the following manner. Polymer P-3 is an alkali-soluble resin. Propylene glycol monomethyl ether 113.5g was charged to the flask and heated to 90℃under a nitrogen stream. To this liquid, a solution prepared by dissolving 172g of styrene, 4.7g of methyl methacrylate, 112.1g of methacrylic acid in 30g of propylene glycol monomethyl ether and a solution prepared by dissolving 27.6g of a polymerization initiator V-601 (FUJIFILM Wako Pure Chemical Corporation) in 57.7g of propylene glycol monomethyl ether were simultaneously added dropwise over 3 hours. After the completion of the dropwise addition, 2.5g of V-601 was added 3 times every 1 hour. Then, it was allowed to react for 3 hours. Then, 160.7g of propylene glycol monomethyl ether acetate and 233.3g of propylene glycol monomethyl ether were used for dilution. The reaction solution was warmed to 100℃under an air flow, and 1.8g of tetraethylammonium bromide and 0.86g of p-methoxyphenol were added. To this, 71.9G of glycidyl methacrylate (BLEMER G manufactured by NOF CORPORATION) was added dropwise over a period of 20 minutes. This was allowed to react at 100℃for 7 hours to give a solution of polymer P-3. The solid content concentration of the obtained solution was 36.2%. Regarding the polymer P-3, the weight average molecular weight in terms of standard polystyrene in GPC was 18000, the dispersity was 2.3, and the acid value was 124mgKOH/g. The residual monomer amount as determined by gas chromatography was less than 0.1 mass% in any of the monomers with respect to the solid content of the polymer P-3. The structure of polymer P-3 is shown below. Wherein the molar ratio of the repeating units is 55.1:26.5:1.6:16.8 in this order from the repeating units on the left.

[ chemical formula 33]

(preparation of P-4 solution)

In the synthesis of polymer P-3, a 36.2 mass% solution of polymer P-4 in terms of solid content (solvent: propylene glycol monomethyl ether acetate) was prepared as a polymer P-4 solution by changing the kind and amount of the monomer. Polymer P-4 is an alkali-soluble resin. The weight average molecular weight of the obtained polymer P-4 was 18000, the dispersity was 2.3, and the acid value was 124mgKOH/g. The structure of polymer P-4 is shown below. In the following, the molar ratio of the repeating units in the formula was 55.1:24.6:1.6:17.0:1.7 in order from the repeating unit on the left side.

[ chemical formula 34]

< preparation of composition for Forming refractive index adjustment layer >

Next, refractive index adjustment layer-forming compositions B-1 to B-4 having the compositions shown in the following tables were prepared, respectively. The numerical values in the following table represent "parts by mass".

TABLE 8

/>

(Polymer A)

Polymer A in the above table was synthesized as follows.

Into a 1L three-necked flask, 1-methoxypropanol (Tokyo Chemical Industry Co., ltd.) (270.0 g) was introduced, and the mixture was heated to 70℃under a nitrogen flow while stirring. On the other hand, allyl methacrylate (45.6 g) (manufactured by FUJIFILM Wako Pure Chemical Corporation) and methacrylic acid (14.4 g) (manufactured by FUJIFILM WakoPure Chemical Corporation) were dissolved in 1-methoxypropanol (Tokyo Chemical Industry co., manufactured by ltd.) (270.0 g), and 3.94g of V-65 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was further dissolved, whereby a dropping liquid was produced, and it took 2.5 hours to perform dropping of the dropping liquid into the flask. The reaction was carried out while stirring for 2.0 hours.

Then, the temperature was returned to room temperature, and ion-exchanged water (2.7L) in a stirred state was added dropwise thereto, followed by reprecipitation, whereby a suspension was obtained. The suspension was introduced and filtered by a suction filter from which the filter paper was removed, and the filtrate was washed with ion-exchanged water to obtain a wet powder. Air drying at 45℃was carried out, and it was confirmed that the polymer A was obtained as a powder in a yield of 70%.

The ratio of methacrylic acid/allyl methacrylate of the obtained polymer A was 76% by mass/24% by mass. The weight average molecular weight Mw was 38000.

< examples 16 to 31>

The coating amount was adjusted to a coating amount such that the film thickness after drying became the thickness described in the following table, and any one of the photosensitive resin layer forming compositions a-1 to a-10 described in the following table was applied to the 2 nd surface of the temporary support 1 using a slit nozzle, thereby forming a photosensitive resin layer. After the solvent was volatilized in the drying zone at 100 ℃, the coating amount was adjusted so that the film thickness after drying became the film thickness amount described in the following table by using any one of the refractive index adjustment layer forming compositions B-1 to B-4 in combination of the following tables, and after coating on the photosensitive resin layer, the film was dried at a drying temperature of 80 ℃ to form a refractive index adjustment layer. Photosensitive transfer materials 1 to 16 were produced by pressing a protective film (manufactured by LUMIRROR 16KS40,Toray Industries,Inc) onto the refractive index adjustment layer.

TABLE 9

By the above method, L of the temporary support was measured ^* Values. The measurement results are shown in table 10.

< minimum resolution linewidth and linearity >

A copper layer having a thickness of 200nm was formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by sputtering, thereby producing a PET substrate with a copper layer. The protective film was peeled off from the photosensitive transfer material, and the photosensitive transfer material and the copper-layer-equipped PET substrate were bonded by a roll-to-roll method using a vacuum laminator (MCK co., ltd., roll temperature: 110 ℃, linear pressure: 1.0MPa, linear velocity: 0.5 m/min). The obtained laminate contains a PET film, a copper layer, a refractive index adjusting layer, a photosensitive resin layer, and a temporary support in this order. The obtained laminate was defoamed under pressure at 0.6MPa and 60℃for 0.5 hours using an autoclave apparatus. The photosensitive resin layer was exposed to light through a line-space pattern mask (Duty ratio: 1, line width was changed stepwise from 5 μm to 100 μm every 5 μm) without peeling the temporary support using an ultra-high pressure mercury lamp. Development is performed after the temporary support is peeled off. For development, a 1.0 mass% aqueous sodium carbonate solution at 33 ℃ was used and development by spraying was performed for 45 seconds. By the above method, an exposure amount (hereinafter, referred to as "reference exposure amount") was obtained in which the line width of the resin pattern corresponding to the line of 70 μm of the mask and the space pattern was exactly 70 μm. Next, a resin pattern was formed by the same method as the above method except that the photosensitive resin layer was exposed to the reference exposure amount. The resin pattern was observed using a Scanning Electron Microscope (SEM). The minimum value of the line width of the resin pattern without peeling of the resin pattern and without residue in the space portion of the resin pattern is adopted as the minimum resolution line width. The measurement results are shown in table 10 below. The smaller the minimum resolution line width, the better the resolution.

Next, a minimum resolution line width of the obtained resin pattern was observed by a Scanning Electron Microscope (SEM), and a maximum value-minimum value of line width (hereinafter, referred to as "line width variation value") was measured in a range of 100 μm in length. The linearity of the resin pattern was evaluated based on the line width fluctuation value according to the following criteria. The evaluation results are shown in table 10.

A: the variation of the line width is less than 0.4 μm.

B: the variation of the line width is more than 0.4 μm and less than 0.7 μm.

C: the variation of the line width is more than 0.7 μm and less than 1.0 μm.

D: the variation of the line width is 1.0 μm or more and less than 1.5 μm.

E: the variation of the line width is more than 1.5 mu m.

< transport Property >

The conveyability was evaluated by the above method. The evaluation results are shown in table 10.

TABLE 10

< examples 32 to 44>

(production of polyester A particles)

86.5 parts by mass of terephthalic acid and 37.1 parts by mass of ethylene glycol were subjected to esterification while water was distilled off at 255 ℃. After the esterification reaction was completed, 0.02 parts by mass of trimethylphosphoric acid, 0.06 parts by mass of magnesium acetate, 0.01 parts by mass of lithium acetate, and 0.0085 parts by mass of antimony trioxide were added, followed by heating to 290 ℃ under reduced pressure, and polycondensation reaction was performed after heating to obtain polyester a particles having an intrinsic viscosity of 0.63dl/g (expressed as polyester a in table 11).

(production of polyester C particles)

Terephthalic acid was used as the dicarboxylic acid component, CHDM (cyclohexanedimethanol) was used as the diol component, and polycondensation was carried out in the presence of 200ppm of butyltin tris (2-ethylhexanoate) to obtain polyester C particles having an alicyclic structure (in table 11, expressed as polyester C).

(production of polyester E particles)

In the same manner as described above, polyester a particles were produced, after the esterification reaction was completed, spherical silica having a volume average particle diameter of 0.2 μm, a volume shape factor f=0.51, a volume average particle diameter of 0.06 μm, a volume shape factor f=0.51, and mohs hardness of 7 was added, and then polycondensation reaction was performed, to obtain silica-containing polyester E particles containing 1 mass% of 2 kinds of spherical silica relative to the mass of polyester a (expressed as polyester E in table 11).

The spherical silica is the following monodisperse silica particles: the method comprises the steps of adding a mixed solution of ethanol, pure water and ammonia water to a mixed solution of ethanol and ethyl silicate while stirring the mixed solution, and stirring the obtained reaction solution to perform hydrolysis reaction of ethyl silicate and polycondensation reaction of the hydrolysis product, and then stirring the obtained reaction solution after the reaction.

(production of polyester G particles)

To 100 parts by mass of dimethyl terephthalate and 64 parts by mass of ethylene glycol, 0.04 parts by mass of manganese acetate and 0.03 parts by mass of antimony trioxide as catalysts were added to carry out transesterification, and then a slurry containing coagulated alumina was added to the reaction product, and then antimony trioxide was added to carry out polycondensation, thereby obtaining polyester G particles (expressed as polyester G in table 11) having an intrinsic viscosity of 0.62dl/G and containing 2% by mass of coagulated alumina.

The slurry containing the above-mentioned agglomerated alumina was the following slurry: using delta-alumina as the agglomerated alumina, a 10 mass% ethylene glycol slurry was prepared, and the slurry was subjected to pulverization and dispersion treatment by a sand mill, and further was filtered by a 3 μm filter having a collection efficiency of 95%.

(production of temporary supporting bodies 12 to 17)

The mixture of the raw materials prepared in the formulations shown in table 11 was stirred in a stirrer and then fed to a twin-screw extruder with a vent for the layer a and the layer B. Melt extrusion was performed at 275℃and filtration was performed with a high-precision filter for collecting 95% or more of impurities of 5 μm or more, and then, confluence lamination was performed with rectangular 3-layer hinge blocks, whereby a 3-layer laminate composed of A layer/B layer/A layer was produced. Then, the film was wound on a casting roll having a surface temperature of 25 ℃ by an electrostatic casting method via a slit die maintained at 285 ℃ on a cooling roll, and cooled and solidified to obtain an unstretched laminated film.

The unstretched laminate film was subjected to successive stretching (longitudinal direction and width direction). First, stretching in the longitudinal direction is performed, and then stretching in the width direction is performed. After carrying by a teflon (registered trademark) roll at 105 ℃, stretching in the longitudinal direction was 4.0 times by a peripheral speed difference of the roll at 120 ℃, and a uniaxially stretched film was produced. Subsequently, the uniaxially stretched film was stretched 4.0 times in the tenter at 115℃and then heat-set at 230℃to relax 5% in the width direction, and cooled by the carrying step. Then, the edges were cut and wound, and an intermediate product of biaxially stretched film having the thickness of each layer shown in table 11 was obtained. The intermediate product was split by a splitting machine, and a roll of a polyester film consisting of 3 layers was obtained.

The obtained 3-layer laminated polyester films composed of a layer/B layer/a layer were used as temporary supports 12 to 17.

(production of temporary supporting bodies 18 to 21 and 23)

The mixture of the raw materials prepared in the formulations shown in table 11 was stirred in a stirrer and then fed to a twin-screw extruder with a vent for layer a, layer B, and layer C. A roll of a polyester film composed of 3 layers was obtained in the same manner as in the production of the temporary support 12 except that the 3 layers were laminated by fusion extrusion at 275 ℃ with a high-precision filter for capturing 95% or more of impurities of 5 μm or more and then joined and joined with a rectangular 3-layer hinge block to produce a 3-layer laminate composed of a layer/B layer/C layer.

(production of temporary support 22)

A roll of a polyester film composed of 2 layers was obtained in the same manner as in the production of the temporary support 12 except that 2 layers of a 2-layer laminate composed of a layer/B layer was produced using a mixture of raw materials prepared in the formulation shown in table 11 and using a rectangular 2-layer hinge block for each layer.

(production of temporary support 24)

The temporary support 24 (a single-layer polyethylene terephthalate film having a thickness of 16 μm) was produced by thermal nanoimprint (heating temperature: 130 ℃ C. And pressure: 0.08 MPa) to form surface irregularities on the 1 st surface of the temporary support 5. The arithmetic average roughness Ra of the 1 st surface of the temporary support 24 was 28nm.

The thickness (thickness of each layer), the presence or absence of particles in the surface layer, and the arithmetic average roughness Ra of the 1 st surface were measured on the obtained temporary supports 12 to 23 by the methods described above.

The results are shown in Table 11.

The layer structures of the temporary supports 12 to 23 are also shown in table 11, and a/B/a means a layer structure of a polyester film composed of 3 layers of a layer/B layer/a layer, a/B/C means a layer structure of a polyester film composed of 3 layers of a layer/B layer/C layer, and a/B means a layer structure of a polyester film composed of 2 layers of a layer/B layer.

The temporary supports 12 to 23 are each a layer disposed as the outermost layer on the 2 nd side, the layer being a (i.e., layer a) on the left side of the column of the layer structure described in table 11.

TABLE 11

The photosensitive resin layer-forming composition 1 was applied to the 2 nd surfaces of the temporary supports 12 to 24 using a slit nozzle. The applied composition 1 for forming a photosensitive resin layer was dried at 100℃for 120 seconds to form a photosensitive resin layer having a thickness of 5. Mu.m. The photosensitive transfer material obtained by the above steps contains a temporary support and a photosensitive resin layer in this order.

Regarding the photosensitive transfer material obtained, L of the temporary support was measured and evaluated by the method described above ^* Value, minimum resolution line width, linearity and transmissibility. The results are shown in table 12.

TABLE 12

Tables 10 and 12 show that the resin patterns of examples 16 to 44 are excellent in linearity in the resin pattern of comparative example 1.

Symbol description

10. 11-temporary support, 10a, 11 a-1 st side of temporary support, 10b, 11 b-2 nd side of temporary support, 11-1-particle-containing layer, 11-2-substrate, 20-photosensitive resin layer, 30-protective film, 40-thermoplastic resin layer, 50-intermediate layer, 100, 110, 120-photosensitive transfer material.

The disclosures of Japanese patent applications 2020-143492, 2020-10 and 12 in 2020, 2020-207813 and 2021-7 and 6 in 2020 are incorporated herein by reference in their entireties. All documents, patent applications and technical standards described in the present specification are incorporated by reference into the present specification as if each were specifically and individually described.

Claims

1. A photosensitive transfer material, comprising:

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

the temporary support has a thickness of 16 μm or less.

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

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

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

the thickness of the photosensitive resin layer is 1-10 mu m.

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

the temporary support includes a particle-containing layer and a base material disposed as the outermost layer of the temporary support in this order in the stacking direction from the temporary support toward the photosensitive resin layer.

7. A photosensitive transfer material, comprising:

8. The photosensitive transfer material according to claim 7, wherein,

9. The photosensitive transfer material according to claim 7 or 8, wherein,

The surface layer on the 1 st surface side of the temporary support does not contain particles.

10. The photosensitive transfer material according to any one of claims 7 to 9, wherein,

11. The photosensitive transfer material according to any one of claims 7 to 10, wherein,

12. The photosensitive transfer material according to any one of claims 7 to 11, wherein,

the arithmetic average roughness Ra of the 1 st surface of the temporary support is 1 nm-50 nm.

13. The photosensitive transfer material according to any one of claims 7 to 12, wherein,

the surface layer has a phase separation structure.

14. The photosensitive transfer material according to any one of claims 7 to 13, wherein,

the surface layer contains a polyester resin having an alicyclic structure.

15. The photosensitive transfer material according to claim 14, wherein,

the alicyclic structure is cyclohexane ring.

16. The photosensitive transfer material according to claim 14 or 15, wherein,

the surface layer contains a copolymerized polyethylene terephthalate having isophthalic acid as a copolymerization component.

17. A method for producing a resin pattern using the photosensitive transfer material according to any one of claims 1 to 16, the method comprising:

a step of preparing a substrate;

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