CN116710845A

CN116710845A - Transfer material and method for producing laminate

Info

Publication number: CN116710845A
Application number: CN202180086959.XA
Authority: CN
Inventors: 藤本进二; 佐藤守正; 片山晃男; 有富隆志
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2020-12-25
Filing date: 2021-12-16
Publication date: 2023-09-05
Also published as: JPWO2022138468A1; WO2022138468A1; TW202229012A

Abstract

A transfer material comprising, in order, a temporary support, an intermediate layer in contact with the temporary support, and a photosensitive layer, wherein the surface of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer has a roughness Ra of 2nm or more, and a method for producing a laminate using the transfer material.

Description

Transfer material and method for producing laminate

Technical Field

The present invention relates to a transfer material and a method for producing a laminate.

Background

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

Patent document 1: international publication No. 2019/146380

Disclosure of Invention

Technical problem to be solved by the invention

In the pattern formation method using a conventional transfer material such as the photosensitive transfer material described in patent document 1, a method of peeling off a temporary support together with an adhesive layer before exposure of a photosensitive layer may be used in various cases, such as improvement of resolution and reduction of defects generated in the pattern. However, in the conveyance process after the temporary support is peeled off, the intermediate layer exposed by the peeling off of the temporary support may adhere to a conveyance device such as a roller, and the conveyability may be degraded. Such a phenomenon is likely to occur when the transport object that is temporarily stationary is moved again. When the intermediate layer exposed by peeling of the temporary support is brought into contact with the photomask to expose the photosensitive layer, the intermediate layer may adhere to the photomask, and alignment of the photomask may be difficult.

An object of an embodiment of the present invention is to provide a transfer material including an intermediate layer having excellent slidability.

Another embodiment of the present invention is directed to a method for manufacturing a laminate using a transfer material including an intermediate layer having excellent slidability.

Means for solving the technical problems

The present invention includes the following embodiments.

<1> a transfer material comprising, in order, a temporary support, an intermediate layer in contact with the temporary support, and a photosensitive layer, wherein the roughness Ra of the surface of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer is 2nm or more.

<2> the transfer material according to <1>, wherein the surface roughness Ra of the temporary support exposed when the temporary support is peeled off from the intermediate layer is 2nm or more.

<3> the transfer material according to <1> or <2>, wherein a roughness Ra of a surface of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer is 1,000nm or less.

<4> the transfer material according to any one of <1> to <3>, wherein a roughness Ra of a surface of the temporary support exposed when the temporary support is peeled off from the intermediate layer is 1,000nm or less.

<5> the transfer material according to any one of <1> to <4>, wherein a static friction coefficient of a surface of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer is 1.0 or less.

<6> the transfer material according to any one of <1> to <5>, wherein the above intermediate layer contains a water-soluble resin.

<7> the transfer material according to <6>, wherein the water-soluble resin is at least one selected from the group consisting of cellulose derivatives, polyol compounds, alkylene oxide adducts of polyol compounds, polyether compounds, phenol derivatives and amide compounds.

<8> the transfer material according to any one of <1> to <7>, wherein the above intermediate layer contains a surfactant.

<9> the transfer material according to any one of <1> to <8>, wherein the photosensitive layer contains a polymerizable compound having 2 or more polymerizable groups.

<10> the transfer material according to any one of <1> to <8>, wherein the photosensitive layer contains a polymerizable compound having 2 polymerizable groups and a polymerizable compound having 3 or more polymerizable groups.

<11> the transfer material according to <9> or <10>, wherein the polymerizable compound contains an oxyethylene chain.

<12> the transfer material according to any one of <1> to <11>, wherein the thickness of the photosensitive layer is 5 μm or less.

<13> a method for producing a laminate, comprising the following steps in order: bonding a transfer material comprising a temporary support, an intermediate layer in contact with the temporary support, and a photosensitive layer in this order to a substrate, and disposing the photosensitive layer, the intermediate layer, and the temporary support in this order on the substrate; peeling the temporary support from the intermediate layer; and patterning the intermediate layer and the photosensitive layer by performing exposure treatment and development treatment, wherein the roughness Ra of the surface of the intermediate layer exposed by peeling the temporary support from the intermediate layer is 2nm or more.

<14> the method for producing a laminate according to <13>, wherein the surface roughness Ra of the intermediate layer exposed by peeling the temporary support from the intermediate layer is 1,000nm or less.

<15> the method for producing a laminate according to <13> or <14>, wherein the exposure process comprises the steps of: the intermediate layer is brought into contact with a photomask to expose the intermediate layer and the photosensitive layer.

Effects of the invention

According to an embodiment of the present invention, there may be provided a transfer material including an intermediate layer having excellent slidability.

According to another embodiment of the present invention, there may be provided a method of manufacturing a laminate using a transfer material including an intermediate layer having excellent slidability.

Drawings

Fig. 1 is a schematic diagram showing an example of the structure of a transfer material according to one embodiment.

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

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

Detailed Description

The following describes the content of the present invention. Note that, although the description is given with reference to the drawings, the reference numerals may be omitted.

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

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

In the present invention, the amounts of the respective components in the composition, when a plurality of substances corresponding to the respective components are present in the composition, refer to the total amount of the corresponding plurality of substances present in the composition unless otherwise specified.

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

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

In 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 or an ion beam. The light used for exposure generally includes an open line spectrum of a mercury lamp, extreme ultraviolet rays (EUV light), active light rays (active energy rays) such as X-rays and electron beams, which are represented by excimer laser light.

The chemical structural formula in the present invention is sometimes described in a simplified structural formula in which a hydrogen atom is omitted.

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

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

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

Unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are molecular weights converted by using a column of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (both trade names manufactured by TOSOH CORPORATION) and detecting by a solvent THF (tetrahydrofuran), a differential refractometer, and using polystyrene as a standard substance.

In the present invention, unless otherwise specified, the content of the metal element is a value measured using an inductively coupled plasma (ICP: inductively Coupled P asa) spectroscopic analysis device.

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

In the present invention, "water-soluble" means that the solubility in 100g of water at pH7.0 at a liquid temperature of 22℃is 0.1g or more. Thus, for example, a water-soluble resin refers to a resin that satisfies the above solubility conditions.

In the present invention, "solid component" means all components except a solvent.

In the present invention, the layer thickness of each layer provided in the transfer material is measured by the following steps: the cross section in the direction perpendicular to the main surface of the transfer material was observed by a Scanning Electron Microscope (SEM), and the thickness of each layer was measured at 5 or more points from the obtained observation image, and the average value was calculated.

< transfer Material >

The transfer material according to an embodiment of the present invention includes, in order, a temporary support, an intermediate layer in contact with the temporary support, and a photosensitive layer, and the roughness Ra of the surface of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer is 2nm or more. According to the above embodiment, a transfer material including an intermediate layer having excellent slidability can be provided. The reason why the sliding property of the intermediate layer is improved is considered as follows. When the roughness Ra of the surface of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer is 2nm or more, friction generated on the surface of the intermediate layer is reduced. Therefore, it is presumed that the surface slidability of the intermediate layer is improved. Hereinafter, the transfer material will be specifically described. In the following description, the surface of the intermediate layer facing the intermediate layer in the transfer material is sometimes referred to as "the 1 st surface of the intermediate layer" and the surface of the intermediate layer facing the intermediate layer in the transfer material is sometimes referred to as "the 1 st surface of the intermediate layer". The 1 st surface of the temporary support faces the 1 st surface of the intermediate layer.

In the transfer material according to an embodiment of the present invention, another layer may be laminated on the photosensitive layer on the opposite side of the surface facing the temporary support. Examples of the other layer include a refractive index adjusting layer and a protective film. Each layer may be a single layer or a plurality of layers of two or more layers. An example of the constitution of the transfer material is shown below. However, the constitution of the transfer material is not limited to the following examples. In each of the following configurations, the photosensitive layer is preferably a negative type photosensitive layer. The photosensitive layer is also preferably a colored resin layer.

(1) "temporary support/intermediate layer/photosensitive layer/refractive index adjusting layer/protective film"

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

The configuration of the transfer material will be described with reference to fig. 1. Fig. 1 is a schematic diagram showing a configuration of a transfer material according to an embodiment. The transfer material 100 shown in fig. 1 includes, in order, a temporary support 10, an intermediate layer 20, a photosensitive layer 30, and a protective film 40. The protective film 40 of the transfer material 100 may not be provided.

When the transfer material includes other layers on the side of the photosensitive layer opposite to the temporary support, the total thickness of the other layers is preferably 0.1% to 30%, more preferably 0.1% to 20%, with respect to the thickness of the photosensitive layer.

The maximum width of the transfer material waviness is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less, from the viewpoint of suppressing the occurrence of air bubbles in the bonding step described later. The maximum width of the waves of the transfer material is preferably 0 μm or more, more preferably 0.1 μm or more, and still more preferably 1 μm or more. The maximum width of the waves of the transfer material was measured by the following procedure. First, a test sample was produced by cutting the transfer material into dimensions of 20cm long by 20cm wide in a direction perpendicular to the main surface. In addition, when the transfer material includes a protective film, the protective film is peeled off. Then, the test sample was allowed to stand on a flat and horizontal stage with the surface of the temporary support facing the stage. After standing, the surface of the test specimen was scanned with a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) over a range of 10cm square at the center of the test specimen to obtain a three-dimensional surface image, and the lowest concave surface height was subtracted from the maximum convex surface height observed in the obtained three-dimensional surface image. The above operation was performed on 10 test samples, and the arithmetic average value was taken as "maximum width of the waves of the transfer material".

Temporary support

A transfer material according to an embodiment of the present invention includes a temporary support. The temporary support is a support that supports at least the intermediate layer and the photosensitive layer and can be peeled off. The temporary support is in contact with the intermediate layer. The surface of the temporary support facing the intermediate layer, i.e., the 1 st surface of the temporary support, in the transfer material is in contact with the intermediate layer and can be exposed by peeling the temporary support from the intermediate layer.

The roughness of the 1 st surface of the temporary support can affect the roughness of the 1 st surface of an intermediate layer described later. For example, in the process of manufacturing the transfer material, if the roughness of the 1 st surface of the temporary support is small, the roughness of the 1 st surface of the intermediate layer tends to be small. On the other hand, if the roughness of the 1 st surface of the temporary support is increased, the roughness of the 1 st surface of the intermediate layer tends to be increased. From the viewpoint of the above, the roughness Ra of the 1 st surface of the temporary support, which is the surface of the temporary support exposed when the temporary support is peeled off from the intermediate layer, is preferably 1,000nm or less, more preferably 500nm or less, and further preferably 200nm or less. The roughness Ra of the 1 st surface of the temporary support is preferably 2nm or more, more preferably 50nm or more, and still more preferably 100nm or more. When the roughness Ra of the 1 st surface of the temporary support is 1,000nm or less, for example, the linearity of the wiring pattern formed by using the transfer material is improved. The roughness Ra of the 1 st surface of the temporary support is preferably 2nm to 1,000nm, more preferably 50nm to 500nm, and still more preferably 100nm to 200nm. The method for adjusting the roughness of the 1 st surface of the temporary support is not limited. As a method for adjusting the roughness Ra of the 1 st surface of the temporary support, for example, a method of bringing a matte-finished roller (hereinafter, sometimes referred to as a "matte roller") into contact with the 1 st surface of the temporary support is mentioned. In the above method, the roughness Ra of the 1 st surface of the temporary support is adjusted according to the surface roughness of the matte-finished roller. Further, there is a method of projecting fine sand on the 1 st surface of the temporary support to impart irregularities to the surface (for example, sand blast method). In the above method, the roughness Ra of the 1 st surface of the temporary support is adjusted according to the size or the projection intensity of the projected sand.

In the present invention, the roughness Ra of the 1 st surface of the temporary support is measured by using a surface roughness and surface shape measuring machine (NewView 6300, manufactured by Zygo corporation). First, the temporary support is peeled off from the photosensitive layer. Next, "Image Zoom" of "Mesurement Control was set to x0.5, and" Scan Length "was set to 40 μm using a 50-fold objective lens, and" Cylynder "was selected from" Remove "of" analysis Control ", and the value of the center plane average roughness Ra indicated by" Surface map "was used as roughness Ra.

The temporary support may be a single-layer structure or a multi-layer structure. The temporary support is preferably a film, more preferably a resin film. The temporary support is preferably a film which is flexible and does not significantly deform, shrink or elongate under pressure or under pressure and heat. Examples of the film include polyethylene terephthalate (PET) film (for example, biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film. As the temporary support, a polyethylene terephthalate film is preferable. Further, the film used as the temporary support is preferably free from deformation such as wrinkles and scratches. In the case of a multilayer structure, the layer constituting the 1 st face of the temporary support preferably contains a thermoplastic resin. In other words, the temporary support preferably includes a thermoplastic resin layer in contact with the intermediate layer. The temporary support includes a thermoplastic resin layer in contact with the intermediate layer, that is, the 1 st surface of the temporary support is constituted of the thermoplastic resin layer, and is preferable in view of easy control of the roughness of the 1 st surface of the temporary support. Examples of the thermoplastic resin include polyolefin resins (for example, polyethylene, polypropylene, ethylene- (meth) acrylic acid copolymer resins, ethylene- (meth) acrylic acid metal salt copolymer resins, ethylene-vinyl acetate copolymer resins, and ethylene-vinyl alcohol copolymer resins), polyester resins, styrene-butadiene copolymer resins, acrylic resins, urethane resins, epoxy resins, and polyamide resins. Among them, the polyolefin resin is preferred because it is easily peeled from the intermediate layer. The reason why the thermoplastic resin layer is easily peeled off from the intermediate layer is considered to be caused by intermolecular interaction between the thermoplastic resin layer and the intermediate layer, and it is estimated that hydrogen bonding interaction and dipole interaction are suppressed by using the polyolefin resin in the thermoplastic resin. Among polyolefin resins, polyethylene having low hydrogen bonding interaction and dipole interaction and low softening temperature is most preferred.

Preferably, the temporary support has high transparency. The transmittance of the temporary support for light having a wavelength of 365nm is preferably 60% or more, more preferably 70% or more. From the viewpoint of transparency of the temporary support, it is preferable that the temporary support has a small haze. The haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and still more preferably 0.1% or less. From the viewpoint of transparency of the temporary support, it is preferable that the number of coarse particles, foreign matters, and defects contained in the temporary support be small. Diameter 1 μm in temporary supportThe number of particles, foreign matters and defects is preferably 50/10 mm ² Hereinafter, more preferably 10 pieces/10 mm ² Hereinafter, it is more preferably 3/10 mm ² Hereinafter, it is particularly preferably 0/10 mm ² 。

The thickness of the temporary support is preferably 5 μm to 200 μm, more preferably 10 μm to 150 μm, and still more preferably 10 μm to 50 μm from the viewpoints of ease of handling and versatility. The thickness of the temporary support was calculated as an average value of the thickness of any 5 points measured by cross-sectional observation using a scanning electron microscope (SEM: scanning Flectron Microscope).

Examples of the temporary support 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.

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

From the viewpoint of imparting handleability, the temporary support may have a layer containing fine particles (also referred to as a "lubricant layer") on the surface. The lubricant layer may be provided on one side or both sides of the temporary support. The particles contained in the lubricant layer preferably have a diameter of 0.05 μm to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 μm to 1.0 μm. When the temporary support has a lubricant layer, in the transfer material of the present invention, the temporary support and the intermediate layer may be in contact via the lubricant layer.

Intermediate layer

A transfer material according to an embodiment of the present invention includes an intermediate layer in contact with a temporary support. The intermediate layer is disposed between the temporary support and the photosensitive layer. The surface of the intermediate layer facing the temporary support, i.e., the 1 st surface of the intermediate layer, in the transfer material is in contact with the temporary support and can be exposed by peeling the temporary support from the intermediate layer. The intermediate layer can suppress mixing of components at the time of coating a plurality of layers and at the time of storage after coating in the production of the transfer material. The intermediate layer is preferably a water-soluble layer from the viewpoints of developability and suppression of mixing of components at the time of coating a plurality of layers and at the time of storage after coating.

The roughness Ra of the 1 st surface of the intermediate layer, which is the surface of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer, is 2nm or more. When the roughness Ra of the 1 st surface of the intermediate layer is 2nm or more, the surface slipperiness of the intermediate layer is improved. The roughness Ra of the 1 st surface of the intermediate layer is preferably 10nm or more, more preferably 50nm or more, and further preferably 100nm or more. The roughness Ra of the 1 st surface of the intermediate layer is preferably 1,000nm or less, more preferably 500nm or less, and further preferably 200nm or less. In one embodiment, the roughness Ra of the 1 st surface of the intermediate layer may be 100nm or less. If the roughness Ra of the 1 st surface of the intermediate layer is 1,000nm or less, the linearity of the pattern formed by the intermediate layer is improved. From the viewpoints of slidability of the intermediate layer and straightness of the pattern, the roughness Ra of the 1 st surface of the intermediate layer is preferably 2nm to 1,000nm, more preferably 50nm to 500nm, and still more preferably 100nm to 200nm. The roughness Ra of the 1 st surface of the intermediate layer is measured by a method according to the method for measuring the roughness Ra of the 1 st surface of the temporary support described in the item "temporary support".

The static friction coefficient of the surface of the intermediate layer (i.e., the 1 st surface of the intermediate layer) exposed when the temporary support is peeled off from the intermediate layer is preferably less than 2.0, more preferably 1.0 or less, and still more preferably 0.6 or less. If the static friction coefficient of the 1 st surface of the intermediate layer is less than 2.0, the surface slipperiness of the intermediate layer is improved. For example, the reduction of the static friction coefficient of the 1 st surface of the intermediate layer can prevent the intermediate layer exposed by the peeling of the temporary support from adhering to a conveying device such as an exposure mask and a conveying roller during the conveying process after the peeling of the temporary support, and can smoothly move the temporarily stationary conveyed object again. The static friction coefficient of the 1 st surface of the intermediate layer is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more. When the static friction coefficient of the 1 st surface of the intermediate layer is 0.1 or more, the holding force against a conveying device such as a conveying roller is improved, and occurrence of meandering and winding deviation is suppressed. The static friction coefficient of the 1 st surface of the intermediate layer is preferably 0.1 or more and less than 2.0, more preferably 0.2 to 1.0, and still more preferably 0.3 to 0.6.

The dynamic friction coefficient of the 1 st surface of the intermediate layer, which is the surface of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer, is preferably less than 1.5, more preferably 1.0 or less, and still more preferably 0.5 or less. If the dynamic friction coefficient of the 1 st surface of the intermediate layer is less than 1.5, the surface slipperiness of the intermediate layer is improved. The dynamic friction coefficient of the 1 st surface of the intermediate layer is preferably 0.05 or more, more preferably 0.1 or more, and still more preferably 0.2 or more. When the dynamic friction coefficient of the 1 st surface of the intermediate layer is 0.05 or more, the holding force against a conveying device such as a conveying roller is improved, and occurrence of meandering and winding displacement is suppressed. The dynamic friction coefficient of the 1 st surface of the intermediate layer is preferably 0.05 or more and less than 1.5, more preferably 0.1 to 1.0, and still more preferably 0.2 to 0.5.

In the present invention, the static friction coefficient and the dynamic friction coefficient of the 1 st surface of the intermediate layer were measured by the following methods. The transfer material was laminated on a polyethylene terephthalate (PET) substrate with a copper layer under lamination conditions of an inline pressure of 0.6MPa and a line speed (lamination speed) of 0.5 m/min. The photosensitive layer, the intermediate layer, and the temporary support are sequentially disposed on the copper layer of the copper-clad PET substrate by laminating the transfer material on the copper-clad PET substrate. When the transfer material includes a protective film, the protective film is peeled off before lamination. Stripping the temporary support to separate the exposed intermediate layer from the transparent sodium glass having a thickness of 5mm ) And (3) contact. Using a Tensilon Universal Material tester (RTF 1210, A&D Company, limited) and plastic coefficient of friction clamps (J-PZ 2-50N, A)&D Company, limited) by a plastic-film and sheet friction coefficient test method (JIS K7125:1999 The static friction coefficient and the dynamic friction coefficient are measured. The test conditions are shown below.

Load: 200g of

Contact area: 63mm by 63mm

Test speed: 100 mm/min

The intermediate layer may be an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in JP-A-5-72724. If the intermediate layer is an oxygen barrier layer, the sensitivity at the time of exposure is improved, and the time load of the exposure machine is reduced, so that the productivity is improved, which is preferable. The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers described in the above-mentioned publications and the like. Among them, an oxygen barrier layer which exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (1 mass% aqueous solution of sodium carbonate at 22 ℃) is preferable.

The intermediate layer preferably contains a resin. Examples of the resin contained in the intermediate layer include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. As the resin contained in the intermediate layer, a water-soluble resin is preferable. In addition, from the viewpoint of suppressing mixing of components between the layers, the resin contained in the intermediate layer is preferably a resin different from the polymer a contained in the photosensitive layer.

The water-soluble resin is preferably at least one selected from the group consisting of cellulose derivatives, polyol compounds, alkylene oxide adducts of polyol compounds, polyether compounds, phenol derivatives, and amide compounds.

Examples of the cellulose derivative include hydroxypropyl methylcellulose and hydroxypropyl cellulose. As a commercial product of hydroxypropyl methylcellulose, for example, METOLOSE 60SH-03 (Shin-Etsu Chemical Co., ltd.) is mentioned.

Examples of the polyol compound include polyvinyl alcohol and modified polyvinyl alcohol. Examples of commercially available polyvinyl alcohol include PVA-105 (manufactured by KURARAY CO., LTD.), PVA-117 (manufactured by KURARAY CO., LTD.), PVA-205 (manufactured by KURARAY CO., LTD.), PVA-217 (manufactured by KURARAY CO., LTD.), JMR-3M (manufactured by JAPAN VAM & POVAL CO., LTD.), and JMR-3H (manufactured by JAPAN VAM & POVAL CO., LTD.). Examples of commercial products of the modified polyvinyl alcohol include GOHSENO CKS-50 (manufactured by MitsubisLi Chemical Corporation) and GOHSENO K-434 (manufactured by Mitsubishi Chemical Corporation).

Examples of the alkylene oxide adduct of the polyol compound include GOHSENO WO-320N (manufactured by Mitsubishi Chemical Corporation).

Examples of the polyether compound include polyethylene glycol 4000 (manufactured by FUJIFILM Wako Pure Chemical Corporation).

Examples of the phenol derivative include PHENOLITE GG-1402 (manufactured by DIC Corporation) and PHENOLITE OG-660 (manufactured by DIC Corporation).

Examples of the amide compound include polyvinylpyrrolidone and water-soluble nylon. Examples of the commercial product of the amide compound include polyvinylpyrrolidone K-30 (manufactured by NIPPON shokubaci co., ltd.) and polyvinylpyrrolidone K-90 (manufactured by NIPPON shokubaci co., ltd.). Examples of the water-soluble nylon include AQ nylon P-95 (manufactured by Toray Industries, inc.).

The intermediate layer preferably contains polyvinyl alcohol, more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoints of oxygen barrier property and suppression of mixing of components at the time of coating the multilayer and at the time of storage after coating.

The intermediate layer may contain one kind of the above resin alone or two or more kinds thereof. The content of the resin in the intermediate layer is not particularly limited, but is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass relative to the total mass of the intermediate layer, from the viewpoints of oxygen barrier property and suppression of mixing of components at the time of coating a plurality of layers and storage after coating.

The intermediate layer may contain an additive such as a surfactant, if necessary. The intermediate layer preferably comprises a surfactant. Examples of the surfactant include those described in the following "photosensitive layer". The preferred embodiments of the surfactant in the intermediate layer are the same as those described in the "photosensitive layer" section below.

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 mixing of the components at the time of coating the multiple layers and at the time of storage after coating can be suppressed without reducing the oxygen barrier property, and the increase in the intermediate layer removal time at the time of development can be suppressed.

The method for forming the intermediate layer is not particularly limited, and examples thereof include a method in which a composition for an intermediate layer containing the above resin and any additive is prepared, applied to the surface of a temporary support, and a coating film of the composition for an intermediate layer is dried to form an intermediate layer. From the viewpoint of controlling the roughness Ra of the 1 st surface of the intermediate layer, the intermediate layer is preferably formed by coating the intermediate layer composition on the surface of the temporary support. In order to adjust the viscosity of the composition for an intermediate layer and to facilitate formation of an intermediate layer, the composition for an intermediate layer preferably contains a solvent.

The solvent contained in the intermediate layer composition is not particularly limited as long as the resin can be dissolved or dispersed, and at least one selected from the group consisting of water and water-miscible organic solvents is preferable, and water or a mixed solvent of water and water-miscible organic solvents is more preferable. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, preferably alcohols having 1 to 3 carbon atoms, and more preferably methanol or ethanol.

Photosensitive layer

A transfer material according to an embodiment of the present invention includes a photosensitive layer. The photosensitive layer can be patterned by exposure and development after transfer onto a substrate, for example.

[ kind and component ]

The photosensitive layer may be a negative type photosensitive layer or a positive type photosensitive layer. The photosensitive layer is preferably a negative type photosensitive layer. When the photosensitive layer is a negative type photosensitive layer, the formed pattern corresponds to a hardened layer. When the photosensitive layer is a negative type photosensitive layer, the negative type photosensitive layer preferably contains a resin, a polymerizable compound, and a polymerization initiator. When the photosensitive layer is a negative photosensitive layer, an alkali-soluble resin is preferably contained as a part or all of the resin. That is, in one embodiment, the photosensitive layer preferably includes a resin containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. The photosensitive layer preferably contains 10 to 90 mass% of an alkali-soluble resin, 5 to 70 mass% of an ethylenically unsaturated compound, and 0.01 to 20 mass% of a photopolymerization initiator, relative to the total mass of the photosensitive layer.

(alkali-soluble resin)

The photosensitive layer preferably contains an alkali-soluble resin. As the alkali-soluble resin, for example, a known alkali-soluble resin used for a resist (etching resist) can be preferably used. And, the alkali-soluble resin is preferably a binder polymer. The alkali-soluble resin is preferably an alkali-soluble resin having an acid group. As the alkali-soluble resin, a polymer a described later is preferable.

Polymer A-

The photosensitive layer preferably contains a polymer a as an alkali-soluble resin. The acid value of the polymer a is preferably 220mgKOH/g or less, more preferably less than 200mgKOH/g, and even more preferably less than 190mgKOH/g, from the viewpoint of further excellent resolution by suppressing swelling of the photosensitive layer by the developer. The lower limit of the acid value of the polymer a is not particularly 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 was the mass [ mg ] of potassium hydroxide required for neutralizing 1g of the sample, and the unit was referred to as mgKOH/g in the present invention. The acid value can be calculated, for example, from the average content of acid groups in the compound. The acid value of the polymer a may be adjusted by the kind of the constituent unit constituting the polymer a and the content of the constituent unit containing an acid group.

The weight average molecular weight of polymer a is preferably 5,000 ～ 500,000. From the viewpoint of improving resolution and developability, the weight average molecular weight is preferably 500,000 or less. The weight average molecular weight of the polymer a is more preferably 100,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film such as edge meltability and chipping property in the photosensitive layer, the weight average molecular weight is preferably 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 layer easily overflows from the end face of the roller when the transfer material is wound into a roller shape. The chipability means the degree of scattering of chips when the unexposed film is cut by a cutting tool. If the chips adhere to the upper surface of the photosensitive layer or the like, the chips are transferred to a mask in a subsequent exposure step or the like, which causes defective products. The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, particularly preferably 1.0 to 3.0. Dispersity is the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight/number average molecular weight).

From the viewpoint of suppressing deterioration of line width thickness and resolution when the focus position is deviated during exposure, the polymer a preferably has an aromatic hydrocarbon group, and more preferably has a constituent unit 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 ratio of the constituent 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 based on the total mass of the polymer a. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 85% by mass or less. The content of the constituent units having an aromatic hydrocarbon group in the case of containing a plurality of polymers a was determined as a weight average value.

Examples of the monomer forming the constituent unit 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-monovinylbenzoic acid, styrene dimer, styrene trimer, and the like). Among them, monomers having an aralkyl group or styrene are preferable. In one embodiment, when the monomer forming the constituent unit having an aromatic hydrocarbon group in the polymer a is styrene, the content of the constituent unit derived from styrene is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, still more preferably 30 to 40% by mass, and particularly preferably 30 to 35% by mass based on the total mass of the polymer a. In another embodiment, when the monomer forming the constituent unit having an aromatic hydrocarbon group in the polymer a is styrene, the content of the constituent unit derived from styrene is preferably 40 to 60 mass%, more preferably 45 to 55 mass%, based on the total mass of the polymer a.

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

Examples of the monomer having a phenylalkyl group other than a substituted or unsubstituted benzyl group include phenylethyl (meth) acrylate and the like.

Examples of the monomer having a substituted or unsubstituted benzyl group include (meth) acrylic esters having a substituted or unsubstituted benzyl group (for example, benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, and the like); vinyl monomers having a benzyl group (e.g., vinylbenzyl chloride, vinylbenzyl alcohol, etc.). Among them, benzyl (meth) acrylate is preferable. In one embodiment, when the monomer forming the constituent unit having an aromatic hydrocarbon group in the polymer a is benzyl (meth) acrylate, the content of the constituent 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 based on the total mass of the polymer a.

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

The polymer a having no constituent unit having an aromatic hydrocarbon group is preferably a polymer obtained by polymerizing at least one of the first monomers described later, and more preferably a polymer obtained by copolymerizing at least one of the first monomers with at least one of the second monomers described later.

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

In one embodiment, the content of the constituent unit derived from the first monomer in the polymer a is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, relative to the total mass of the polymer a.

In another embodiment, the content of the constituent unit derived from the first monomer is preferably 10 to 50% by mass based on the total mass of the polymer a. The above ratio is preferably 10 mass% or more, more preferably 15 mass% or more, and still more preferably 20 mass% or more from the viewpoint of exhibiting good developability, controlling edge meltability, and the like. The content ratio is preferably 50 mass% or less from the viewpoint of high resolution of the resist pattern and the shape of the skirt portion, and more preferably 35 mass% or less, further preferably 30 mass% or less, particularly preferably 27 mass% or less from the viewpoint of chemical resistance of the resist pattern.

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

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

In addition, from the viewpoint of suppressing deterioration of line width thickness and resolution when the focus position is deviated during exposure, the polymer a preferably contains a constituent unit having an aralkyl group and at least one constituent unit selected from the group consisting of constituent units derived from styrene. The polymer a is preferably, for example, a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate and styrene, or the like.

In one embodiment, the polymer a preferably contains 25 to 40 mass% of a constituent unit having an aromatic hydrocarbon group, 20 to 35 mass% of a constituent unit derived from a first monomer, and 30 to 45 mass% of a constituent unit derived from a second monomer. In another embodiment, the polymer preferably contains 70 to 90 mass% of the constituent unit having an aromatic hydrocarbon group and 10 to 25 mass% of the constituent unit derived from the first monomer. In still another embodiment, it is preferable that the polymer contains 40 to 60 mass% of the constituent unit having an aromatic hydrocarbon group, 15 to 30 mass% of the constituent unit derived from the first monomer, and 20 to 45 mass% of the constituent unit derived from the second monomer.

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

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

Specific examples of the monomer having a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Further, there may be mentioned (meth) acrylic esters having an alicyclic hydrocarbon group having 5 to 20 carbon atoms (the number of carbon atoms). More specific examples thereof include (bicyclo [2.2.1] heptyl-2) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 3-methyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyl adamantyl (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl (meth) acrylate, 3,5, 8-triethyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4, 7-methanoindene (meth) 5-yl (meth) acrylate, 3, 5-triethyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, octahydro-4, 7-methanoindene (meth) acrylate, 1-menthyl (meth) acrylate, and menthyl (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, camphene (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.

Among these (meth) acrylic esters, cyclohexyl (meth) acrylate, camphene (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthol (meth) acrylate or tricyclodecane (meth) acrylate is preferable, cyclohexyl (meth) acrylate, camphene (meth) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate or tricyclodecane (meth) acrylate is more preferable.

The photosensitive layer may contain one polymer a alone or two or more kinds. Preferably, when two or more kinds are contained, two kinds of polymers a having an aromatic hydrocarbon group are used in combination or two kinds of polymers a having an aromatic hydrocarbon group and polymers a having no aromatic hydrocarbon group are used in combination. In the latter case, the content of the polymer a having an aromatic hydrocarbon group is preferably 50 mass% or more, more preferably 70 mass% or more, still more preferably 80 mass% or more, and particularly preferably 90 mass% or more, relative to the total mass of the polymer a.

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

The glass transition temperature Tg of the polymer A is preferably 30℃or more and 135℃or less. By using the polymer a having a Tg of 135 ℃ or less in the photosensitive layer, deterioration of line width thickness or resolution at the time of focus position deviation at the time of exposure can be suppressed. From this viewpoint, the Tg of the polymer A is more preferably 130℃or lower, still more preferably 120℃or lower, and particularly preferably 110℃or lower. Further, from the viewpoint of improving the edge melting resistance, it is preferable to use the polymer a having Tg of 30 ℃ or higher. From this viewpoint, the Tg of the polymer A is more preferably 40℃or higher, still more preferably 50℃or higher, particularly preferably 60℃or higher, and most preferably 70℃or higher.

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

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

The photosensitive layer may contain a resin other than the alkali-soluble resin. Examples of the resin other than the alkali-soluble resin include resins having a solubility of less than 0.1g in 100g of a 1 mass% aqueous solution of sodium carbonate having a liquid temperature of 22 ℃, such as acrylic resins, styrene-acrylic copolymers (styrene-acrylic copolymers having a styrene content of 40 mass% or less), urethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamine and polyalkylene glycols (polyalkylene glycol).

(polymerizable Compound)

When the photosensitive layer is a negative photosensitive layer, the negative photosensitive layer preferably contains a polymerizable compound having a polymerizable group. In the present invention, the "polymerizable compound" is a compound that is polymerized by the action of a polymerization initiator described later, and refers to a compound different from the alkali-soluble resin. The molecular weight of the polymerizable compound is preferably 1,500 or less. The molecular weight of the polymerizable compound is preferably 150 or more.

The kind of the polymerizable group is not limited as long as it is a group participating in polymerization. Examples of the polymerizable group include a group having an ethylenically unsaturated group such as a vinyl group, an acryl group, a methacryl group, a styryl group, and a maleimide group. Examples of the polymerizable group include a group having a cationic polymerizable group such as an epoxy group and an oxetane. The polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryl group or a methacryl group.

The polymerizable compound preferably contains a polymerizable compound having 2 or more polymerizable groups. The polymerizable compound more preferably contains a polymerizable compound having 2 polymerizable groups and a polymerizable compound having 3 or more polymerizable groups.

The polymerizable compound is preferably a compound having 1 or more ethylenically unsaturated groups (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), from the viewpoint that photosensitivity of the negative photosensitive layer is more excellent. In addition, from the viewpoint of further excellent resolution and releasability, the number of the ethylenically unsaturated groups in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and further preferably 2 or less.

From the viewpoint of more excellent balance of photosensitivity, resolution and releasability of the negative photosensitive layer, the photosensitive 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 contains 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 relative to the total mass of the polymerizable compound is preferably 20 mass% or more, more preferably more than 40 mass%, and still more preferably 55 mass% or more. The upper limit is not particularly limited and may be 100 mass%. That is, the polymerizable compounds may be all 2-functional ethylenically unsaturated compounds. Further, as the ethylenically unsaturated compound, (meth) acrylate compounds having a (meth) acryloyl group as a polymerizable group are preferable.

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

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

Examples of the aromatic ring of the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as a benzene ring, naphthalene ring, and anthracene ring, aromatic heterocyclic rings such as a thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring, and condensed rings thereof, and aromatic hydrocarbon rings are preferable, and benzene rings are more preferable. The aromatic ring may have a substituent. The ethylenically unsaturated compound B1 may have only 1 aromatic ring or may have 2 or more aromatic rings.

The ethylenically unsaturated compound B1 preferably has a bisphenol structure from the viewpoint of resolution improvement by suppressing swelling of the photosensitive layer by the developer. Examples of the bisphenol skeleton include bisphenol A skeleton derived from bisphenol A (2, 2-bis (4-hydroxyphenyl) propane), bisphenol F skeleton derived from bisphenol F (bis (4-hydroxyphenyl) methane), and bisphenol B skeleton derived from bisphenol B (2, 2-bis (4-hydroxyphenyl) butane), and bisphenol A structure is preferable.

Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include compounds having a bisphenol structure and 2 polymerizable groups (preferably, (meth) acryloyl groups) bonded to both ends of the bisphenol structure. The bisphenol structure may be directly bonded to 2 polymerizable groups at both ends, or may be bonded via 1 or more alkyleneoxy groups. The alkyleneoxy group or the propyleneoxy group added to both ends of the bisphenol structure is preferably ethyleneoxy group, and more preferably ethyleneoxy group. The number of alkylene oxide groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14, per 1 molecule. The olefinically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of Japanese patent application laid-open No. 2016-224162, the contents of which are incorporated into the present specification.

As the ethylenically unsaturated compound B1, a 2-functional ethylenically unsaturated compound having a bisphenol a structure is preferable, and 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane is more preferable. Examples of the 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane include 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane (manufactured by FA-324M,Showa Denko Materials Co, ltd.), 2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane (BPE-500, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydodecaethoxy tetrapropoxy) phenyl) propane (manufactured by FA-3200MY,Showa Denko Materials Co, ltd.), 2-bis (4- (methacryloxypentaethoxy) phenyl) propane (BPE-1300, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, shin-Nakamura Chemical co), and manufactured by ltd.10-b.10, and also, the use of the same.

The ethylenically unsaturated compound B1 preferably contains a compound represented by the following formula (Bis) from the viewpoints of change in line width over time, change in line width at development temperature, and sensitivity.

[ chemical formula 1]

In the formula (Bis), R ₁ R is R ₂ Each independently represents a hydrogen atom or a methyl group, A isC ₂ H ₄ B is C ₃ H ₆ ，n ₁ N is as follows ₃ Are each independently an integer of 1 to 39, and n ₁ +n ₃ Is an integer of 2 to 40, n ₂ N is as follows ₄ Each independently is an integer of 0 to 29, and n ₂ +n ₄ The repeating units of- (A-0) -and- (B-O) -may be arranged in a random or block form, and are integers of 0 to 30. Also, in the case of the block, any one of- (A-O) -and- (B-O) -may be on the bisphenol structure side. In one embodiment, n ₁ +n ₂ +n ₃ +n ₄ Preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 12. And n is ₂ +n ₄ Preferably an integer of 0 to 10, more preferably an integer of 0 to 4, still more preferably an integer of 0 to 2, and particularly preferably 0.

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

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

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

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

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

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

Examples of urethane di (meth) acrylate include propylene oxide modified urethane di (meth) acrylate and ethylene oxide and propylene oxide modified urethane di (meth) acrylate. Examples of 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 dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, neopentyl tetraol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, tris (meth) isocyanurate acrylate, glycerol tri (meth) acrylate, and alkylene oxide modified products thereof. Wherein, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate. In one embodiment, the photosensitive layer preferably contains the above-mentioned ethylenically unsaturated compounds B1 and 3-functional or more ethylenically unsaturated compounds, more preferably contains the above-mentioned ethylenically unsaturated compounds B1 and two or more 3-functional or more ethylenically unsaturated compounds. In this case, the mass ratio of the ethylenically unsaturated compound B1 to the ethylenically unsaturated compound having 3 or more functions is preferably (total mass of the ethylenically unsaturated compounds B1): (total mass of the ethylenically unsaturated compounds having 3 or more functions) =1:1 to 5:1, more preferably 1.2:1 to 4:1, still more preferably 1.5:1 to 3:1. In one embodiment, the photosensitive layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and two or more 3-functional ethylenically unsaturated compounds.

Examples of the alkylene oxide modified product of the ethylenically unsaturated compound having 3 functions or more include caprolactone-modified (meth) acrylate compounds (such as KAYARAD (registered trademark) DPCA-20, shin-Nakamura Chemical co, a-9300-1CL (registered trademark) by ltd), alkylene oxide-modified (meth) acrylate compounds (such as KAYARAD RP-1040, shin-Nakamura Chemical co, ATM-35E and a-9300 (registered trademark) by ltd, and EBECRYL-alinled ltd (such as EBECRYL (registered trademark) 135) by Nippon Kayaku co, ltd), ethoxylated glycerol triacrylate (such as Shin-Nakamura Chemical co, a-GLY-9E (registered trademark) by milk, and so on) by aroix (such as a-2300-1 CL (manufactured by ltd), aroix M-520 (manufactured by toagi co, ltd), and other than one or more, and one or more.

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

From the viewpoints of resolution and linearity, the value of the ratio Mm/Mb of the content Mm of the ethylenically unsaturated compound in the photosensitive layer to the content Mb of the alkali-soluble resin is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less. Further, from the viewpoints of hardenability and resolution, the ethylenically unsaturated compound in the photosensitive layer preferably contains a (meth) acrylic compound, and more preferably contains a (meth) acrylate compound. Further, from the viewpoints of hardenability, resolution, and linearity, the ethylenically unsaturated compound in the photosensitive layer more preferably contains a (meth) acrylic compound, and the content of the acrylic compound is 60 mass% or less with respect to the total mass of the (meth) acrylic compounds contained in the photosensitive layer.

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

The polymerizable compound preferably contains an oxyethylene chain. The oxyethylene chain being-CH ₂ -CH ₂ -a partial structure represented by O-. Examples of the polymerizable compound containing an oxyethylene chain include 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M,Showa Denko Materials Co, manufactured by ltd.) and 2, 2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane (BPE-500, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydodecyloxypropoxy) phenyl) propane (FA-3200MY,Showa Denko Materials Co, manufactured by ltd.), 2-bis (4- (methacryloxypentaethoxy) phenyl) propane (BPE-1300, shin-Nakamura Chemical co, manufactured by ltd.), and 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, shin-Nakamura Chemical, manufactured by ltd.) and ethoxylated (NK) bisphenol a-10 b) (BPE-57 e, manufactured by ltd.).

The polymerizable compound may be used alone or in combination of two or more. The content of the polymerizable compound in the photosensitive layer is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 20 to 50% by mass, relative to the total mass of the photosensitive layer.

(polymerization initiator)

When the photosensitive layer is a negative photosensitive layer, the negative photosensitive layer preferably contains a polymerization initiator. The polymerization initiator may be selected according to the form of polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator. The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

The negative photosensitive layer preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that initiates polymerization of the polymerizable compound by exposure to active light such as ultraviolet light, visible light, and X-ray. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and a photo radical polymerization initiator is preferable.

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

Further, from the viewpoints of photosensitivity, visibility and resolution of an exposed portion and a non-exposed portion, the negative photosensitive layer preferably contains at least one selected from the group consisting of a 2,4, 5-triarylimidazole dimer and a derivative thereof as a photo radical polymerization initiator. In addition, 2,4, 5-triarylimidazole structures in the 2,4, 5-triarylimidazole dimer and the derivative thereof 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 Japanese patent application laid-open No. 2011-95716 and paragraphs 0064 to 0081 of Japanese patent application laid-open No. 2015-14783.

Examples of the photo radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p, p ' -dimethoxybenzyl) anisyl ester, TAZ-110 (Midori Kagaku Co., ltd.), benzophenone, TAZ-111 (Midori Kagaku Co., ltd.), irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF corporation), omnirad651 and 369 (manufactured by IGM Resins B.V.), and 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -bisimidazole (Tokyo Chemical Industry Co., ltd.).

Examples of the commercial products of the photo radical polymerization initiator include 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXF-01, manufactured by BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (0-acetoxime) (trade name: IRGACURE OXE-02, manufactured by BASF corporation), IRGACURE OXE-03 (manufactured by BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (trade name: omni 379EG,IGM Resins B.V. Manufactured by Omni. Product), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name: omni 907,IGM Resins B.V. Manufactured by Omni 907,IGM Resins B.V), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropoyl) benzyl ] propan-1-one (trade name: omni-4-methyl-1-butanone: omnirad 127,IGM Resins B.V), 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) 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, manufactured), 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: omnirad 651,IGM Resins B.V, manufactured), 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (trade name: omnirad TPO H, IGM Resins b.v.), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: manufactured by Omnirad 819,IGM Resils B.V), an oxime ester-based photopolymerization initiator (trade name: lunar 6, dksh Japan k.k. manufactured), 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbiimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford corporation) and 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer (trade name: BCTB, tokyo Chemical Industry co., ltd., manufactured), 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer (trade name: BCTB, tokyo Chemical Industry co., ltd.) 1- [4- (phenylsulfanyl) phenyl ] -3-cyclopentylpropane-1, 2-dione-2- (0-benzoyloxime) (trade name: TR-PBG-305,Changzhou Tronly New Flectronic 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 Electronic Materials CO, manufactured by ltd. 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) octanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1, 2-dione-2- (O-benzoyl oxime) (trade name: TR-PBG-391,Changzhou Tronly New Flectronic Materials CO, ltd.

The photo cation polymerization initiator (photoacid generator) is a compound that generates an acid upon receiving an active light. The photo-cation polymerization initiator is preferably a compound which generates an acid by reacting with an active light having a wavelength of 300nm or more (preferably, a wavelength of 300nm to 450 nm), but the chemical structure thereof is not limited. 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 that generates an acid having a pKa of 4 or less, more preferably a photo-cation polymerization initiator that generates an acid having a pKa of 3 or less, and particularly preferably a photo-cation polymerization initiator that generates an acid having a pKa of 2 or less. The lower limit of pKa is not particularly limited, and is preferably-10.0 or more, for example.

Examples of the photo-cationic polymerization initiator include an ionic photo-cationic polymerization initiator and a nonionic photo-cationic polymerization initiator. Examples of the ionic photo-cation polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. As the ionic photo-cation polymerization initiator, the ionic photo-cation polymerization initiators described in paragraphs 0114 to 0133 of jp 2014-85643 a can be used.

Examples of the nonionic photo-cationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate 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 layer may contain one kind of photopolymerization initiator alone or two or more kinds thereof. The content of the photopolymerization initiator in the photosensitive layer is not particularly limited, but is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and further preferably 1.0 mass% or more relative to the total mass of the photosensitive layer. The upper limit is not particularly limited, but is preferably 10 mass% or less, more preferably 5 mass% or less, relative to the total mass of the photosensitive layer.

(pigment)

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

In the present invention, the "change in the maximum absorption wavelength of the dye by an acid, a base or a radical" may refer to any one of an embodiment in which the dye in a developed state is decolorized by an acid, a base or a radical, an embodiment in which the dye in a decolorized state is developed by an acid, a base or a radical, and an embodiment in which the dye in a developed state is changed to another colored state. Specifically, the dye N may be a compound that changes color from a decolored state by exposure, or may be a compound that changes color from a decolored state by exposure. In this case, the dye may be a dye that changes the state of color development or decoloration by generating and acting an acid, a base or a radical in the photosensitive layer by exposure, or a dye that changes the state of color development or decoloration by changing the state (for example, pH) in the photosensitive layer by an acid, a base or a radical. The coloring matter may be a coloring matter which changes the state of being colored or decolored by directly receiving an acid, an alkali or a radical as a stimulus without exposure.

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

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

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

Examples of the coloring mechanism of the dye N in the present invention include an embodiment in which a radical, an acid or a base generated from a radical polymerization initiator, a photo cation polymerization initiator or a photo base generator after adding a photo radical polymerization initiator, a photo cation polymerization initiator (photo acid generator) or a photo base generator to a photosensitive layer and exposing the photosensitive layer to light is colored by a radical, an acid or a base generated from the radical polymerization initiator, the photo cation polymerization initiator or the photo base generator.

The maximum absorption wavelength in the wavelength range of 400nm to 780nm at the time of color development of the dye N is preferably 550nm or more, more preferably 550nm to 700nm, and even more preferably 550nm to 650nm, from the viewpoint of visibility of the exposed portion and the non-exposed portion. The dye N may have only 1 maximum absorption wavelength in the wavelength range of 400nm to 780nm at the time of color development, or may have 2 or more. When the dye N has a maximum absorption wavelength in the wavelength range of 400nm to 780nm at the time of color development of 2 or more, the maximum absorption wavelength having the highest absorbance among the 2 or more maximum absorption wavelengths may be 450nm or more.

The maximum absorption wavelength of pigment N was measured by using a spectrophotometer in the atmospheric environment: UV3100 (manufactured by Shimadzu Corporation) was obtained by measuring the transmission spectrum of a solution containing pigment N (liquid temperature 25 ℃) in the range of 400nm to 780nm, and detecting a wavelength (maximum absorption wavelength) at which the intensity of light becomes extremely small.

Examples of the coloring matter which is developed or decolored by exposure to light include colorless compounds. Examples of the dye to be decolorized by exposure include a colorless compound, a diarylmethane dye, an oxazine dye, a xanthene dye, an iminonaphthoquinone dye, an azomethine dye, and an anthraquinone dye. As the coloring matter N, colorless compounds are preferable from the viewpoint of visibility of the exposed portion and the non-exposed portion.

Examples of the colorless compound include a colorless compound having a triarylmethane skeleton (triarylmethane-based dye), a colorless compound having a spiropyran skeleton (spiropyran-based dye), a colorless compound having a fluoran parent skeleton (fluoran parent-based dye), a colorless compound having a diarylmethane skeleton (diarylmethane-based dye), a colorless compound having a rhodamine lactam skeleton (rhodamine lactam-based dye), a colorless compound having an indolyl phthalein lactone skeleton (indolyl phthalein-based dye), and a colorless compound having a colorless golden amine skeleton (colorless golden amine-based dye). Among them, triarylmethane-based pigments or fluoran-based pigments are preferable, and colorless compounds having a triphenylmethane skeleton (triphenylmethane-based pigments) or fluoran-based pigments are more preferable.

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

Examples of the dye N include the following dyes and colorless compounds. Specific examples of the dye in pigment N include brilliant green (brilliant green), ethyl violet, methyl green, crystal violet, basic fuchsin (basic fuchsin), methyl violet 2B, quinaldine red (quinaldine red), rose bengal (rose bengal), meter yellow (metandil yellow), thymol sulfophthalein (thymol sulfonphthalein), xylenol (xylenol) blue, methyl orange, para-methyl red, congo red, benzored purpurin (benzopurline) 4B, alpha-naphthyl red, nile blue (nile blue) 2B, nile blue a, methyl violet, malachite green (malachite green), parapsine red (paramfuchsin), victorian pure blue (victoria pure blue) -naphthalene sulfonate, victorian pure blue BOH (Hodogaya Chemical co., ltd, manufactured), oil blue #603 (Orient Chemical Industries co., ltd, manufactured), oil pink #312 (Orient Chemical Industries co., ltd, manufactured), oil red 5B (Orient Chemical Industries co., ltd, manufactured), oil scarlet #308 (Orient Chemical Industries co., ltd, manufactured), oil red OG (Orient Chemical Industries co., ltd, manufactured), oil red RR (Orient Chemical Industries co., ltd, manufactured), oil green #502 (Orient Chemical Industries co., ltd, manufactured), shi Bilong red (spilon red) BEH special (Hodogaya Chemical co., ltd, manufactured), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, golden yellow amine, 4-p-diethylaminophenyl iminonaphthaquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearyl amino-4-p-N, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-beta-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of the pigment N include p, p', p "-hexamethyltriphenylmethane (leuco crystal violet), pergascript Blue SRB (Ciba-Geigy Co.), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) amino fluoran parent, 2-anilino-3-methyl-6- (N-ethyl-p-toluidinyl) fluoran parent, 3, 6-dimethoxy fluoran parent, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamin) fluoran parent, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilino fluoran parent, 3- (N, N-diethylamino) -6-methyl-7-amino fluoran parent, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzyl amino) fluoran parent, n-diethylamino) -7- (4-chloroanilino) fluoran parent, 3- (N, N-diethylamino) -7-chlorofluoran parent, 3- (N, N-diethylamino) -7-benzylamino fluoran parent, 3- (N, N-diethylamino) -7, 8-benzofluoran, 3- (N, N-dibutylamino) -6-methyl-7-anilino fluoran parent, 3- (N, N-dibutylamino) -6-methyl-7-stubble amino fluoran parent, 3-piperidinyl-6-methyl-7-anilino fluoran parent, 3-pyrrolidinyl-6-methyl-7-anilino fluoran parent, 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-phenyl) -3- (1-ethoxy-3-ethyl-3-azalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide and 3',6' -bis (diphenylamino) spiroisobenzofuran-1 (3H), 9' - [9H ] xanthen-3-one.

From the viewpoints of visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution, the dye N is preferably a dye whose maximum absorption wavelength is changed by a radical, and more preferably a dye which develops color by a radical. As pigment N, preference is given to leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalene sulfonate.

The pigment may be used singly or in combination of two or more. The content of the dye 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 layer, from the viewpoints of visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution. Further, from the viewpoints of visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution, the content of the dye N is preferably 0.1 mass% or more, more preferably 0.1 mass% to 10 mass%, further preferably 0.1 mass% to 5 mass%, and particularly preferably 0.1 mass% to 1 mass% relative to the total mass of the photosensitive layer.

The content of the dye N refers to the content of the dye when all the dye N contained in the photosensitive layer is brought into a color development state. Hereinafter, a method for determining the content of the dye N will be described by taking a dye that develops color by a radical as an example. Two solutions each having 0.001g or 0.01g of pigment dissolved in 100mL of methyl ethyl ketone were prepared. To each of the obtained solutions, a photo radical polymerization initiator (trade name, irgacure OXE01, manufactured by BASF corporation) was added, and 365nm light was irradiated, thereby generating radicals and bringing all the pigments into a color development state. Then, the absorbance of each solution having a liquid temperature of 25℃was measured using a spectrophotometer (manufactured by UV3100, shimadzu Corporation) under atmospheric conditions, and a calibration curve was prepared. Next, absorbance of the solution in which all the pigments were developed was measured by the same method as described above, except that 3g of the photosensitive layer was dissolved in methyl ethyl ketone instead of the pigments. Based on the absorbance of the obtained solution containing the photosensitive layer, the content of the pigment contained in the photosensitive layer is calculated from the calibration curve.

(thermally crosslinkable Compound)

The photosensitive 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 invention, the heat-crosslinkable compound having an ethylenically unsaturated group described later is not treated as an ethylenically unsaturated compound, but is treated as a heat-crosslinkable compound. Examples of the thermally crosslinkable compound include a methylol compound and a blocked isocyanate compound. Among them, blocked isocyanate compounds are preferable from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. Since the blocked isocyanate compound reacts with the hydroxyl group and the carboxyl group, for example, when at least one of the hydroxyl group and the carboxyl group is contained in the alkali-soluble resin and/or the ethylenically unsaturated compound, the hydrophilicity of the film formed is reduced, and the function of the film obtained by hardening the photosensitive layer as a protective film tends to be enhanced. The blocked isocyanate compound is 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 by DSC (Differential scanning calorimetry: differential scanning calorimeter) analysis". As the differential scanning calorimeter, for example, a differential scanning calorimeter manufactured by Seiko Instruments inc (model: DSC 6200) can be preferably used. However, the differential scanning calorimeter is not limited thereto.

Examples of the blocking agent having a dissociation temperature of 100℃to 160℃include active methylene compounds [ malonic acid 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 them, 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 can be obtained, for example, by isocyanating 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 that the dissociation temperature is more easily set in a preferable range than a compound having no oxime structure and development residues are easily reduced.

The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radical polymerizable group is preferable. Examples of the polymerizable group include an epoxy group-containing group such as a (meth) acryloyloxy group, an ethylenically unsaturated group such as a (meth) acrylamide group and a styryl group. Among them, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth) acryloyloxy group, and further preferably an acryloyloxy group.

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

[ chemical formula 2]

The thermally crosslinkable compound may be used singly or in combination of two or more. When the photosensitive 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 layer.

(other Components)

The photosensitive layer may contain other components than the alkali-soluble resin, the polymerizable compound, the polymerization initiator, the pigment, and the thermally crosslinkable compound. Examples of the other component include a free-radical polymerization inhibitor, a surfactant, a sensitizer, and various additives. The other components may be used singly or in combination of two or more.

< free radical polymerization inhibitor >

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

The radical polymerization inhibitor may be used alone or in combination of two or more. When the photosensitive layer contains a radical inhibitor, the content of the radical inhibitor is preferably 0.001 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and still more preferably 0.02 to 2.0 mass% with respect to the total mass of the photosensitive layer. The content of the radical polymerization inhibitor is preferably 0.005 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and even more preferably 0.01 to 1.0 mass% based on the total mass of the polymerizable compound.

Surfactant-containing compositions

The photosensitive layer preferably contains a surfactant. Examples of the surfactant include surfactants described in paragraphs 0017 to 0060 to 0071 of JP-A-2009-237362, which are incorporated in Japanese patent publication No. 4502784. The surfactant is preferably a nonionic surfactant, a fluorine surfactant, or a silicone surfactant.

Commercial products of the fluorine-based surfactant, examples of the "may be MEGAFACE" (trade name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP.MFS-330, EXP.MFS-578-2, EXP.S-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, EXP.MFS-578R-41-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation, supra), fluorad (trade name) FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited, supra), surflon (trade name) S-382 SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc. above), polyFox (trade name) PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc. above), KH-40 (manufactured by OMNOVA Solutions Inc.), ftergent (trade name) 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured as Neos Company Limited above), U-120E (Uni-chem Co., ltd.), and the like. The fluorine-based surfactant may preferably be an acrylic compound having a molecular structure including a functional group containing a fluorine atom, and the fluorine atom may be volatilized by cutting a functional group portion containing a fluorine atom when heat is applied. Examples of such a fluorine-based surfactant include the MEGAFACE (trade name) DS series (chemical industry daily report (2016, 2, 22 days), daily-use industry news (2016, 2, 23 days)) manufactured by DIC Corporation, and for example, MEGAFACE (trade name) DS-21.

As the fluorine-based surfactant, a polymer of a vinyl ether compound containing a fluorine atom and a hydrophilic vinyl ether compound, which have a fluorinated alkyl group or a fluorinated alkylene ether group, is also preferably used. As the fluorine-based surfactant, a blocked polymer can also be used. The fluorine-containing surfactant may preferably be a fluorine-containing polymer compound containing a constituent unit derived from a (meth) acrylate compound having a fluorine atom and a constituent unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group). As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used. Examples of the "MEGAFACE" include MEGAFACE (trade name) RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation). As the fluorine-based surfactant, for example, a compound having a linear perfluoroalkyl group having 7 or more carbon atoms may be used. However, from the viewpoint of improving environmental suitability, a substitute material of perfluorooctanoic acid (PFOA) or perfluorooctanoic acid (PFOS) is preferably used as the fluorine-based surfactant.

Examples of the nonionic surfactant include glycerin, trimethylol propane, trimethylol ethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, and the like), 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 (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (trade name above manufactured by BASF corporation), tetronic (trade name) 304, 701, 704, 901, 904, 150R1, hydrostart WE 3323 (trade name above manufactured by BASF corporation), solsperse (trade name) 20000 (trade name above manufactured by Lubrizol Japan limited, NCW-101, NCW-1001, NCW-1002 (trade name) PIONIN (trade name) D-1105, D-6112-W, D-6315 (trade name above manufactured by tamoto Oil & Fat Co., above), ofine (trade name) 1010, ltd.400, ltd.

The silicone surfactant includes a linear polymer composed of siloxane bonds, and a modified siloxane polymer having an organic group introduced into a side chain or a terminal. Specific examples of the silicone surfactant include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (manufactured by DIC Corporation, supra), DOWSIL (trade name) 8032 ADDITIVE, toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH29PA, toray Silicone SH PA, toray Silicone SH8400 (Dow Corning Toray Silicone Co, supra), ltd. Manufactured) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K, L, KF-355, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (above is more than is Sh-co, su's co.) ltd. manufactured), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured above as Momentive Performance Materials inc.), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378 (manufactured above by BYK Chemie corporation), and the like.

The photosensitive layer may contain one kind of surfactant alone or two or more kinds thereof. The content of the surfactant is preferably 0.001 to 10 mass%, more preferably 0.01 to 3 mass%, relative to the total mass of the photosensitive layer.

Sensitizer(s)

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

The sensitizer may be used singly or in combination of two or more. When the photosensitive layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to a light source and improving the hardening speed by balancing the polymerization speed and chain transfer, it is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% with respect to the total mass of the photosensitive layer.

Additive-

The photosensitive layer may contain a known additive as required in addition to the above components. Examples of the additive include plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide and the like), purine bases (adenine and the like) and solvents. The photosensitive layer may contain one kind of each additive alone or two or more kinds thereof.

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

Examples of the 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 carboxybenzotriazoles include commercially available products such as CBT-1 (JOHOKU CHEMICAL CO., LTD., trade name).

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

The photosensitive layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds.

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

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

The photosensitive layer may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid-proliferating agents, development accelerators, conductive fibers, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic deposition inhibitors. The additives contained in the photosensitive layer are described in paragraphs 0165 to 0184 of Japanese unexamined patent publication No. 2014-85643, the contents of which are incorporated herein by reference.

(impurities etc.)

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

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

As a method for setting the impurity in the above range, a substance having a small impurity content is selected as a raw material of the composition, and the mixture of the impurity is prevented and the cleaning and the removal are performed at the time of producing the photosensitive layer. In this way, the impurity amount can be set within the above range.

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

Preferably, the photosensitive layer contains a small amount of compounds such as benzene, formaldehyde, trichloroethylene, 1, 3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide, and hexane. The content of these compounds relative to the total mass of the photosensitive layer is preferably 100ppm or less, more preferably 20ppm or less, and further preferably 4ppm or less on a mass basis. The lower limit may be set to 10ppb or more, or 100ppb or more, based on the total mass of the photosensitive layer. These compounds can be suppressed in content by the same method as the impurities of the above metals. Further, the amount can be determined by a known measurement method.

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

(residual monomer)

The photosensitive layer may contain residual monomers corresponding to the respective constituent units of the alkali-soluble resin. 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, with respect to the total mass of the alkali-soluble resin, from the viewpoints of patterning property and reliability. The lower limit is not particularly limited, but is preferably 1 mass ppm or more, more preferably 10 mass ppm or more. From the viewpoints of patterning properties and reliability, the residual monomer of each constituent unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and still more preferably 100 mass ppm or less, relative to the total mass of the photosensitive layer. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more.

The residual monomer amount of the monomer in synthesizing the alkali-soluble resin by the polymer reaction is also preferably set within the above range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably set within the above range. The amount of the residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.

[ physical Properties and the like ]

The thickness of the photosensitive layer is preferably 20 μm or less, more preferably 10 μm or less, further preferably 8 μm or less, and particularly preferably 5 μm or less from the viewpoints of developability and resolution. The thickness of the photosensitive layer may be 1 μm or more. The thickness of the photosensitive layer is preferably 1 μm or more and 5 μm or less.

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

[ method of Forming ]

The method of forming the photosensitive layer is not particularly limited as long as it is a method capable of forming a layer containing the above-described components. As a method for forming the photosensitive layer, for example, a method formed by: a photosensitive resin composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, a solvent, and the like is prepared, the photosensitive resin composition is applied to the surface of an intermediate layer or the like, and a coating film of the photosensitive resin composition is dried. As a method for drying the coating film of the photosensitive resin composition, heat drying and reduced pressure drying are preferable. In addition, in the present invention, "drying" means removing at least a part of the solvent contained in the composition. Examples of the drying method include natural drying, heat drying, and reduced pressure drying. The above methods can be applied singly or in combination of plural kinds. The drying temperature is preferably 80℃or higher, more preferably 90℃or higher. The upper limit is preferably 130℃or lower, more preferably 120℃or lower. The drying can also be performed by continuously changing the temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and still more preferably 60 seconds or more. The upper limit is not particularly limited, but is preferably 600 seconds or less, more preferably 300 seconds or less.

Examples of the photosensitive resin composition used for forming the photosensitive layer include a composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, any of the above components, and a solvent. In order to adjust the viscosity of the photosensitive resin composition and to facilitate formation of the photosensitive layer, the photosensitive resin composition preferably contains a solvent.

The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the alkali-soluble resin, the ethylenically unsaturated compound, the photopolymerization initiator, and any of the above components, and a known solvent can be used. Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N, N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of these solvents. The photosensitive resin composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Among them, a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable, and a mixed solvent containing at least three selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent and a cyclic ether solvent is further preferable.

Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether. Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate. As the solvent, a solvent described in paragraphs 0092 to 0094 of international publication No. 2018/179640 and a solvent described in paragraph 0014 of japanese patent application laid-open publication No. 2018-177889, which are incorporated herein by reference, may be used.

The photosensitive resin composition may contain one kind of solvent alone or two or more kinds thereof. The content of the solvent in coating the photosensitive resin composition is preferably 50 to 1 part by mass, 900 parts by mass, and more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition.

The method for producing the photosensitive resin composition is not particularly limited, and examples thereof include a method in which a solution in which each component is dissolved in the above-mentioned solvent is prepared in advance, and the obtained solution is mixed at a predetermined ratio to produce the photosensitive resin composition. The photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm before forming the photosensitive layer.

The method of applying the photosensitive resin composition is not particularly limited, and may be applied by a known method. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating. The photosensitive layer can be formed by applying a photosensitive resin composition to a protective film described later and drying the film.

Protective film

The transfer material according to an embodiment of the present invention preferably includes a protective film as an outermost layer on the side opposite to the temporary support side. Also, the protective film is preferably in contact with the photosensitive layer.

As a material constituting the protective film, a resin film and paper are exemplified, and 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 them, a polyethylene film, a polypropylene film or a polyethylene terephthalate film is preferable.

The thickness (layer thickness) of the protective film is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, still more preferably 5 μm to 40 μm, and particularly preferably 15 μm to 30 μm. Further, from the viewpoint of further excellent resolution, the arithmetic average roughness Ra value of the surface of the protective film (hereinafter, also simply referred to as "surface of the protective film") in contact with the photosensitive layer is preferably 0.3 μm or less, more preferably 0.1 μm or less, and still more preferably 0.05 μm or less. It is considered that the Ra value of the surface of the protective film is within the above range, and thus the uniformity of the layer thickness of the photosensitive layer and the resin pattern formed is improved, and the resolution is improved. The lower limit of the Ra value of the surface of the protective film is not particularly limited, but is preferably 0.001 μm or more.

The Ra value of the surface of the protective film was measured by the following method. The surface profile of the optical film was obtained by measuring the surface of the protective film using a three-dimensional optical profiler (New View7300, manufactured by Zygo corporation) under the following conditions. As the measurement/analysis software, microscope Application of MetroPro ver8.3.2 was used. Then, the Surface Map screen is displayed by the analysis software, and histogram data is obtained in the Surface Map screen. An arithmetic average roughness is calculated from the obtained histogram data, thereby obtaining an Ra value of the surface of the protective film. When the protective film is attached to the transfer material, the protective film is peeled from the transfer material, and the Ra value of the surface on the peeled side is measured.

Further, by attaching the protective film to the photosensitive layer or the like, the transfer material can be manufactured. The method of attaching the protective film to the photosensitive layer or the like is not particularly limited, and a known method may be used. As a means for bonding the protective film to the photosensitive layer, a known laminator such as a vacuum laminator and an automatic cutting laminator can be mentioned. Preferably, the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.

Refractive index adjusting layer

The transfer material according to an embodiment of the present invention may include a refractive index adjustment layer (i.e., a contrast enhancement 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 into the present specification.

The total thickness of the layers of the transfer material excluding the temporary support and the protective film is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less, from the viewpoints of resolution and adhesion to the substrate. Further, from the viewpoints of resolution and adhesion to a substrate, the total thickness of the photosensitive layer and the intermediate layer in the transfer material is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

Relationship between temporary support, photosensitive layer and protective film

In the transfer material according to an embodiment of the present invention, the cured film obtained by curing the photosensitive layer has an elongation at break of 15% or more at 120 ℃, and the surface of the temporary support on the photosensitive layer side has an arithmetic average roughness Ra of 50nm or less, preferably 150nm or less.

The transfer material according to the present invention preferably satisfies the following formula (R1).

X Y < 1,500 type (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 layer, and Y represents a value (nm) of arithmetic average roughness Ra of the photosensitive layer-side surface of the temporary support. 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 layer. Elongation at break was measured by tensile test using a cured film obtained by subjecting a photosensitive layer having a thickness of 20 μm to 120mJ/cm using an ultra-high pressure mercury lamp ² After hardening by exposure to light, the mixture was irradiated with a high-pressure mercury lamp at 400mJ/cm ² The cured film was further exposed to additional light and heated at 145℃for 30 minutes.

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

Y is less than or equal to Z type (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 layer side, and Z represents the value (nm) of the arithmetic average roughness Ra of the surface of the protective film on the photosensitive layer side.

Method for producing transfer Material

The method for producing the transfer material according to the present invention is not particularly limited, and a known production method, for example, a known method for forming each layer, can be used. A method for producing a transfer material according to the present invention will be described below with reference to fig. 1. However, the transfer material according to the present invention is not limited to the transfer material having the configuration shown in fig. 1.

As a method for manufacturing the transfer material 100, for example, a method including the steps of: a step of forming an intermediate layer 20 by applying an intermediate layer composition to the surface of the temporary support 10 and then drying a coating film of the intermediate layer composition; and a step of forming the photosensitive layer 30 by applying a photosensitive resin composition containing, for example, an alkali-soluble resin and an ethylenically unsaturated compound to the surface of the intermediate layer 20, and then drying the coating film of the photosensitive resin composition. In the above-mentioned production method, it is preferable to use a composition for an intermediate layer containing at least one selected from the group consisting of water and water-miscible organic solvents, and to use a photosensitive resin composition further containing an alkali-soluble resin, an ethylenically unsaturated compound, and at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents.

The protective film 40 is pressed against the photosensitive layer 30 of the laminate manufactured by the above-described manufacturing method, thereby manufacturing the transfer material 100. As a method for producing the transfer material used in the present invention, it is preferable to produce the transfer material 100 including the temporary support 10, the intermediate layer 20, the photosensitive layer 30, and the protective film 40 by including a step of providing the protective film 40 so as to be in contact with the surface of the photosensitive layer 30 on the opposite side of the temporary support 10. After the transfer material 100 is manufactured by the above manufacturing method, the transfer material 100 may be wound up to manufacture and store a transfer material in a roll form. The transfer material in the form of a roll can be directly supplied to a step of bonding the transfer material to a substrate in a roll-to-roll (roll-to-roll) manner, which will be described later.

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

The transfer material according to an embodiment of the present invention may preferably be an embodiment in which the photosensitive layer includes a colored resin layer containing a pigment. The use of the colored resin layer is applicable to, for example, the use of a colored pixel or a black matrix for forming a color filter used for a Liquid Crystal Display (LCD) and a solid-state imaging device (for example, a CCD (charge-coupled device) and a CMOS (complementary metal oxide semiconductor: complementary metal oxide semiconductor)). In recent years, a cover glass (cover glass) in which a black frame-like light shielding layer is formed on a rear surface peripheral edge portion of a transparent glass substrate or the like is sometimes mounted on a liquid crystal display window included in an electronic device in order to protect the liquid crystal display window. In order to form such a light shielding layer, a colored resin layer can be used. The embodiments other than the pigment in the colored resin layer are the same as the above embodiments.

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

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

From the viewpoint of dispersion stability, the particle diameter of the black pigment is preferably 0.001 μm to 0.1 μm, more preferably 0.01 μm to 0.08 μm in terms of the number average particle diameter. The particle diameter is an average value obtained by obtaining the particle diameter of any 100 particles from the number average particle diameter of a circle having the same area as the area of the pigment particles, taking the area of the pigment particles into consideration when obtaining the area of the pigment particles from a photographic image of the pigment particles taken by an electron microscope, and averaging the obtained 100 particle diameters.

As the pigment other than the black pigment, the white pigment described in paragraphs 0015 and 0114 of japanese patent application laid-open publication No. 2005-007765 can be used. Specifically, among the white pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferable as an inorganic pigment, titanium oxide or zinc oxide is more preferable, and titanium oxide is still more preferable. The inorganic pigment is particularly preferably rutile-type or anatase-type titanium oxide, and rutile-type titanium oxide is particularly preferred. The surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or an organic substance, or may be treated with two or more kinds of treatments. Thus, the catalyst activity of titanium oxide is suppressed, and heat resistance, light fading, and the like are improved. From the viewpoint of reducing the thickness of the heated photosensitive layer, at least one of an alumina treatment and a zirconia treatment is preferable as the surface treatment of the surface of titanium oxide, and both of the alumina treatment and the zirconia treatment are particularly preferable.

In addition, when the photosensitive layer is a colored resin layer, the photosensitive layer preferably further contains a color pigment other than a black pigment and a white pigment from the viewpoint of transferability. When the color pigment is contained, the particle diameter of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of more excellent dispersibility. Examples of the Color pigments include Victoria pure blue BO (Color Index) (hereinafter, C.I.) 42595, auramine (C.I. 41000), fat black (fat black) HB (C.I. 26150), mononet yellow (mount black) GT (C.I. pigment yellow 12), permanent yellow (mount yellow) GR (C.I. pigment yellow 17), permanent yellow HR (C.I. pigment yellow 83), permanent carmine (permanent carmine) FBB (C.I. pigment Red 146), hestabanum red (Hostaum red) ESB (C.I. pigment Violet 19), permanent ruby red (mount red) FBH (C.I. pigment Red 11), fatrel pink (mount red) B (mount red) pigment Red 81), montelco blue (C.I. pigment Red monastral fast blue), rebaut red (C.I. pigment Red 15), heng (C.I. pigment Red 149), hemisa (C.I. pigment Red 15), hex (C.I. pigment Red 180, C.I. pigment C.C.7, C.I. pigment C.C.37, C.I. pigment red (C.I. pigment Red 215), hemisa.C.1, C.I. pigment red (C.I. pigment red) yellow (C.I. pigment red) 37, C.I. pigment red (C.I. pigment red) 3, and the like. Among them, c.i. pigment red 177 is preferred.

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

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

When the photosensitive layer contains a black pigment and the photosensitive layer is formed of a photosensitive resin composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion. The dispersion liquid may be prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent (vehicle) and dispersing it with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant can be used. The vehicle is a part of a medium in which a pigment is dispersed when a pigment dispersion liquid is formed, and is a liquid, and includes a binder component for holding a black pigment in a dispersed state and a solvent component (organic solvent) for dissolving and diluting the binder component.

The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, sand mills, and the like. Further, the fine grinding may be performed by mechanical grinding by friction. For the disperser and the fine pulverization, a description of "pigment dictionary" (manufactured by kubang, first edition, ku shop, 2000, page 438, page 310) can be referred to.

< method for producing laminate >

The method for manufacturing a laminate according to an embodiment of the present invention includes the following steps in order: bonding a transfer material including a temporary support, an intermediate layer in contact with the temporary support, and a photosensitive layer in this order to a substrate, and disposing the photosensitive layer, the intermediate layer, and the temporary support in this order on the substrate (hereinafter, sometimes referred to as a "bonding step"); peeling the temporary support from the intermediate layer (hereinafter, sometimes referred to as a "peeling step"); and patterning the intermediate layer and the photosensitive layer by exposure and development (hereinafter, sometimes referred to as a "patterning step"), wherein the roughness Ra of the surface of the intermediate layer exposed by peeling the temporary support from the intermediate layer is 2nm or more. In the method for producing a laminate according to an embodiment of the present invention, the transfer material described in the above item of "transfer material" is preferably applied as the transfer material. At least a part of the pattern obtained in the patterning step preferably includes a line pattern and a space pattern. The widths of at least 1 group of lines and spaces in the line-space pattern are preferably 20 μm or less in total.

Lamination Process

In the bonding step, a transfer material including a temporary support, an intermediate layer in contact with the temporary support, and a photosensitive layer in this order is bonded to a substrate, and the photosensitive layer, the intermediate layer, and the temporary support are sequentially disposed on the substrate. When the conductive layer is provided on the surface of the substrate, the transfer material is preferably bonded to the conductive layer of the substrate. The bonding of the transfer material to the substrate preferably includes pressing the transfer material against the substrate. Since the adhesion between the transfer material and the substrate is improved, the patterned photosensitive layer after exposure and development can be preferably used as a resist in etching the conductive layer. When the transfer material has a protective film, the protective film may be removed and then bonded.

The method of pressing the transfer material against the substrate is not particularly limited, and a known transfer method and lamination method can be used. The transfer material and the substrate are preferably bonded by laminating the transfer material and the substrate and applying pressure and heat using a mechanism such as a roller. For lamination, a known lamination machine such as a lamination machine, a vacuum lamination machine, and an automatic cutting lamination machine that can further improve productivity can be used. The lamination temperature is not particularly limited, but is preferably, for example, 70℃to 130 ℃.

The method for producing the laminate including the bonding step is preferably performed by a roll-to-roll method. Hereinafter, a roll-to-roll system will be described. The roll-to-roll method is the following: the substrate that can be wound and unwound is used as the substrate, and a step of winding out the substrate or the structure including the substrate (also referred to as a "winding-out step") is included before any step included in the method for manufacturing a laminate, and after any step, a step of winding up the substrate or the structure including the substrate (also referred to as a "winding-in step") is included, and at least any step (preferably all steps or all steps except for a heating step) is performed while conveying the substrate or the structure including the substrate. The winding-out method in the winding-out step and the winding-up method in the winding-up step are not particularly limited, and a known method may be used as long as a roll-to-roll method of manufacturing is applicable.

As the substrate, a known substrate may be used, but a substrate having a conductive layer is preferable, and a conductive layer is more preferable on the surface of the substrate. The substrate may have any layer other than the conductive layer as needed. Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate. A preferred embodiment of the substrate is described in paragraph 0140 of international publication No. 2018/155193, which is incorporated herein by reference. As a material of the resin substrate, cycloolefin polymer and polyimide are preferable. The thickness of the resin substrate is preferably 5 μm to 200. Mu.m, more preferably 10 μm to 100. Mu.m.

The conductive layer may be a conductive layer used for a general circuit wiring or a touch panel wiring. Further, the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and further preferably a copper layer or a silver layer, from the viewpoints of conductivity and wire-alignment property. The substrate may have one conductive layer alone or two or more layers. When there are two or more conductive layers, the conductive layers having different materials are preferably used.

As a material of the conductive layer, a metal and a conductive metal oxide can be given. As the metal, al, zn, cu, fe, ni, cr, mo, ag and Au are exemplified. Examples of the conductive metal Oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide: indium zinc Oxide) and SiO ₂ . In the present invention, "conductivity" means that the volume resistivity is less than 1×10 ⁶ Omega cm. The volume resistivity of the conductive metal oxide is preferably less than 1×10 ⁴ Ωcm。

When the resin pattern is manufactured using a substrate having a plurality of conductive layers, at least one of the plurality of conductive layers preferably contains a conductive metal oxide. The conductive layer is preferably a wiring corresponding to an electrode pattern or a peripheral lead portion of a sensor of a visual recognition portion used in the capacitive touch panel. A preferred embodiment of the conductive layer is described in paragraph 0141 of international publication No. 2018/155193, which is incorporated herein by reference.

As the substrate having the conductive layer, a substrate having at least one of a transparent electrode and a wiring line 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 routing wiring, metal is preferable. Examples of the metal used for the wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and an alloy 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.

For the purpose of protecting the electrode or the like (i.e., at least one of the electrode for a touch panel and the wiring for a touch panel), the electrode protecting film for a touch panel formed using the transfer material according to the present invention is preferably provided so as to cover the electrode or the like directly or via another layer.

Stripping procedure

In the peeling step, the temporary support is peeled from the intermediate layer. The peeling method of the temporary support is not particularly limited. For peeling the temporary support, the same mechanism as the cover film peeling mechanism described in paragraphs 0161 to 0162 of jp 2010-072589 a can be used.

The roughness Ra of the 1 st surface of the intermediate layer, which is the surface of the intermediate layer exposed by peeling the temporary support from the intermediate layer, is 2nm or more. When the roughness Ra of the 1 st surface of the intermediate layer is 2nm or more, the surface slipperiness of the intermediate layer is improved. The preferred range of roughness Ra of the 1 st side of the intermediate layer is described in the above item "intermediate layer".

The static friction coefficient of the surface of the intermediate layer exposed by peeling the temporary support from the intermediate layer, i.e., the 1 st surface of the intermediate layer, is preferably less than 2.0. If the static friction coefficient of the 1 st surface of the intermediate layer is less than 2.0, the surface slipperiness of the intermediate layer is improved. The preferred ranges for the static coefficient of friction of the 1 st side of the intermediate layer are set forth in the "intermediate layer" section above.

The dynamic friction coefficient of the surface of the intermediate layer exposed by peeling the temporary support from the intermediate layer, i.e., the 1 st surface of the intermediate layer, is preferably less than 1.5. If the dynamic friction coefficient of the 1 st surface of the intermediate layer is less than 1.5, the surface slipperiness of the intermediate layer is improved. The preferred range of the dynamic friction coefficient of the 1 st side of the intermediate layer is described in the "intermediate layer" item above.

Pattern forming process

In the pattern forming step, the intermediate layer and the photosensitive layer are subjected to exposure treatment and development treatment to form a pattern. The development process is generally performed after the exposure process.

[ Exposure treatment ]

The exposure process preferably includes pattern exposure of the intermediate layer and the photosensitive layer. The "pattern exposure" refers to exposure in a pattern-like exposure form, that is, in a form in which an exposed portion and a non-exposed portion are present. The positional relationship between the exposed area and the unexposed area in the pattern exposure is not particularly limited, and may be appropriately adjusted. The intermediate layer and the photosensitive layer may be exposed from the side opposite to the side on which the substrate is provided, or may be exposed from the side on which the substrate is provided.

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

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

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

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

As the exposure method, in the case of contact exposure, the exposure method can be appropriately selected and used, and in the case of non-contact exposure, the proximity (proximity) exposure method, the projection exposure method of a lens system or a mirror system, the direct exposure method using an exposure laser, or the like can be appropriately selected and used. In the case of projection exposure by a lens system or a mirror system, an exposure machine having an appropriate lens aperture Number (NA) can be used depending on the required resolving power and focal depth. In the case of the direct exposure method, the photosensitive layer may be directly drawn, or the photosensitive layer may be subjected to reduced projection exposure via a lens. The exposure may be performed not only under the atmosphere but also under reduced pressure or vacuum, and may be performed by interposing a liquid such as water between the light source and the intermediate layer. When the photosensitive layer is exposed using a photomask, the intermediate layer may be exposed by contacting the intermediate layer with the photomask, or the intermediate layer and the photosensitive layer may be exposed by contacting the photomask close to the intermediate layer without contacting the intermediate layer with the photomask. The exposure treatment preferably includes exposing the intermediate layer and the photosensitive layer by bringing the intermediate layer into contact with a photomask.

[ development treatment ]

The development can be performed using a developer. As the developer, for example, a known developer such as the developer described in japanese unexamined patent publication No. 5-72724 can be used. As the developer, an aqueous alkali developer containing a compound having pka=7 to 13 at a concentration of 0.05mol/L to 5mol/L is preferable. The developer may contain a water-soluble organic solvent and/or a surfactant. Examples of the basic compound that can be contained in the basic aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyl trimethylammonium hydroxide). The developer described in paragraph 0194 of International publication No. 2015/093271 is also preferably used. Examples of the development method preferably used include the development method described in paragraph 0195 of international publication No. 2015/093271.

The development method is not particularly limited, and may be any of spin-on immersion development (puddle development), spray development (shower development), spray and spin development, and dip development. The shower development is a development process in which a developing solution is sprayed onto the exposed photosensitive layer to remove the exposed portion or the non-exposed portion. Preferably, after development, a cleaning agent is sprayed and sprayed, and the development residue is removed while wiping with a brush. The liquid temperature of the developer is not particularly limited, but is preferably 20 to 40 ℃.

Peeling off of protective film

When the transfer material includes a protective film, the method of manufacturing the laminate preferably includes a step of peeling the protective film from the transfer material. The method of peeling the protective film is not limited, and a known method can be applied.

Post-exposure Process and post-baking Process

The method for manufacturing a laminate according to an embodiment of the present invention may include a step of exposing a pattern obtained in the patterning step (post-exposure step) and/or a step of heating a pattern obtained in the patterning step (post-baking step). When the method for producing the laminate includes both the post-exposure step and the post-baking step, it is preferable to perform post-baking after the post-exposure step. The exposure amount of the post-exposure is preferably 100mJ/cm ² ～5，000mJ/cm ² More preferably 200mJ/cm ² ～3，000mJ/cm ² . The post-baking temperature is preferably 80 to 250 ℃, more preferably 90 to 160 ℃. The post-baking time is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.

Other procedures

The method for producing a laminate according to an embodiment of the present invention may include any steps other than the above steps. For example, the steps described in the following method for manufacturing a circuit wiring or method for manufacturing a touch panel may be used, but the present invention is not limited to these steps.

Use

The laminate produced by the method for producing a laminate according to an embodiment of the present invention can be applied to various devices. Examples of the device including the laminate include an input device, preferably a touch panel, and more preferably a capacitive touch panel. The input device can be applied to a display device such as an organic electroluminescence display device or a liquid crystal display device. When the laminate is applied to a touch panel, the formed pattern is preferably used as a protective film for an electrode for a touch panel or a wiring for a touch panel. That is, the transfer material according to the present invention is preferably used for forming an electrode protective film for a touch panel or a wiring for a touch panel.

< method for producing Circuit Wiring >

The method for manufacturing a circuit wiring according to an embodiment of the present invention includes the following steps in order: bonding a transfer material comprising a temporary support, an intermediate layer in contact with the temporary support, and a photosensitive layer in this order to a substrate, and disposing the photosensitive layer, the intermediate layer, and the temporary support in this order on the substrate (i.e., a "bonding step"); peeling the temporary support from the intermediate layer (i.e., a "peeling step"); performing an exposure process and a development process on the intermediate layer and the photosensitive layer to form a pattern (i.e., a "pattern forming step"); and etching the substrate in a region where the pattern is not arranged (hereinafter, sometimes referred to as an "etching step"), wherein the roughness Ra of the surface of the intermediate layer exposed by peeling the temporary support from the intermediate layer is 2nm or more. Hereinafter, each step included in the method for manufacturing a circuit wiring will be described, but unless otherwise mentioned, the description of each step included in the method for manufacturing a laminate is also applicable to each step included in the method for manufacturing a circuit wiring.

Etching Process

In the etching step, the substrate in the region where the pattern is not arranged is subjected to etching treatment. That is, in the etching step, the pattern formed by the photosensitive layer is used as a resist to perform etching treatment. As the etching treatment method, known methods can be applied, and examples thereof include the methods described in paragraphs 0209 to 0210 of japanese patent application laid-open publication No. 2017-120435, the methods described in paragraphs 0048 to 0054 of japanese patent application laid-open publication No. 2010-152155, wet etching methods in an etching solution, and dry etching methods by plasma etching or the like.

The etching liquid used in the wet etching may be an acidic or alkaline etching liquid appropriately selected according to the object to be etched. Examples of the acidic etching solution include aqueous solutions of acidic components alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, fluoric acid, oxalic acid and phosphoric acid, and aqueous solutions of mixed acidic components and salts selected from ferric chloride, ammonium fluoride and potassium permanganate. The acidic component may be a component obtained by combining a plurality of acidic components. Examples of the alkaline etching liquid include an aqueous solution of an alkali component alone selected from sodium hydroxide, potassium hydroxide, ammonia, an organic amine and a salt of an organic amine (tetramethylammonium hydroxide, etc.), and a mixed aqueous solution of an alkali component and a salt (potassium permanganate, etc.). 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 a residual pattern (hereinafter, sometimes referred to as "removing step"). The removal step is preferably performed after the etching step. The method for removing the residual pattern is not particularly limited, and a method for removing by chemical treatment is exemplified, and a method for removing by using a removing liquid is preferable. The method of removing the residual pattern includes immersing the substrate having the residual pattern in a removing liquid under stirring for 1 to 30 minutes, and the liquid temperature of the removing liquid is preferably 30 to 80 ℃, more preferably 50 to 80 ℃.

Examples of the removing liquid include a removing liquid obtained by dissolving an inorganic base component or an organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic alkali component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. The liquid may be removed by a known method such as spraying, sprinkling, or spin-coating immersion.

Other procedures

The method for manufacturing a circuit wiring according to an embodiment of the present invention may include any steps other than the above steps. For example, the following steps may be mentioned, but the present invention is not limited to these steps. Further, examples of the exposure step, the development step, and other steps which can be applied to the method for producing a circuit wiring include the steps described in paragraphs 0035 to 0051 of JP 2006-23696A. Examples of the other steps include, but are not limited to, a step of reducing the reflectance of visible light described in paragraph 0172 of international publication No. 2019/022089, a step of forming a new conductive layer on an insulating film described in paragraph 0173 of international publication No. 2019/022089, and the like.

[ procedure for reducing visible ray reflectance ]

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 visible ray reflectance of a part or all of the plurality of conductive layers included in the substrate. As the treatment for reducing the reflectance of visible light, an oxidation treatment is given. When the substrate has a conductive layer containing copper, the conductive layer is blackened by oxidizing copper to form copper oxide, whereby the visible ray reflectivity 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, and the contents described in these publications are incorporated herein by reference.

[ step of Forming an insulating film, step of Forming a New 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 further 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. The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film may be used. Further, an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive material. The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern can be formed by photolithography using a photosensitive material having conductivity.

In the method for manufacturing a circuit wiring according to an embodiment of the present invention, it is preferable that a substrate having a plurality of conductive layers on both surfaces of the substrate is used, and a circuit is formed sequentially or simultaneously with respect to the conductive layers formed on both surfaces of the substrate. With this configuration, a circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the substrate and the second conductive pattern is formed on the other surface can be formed. Further, it is also preferable to form the circuit wiring for the touch panel in such a configuration from both surfaces of the substrate in a roll-to-roll manner.

Use of Circuit Wiring

The circuit wiring manufactured by the method for manufacturing a circuit wiring according to an embodiment of the present invention can be applied to various devices. Examples of the device having the circuit wiring manufactured by the above manufacturing method include an input device, preferably a touch panel, and more preferably a capacitive touch panel. The input device can be applied to a display device such as an organic EL display device or a liquid crystal display device.

(method for manufacturing touch Panel)

The method for manufacturing a touch panel according to an embodiment of the present invention sequentially includes the steps of: bonding a transfer material comprising a temporary support, an intermediate layer in contact with the temporary support, and a photosensitive layer in this order to a substrate, and disposing the photosensitive layer, the intermediate layer, and the temporary support in this order on the substrate (i.e., a "bonding step"); peeling the temporary support from the intermediate layer (i.e., a "peeling step"); performing an exposure process and a development process on the intermediate layer and the photosensitive layer to form a pattern (i.e., a "pattern forming step"); and etching the substrate in the region where the pattern is not arranged (i.e., an "etching step"), wherein the roughness Ra of the surface of the intermediate layer exposed by peeling the temporary support from the intermediate layer is 2nm or more.

The specific embodiments of each step in the method for manufacturing a touch panel, the order in which each step is performed, and the like are the same as those described in the above-described items of "method for manufacturing a laminate" and "method for manufacturing a circuit wiring". The method for manufacturing a touch panel may be a known method for manufacturing a touch panel, except that the wiring for a touch panel is formed by the above method. The method for manufacturing the touch panel may include any process (other process) other than the above.

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

By the above method for manufacturing a touch panel, a touch panel having at least wiring for a touch panel can be manufactured. The touch panel preferably has a transparent substrate, electrodes, and an insulating layer or a protective layer. As a detection method in the touch panel, a known method such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method can be given. Among them, the electrostatic capacitance system is preferable.

Examples of the Touch panel type include a so-called in-cell type (for example, the contents described in fig. 5, 6, 7, and 8 of japanese patent application laid-open No. 2012-517051), a so-called out-of-cell type (for example, the contents described in fig. 19 of japanese patent application laid-open No. 2013-168125, the contents described in fig. 1 and 5 of japanese patent application laid-open No. 2012-89102), an OGS (One Glass Solution: monolithic glass Touch type), a TOL (for example, the contents described in fig. 2 of japanese patent application laid-open No. 2013-54727), various external types (out-cell type) (so-called GG, G1/G2, GFF, GF2, GF1, G1F, and the like), and other configurations (for example, the contents described in fig. 6 of japanese patent application laid-open No. 2013-164871). Examples of the touch panel include those described in paragraph 0229 of japanese patent application laid-open publication No. 2017-120435.

Examples

Hereinafter, embodiments of the present invention will be described in further detail with reference to examples. The materials, amounts used, proportions, treatment contents, treatment steps and the like shown in the following examples can be appropriately modified without departing from the gist of the embodiment of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass references. In the following examples, the weight average molecular weight of the resin was determined by conversion to polystyrene by Gel Permeation Chromatography (GPC). The theoretical acid value was used as the acid value.

< temporary support >

A temporary support shown in the following table was prepared.

TABLE 1

(temporary support S-1)

The temporary support S-1 is LUMIRROR 16Q62 manufactured by Toray Industries, inc.

(temporary support S-2)

Polyethylene was melt-extruded and laminated on a polyethylene terephthalate (PET) film having a thickness of 16 μm so that the thickness of the polyethylene became 10 μm. In lamination, a matte roll having a surface roughness Ra of 0.1 μm was pressed against the polyethylene layer. Through the above steps, a PET film with a matte polyethylene was produced as a temporary support S-2. The roughness Ra of the 1 st surface of the temporary support S-2 shown in Table L is a value measured on the surface of the polyethylene layer.

(temporary support S-3)

The temporary support S-3 was obtained by a method according to the method for producing the temporary support S-2, except that the surface roughness Ra of the matte roll was changed to 0.2. Mu.m. The roughness Ra of the 1 st surface of the temporary support S-3 shown in Table 1 is a value measured on the surface of the polyethylene layer.

(temporary support S-4)

Temporary support S-4 is a film type S manufactured by KAISEI matt co., ltd.

(temporary support S-5)

Temporary support S-5 is KAISEI matt co., ltd.

< preparation of photosensitive resin composition >

The components shown in the following table were mixed to prepare a photosensitive resin composition. In table 2, the unit of the blending amount of the components is parts by mass.

TABLE 2

(Polymer)

A-1: a composition comprising 30% by mass of Polymer A-1 produced by the method described below

A-2: a composition comprising 30% by mass of Polymer A-2 produced by the method described below

〔A-1〕

A composition containing 30% by mass of polymer A-1 was obtained by the following method. In the following methods, the following abbreviations represent the following compounds, respectively.

St: styrene (FUJIFILM Wako Pure Chemical Corporation manufacture)

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

MMA: methyl methacrylate (FUJIFILM Wako Pure Chemical Corporation manufacture)

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

PGMEA: propylene glycol monomethyl ether acetate

PGMEA (116.5 parts by mass) was placed in a 3-neck flask, and the temperature was raised to 90 ℃ under a nitrogen atmosphere. While maintaining the liquid temperature in the 3-neck flask at 90.+ -. 2 ℃, a mixture of St (52.0 parts by mass), MMA (19.0 parts by mass), MAA (29.0 parts by mass), V-601 (4.0 parts by mass) and PGMEA (116.5 parts by mass) was added dropwise to the 3-neck flask over 2 hours. After completion of the dropwise addition, the mixed solution was stirred for 2 hours while maintaining the liquid temperature at 90.+ -. 2 ℃ to thereby obtain a composition comprising 30% by mass of polymer A-1. The properties of polymer A-1 are shown in the following table.

〔A-2〕

A composition containing 30% by mass of Polymer A-2 was obtained by a method according to the method of synthesizing Polymer A-1, except that the amount of V-601 added was changed to 12.0 parts by mass. The properties of polymer A-2 are shown in the following table.

TABLE 3

Polymer	A-1	A-2
			Acid value	189mgKOH/g	189mgKOH/g
Molecular weight	60000	20000
			Glass transition temperature Tg	131℃	131℃

(ethylenically unsaturated Compound)

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

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

B-3: sartomer SR-454 (made by epoxy trimethylolpropane triacrylate, arkema S.A.)

(photopolymerization initiator)

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

(sensitizer)

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

(pigment)

LCV (colorless crystal violet, tokyo Chemical Industry co., ltd. Manufactured, pigment developed by free radical)

(chain transfer agent)

N-phenylglycine (Tokyo Chemical Industry co., ltd. & gt)

(antirust agent)

CBT-1 (carboxybenzotriazole, manufactured by Johoku Chemical Co., ltd.)

(polymerization inhibitor)

TDP-G (phenothiazine, kawaguchi Chemical Industry Company, manufactured by Limited)

(antioxidant)

Phenanthrone (Tokyo Chemical Industry Co., ltd.)

(surfactant)

MEGAFACE F-552 (fluorine-based surfactant, manufactured by DIC Corporation)

(solvent)

Methyl ethyl ketone (SANKYO chemistry co., ltd.)

PGMEA (propylene glycol monomethyl ether acetate, manufactured by SHOWA DENKO k.k.)

< preparation of composition for intermediate layer >

The components shown in the following table were mixed and filtered through a polytetrafluoroethylene filter having a pore size of 5.0 μm, to prepare a composition for an intermediate layer. In table 4, the unit of the blending amount of the components is parts by mass.

TABLE 4

(Water-soluble resin)

PVA-105 (polyvinyl alcohol, manufactured by KURARAY CO., LTD.)

PVA-117 (polyvinyl alcohol, manufactured by KURARAY CO., LTD.)

PVA-205 (polyvinyl alcohol, manufactured by KURARAY CO., LTD.)

PVA-217 (polyvinyl alcohol, manufactured by KURARAY CO., LTD.)

PVP-K30 (polyvinylpyrrolidone K-30,NIPPON SHOKUBAI CO, LTD.)

PVP-K90 (polyvinylpyrrolidone K-90,NIPPON SHOKUBAI CO, LTD. Manufactured)

Metolose 60SH-03 (hydroxypropyl methylcellulose, shin-Etsu Chemical Co., ltd.)

(surfactant)

MEGAFACE F-444 (fluorine-based surfactant, manufactured by DIC Corporation)

(particles)

SNOWTEX O (water-dispersible silica sol, manufactured by Nissan Chemical Corporation) with a solid content of 20 mass%

(solvent)

Methanol (Mitsubishi Chemical Corporation manufacture)

Example 1 ]

(production of transfer Material)

Composition C-1 for an intermediate layer was applied to the polyethylene layer of the temporary support S-2 so that the dry film thickness became 1.0. Mu.m, and dried in an oven at 100℃for 2 minutes to prepare an intermediate layer. The photosensitive layer was produced by applying the photosensitive resin composition P-1 to the intermediate layer using a slit nozzle so that the dry film thickness became 3.0. Mu.m, and drying it in an oven at 100℃for 2 minutes. A transfer material was produced by laminating a polypropylene film (TORAYFAN#30-2500H, 26 μm thick, manufactured by Toray Industries, inc.) as a protective film on the photosensitive layer.

(production of PET substrate with copper layer)

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

(production of resin Pattern)

After the protective film was peeled off, the transfer material was laminated on a copper-layer-equipped PET substrate under lamination conditions of an inline pressure of 0.6MPa and a line speed (lamination speed) of 3.6 m/min. The temporary support is peeled off. The exposed intermediate layer was brought into contact with a glass mask having a line width of 3 to 20 μm and a space pattern (Duty ratio 1:1) while adjusting the exposure position (alignment), and the photosensitive layer was exposed via an extra-high pressure mercury lamp for mask, and then left to stand for 30 minutes and developed to form a resin pattern. The development was 40 seconds spray development using a 1.0 mass% aqueous sodium carbonate solution at 28 ℃. Through the above steps, a laminate including a resin pattern was obtained.

(production of Circuit Wiring Pattern)

A circuit wiring pattern was produced by performing resist stripping using a copper etching solution (Cu-02,KANTO CHEMICAL CO, inc.) at 23 ℃ for 30 seconds Zhong Shike on the laminate including the resin pattern, and using a 4 mass% sodium hydroxide solution. The circuit wiring pattern obtained in example 1 was observed under a microscope, and as a result, the circuit wiring pattern was free from peeling and missing, and was a complete pattern.

< examples 2 to 10 and comparative examples 1 to 2>

The transfer material, the copper-layer-equipped PET substrate, the resin pattern, and the circuit wiring pattern were produced by the method according to example 1, except that the types of the temporary support, the intermediate layer composition, and the photosensitive resin composition were changed as appropriate according to the descriptions in table 5.

< coefficient of static friction and coefficient of dynamic friction >

After the protective film was peeled off, the transfer material was laminated on a copper-layer-equipped PET substrate under lamination conditions of an inline pressure of 0.6MPa and a line speed (lamination speed) of 0.5 m/min. The photosensitive layer, the intermediate layer, and the temporary support are sequentially disposed on the copper layer of the copper-clad PET substrate by laminating the transfer material on the copper-clad PET substrate. Stripping the temporary support to separate the exposed intermediate layer from the transparent sodium glass having a thickness of 5mm ) And (3) contact. Using a Tensilon Universal Material tester (RTF 1210, A&D Company, limited) and plastic coefficient of friction clamps (J-PZ 2-50N, A)&D Company, limited) by the plastic-film and sheet coefficient of friction test method (JTS K7125:1999 The static friction coefficient and the dynamic friction coefficient were measured. The test conditions are shown below, and the measurement results are shown in table 5.

Load: 200g of

Contact area: 63mm by 63mm

Test speed: 100 mm/min

< slidability (static Friction) >

The sliding properties were evaluated according to the following criteria based on the coefficient of static friction. The evaluation results are shown in table 5.

5: less than 0.4

4:0.4 or more and less than 0.6

3:0.6 or more and less than 1.0

2:1.0 or more and less than 2.0

1:2.0 or more or not

< slidability (dynamic Friction) >

The sliding properties were evaluated according to the following criteria based on the coefficient of dynamic friction. The evaluation results are shown in table 5.

5: less than 0.3

4:0.3 or more and less than 0.45

3:0.45 or more and less than 0.75

2:0.75 or more and less than 1.5

1:1.5 or more or not

< linearity >

After the protective film was peeled off, the transfer material was laminated on a copper-layer-equipped PET substrate under lamination conditions of an inline pressure of 0.6MPa and a line speed (lamination speed) of 0.5 m/min. The temporary support was peeled off, and the photosensitive layer of the transfer material was brought into contact with a glass mask having a line-space pattern (Duty ratio=1:1) with a line width of 10 μm. The photosensitive layer was exposed to light including g-rays (436 nm), h-rays (405 nm) and i-rays (365 nm) through a mask by irradiation with an extra-high pressure mercury lamp at a line width of 10 μm and an exposure amount of 10 μm after development of the space pattern. Development was performed after standing for 30 minutes. In the development, a resin pattern was produced by performing 40 seconds of spray development using a 1.0 mass% sodium carbonate aqueous solution at 28 ℃. A laminate including a resin pattern was subjected to resist stripping using a 4 mass% sodium hydroxide solution at 23 ℃ for 30 seconds Zhong Shike using a copper etching solution (Cu-02,KANTO CHEMICAL CO, manufactured by inc.). The line width of the wiring pattern was measured at 100 points, and LWR (i.e., standard deviation of the line width) was calculated. According to LWR, the linearity of the wiring was evaluated according to the following criteria. The evaluation results are shown in table 5. The larger the values of the references 1 to 5 shown below, the more excellent the linearity of the wiring pattern.

5: less than 15Onm

4:150nm or more and less than 200nm

3:200nm or more and less than 300nm

2:300nm or more and less than 500nm

1:500nm or more

TABLE 5

Table 5 shows that the slidability (static friction) in examples 1 to 10 is more excellent than the slidability (static friction) in comparative examples 1 to 2. Table 5 shows that the slidability (dynamic friction) in examples 1 to 10 is more excellent than the slidability (dynamic friction) in comparative examples 1 to 2.

The disclosure of japanese patent application 2020-217656 filed on 12 months and 25 days 2020 is incorporated by reference in its entirety into the present specification.

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

Claims

1. A transfer material comprising, in order, a temporary support, an intermediate layer in contact with the temporary support, and a photosensitive layer,

the surface roughness Ra of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer is 2nm or more.

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

the surface of the temporary support exposed when the temporary support is peeled from the intermediate layer has a roughness Ra of 2nm or more.

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

the surface roughness Ra of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer is 1000nm or less.

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

the surface of the temporary support exposed when the temporary support is peeled from the intermediate layer has a roughness Ra of 1000nm or less.

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

the surface of the intermediate layer exposed when the temporary support is peeled off from the intermediate layer has a static friction coefficient of 1.0 or less.

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

the intermediate layer includes a water-soluble resin.

7. The transfer material according to claim 6, wherein,

the water-soluble resin is at least one selected from the group consisting of cellulose derivatives, polyol compounds, alkylene oxide adducts of polyol compounds, polyether compounds, phenol derivatives, and amide compounds.

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

the intermediate layer comprises a surfactant.

9. The transfer material according to any one of claims 1 to 8, wherein,

the photosensitive layer contains a polymerizable compound having 2 or more polymerizable groups.

10. The transfer material according to any one of claims 1 to 8, wherein,

the photosensitive layer includes a polymerizable compound having 2 polymerizable groups and a polymerizable compound having 3 or more polymerizable groups.

11. The transfer material according to claim 9 or 10, wherein,

the polymerizable compound includes an oxyethylene chain.

12. The transfer material according to any one of claims 1 to 11, wherein,

the thickness of the photosensitive layer is 5 μm or less.

13. A method for producing a laminate, comprising the following steps in this order:

attaching a transfer material comprising a temporary support, an intermediate layer in contact with the temporary support, and a photosensitive layer in this order to a substrate, and disposing the photosensitive layer, the intermediate layer, and the temporary support in this order on the substrate;

peeling the temporary support from the intermediate layer; a kind of electronic device with high-pressure air-conditioning system

Exposing and developing the intermediate layer and the photosensitive layer to form a pattern,

the surface roughness Ra of the intermediate layer exposed by peeling the temporary support from the intermediate layer is 2nm or more.

14. The method for producing a laminate according to claim 13, wherein,

the surface of the intermediate layer exposed by peeling the temporary support from the intermediate layer has a roughness Ra of 1000nm or less.

15. The method for producing a laminate according to claim 13 or 14, wherein,

the exposure process includes the following steps: the intermediate layer is exposed to light by contacting the intermediate layer with a photomask.