CN115917430A

CN115917430A - Transfer film and method for manufacturing laminate

Info

Publication number: CN115917430A
Application number: CN202180037878.0A
Authority: CN
Inventors: 霜山达也; 松田知树
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2020-06-01
Filing date: 2021-05-31
Publication date: 2023-04-04
Also published as: JPWO2021246366A1; WO2021246366A1

Abstract

The invention provides a transfer film and a method for manufacturing a laminated body, wherein undercutting is not easy to generate in a pattern formed by a refractive index adjusting layer and a photosensitive composition layer. The transfer film of the present invention comprises a temporary support, a photosensitive composition layer, and a refractive index adjustment layer in this order, wherein the refractive index adjustment layer comprises at least one material selected from the group consisting of metal oxides, compounds having a triazine ring, and compounds having a fluorene skeleton, and a polymer containing a structural unit having a (meth) acryloyl group.

Description

Transfer film and method for manufacturing laminate

Technical Field

The present invention relates to a transfer film and a method for manufacturing a laminate.

Background

Since the number of steps for obtaining a predetermined pattern is small, the following method is widely used: a photosensitive composition layer is disposed on an arbitrary substrate using a transfer film, and the photosensitive composition layer is exposed to light through a mask and then developed.

For example, patent document 1 discloses a transfer film including a second transparent resin layer that functions as a refractive index adjustment layer. The second transparent resin layer described in the example column of patent document 1 contains a copolymer of methacrylic acid/allyl methacrylate.

Prior art documents

Patent document

Patent document 1: international publication No. 2017/057348

Disclosure of Invention

Technical problem to be solved by the invention

The present inventors evaluated the characteristics of the transfer film including the refractive index adjustment layer described in patent document 1, and as a result, they confirmed that undercuts were generated in the vicinity of the edge of the pattern obtained by transferring the refractive index adjustment layer and the photosensitive composition layer in the transfer film onto the object to be transferred and subjecting these to the exposure treatment and the development treatment. The undercut refers to a crack of the obtained pattern caused by cohesive failure occurring from the side surface near the transferred body toward the central portion, and the occurrence of such undercut causes pattern lifting. If pattern floating occurs, various components (e.g., sweat) may penetrate from the side to the inside of the pattern, for example, which may affect the conductive layer protected by the pattern.

In view of the above circumstances, an object of the present invention is to provide a transfer film in which undercuts are not easily generated in a pattern formed by a refractive index adjustment layer and a photosensitive composition layer.

Another object of the present invention is to provide a method for manufacturing a laminate using the transfer film.

Means for solving the technical problems

As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by the following configurations.

(1) A transfer film comprising a temporary support, a photosensitive composition layer, and a refractive index adjustment layer in this order,

the refractive index adjustment layer contains at least one material selected from a metal oxide, a compound having a triazine ring, and a compound having a fluorene skeleton, and a polymer containing a structural unit having a (meth) acryloyl group.

(2) The transfer sheet according to (1), wherein,

the content of (meth) acryloyl groups in the polymer is 2.50mmol/g or more.

(3) The transfer sheet according to (1) or (2), wherein,

the polymer also contains structural units having acid groups.

(4) The transfer film according to any one of (1) to (3), wherein the polymer has an acid value of 60mgKOH/g or more.

(5) The transfer film according to any one of (1) to (4),

the refractive index adjustment layer has a thickness of 500nm or less.

(6) The transfer film according to any one of (1) to (5),

the refractive index adjustment layer contains at least one selected from zirconia and titania.

(7) The transfer film according to any one of (1) to (6), wherein a content of the material is 50% by mass or more with respect to a total mass of the refractive index adjustment layer.

(8) The transfer film according to any one of (1) to (7),

the refractive index adjustment layer has a refractive index of 1.60 or more.

(9) The transfer film according to any one of (1) to (8),

the photosensitive composition layer contains a binder polymer, a polymerizable compound, and a polymerization initiator.

(10) The transfer film according to (9), wherein,

the polymerization initiator contains at least one selected from an oxime ester compound and a phosphine oxide compound.

(11) The transfer film according to any one of (1) to (10),

the photosensitive composition layer is used for forming an electrode protection film for a touch panel.

(12) A method of manufacturing a laminate, comprising:

a bonding step of bonding a substrate with a conductive layer, which has a substrate and a conductive layer disposed on the substrate, and the transfer film according to any one of (1) to (11) to obtain a substrate with a photosensitive composition layer, which has the substrate, the conductive layer, the refractive index adjustment layer, the photosensitive composition layer, and the temporary support in this order;

an exposure step of performing pattern exposure on the refractive index adjustment layer and the photosensitive composition layer; and

a developing step of developing the exposed refractive index adjusting layer and the photosensitive composition layer to form a pattern,

the method for producing a laminate further comprises a peeling step of peeling the temporary support from the substrate having the photosensitive composition layer between the bonding step and the exposure step or between the exposure step and the development step.

(13) The method for producing a laminate according to item (12), wherein,

the substrate with a conductive layer is a substrate having at least one of an electrode for a touch panel and a wiring for a touch panel.

Effects of the invention

According to the present invention, it is possible to provide a transfer film in which undercutting is less likely to occur in a pattern formed of a refractive index adjustment layer and a photosensitive composition layer.

Further, according to the present invention, a method for manufacturing a laminate using the transfer film can be provided.

Detailed Description

The present invention will be described in detail below.

In the present specification, a numerical range expressed by "to" means a range in which numerical values before and after "to" are included as a lower limit value and an upper limit value.

In the present specification, in the numerical ranges recited in the stepwise manner, the upper limit value or the lower limit value recited in a certain numerical range may be replaced with the upper limit value or the lower limit value recited in another stepwise manner. In the numerical ranges described in the present specification, the upper limit or the lower limit described in a certain numerical range may be replaced with the values shown in the examples.

In the present specification, the term "step" includes not only an independent step but also a step that can achieve the intended purpose of the step even when the step is not clearly distinguished from other steps.

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

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

In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values in terms of polystyrene as a standard substance measured as follows: TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation) was used as a column, THF (tetrahydrofuran) was used as an eluent, a differential refractometer was used as a detector, polystyrene was used as a standard substance, and the measurement was carried out by a Gel Permeation Chromatography (GPC) analysis apparatus.

In the present specification, the molecular weight of the compound having a molecular weight distribution is a weight average molecular weight (Mw) unless otherwise specified.

In the present specification, unless otherwise specified, the content of the metal element is a value measured by an Inductively Coupled Plasma (ICP) spectroscopic analyzer.

In this specification, unless otherwise specified, the refractive index is a value measured with an ellipsometer at a wavelength of 550 nm.

In the present specification, unless otherwise specified, the hue is a value measured by a color difference meter (CR-221, manufactured by minolta Co., ltd.).

In the present specification, "(meth) acrylic acid" is a concept including both acrylic acid and methacrylic acid, and "(meth) acryl" is a concept including both acryl and methacryl.

The transfer film of the present invention is characterized in that the refractive index adjustment layer contains a polymer containing a structural unit having a (meth) acryloyl group. When the refractive index adjustment layer contains the polymer, polymerization proceeds between the (meth) acryloyl groups, and a crosslinked structure is formed in the refractive index adjustment layer, and as a result, a desired effect can be obtained.

The transfer film of the present invention includes a temporary support, a photosensitive composition layer, and a refractive index adjustment layer containing a predetermined component in this order. The photosensitive composition layer and the refractive index adjustment layer may be in direct contact, or another layer may be disposed between the photosensitive composition layer and the refractive index adjustment layer. Among them, the photosensitive composition layer and the refractive index adjusting layer are preferably in direct contact.

Hereinafter, each member constituting the transfer film will be described in detail.

Hereinafter, the refractive index adjustment layer, which is a characteristic point of the present invention, will be described in detail, and then the temporary support and the photosensitive composition layer will be described in detail.

< refractive index adjusting layer >

The transfer film has a refractive index adjustment layer. The refractive index adjustment layer is a layer disposed on the photosensitive composition layer.

The refractive index adjustment layer contains at least one material (hereinafter, also referred to as "specific material") selected from a metal oxide, a compound having a triazine ring, and a compound having a fluorene skeleton. The material is a material for adjusting the refractive index of the refractive index adjustment layer.

The kind of the metal oxide is not particularly limited, and known metal oxides can be mentioned. The metal in the metal oxide includes semimetals such As B, si, ge, as, sb and Te.

Examples of the metal oxide include zirconium oxide, titanium oxide, tin oxide, zinc oxide, indium tin oxide, indium oxide, aluminum oxide, and yttrium oxide.

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

The metal oxide is preferably in the form of particles.

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

The average primary particle size of the particles is calculated by measuring the particle sizes of arbitrary 200 particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particles is not spherical, the longest side is defined as the particle diameter.

Examples of commercially available products of the metal oxide particles include calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F04), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F74), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F75), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F76), zirconia particles (NanoUse OZ-S30M, manufactured by Nissan Chemical Corporation), and zirconia particles (NanoUse OZ-S30K, manufactured by Nissan Chemical Corporation).

Examples of the compound having a triazine ring include polymers having a triazine ring in a structural unit, and examples include compounds having a structural unit represented by the following formula (X).

[ chemical formula 1]

Wherein Ar represents a 2-valent group containing at least 1 selected from an aromatic ring (having 6 to 20 carbon atoms, for example) and a heterocyclic ring (having 5 to 20 carbon atoms, for example).

X independently represent NR ¹ 。R ¹ Each independently represents a hydrogen atom, an alkyl group (having, for example, 1 to 20 carbon atoms), an alkoxy group (having, for example, 1 to 20 carbon atoms), an aryl group (having, for example, 6 to 20 carbon atoms), or an aralkyl group (having, for example, 7 to 20 carbon atoms). Each of the plurality of xs may be the same or different.

Specifically, hyperbranched polymers having triazine rings are preferable, and are available, for example, as HYPERTECH series (manufactured by Nissan Chemical Corporation, product name).

As the compound having a fluorene skeleton, a compound having a 9,9-bis [4-2- (meth) acryloyloxyethoxyphenyl ] fluorene skeleton is preferable. The above-mentioned compounds may be modified by a (poly) oxyethylene group or a (poly) oxypropylene group. These are available, for example, as FA-0200 (product name, manufactured by Osaka Gas Chemicals Co., ltd.). Furthermore, the epoxy modification can be performed by epoxy acrylate. These are available, for example, as commercially available products GA5000 and EG200 (product name, manufactured by Osaka GAs Chemicals co., ltd.).

The specific material may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The content of the specific material in the refractive index adjustment layer is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, based on the total mass of the refractive index adjustment layer. The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 90% by mass or less.

The refractive index adjustment layer contains a polymer (hereinafter, also referred to as a "specific polymer") containing a structural unit having a (meth) acryloyl group.

The structure of the structural unit having a (meth) acryloyl group (hereinafter, also referred to as "specific unit") is not particularly limited as long as it has a (meth) acryloyl group.

As the specific unit, a structural unit represented by formula (1) is preferable.

[ chemical formula 2]

R ¹ Represents a hydrogen atom, a halogen atom or an alkyl group.

L ¹ Represents a single bond or a 2-valent linking group. <xnotran> 2 , , -O-, -CO-, -COO-, -S-, -NH-, CS-, -SO-, -SO </xnotran> ₂ A 2-valent hydrocarbon group which may have a substituent (e.g., alkylene group, cycloalkylene group, alkenylene group, arylene group, etc.), and a linking group formed by linking a plurality of these groups (e.g., -COO-2-valent hydrocarbon group which may have a substituent-O-).

Examples of the substituent that the 2-valent hydrocarbon group may have include a halogen atom, a hydroxyl group, an amino group, a cyano group, a nitro group, a carboxylic acid group, and a sulfonic acid group.

X ¹ Represents a (meth) acryloyl group.

The content of the specific unit in the specific polymer is not particularly limited, and is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more, based on all the structural units of the specific polymer, from the viewpoint that cuts are less likely to occur in a film formed of the refractive index adjustment layer and the photosensitive composition layer (hereinafter, also referred to as "the aspect in which the effect of the present invention is more excellent"). The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less.

The specific polymer may have other structural units than the specific unit.

Examples of the other structural unit include a structural unit having an acid group. When the specific polymer contains a structural unit having an acid group, development residue is less likely to remain.

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

As the structural unit having an acid group, a structural unit represented by formula (2) is preferable.

[ chemical formula 3]

R ² Represents a hydrogen atom, a halogen atom or an alkyl group.

L ² Represents a single bond or a 2-valent linking group. <xnotran> 2 , , -O-, -CO-, -COO-, -S-, -NH-, CS-, -SO-, -SO </xnotran> ₂ A 2-valent hydrocarbon group which may have a substituent (e.g., alkylene, cycloalkylene, alkenylene, arylene, etc.), and a linking group in which a plurality of these groups are linked (e.g., -COO-2-valent hydrocarbon group which may have a substituent).

Examples of the substituent which the 2-valent hydrocarbon group may have include a halogen atom, a hydroxyl group, an amino group, a cyano group, a nitro group, a carboxylic acid group, and a sulfonic acid group.

X ² Represents an acid group.

The content of the structural unit having an acid group in the specific polymer is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 13% by mass or more, based on the whole structural units of the specific polymer, from the viewpoint that residue is not easily generated after the development treatment. The upper limit is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, from the viewpoint of further improving the effects of the present invention.

The specific polymer may have, as another structural unit, a structural unit having an alkyl group, which is different from the specific unit and the unit having an acid group.

As the structural unit having an alkyl group, a structural unit represented by formula (3) is preferable.

[ chemical formula 4]

R ³ Represents a hydrogen atom, a halogen atom or an alkyl group.

L ³ Represents a single bond or a 2-valent linking group. <xnotran> 2 , , -O-, -CO-, -COO-, -S-, -NH-, CS-, -SO-, -SO </xnotran> ₂ And a plurality of theseThe resulting linker (e.g., -CO-NH-).

X ³ Represents an alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5.

The content of the structural unit having an alkyl group in the specific polymer is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 20% by mass or less, and particularly preferably 10% by mass or less, relative to all the structural units of the specific polymer, from the viewpoint of further improving the effect of the present invention. The lower limit is not particularly limited, and may be 0 mass%.

The content of the (meth) acryloyl group in the specific polymer is not particularly limited, but is usually 2.00mmol/g or more, and from the viewpoint of further improving the effect of the present invention, it is preferably 2.50mmol/g or more, more preferably 3.00mmol/g or more, and still more preferably 3.50mmol/g or more. The upper limit is not particularly limited, but is preferably 6.00mmol/g or less.

As a method of calculating the content of the (meth) acryloyl group described above, first, the mass (g) of the structural unit having a (meth) acryloyl group in the specific polymer 1g is calculated using the content (mass%) of the structural unit having a (meth) acryloyl group with respect to all the structural units of the specific polymer. Specifically, it is calculated by the following equation.

Mass of structural unit =1 (g) × (content (% by mass) of structural unit having a (meth) acryloyl group with respect to all structural units of the specific polymer/100)

Next, the calculated value is divided by the molecular weight of the structural unit having a (meth) acryloyl group, whereby the content (mmol/g) of the above-mentioned (meth) acryloyl group can be calculated.

The acid value of the specific polymer is not particularly limited, but is usually not less than 40mgKOH/g, and is preferably not less than 60mgKOH/g, more preferably not less than 70mgKOH/g, and still more preferably not less than 80mgKOH/g, from the viewpoint that residue is not easily generated after the development treatment. The upper limit is not particularly limited, but is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less.

The weight average molecular weight of the specific polymer is not particularly limited, but is preferably 5000 to 100000, more preferably 8000 to 50000, in view of further improving the effect of the present invention.

The specific polymer may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The content of the specific polymer in the refractive index adjustment layer is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, further preferably 5 to 30% by mass, and particularly preferably 5 to 20% by mass, based on the total mass of the refractive index adjustment layer.

The refractive index adjustment layer may contain other materials than the specific materials and the specific polymers described above.

As the other material, a binder polymer may be mentioned. The binder polymer is not particularly limited, and examples thereof include binder polymers that can be contained in a photosensitive composition layer described later.

Further, as the other material, a polymerizable compound can be exemplified. The polymerizable compound is not particularly limited, and examples thereof include polymerizable compounds that can be contained in a photosensitive composition layer described later.

Further, as the other material, a polymerization initiator may be mentioned. The polymerization initiator is not particularly limited, and examples thereof include those which can be contained in a photosensitive composition layer described later.

Examples of the other materials include, in addition to the above, heterocyclic compounds, surfactants, and hydrogen-donating compounds described later.

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

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

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

The thickness of the refractive index adjustment layer was calculated as an average value at arbitrary 5 points measured by cross-sectional observation based on a Scanning Electron Microscope (SEM).

< temporary support >

The transfer film has a temporary support.

The temporary support is a member for supporting the photosensitive composition layer described later, and is finally removed by a peeling treatment.

The temporary support may have a single-layer structure or a multilayer structure.

The temporary support is preferably a film, more preferably a resin film. As the temporary support, a film which is flexible and does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and heat is preferable.

Examples of the film include a polyethylene terephthalate film (e.g., a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film.

Among them, a polyethylene terephthalate film is preferable as the temporary support.

Further, the film used as the temporary support is preferably free from deformation such as wrinkles and scratches.

The temporary support is preferably high in transparency from the viewpoint of enabling pattern exposure through the temporary support, and the transmittance at 365nm is preferably 60% or more, more preferably 70% or more.

The temporary support is preferably low in haze from the viewpoint of pattern formability when pattern exposure is performed through the temporary support and transparency of the temporary support. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and further preferably 0.1% or less.

In view of pattern formability in pattern exposure through the temporary support and transparency of the temporary support, the number of fine particles, foreign substances, and defects contained in the temporary support is preferably small. The number of particles, foreign matters and defects having a diameter of 1 μm or more in the temporary support is preferably 50/10 mm ² Hereinafter, more preferably 10/10 mm ² Hereinafter, 3/10 mm is more preferable ² Hereinafter, particularly preferably 0 piece/10 mm ² 。

The thickness of the temporary support is not particularly limited, but is preferably 5 to 200. Mu.m, more preferably 10 to 150. Mu.m, and still more preferably 10 to 50 μm, from the viewpoint of easy handling and versatility.

The thickness of the temporary support was calculated as an average value at any 5 points measured by cross-sectional observation based on SEM (Scanning Electron Microscope).

Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 μm.

Preferable examples of the temporary support include paragraphs [0017] to [0018] in Japanese patent laid-open No. 2014-085643, paragraphs [0019] to [0026] in Japanese patent laid-open No. 2016-027363, paragraphs [0041] to [0057] in International publication No. 2012/081680, and paragraphs [0029] to [0040] in International publication No. 2018/179370, the contents of which are incorporated herein.

Commercially available temporary supports include Lumirror 16KS40, lumirror 16FB40 (made by TORAY INDUSTRIES, INC.), COSMOSHINE A4100, COSMOSHINE A4300, and COSMOSHINE A8300 (made by TOYOBO CO., LTD.).

In order to impart handling properties, a layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support. The lubricant layer may be provided on one surface of the temporary support or on both surfaces. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm.

The thickness of the lubricant layer is preferably 0.05 to 1.0. Mu.m.

< photosensitive composition layer >

The transfer film has a photosensitive composition layer.

The photosensitive composition layer is transferred onto a transfer object, and then exposed and developed, whereby a pattern can be formed on the transfer object.

As the photosensitive composition layer, a known photosensitive composition layer can be used, and a negative type is preferable. The negative photosensitive composition layer is a photosensitive composition layer in which the solubility of an exposed portion in a developer is reduced by exposure. When the photosensitive composition layer is a negative photosensitive composition layer, the pattern formed corresponds to the cured layer.

Hereinafter, the components contained in the photosensitive composition layer (particularly, the negative photosensitive composition layer) will be described in detail.

(adhesive Polymer)

The photosensitive composition layer may include a binder polymer.

Examples of the binder polymer include (meth) acrylic resins, styrene resins, epoxy resins, polyamide epoxy resins, alkyd resins, phenol resins, polyester resins, urethane resins, epoxy acrylate resins obtained by reaction of an epoxy resin with (meth) acrylic acid, and acid-modified epoxy acrylate resins obtained by reaction of an epoxy acrylate resin with an acid anhydride.

As one of preferable embodiments of the binder polymer, a (meth) acrylic resin is mentioned in view of excellent alkali developability and film forming property.

In the present specification, the (meth) acrylic resin refers to a resin having a structural unit derived from a (meth) acrylic compound. The content of the structural unit derived from the (meth) acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more, relative to all the structural units of the (meth) acrylic resin.

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

Examples of the (meth) acrylic compound include (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamides, and (meth) acrylonitriles.

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

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

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

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

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

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

These polymerizable monomers may be used in 1 kind or in combination of 2 or more kinds.

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

Among these, (meth) acrylic resins more preferably contain a structural unit having a carboxyl group, and still more preferably have a structural unit derived from the above (meth) acrylic acid.

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

The (meth) acrylic resin more preferably has a structural unit derived from the above-mentioned alkyl (meth) acrylate.

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

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

Further, as the (meth) acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.

In addition, from the viewpoint of further improving the effects of the present invention, the (meth) acrylic resin preferably has at least one member selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate, and preferably has both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate.

From the viewpoint of further improving the effect of the present invention, the total content of the structural unit derived from methacrylic acid and the structural unit derived from alkyl methacrylate in the (meth) acrylic resin is preferably 40% by mass or more, and more preferably 60% by mass or more, based on all the structural units of the (meth) acrylic resin. The upper limit is not particularly limited, and may be 100 mass% or less, preferably 80 mass% or less.

In addition, from the viewpoint of more excellent effects of the present invention, the (meth) acrylic resin preferably further has at least one selected from a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate and at least one selected from a structural unit derived from acrylic acid and a structural unit derived from an alkyl acrylate.

From the viewpoint of further improving the effect of the present invention, the total content of the structural unit derived from methacrylic acid and the structural unit derived from alkyl methacrylate is preferably 60/40 to 80/20 in terms of a mass ratio to the total content of the structural unit derived from acrylic acid and the structural unit derived from alkyl acrylate.

The (meth) acrylic resin preferably has an ester group at a terminal thereof in view of excellent developability of the photosensitive composition layer after transfer.

In addition, the terminal portion of the (meth) acrylic resin is constituted by a site derived from a polymerization initiator used for synthesis. The (meth) acrylic resin having an ester group at the terminal is synthesized by using a polymerization initiator that generates a radical having an ester group.

In addition, another preferable embodiment of the binder polymer is an alkali-soluble resin.

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

For example, the binder polymer is preferably a binder polymer having an acid value of 60mgKOH/g or more from the viewpoint of developability.

Further, for example, from the viewpoint of facilitating the formation of a strong film by thermal crosslinking with the crosslinking component by heating, the binder polymer is more preferably a resin having a carboxyl group with an acid value of 60mgKOH/g or more (so-called carboxyl group-containing resin), and still more preferably a (meth) acrylic resin having a carboxyl group with an acid value of 60mgKOH/g or more (so-called carboxyl group-containing (meth) acrylic resin).

When the binder polymer is a resin having a carboxyl group, for example, a thermally crosslinkable compound such as a blocked isocyanate compound is added to thermally crosslink the binder polymer, whereby the three-dimensional crosslinking density can be increased. In addition, the moist heat resistance can be improved by dehydrating and hydrophobizing the carboxyl group of the resin having a carboxyl group.

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

For example, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraph [0025] of Japanese patent application laid-open No. 2011-095716, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraphs [0033] to [0052] of Japanese patent application laid-open No. 2010-237589, or the like can be preferably used.

Another preferable embodiment of the binder polymer is a styrene-acrylic acid copolymer.

In the present invention, the styrene-acrylic acid copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic acid compound, and the total content of the structural unit derived from the styrene compound and the structural unit derived from the (meth) acrylic acid compound is preferably 30% by mass or more, and more preferably 50% by mass or more, based on all the structural units of the copolymer.

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

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

From the viewpoint of further improving the effect of the present invention, the binder polymer preferably has an aromatic ring structure, and more preferably contains a structural unit having an aromatic ring structure.

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

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

Further, from the viewpoint of more excellent effects of the present invention, the binder polymer more preferably has a structural unit (structural unit derived from styrene) represented by the following formula (S).

[ chemical formula 5]

When the binder polymer contains a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass, based on all the structural units of the binder polymer, from the viewpoint of further improving the effects of the present invention.

In addition, from the viewpoint of further improving the effects of the present invention, the content of the structural unit having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 60 mol% based on all the structural units of the binder polymer.

In addition, from the viewpoint of further improving the effects of the present invention, the content of the structural unit represented by the formula (S) in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 60 mol% based on all the structural units of the binder polymer.

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

From the viewpoint of further excellence in the effect of the present invention, the binder polymer preferably has an aliphatic hydrocarbon ring structure. That is, the binder polymer preferably contains a structural unit having an aliphatic hydrocarbon ring structure. Among them, the binder polymer more preferably has a ring structure in which 2 or more aliphatic hydrocarbon rings are condensed.

The ring constituting the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure may be a monocyclic ring or a polycyclic ring, and specific examples thereof include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring and an isophorone ring.

Among these, from the viewpoint of more excellent effects of the present invention, a ring obtained by fusing 2 or more aliphatic hydrocarbon rings is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo [5.2.1.0 ] is more preferable ^2，6 ]A decane ring).

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

Further, from the viewpoint of further improving the effects of the present invention, the binder polymer preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[ chemical formula 6]

In the formula (Cy), R ^M Represents a hydrogen atom or a methyl group, R ^Cy Represents a 1-valent group having an aliphatic hydrocarbon ring structure.

R in the formula (Cy) ^M Preferably methyl.

In the formula (Cy), R is more effective ^Cy The aliphatic hydrocarbon ring structure-containing 1-valent group preferably has 5 to 20 carbon atoms, more preferably has 6 to 16 carbon atoms, and still more preferably has 8 to 14 carbon atoms.

Further, from the viewpoint of further improving the effect of the present invention, R of the formula (Cy) ^Cy The aliphatic hydrocarbon ring structure in (2) is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure or an isophorone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and still more preferably a tetrahydrodicyclopentadiene ring structure.

Further, from the viewpoint of further excellent effects of the present invention, R of the formula (Cy) ^Cy The aliphatic hydrocarbon ring structure in (2) is preferably a ring structure obtained by fusing 2 or more aliphatic hydrocarbon rings, and more preferably a ring structure obtained by fusing 2 to 4 aliphatic hydrocarbon rings.

Further, from the viewpoint of further improving the effect of the present invention, R in the formula (Cy) is ^Cy The aliphatic hydrocarbon ring group, which is a group in which an oxygen atom of — C (= O) O — in the formula (Cy) is directly bonded to an aliphatic hydrocarbon ring structure, is preferable, and the cyclohexyl group or the dicyclopentyl group is more preferable, and the dicyclopentyl group is further more preferable.

The binder polymer may have 1 kind of structural unit having an aliphatic hydrocarbon ring structure alone or 2 or more kinds.

When the binder polymer contains a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 70% by mass, based on all the structural units of the binder polymer, from the viewpoint that the effect of the present invention is more excellent.

In addition, from the viewpoint of further improving the effects of the present invention, the content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the binder polymer.

In addition, from the viewpoint of further improving the effects of the present invention, the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the binder polymer.

When the binder polymer contains a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 40 to 75% by mass, based on all the structural units of the binder polymer, from the viewpoint of further improving the effects of the present invention.

In addition, from the viewpoint of further improving the effects of the present invention, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 40 to 60 mol% based on all the structural units of the binder polymer.

In addition, from the viewpoint of further improving the effects of the present invention, the total content of the structural unit represented by the formula (S) and the structural unit represented by the formula (Cy) in the binder polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 40 to 60 mol%, based on all the structural units of the binder polymer.

Further, from the viewpoint of further improving the effects of the present invention, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the adhesive polymer preferably satisfy the relationship represented by the following formula (SCy), more preferably satisfy the following formula (SCy-1), and further preferably satisfy the following formula (SCy-2).

nS/(nS + nCy) is not less than 0.2 and not more than 0.8 (SCy)

nS/(nS + nCy) not less than 0.30 but not more than 0.75 type (SCy-1)

nS/(nS + nCy) not less than 0.40 but not more than 0.70 (SCy-2)

From the viewpoint of more excellent effects of the present invention, the binder polymer preferably contains a structural unit having an acid group.

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

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

[ chemical formula 7]

The binder polymer may contain 1 kind of structural unit having an acid group alone, or may contain 2 or more kinds.

When the binder polymer contains a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass, based on all the structural units of the binder polymer, from the viewpoint that the effect of the present invention is more excellent.

In addition, from the viewpoint of further improving the effects of the present invention, the content of the structural unit having an acid group in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol% based on all the structural units of the binder polymer.

In addition, from the viewpoint of further improving the effect of the present invention, the content of the structural unit derived from (meth) acrylic acid in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol% based on all the structural units of the binder polymer.

From the viewpoint of further excellence in the effect of the present invention, the binder polymer preferably has a reactive group, and more preferably contains a structural unit having a reactive group.

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

In the present invention, "main chain" refers to a relatively longest bonding chain in a molecule of a polymer compound constituting a resin, and "side chain" refers to a group of atoms branched from the main chain.

As the ethylenically unsaturated group, (meth) acryloyl group is preferable, and (meth) acryloyloxy group is more preferable.

Examples of the structural unit having a reactive group include, but are not limited to, those described below.

[ chemical formula 8]

The binder polymer may contain 1 kind of structural unit having a reactive group alone, or may contain 2 or more kinds.

When the binder polymer contains a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 20 to 40% by mass, based on all the structural units of the binder polymer, from the viewpoint that the effect of the present invention is more excellent.

In addition, from the viewpoint of further improving the effect of the present invention, the content of the structural unit having a reactive group in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the binder polymer.

Examples of a method for introducing a reactive group into the binder polymer include a method in which a compound such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, or a carboxylic anhydride is reacted with a functional group such as a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group, or a sulfo group.

Preferred examples of the method for introducing a reactive group into the binder polymer include the following methods: after a polymer having a carboxyl group is synthesized by polymerization, a glycidyl (meth) acrylate is reacted with a part of the carboxyl group of the obtained polymer by polymer reaction, thereby introducing a (meth) acryloyloxy group into the polymer. By this method, a binder polymer having a (meth) acryloyloxy group in a side chain can be obtained.

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

As the binder polymer, the following polymers are preferable from the viewpoint of further excellent effects of the present invention. The content ratios (a to d) of the respective structural units shown below, the weight average molecular weight Mw, and the like can be appropriately changed according to the purpose.

[ chemical formula 9]

In the above formula, a is preferably 20 to 60% by mass, b is preferably 10 to 50% by mass, c is preferably 5 to 25% by mass, and d is preferably 10 to 50% by mass.

[ chemical formula 10]

/>

[ chemical formula 11]

In the above formula, a is preferably 20 to 60% by mass, b is preferably 1 to 20% by mass, c is preferably 5 to 25% by mass, and d is preferably 10 to 50% by mass.

[ chemical formula 12]

In the above formula, a is preferably 1 to 20% by mass, b is preferably 20 to 60% by mass, c is preferably 5 to 25% by mass, and d is preferably 10 to 50% by mass.

[ chemical formula 13]

In the above formula, a is preferably 10 to 60% by mass, b is preferably 10 to 40% by mass, c is preferably 5 to 40% by mass, and d is preferably 0to 30% by mass.

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

The carboxylic anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, and is preferably a cyclic carboxylic anhydride structure.

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

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

[ chemical formula 14]

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

As a group consisting of R ^A1a Examples of the substituent include an alkyl group.

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

n ^1a Represents an integer of 0 or more. At Z ^1a When it represents an alkylene group having 2 to 4 carbon atoms, n ^1a Preferably an integer of 0to 4, more preferably an integer of 0to 2, and still more preferably 0.

n ^1a When an integer of 2 or more is represented, a plurality of R's are present ^A1a May be the same or different. And, there are a plurality of R ^A1a The ring may be formed by bonding to each other, but preferably the ring is formed by not bonding to each other.

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

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

[ chemical formula 15]

[ chemical formula 16]

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

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

The photosensitive composition layer may contain only 1 kind of the polymer X, or may contain 2 or more kinds.

When the photosensitive composition layer contains the polymer X, the content of the polymer X is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, even more preferably 0.5 to 20% by mass, and even more preferably 1 to 20% by mass, based on the total mass of the photosensitive composition layer, from the viewpoint of further improving the effect of the present invention.

From the viewpoint of further improving the effect of the present invention, the weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 50,000, and particularly preferably 20,000 to 30,000.

The acid value of the binder polymer is preferably 10 to 200mgKOH/g, more preferably 60 to 200mgKOH/g, still more preferably 60 to 150mgKOH/g, and particularly preferably 60 to 110mgKOH/g.

The acid value of the adhesive polymer was as follows JIS K0070: 1992.

The photosensitive composition layer may contain only 1 binder polymer, or may contain 2 or more kinds.

From the viewpoint of further improving the effect of the present invention, the content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30to 70% by mass, based on the total mass of the photosensitive composition layer.

The dispersion degree of the binder polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0, from the viewpoint of developability.

(polymerizable Compound)

The photosensitive composition layer may contain a polymerizable compound.

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

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

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

The ethylenically unsaturated compound in the present invention is a compound other than the above-mentioned binder polymer, and the molecular weight is preferably less than 5,000.

As one of preferable embodiments of the polymerizable compound, a compound represented by the following formula (M) (also simply referred to as "compound M") can be mentioned.

Q ² -R ¹ -Q ¹ Formula (M)

In the formula (M), Q ¹ And Q ² Each independently represents a (meth) acryloyloxy group, R ¹ Represents a 2-valent linking group having a chain structure.

With respect to Q in the formula (M) ¹ And Q ² From the viewpoint of ease of synthesis, Q ¹ And Q ² Preferably the same groups.

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

As R in formula (M) ¹ From the viewpoint of further excellent effects of the present invention, preferred are alkylene groups and alkyleneoxyalkylene groups (-L) ¹ -O-L ¹ -) or polyalkyleneoxyalkylene (- (L) ¹ -O) _p -L ¹ -) more preferably a hydrocarbon group or a polyalkyleneoxyalkylene group having 2 to 20 carbon atoms, still more preferably an alkylene group having 4 to 20 carbon atoms, and particularly preferably a linear alkylene group having 6 to 18 carbon atoms.

The hydrocarbon group may have a chain structure in at least a part thereof, and the part other than the chain structure is not particularly limited, and may be, for example, any of a branched, cyclic or linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, and a combination thereof, and is preferably an alkylene group or a combination of 1 or more arylene groups and 2 or more alkylene groups, more preferably an alkylene group, and further preferably a linear alkylene group.

Further, L is as defined above ¹ Each independently represents an alkylene group, preferably an ethenyl, propenyl, or butenyl group, more preferably an ethenyl or 1,2-propenyl group. p represents an integer of 2 or more, preferably an integer of 2 to 10.

Further, in view of further excellent effects of the present invention, Q is bonded to the compound M ¹ And Q ² The number of atoms of the shortest connecting chain therebetween is preferably 3 to 50, more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12.

In the present invention, "connection Q ¹ And Q ² The number of atoms of the shortest connecting chain therebetween "means the number of atoms from ¹ Attached R ¹ Is connected to Q ² Attached R ¹ The shortest atom number of (a).

Specific examples of the compound M include 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, di (meth) acrylate of hydrogenated bisphenol A, di (meth) acrylate of hydrogenated bisphenol F, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol/propylene glycol) di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate. The above ester monomers can also be used as mixtures.

Among the above compounds, from the viewpoint of more excellent effects of the present invention, at least one compound selected from 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate is preferable, at least one compound selected from 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate and 1, 10-decanediol di (meth) acrylate is more preferable, and at least one compound selected from 1,9-nonanediol di (meth) acrylate and 1, 10-decanediol di (meth) acrylate is further preferable.

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

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

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

As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.

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

Examples of the 2-functional ethylenically unsaturated compound other than the compound M include tricyclodecanedimethanol di (meth) acrylate.

Commercially available products of the 2-functional ethylenically unsaturated compound include tricyclodecane dimethanol diacrylate (trade name: NK ESTER A-DCP, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK ESTER DCP, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.), 1,9-nonanediol diacrylate (trade name: NK ESTER A-NOD-N, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.), and 3763 zxf3763-3763-hexanediol diacrylate (trade name: NK ESTER A-HD-N, SHIN-NAKARA MUCHEMICL Co., manufactured by Ltd.), dioxane glycol diacrylate (Nippon Kayaku Co., manufactured by Ltd., KAR-604), and the like.

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

Examples of the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and a (meth) acrylate compound having a glycerin tri (meth) acrylate skeleton.

Here, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.

Examples of the polymerizable compound include caprolactone-modified compounds of (meth) acrylate compounds (e.g., nippon Kayaku Co., ltd., KAYARAD (registered trademark) DPCA-20, SHIN-NAKAMURA CHEMICAL Co., ltd., A-9300-1CL, manufactured by Ltd.), alkylene oxide-modified compounds of (meth) acrylate compounds (e.g., nippon Kayaku Co., ltd., KAYARAD (registered trademark) RP-1040, SHIN-NAKAMURA CHEMICAL Co., ltd., ATM-35E, A-9300, DAICEL-ALLNEX LTD, EBECRYL (registered trademark) 135, manufactured by Ltd.), and ethoxylated glycerides (e.g., SHIN-NAKAMURA CHEMICAL Co., ltd., NK NAKAESTER A-GLY-9E, manufactured by Ltd.).

The polymerizable compound may also be a urethane (meth) acrylate compound [ preferably a 3-or more-functional urethane (meth) acrylate compound ].

Examples of the 3-or more-functional urethane (meth) acrylate compound include 8UX-015A (manufactured by Taisei Fine Chemical Co., ltd.), NK ESTER UA-32P (manufactured by SHIN-NAKAMURA CHEMICAL Co., ltd.), and NK ESTER UA-1100H (manufactured by SHIN-NAKAMURA CHEMICAL Co., ltd.).

As one of preferred embodiments of the polymerizable compound, an ethylenically unsaturated compound having an acid group is exemplified.

Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group.

Among these, the acid group is preferably a carboxyl group.

Examples of the ethylenically unsaturated compound having an acid group include a 3 to 4-functional ethylenically unsaturated compound having an acid group [ a compound obtained by introducing a carboxyl group into a pentaerythritol tri-and tetraacrylate (PETA) skeleton (acid value: 80 to 120 mgKOH/g) ], a5 to 6-functional ethylenically unsaturated compound having an acid group [ a compound obtained by introducing a carboxyl group into a dipentaerythritol penta-and hexaacrylate (DPHA) skeleton (acid value: 25 to 70 mgKOH/g) ], and the like.

These ethylenically unsaturated compounds having 3 or more functions of the acid group may be used together with the ethylenically unsaturated compounds having 2 functions of the acid group, if necessary.

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

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

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

Examples of the ethylenically unsaturated compound having 2 or more functional groups and having a carboxyl group include ARONIX (registered trademark) TO-2349 (TOAGOSEI co., ltd., manufactured), ARONIX (registered trademark) M-520 (TOAGOSEI co., ltd., manufactured), and ARONIX (registered trademark) M-510 (TOAGOSEI co., ltd., manufactured).

As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs [0025] to [0030] of Japanese patent laid-open No. 2004-239942 is preferable, and the contents described in this publication are incorporated in the present invention.

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

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

Examples of the compound obtained by reacting a polyhydric alcohol with an α, β -unsaturated carboxylic acid include bisphenol a (meth) acrylate compounds such as 2,2-bis (4- ((meth) acryloyloxypolyethoxy) phenyl) propane, 2,2-bis (4- ((meth) acryloyloxypolypropoxy) phenyl) propane and 2,2-bis (4- ((meth) acryloyloxypolyethoxy polypropoxy) phenyl) propane, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, polyethylene glycol polypropylene glycol di (meth) acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytrimethylol tri (meth) acrylate, trimethylolpropane triethoxytrimethylol tri (meth) acrylate, trimethylolpropane tetraethoxy (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol trimethylolpropane triethoxytrimethylol methacrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

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

Examples of the polymerizable compound include caprolactone-modified compounds of ethylenically unsaturated compounds (e.g., nippon Kayaku Co., ltd., KAYARAD (registered trademark) DPCA-20, SHIN-NAKAMUR A CHEMICAL Co., ltd., A-9300-1CL Co., ltd.), alkylene oxide-modified compounds of ethylenically unsaturated compounds (e.g., nippon Kayaku Co., ltd., KAYARAD RP-1040, SHIN-NAKAMURA C HEMICAL Co., ltd., ATM-35E, A-9300, DAICEL-ALLNEX LTD. EBECRYL (registered trademark) 135), ethoxylated glycerol triacrylate (SHIN-NAMUKARA CHEMICAL Co., ltd., A-GLY-9E., ltd.), and the like.

Among them, the polymerizable compound (particularly, ethylenically unsaturated compound) preferably further contains an ester bond in view of excellent developability of the photosensitive composition layer after transfer.

The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, and from the viewpoint of the excellent effect of the present invention, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, or ditrimethylolpropane tetraacrylate is more preferable.

From the viewpoint of providing reliability, the ethylenically unsaturated compound preferably includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and an ethylenically unsaturated compound having the above-described tetramethylolmethane structure or trimethylolpropane structure.

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

One of preferred embodiments of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably, a 2-functional ethylenically unsaturated compound).

The polymerizable compound is preferably a polymerizable compound having a ring structure in which 2 or more aliphatic hydrocarbon rings are condensed (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure), more preferably a 2-functional ethylenically unsaturated compound having a ring structure in which 2 or more aliphatic hydrocarbon rings are condensed, and still more preferably tricyclodecanedimethanol di (meth) acrylate.

The aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure or an isophorone structure in view of further improving the effects of the present invention.

The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

The proportion of the content of the polymerizable compound having a molecular weight of 300 or less in the polymerizable compounds contained in the photosensitive composition layer is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less, relative to the content of all the polymerizable compounds contained in the photosensitive composition layer.

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

In addition, as one of preferable embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer containing a structural unit having an aliphatic hydrocarbon ring.

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

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

In addition, as one of preferable embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a 2-functional ethylenically unsaturated compound (preferably a 2-functional (meth) acrylate compound) and an ethylenically unsaturated compound having 3 or more functions (preferably a 3-or more-functional (meth) acrylate compound).

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

Further, as one of preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains the compound M and an ethylenically unsaturated compound having an acid group, more preferably contains the compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an ethylenically unsaturated compound having an acid group, further preferably contains the compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having 3 or more functions and an ethylenically unsaturated compound having an acid group, and particularly preferably contains the compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having 3 or more functions, an ethylenically unsaturated compound having an acid group and a urethane (meth) acrylate compound, from the viewpoints of substrate adhesion, development residue inhibition and rust prevention.

In addition, as one of preferable embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, still more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group and a urethane acrylate compound, from the viewpoint of substrate adhesion, development residue suppression property and rust prevention property.

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

The content of the ethylenic unsaturated compound having 2 or more functions in the ethylenic unsaturated compound is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass, based on the total content of all the ethylenic unsaturated compounds contained in the photosensitive composition layer.

The polymerizable compound (particularly, ethylenically unsaturated compound) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The content of the polymerizable compound (particularly, ethylenically unsaturated compound) in the photosensitive composition layer is preferably 1 to 70% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass, and particularly preferably 20 to 50% by mass, based on the total mass of the photosensitive composition layer.

(polymerization initiator)

The photosensitive composition layer may contain a polymerization initiator.

As the polymerization initiator, a photopolymerization initiator is preferable.

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

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

The photopolymerization initiator preferably contains at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α -aminoalkylphenyl ketone-based photopolymerization initiator, an α -hydroxyalkylphenyl ketone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator, and more preferably contains at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α -aminoalkylphenyl ketone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator.

In addition, from the viewpoint of further excellent effects of the present invention, it is preferable to use 2 or more types of photopolymerization initiators at the same time, more preferable to include an oxime-based photopolymerization initiator and a d-aminoalkylphenone-based photopolymerization initiator, and still more preferable to include 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime) and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one.

Further, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs [0031] to [0042] of Japanese patent application laid-open No. 2011-095716 and paragraphs [0064] to [0081] of Japanese patent application laid-open No. 2015-014783 may be used.

Examples of commercially available photopolymerization initiators include 1- [4- (phenylthio) phenyl ] -1,2-octanedione-2- (O-benzoyloxime) [ trade name: [ RGACURE (registered trademark) OXE-01, manufactured by BASF corporation ], 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime) [ trade name: IRGACURE (registered trademark) OXE-02, BASF corporation ], [8- [5- (2,4,6-trimethylphenyl) -11- (2-ethylhexyl) -11H-benzo [ a ] carbazolyl ] [2- (2,2,3,3-tetrafluoropropoxy) phenyl ] methanone- (O-acetoxime) [ trade name: IRGACURE (registered trademark) OXE-03, manufactured by basf corporation, 1- [4- [4- (2-benzofuranylcarbonyl) phenyl ] thio ] phenyl ] -4-methylpentanone-1- (O-acetyloxime) [ product name: IRGACURE (registered trademark) OXE-04 (manufactured by BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone [ trade name: IRGACURE (registered trademark) 379EG, manufactured by BASF corporation), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE (registered trademark) 907, manufactured by BASF corporation), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one [ trade name: IRGACURE (registered trademark) 127, manufactured by basf corporation), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 [ trade name: IRGACURE (registered trademark) 369, manufactured by basf corporation), 2-hydroxy-2-methyl-1-phenylpropan-1-one [ trade name: IRGACURE (registered trademark) 1173, manufactured by basf corporation, 1-hydroxycyclohexyl phenyl ketone [ trade name: IRGACURE (registered trademark) 184, manufactured by BASF corporation, 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: IRGACURE 651, BASF CORPORATION, and the like, and oxime ester type photopolymerization initiators [ trade name: lunar (registered trademark) 6, manufactured by dksh Japan k.k., product.), 1- (biphenyl-4-yl) -2-methyl-2-morpholinopropan-1-one [ trade name: APi-307 (registered trademark), shenzhen UV-Chemtech Ltd. ], 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane-1,2-dione-2- (O-benzoyloxime) (trade name: TR-PBG-305, changzhou Tronly New Electronic Materials Co., ltd.), 1,2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furylcarboxyl) -9H-carbazol-3-yl ] -,2- (O-acetyloxime) (trade name: TR-PBG-326, changzhou Tronly New Electronic Materials Co., ltd.), and 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) hexanoyl) -9-ethyl-9H-3-yl) -propanedione (trade name: changzhou Troch-3-dione) (trade name: changzhou-J-3-ethyl-3-propanedione, changzhou-3- (2- (benzoyloxyimino) hexanoyl) -9-ethyl-9H-carbazole-3-dione (PBG-3763, changzhou-benzoyl oxime, tokyo, brand.) (trade name: wyol-3-Benzyl-3-J).

As the polymerization initiator, from the viewpoint of more excellent transparency and pattern forming ability of 10 μm or less, an oxime ester compound or a phosphine oxide compound is preferable, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1,2-octanedione-1- [4- (phenylthio) phenyl ] -2- (O-benzoyloxime) or 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide is more preferable.

The polymerization initiator may be used alone in 1 kind or in combination of 2 or more kinds.

The content of the polymerization initiator in the photosensitive composition layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more, based on the total mass of the photosensitive composition layer.

The content of the polymerization initiator in the photosensitive composition layer is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the photosensitive composition layer.

(heterocyclic compound)

The photosensitive composition layer may contain a heterocyclic compound.

The heterocyclic ring of the heterocyclic compound may be any of monocyclic and polycyclic heterocyclic rings.

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

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

Among the above, the heterocyclic compound is preferably at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzimidazole compound and a benzoxazole compound, and more preferably at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound and a benzoxazole compound.

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

[ chemical formula 17]

[ chemical formula 18]

Examples of the tetrazole compound include the following compounds.

[ chemical formula 19]

[ chemical formula 20]

Examples of the thiadiazole compound include the following compounds.

[ chemical formula 21]

Examples of the triazine compound include the following compounds.

[ chemical formula 22]

Examples of the rhodanine compound include the following compounds.

[ chemical formula 23]

Examples of the thiazole compound include the following compounds.

[ chemical formula 24]

Examples of the benzothiazole compound include the following compounds.

[ chemical formula 25]

Examples of the benzimidazole compound include the following compounds.

[ chemical formula 26]

[ chemical formula 27]

/>

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

[ chemical formula 28]

The heterocyclic compounds can be used alone in 1, also can be used simultaneously more than 2.

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

(aliphatic thiol Compound)

The photosensitive composition layer may contain an aliphatic thiol compound.

When the photosensitive composition layer contains an aliphatic thiol compound, curing shrinkage and stress relaxation of a film formed by an ene-thiol reaction between the aliphatic thiol compound and a radical polymerizable compound having an ethylenically unsaturated group are suppressed.

As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (i.e., an aliphatic thiol compound having 2 or more functions) is preferable.

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

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

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

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

Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolethane tris (3-mercaptobutyrate), tris [ (3-mercaptopropionyloxy) ethyl ] isocyanurate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,2-ethanedithiol, 1,3-propane dithiol, 1,6-hexamethylene dithiol, 4234' - (ethylene dithiol) diethylene thiol, succinic acid-zxft 5364, and dimercaptoethyl 5364 (mercaptoethyl) ether.

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

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

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

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

(thermally crosslinkable Compound)

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

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

Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, for example, when at least one of the binder polymer and the radical polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film tends to decrease and the function as a protective film tends to increase.

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

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

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

As the differential scanning calorimeter, for example, a differential scanning calorimeter made 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 an active methylene compound [ malonic diester (dimethyl malonate, diethyl malonate, di-N-butyl malonate, di-2-ethylhexyl malonate, etc.) ]), an oxime compound (a compound having a structure represented by-C (= N-OH) -in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime).

Among these, the blocking agent having a dissociation temperature of 100 to 160 ℃ is preferably at least one selected from oxime compounds, for example, from the viewpoint of storage stability.

For example, the blocked isocyanate compound preferably has an isocyanurate structure in terms of improving the brittleness of the film, improving the adhesion to the transfer target, and the like.

The blocked isocyanate compound having an isocyanurate structure is protected by isocyanurating hexamethylene diisocyanate, for example.

Among the blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferable from the following points of view: compared with a compound having no oxime structure, the dissociation temperature is more easily set to a preferable range and the development residue is 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 preferred.

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

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

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

Examples of commercially available products of the blocked isocyanate compound include Karenz (registered trademark) AOI-BM, karenz (registered trademark) MOI-BP, and the like (hereinafter, SHOWA DENKO K.K), and blocked Duranate series (for example, duranate (registered trademark) TPA-B80E, duranate (registered trademark) WT32-B75P, and the like, manufactured by Asahi Kasei Corporation).

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

[ chemical formula 29]

The thermally crosslinkable compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When the photosensitive composition 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, based on the total mass of the photosensitive composition layer.

(surfactant)

The photosensitive composition layer may contain a surfactant.

Examples of the surfactant include surfactants described in paragraph [0017] of Japanese patent No. 4502784 and paragraphs [0060] to [0071] of Japanese patent laid-open No. 2009-237362.

The surfactant is preferably a nonionic surfactant, a fluorine surfactant, or a silicone surfactant, and more preferably a silicone surfactant.

Commercially available fluorine-based surfactants include, for example, MEGAFACE (registered trademark) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, 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, R-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 (registered trademark) FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited, supra), surflon (registered trademark) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc, supra), polyFox (registered trademark) PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions, supra), ftergene (registered trademark) 710FM, 610FM, AD 601, ADH2, 602A, 215M, 245F, 251, 212M, 250, F209, 222F, 208G, LA, FS 710, 730, LM, 650AC, 681 (manufactured by MeOs Corporation, supra), and the like.

Further, the following acrylic compounds can also be preferably used as the fluorine-based surfactant: has a molecular structure containing a functional group containing a fluorine atom, and when heated, a part of the functional group containing a fluorine atom is cleaved and the fluorine atom is volatilized. Examples of such a fluorine-based surfactant include MEGAFACE (registered trademark) DS series (The Chemical Daily Co., ltd. (2016: 2/22 days), NIKKEI BUSIMESS DAILY (2016: 2/23 days)), such as MEGAFACE (registered trademark) DS-21, manufactured by DIC Corporation.

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

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

As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in a side chain can also be used. Specific examples thereof include MEGAFACE (registered trademark) RS-101, RS-102, RS-718K, RS-72-K (see DIC Corporation).

As the fluorine-based surfactant, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferable from the viewpoint of improving environmental compatibility.

Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminals thereof.

Specific examples of the surfactant include DOWFIL (registered trademark) 8032ADDITIVE, TORAY SILICON DC3PA, TORAY SILICON SH7PA, TORAY SILICON DC11PA, TORAY SILICON SH21PA, TORAY SILICON SH28PA, TORAY SILICON SH29PA, TORAY SILICON SH30PA, TORAY SILICON SH8400 (made by Dow Corning Co., manufactured by Ltd.), X-22-4952, X-22-4272, X-22-6266, KF-3236 zxft 523236 zxft 5262-355 zxft 3763-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KFBYt-6004, KP-600351, KP-37341, TST-3763-945, gmTSF 4432, KF-444432, KF-44323, KF-4460, and so-4460 (made by KF 4432, by-44323, KF 4440, KF 44323, by-4423, KF 4452, by-4423, by-4452, and so on.

The surfactant may be other than the above surfactants, and examples thereof include nonionic surfactants.

Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylated and propoxylated compounds thereof (for example, propoxylated glycerin, ethoxylated glycerin, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (the same applies to BASF corporation), TE, and the likeTRONIC (registered trademark) 304, 701, 704, 901, 904, 150R1 (manufactured by BASF Corporation, supra), SOLSPERSE (registered trademark) 20000 (manufactured by The Lubrizol Corporation, supra), NCW-101, NCW-1001, NCW-1002 (manufactured by The FUJIFILM Wako Pure Chemical Corporation, supra), PIONIN (registered trademark) D-6112, D-6112-W, D-6315 (manufactured by The TAKEMOTO OIL Corporation, supra)&FAT C _o Ltd), OLFINE E1010, surfynol 104, 400, 440 (Nissin Chemical Industry co., ltd).

The surfactant may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.05 to 1.0% by mass, and still more preferably 0.10 to 0.80% by mass, based on the total mass of the photosensitive composition layer.

(phosphoric acid ester Compound)

The photosensitive composition layer preferably contains a phosphate ester compound in order to further improve adhesion of the photosensitive composition layer to the substrate or the conductive layer.

As the phosphate ester compound, as long as phosphoric acid (O = P (OH) ₃ ) At least 1 or more of the 3 hydrogens in (A) are substituted with an organic group, and there are no particular restrictions, and examples thereof include those of the Phosmer series manufactured by Uni-Chemical Co., ltd.,. Products by Ltd. (Phosmer-M, phosmer-CL, phosmer-PE, phosmer-MH, phosmer-PP), nippon Kayaku Co., products by Ltd. (KAYAMER PM-21, KAYAMER PM-2) and KYOEISHA CHEMICAL Co., products by LTD.products LIGHT ESTER (LIGHT ESTER P-2M (trade name)).

The phosphate ester compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When the photosensitive composition layer contains a phosphate compound, the content of the phosphate compound is not particularly limited, but is preferably 0.05 to 3.0% by mass, more preferably 0.1 to 2.0% by mass, and still more preferably 0.2 to 1.0% by mass, based on the total mass of the photosensitive composition layer.

When the photosensitive composition layer contains a phosphate compound, the content of the phosphate compound is not particularly limited, and is preferably 10 parts by mass or less, more preferably 3 parts by mass or less, based on 100 parts by mass of the total of the binder polymer and the polymerizable compound, in order to further improve the adhesion of the photosensitive composition to the substrate or the conductive layer. Further, it is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more.

(polymerization inhibitor)

The photosensitive composition layer may contain a polymerization inhibitor.

The polymerization inhibitor means a compound having a function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, a known compound used as a polymerization inhibitor can be used.

Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine and 3,7-dioctylphenothiazine; hindered phenol compounds such as bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid ] [ vinylbis (oxyethylene) ], 2,4-bis [ (laurylthio) methyl ] -o-cresol, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylamino) -1,3,5-triazine, and pentaerythritol tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate; nitroso compounds such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine and N-nitrosophenylhydroxylamine, or salts thereof; quinone compounds such as methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and tert-butylcatechol; metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate and manganese diphenyldithiocarbamate.

Among them, from the viewpoint of more excellent effects of the present invention, the polymerization inhibitor is preferably at least one selected from phenothiazine compounds, nitroso compounds, salts thereof and hindered phenol compounds, and more preferably phenothiazine, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid ] [ vinylbis (oxyethylene) ], 2,4-bis [ (laurylthio) methyl ] -o-cresol, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) and N-nitrosophenylhydroxylamine aluminum salt.

The polymerization inhibitor may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When the photosensitive composition layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5.0% by mass, and still more preferably 0.10 to 3.0% by mass, based on the total mass of the photosensitive composition layer.

(Hydrogen donor Compound)

The photosensitive composition layer may contain a hydrogen donor compound.

The hydrogen donor compound has the effects of further improving the sensitivity of the photopolymerization initiator to active rays, suppressing inhibition of polymerization of the polymerizable compound by oxygen, and the like.

Examples of the hydrogen donor compound include amines and amino acid compounds.

Examples of the amines include compounds described in "Journal of Polymer Society" of, for example, M.R. Sander, vol.10, p.3173 (1972), japanese patent application laid-open No. 44-020189, japanese patent application laid-open No. 51-082102, japanese patent application laid-open No. 52-134692, japanese patent application laid-open No. 59-138205, japanese patent application laid-open No. 60-084305, japanese patent application laid-open No. 62-018537, japanese patent application laid-open No. 64-033104, and Research Disclean 33825. More specifically, 4,4' -bis (diethylamino) benzophenone, tris (4-dimethylaminophenyl) methane (otherwise known as leuco crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline and p-methylthiodimethylaniline are exemplified.

Among them, in view of further improving the effect of the present invention, the amine is preferably at least one selected from the group consisting of 4,4' -bis (diethylamino) benzophenone and tris (4-dimethylaminophenyl) methane.

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

Among them, N-phenylglycine is preferable as the amino acid compound in view of further improving the effect of the present invention.

Further, examples of the hydrogen donor compound include an organic metal compound (tributyltin acetate, etc.) described in Japanese patent publication No. 48-042965, a hydrogen donor described in Japanese patent publication No. 55-034414, and a sulfur compound (trithiane, etc.) described in Japanese patent publication No. 6-308727.

The hydrogen donor compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When the photosensitive composition layer contains a hydrogen donor compound, the content of the hydrogen donor compound is preferably 0.01 to 10.0% by mass, more preferably 0.03 to 8.0% by mass, and further preferably 0.10 to 5.0% by mass, based on the total mass of the photosensitive composition layer, from the viewpoint of improvement of the curing rate based on the balance between the polymerization growth rate and the chain transfer.

(impurities, etc.)

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

Specific examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, the halide ions, sodium ions and potassium ions are preferably contained in the following amounts because they are easily mixed as impurities.

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

Examples of the method of setting the impurity to the above range include a method of selecting a raw material having a small content of the impurity as a raw material of the photosensitive composition layer; a method for preventing impurities from being mixed in the process of forming the photosensitive composition layer; and a cleaning and removing method. By this method, the amount of impurities can be made within the above range.

For example, the impurities can be quantified by a known method such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, or ion chromatography.

The photosensitive composition layer preferably 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 in the photosensitive composition layer is preferably 100ppm or less, more preferably 20ppm or less, and still more preferably 4ppm or less on a mass basis.

The lower limit may be 10ppb or more, and may be 100ppb or more on a mass basis. These compounds can be inhibited 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 composition 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 properties.

(residual monomer)

The photosensitive composition layer may contain a residual monomer of each structural unit 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 further preferably 500 mass ppm or less, with respect to the total mass of the alkali-soluble resin, from the viewpoint of pattern formability 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 viewpoint of pattern formability and reliability, the residual monomer in each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and still more preferably 100 mass ppm or less, with respect to the total mass of the photosensitive composition layer. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and 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 within the above range. For example, when the alkali-soluble resin is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range.

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

(other Components)

The photosensitive composition layer may contain a component other than the above-described components (hereinafter, also referred to as "other component"). Examples of the other components include a colorant, an antioxidant, and particles (for example, metal oxide particles). Further, as other components, there may be mentioned other additives described in paragraphs [0058] to [0071] of Japanese patent laid-open No. 2000-310706.

Particles-

As the particles, metal oxide particles are preferable.

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

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

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

When the photosensitive composition layer contains particles, only 1 kind of particles having different metal species, sizes, and the like may be contained, or 2 or more kinds may be contained.

The photosensitive composition layer contains no particles, or when the photosensitive composition layer contains particles, the content of the particles is preferably more than 0 mass% and 35 mass% or less with respect to the total mass of the photosensitive composition layer; more preferably, the photosensitive composition contains no particles, or the content of the particles is more than 0 mass% and 10 mass% or less with respect to the total mass of the photosensitive composition; further preferably, the photosensitive composition layer contains no particles, or the content of the particles is more than 0 mass% and 5 mass% or less with respect to the total mass of the photosensitive composition layer; further preferably, the photosensitive composition layer contains no particles, or the content of the particles is more than 0 mass% and 1 mass% or less with respect to the total mass of the photosensitive composition layer; it is particularly preferred that no particles are included.

Colorants-

The photosensitive composition may contain a small amount of a colorant (pigment, dye, etc.), but preferably contains substantially no colorant, for example, from the viewpoint of transparency.

When the photosensitive composition layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, relative to the total mass of the photosensitive composition layer.

Antioxidants-

Examples of the antioxidant include 3-pyrazolones such as 1-phenyl-3-pyrazolone (also referred to as phenanthridone), 1-phenyl-4,4-dimethyl-3-pyrazolone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone and chlorohydroquinone; p-methyl aminophenol, p-hydroxyphenylglycine and p-phenylenediamine.

Among these, 3-pyrazolones are preferable, and 1-phenyl-3-pyrazolone is more preferable as the antioxidant from the viewpoint of further improving the effect of the present invention.

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

(thickness of photosensitive composition layer)

The thickness of the photosensitive composition layer is not particularly limited, but is usually 30 μm or less, and from the viewpoint of further improving the effect of the present invention, it is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is not particularly limited, but is preferably 0.05 μm or more.

For example, the thickness of the photosensitive composition layer can be calculated as an average value at arbitrary 5 points measured by cross-sectional observation based on a Scanning Electron Microscope (SEM).

(refractive index of photosensitive composition layer)

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

(color of photosensitive composition layer)

The photosensitive composition layer is preferably achromatic. In particular, the total reflection (incident angle 8, light source: D-65 (2 view)) is in CIE1976 (L, a, b) color space, L ^* The value is preferably from 10 to 90,a ^* The value is preferably-1.0 to 1.0 ^* The value is preferably-1.0 to 1.0.

In addition, the pattern obtained by curing the photosensitive composition layer (cured film of the photosensitive composition layer) is preferably achromatic.

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

[ transmittance of photosensitive composition layer ]

The visible light transmittance per 1.0 μm film thickness of the photosensitive composition layer is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more.

As the transmittance of visible light, the average transmittance at a wavelength of 400nm to 800nm, the minimum value of the transmittance at a wavelength of 400nm to 800nm, and the transmittance at a wavelength of 400nmm all satisfy the above-mentioned requirements.

Preferable values of the transmittance include 87%, 92%, 98%, and the like. The transmittance per 1.0 μm film thickness of the cured film of the photosensitive composition layer was also the same.

[ moisture permeability of photosensitive composition layer ]

From the viewpoint of rust prevention of electrodes or wirings and reliability of devices, the moisture permeability of a pattern (cured film of the photosensitive composition layer) obtained by curing the photosensitive composition layer at a film thickness of 40 μm is preferably 500g/m ² Less than 24hr, more preferably 300g/m ² Less than 24hr, more preferably 100g/m ² And/24 hr or less.

Regarding the moisture permeability, the cured film obtained as follows was used for measurement: by i-ray, at an exposure of 300mJ/cm ² After the photosensitive composition layer was exposed to light, post baking was performed at 145 ℃ for 30 minutes, thereby curing the photosensitive composition layer.

The moisture permeability was measured in accordance with cup method (cup method) of JIS Z0208. The moisture permeability is preferably set to any one of the test conditions of a temperature of 40 ℃/humidity 90%, a temperature of 65 ℃/humidity 90% and a temperature of 80 ℃/humidity 95%.

A preferable specific numerical value is, for example, 80g/m ² /24hr、150g/m ² /24hr、220g/m ² /24hr, etc.

[ dissolution Rate of photosensitive composition layer ]

The dissolution rate of the photosensitive composition layer in a 1.0% aqueous solution of sodium carbonate is preferably 0.01 μm/sec or more, more preferably 0.10 μm/sec or more, and still more preferably 0.20 μm/sec or more, from the viewpoint of suppressing the residue during development.

From the viewpoint of the edge shape of the pattern, it is preferably 5.0 μm/sec or less, more preferably 4.0 μm/sec or less, and still more preferably 3.0 μm/sec or less.

Preferable specific numerical values include, for example, 1.8 μm/sec, 1.0 μm/sec, and 0.7 μm/sec.

The dissolution rate of the photosensitive composition layer per unit time in a 1.0 mass% aqueous sodium carbonate solution was measured as follows.

The photosensitive composition layer (film thickness in the range of 1.0 to 10 μm) formed on the glass substrate from which the solvent was sufficiently removed was subjected to shower development at 25 ℃ using a 1.0 mass% aqueous solution of sodium carbonate until the photosensitive composition layer was completely dissolved (but 2 minutes at the maximum). The dissolution rate per unit time of the photosensitive composition layer is determined by dividing the film thickness of the photosensitive composition layer by the time required for complete dissolution of the photosensitive composition layer. If the film is not completely dissolved within 2 minutes, the amount of change in film thickness to 2 minutes is calculated in the same manner.

The dissolution rate of the cured film (film thickness in the range of 1.0 to 10 μm) of the photosensitive composition layer in a 1.0% aqueous solution of sodium carbonate is preferably 3.0 μm/sec or less, more preferably 2.0 μm/sec or less, still more preferably 1.0 μm/sec or less, and particularly preferably 0.2 μm/sec or less. The cured film of the photosensitive composition layer was obtained by exposing the cured film to an exposure dose of 300mJ/cm with i-rays ² And a film obtained by exposing the photosensitive composition layer.

Preferable specific numerical values include, for example, 0.8 μm/sec, 0.2 μm/sec, and 0.001 μm/sec.

A1/4 MINJJX030PP nozzle manufactured by Ltd was used for development, and the spray pressure of a shower was set to 0.08MPa. Under the above conditions, the spray flow rate per unit time was set to 1, 800mL/min.

[ swelling ratio of photosensitive composition layer ]

The swelling ratio of the photosensitive composition layer after exposure in a 1.0 mass% aqueous solution of sodium carbonate is preferably 100% or less, more preferably 50% or less, and still more preferably 30% or less, from the viewpoint of improving the pattern formability.

The swelling ratio of the photosensitive composition layer after exposure in a 1.0 mass% aqueous solution of sodium carbonate was measured as follows.

Using an ultra-high pressure mercury lamp at 500mj/cm ² (i-ray measurement) the photosensitive composition layer (film thickness in the range of 1.0 to 10 μm) formed on the glass substrate from which the solvent was sufficiently removed was exposed. Each glass substrate was immersed in a 1.0 mass% aqueous solution of sodium carbonate at 25 ℃, and the film thickness was measured at the time point of passage of 30 seconds. Then, the ratio of the increase in the film thickness after immersion to the film thickness before immersion was calculated.

Preferable specific numerical values include, for example, 4%, 13%, and 25%.

[ foreign matter in photosensitive composition layer ]

In view of pattern formability, the number of foreign matters having a diameter of 1.0 μm or more in the photosensitive composition layer is preferably 10/mm ² Hereinafter, more preferably 5 pieces/mm ² The following.

The number of foreign matters was measured as follows.

The number of foreign matters was calculated by visually observing arbitrary 5 regions (1 mm × 1 mm) on the surface of the photosensitive composition layer from the normal direction of the surface of the photosensitive composition layer with an optical microscope, measuring the number of foreign matters having a diameter of 1.0 μm or more in each region, and arithmetically averaging the measured numbers.

As a preferred specific numerical value, for example, can give 0/mm ² 1 pieces/mm ² 4 pieces/mm ² 8 pieces/mm ² And the like.

[ haze of dissolved substance in photosensitive composition layer ]

From the viewpoint of suppressing generation of aggregates during development, 1.0cm was dissolved in 1.0 liter of a 30 ℃ aqueous solution of 1.0 mass% sodium carbonate ³ The haze of the solution obtained from the photosensitive composition layer of (3) is preferably 60% or less, more preferably 30% or less, still more preferably 10% or less, and particularly preferably 1% or less.

Haze was measured as follows.

First, a 1.0 mass% sodium carbonate aqueous solution was prepared, and the solution temperature was adjusted to 30 ℃. Adding into 1.0L sodium carbonate aqueous solution 1.0cm ³ The photosensitive composition layer of (1). The mixture was stirred at 30 ℃ for 4 hours while paying attention to no air bubbles. After stirring, the haze of the solution in which the photosensitive composition layer was dissolved was measured. The haze was measured by a haze meter (product name "NDH4000", NIPPON DENSHOKU INDUSTRIES co., ltd. System) using a unit for measuring a liquid and a tank for measuring a liquid having an optical path length of 20 mm.

Specific preferable numerical values include, for example, 0.4%, 1.0%, 9%, 24%, and the like.

< protective film >

The transfer film may have a protective film on the refractive index adjustment layer. More specifically, the transfer film may have a protective film on the surface of the refractive index adjustment layer opposite to the photosensitive composition layer side.

As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films.

As the protective film, a resin film made of the same material as the temporary support can be used.

Among these, as the protective film, a polyolefin film is preferable, a polypropylene film or a polyethylene film is more preferable, and a polyethylene film is further preferable.

The thickness of the protective film is preferably 1 to 100. Mu.m, more preferably 5 to 50 μm, still more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm.

The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and preferably 100 μm or less from the viewpoint of relative inexpensiveness.

In the protective film, the number of fish eyes having a diameter of 80 μm or more contained in the protective film is preferably 5 fish eyes/m ² The following.

The term "fish eye" refers to a defect in which foreign matter, undissolved matter, oxidized and degraded matter of a material are introduced into a film when the material is thermally melted and the film is formed by a method such as kneading, extrusion, biaxial stretching, or casting.

The number of particles having a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm ² Hereinafter, more preferably 10 pieces/mm ² Hereinafter, more preferably 5 pieces/mm ² The following.

From the viewpoint of imparting windup properties, the arithmetic average roughness Ra of the surface of the protective film on the side opposite to the surface contacting the refractive index adjustment layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50. Mu.m, more preferably 0.40 μm or less, and further preferably 0.30 μm or less.

The surface roughness Ra of the surface of the protective film in contact with the refractive index adjustment layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more, from the viewpoint of suppressing defects at the time of transfer. On the other hand, it is preferably less than 0.50. Mu.m, more preferably 0.40 μm or less, and further preferably 0.30 μm or less.

< method for producing transfer film >

The method for producing the transfer film of the present invention is not particularly limited, and a known method can be used.

Among them, from the viewpoint of excellent productivity, a method (hereinafter, this method is also referred to as "coating method") is preferred in which the photosensitive composition is coated on the temporary support, and if necessary, a drying treatment is performed to form the photosensitive composition layer, and then the composition for forming the refractive index adjustment layer is coated on the photosensitive composition layer, and if necessary, a drying treatment is performed to form the refractive index adjustment layer.

Further, a protective film may be laminated on the refractive index adjustment layer as necessary.

The photosensitive composition used in the coating method preferably contains a component (for example, a binder polymer, a polymerizable compound, a polymerization initiator, and the like) constituting the photosensitive composition layer and a solvent.

As the solvent, an organic solvent is preferable. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether acetate (alternatively referred to as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol and 2-propanol.

Further, as the solvent, an organic solvent having a boiling point of 180 to 250 ℃ (high boiling point solvent) may be used as necessary.

The solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When the photosensitive composition contains a solvent, the total solid content of the photosensitive composition is preferably 1 to 80% by mass, more preferably 3 to 40% by mass, and still more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition.

The solid component is a component constituting the photosensitive composition layer other than the solvent. The properties of the components constituting the photosensitive composition layer are calculated as solid components even when they are liquid.

When the photosensitive composition contains a solvent, the viscosity of the photosensitive composition at 25 ℃ is preferably 1 to 50 mPas, more preferably 2 to 40 mPas, and further preferably 3 to 30 mPas, from the viewpoint of coatability, for example. The viscosity was measured using a viscometer. As the VISCOMETER, for example, TOKI SANGYO CO., LTD. VISCOMETER (trade name: VISCOMETER TV-22) can be preferably used. However, the viscometer is not limited to the above-described viscometer.

When the photosensitive composition contains a solvent, the surface tension of the photosensitive composition at 25 ℃ is, for example, preferably 5 to 100mN/m, more preferably 10 to 80mN/m, and still more preferably 15 to 40mN/m, from the viewpoint of coatability. The surface tension was measured using a surface tensiometer. As the Surface Tensiometer, for example, kyowa Interface Science Co., ltd. (product name: automatic Surface Tensiometer CBVP-Z) can be preferably used. However, the surface tension meter is not limited to the above surface tension meter.

Examples of the method of applying the photosensitive composition include a printing method, a spray coating method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method).

Examples of the drying method include natural drying, heat drying, and drying under reduced pressure. The above-described methods can be used alone or in combination of a plurality of them.

In the present invention, "drying" means removing at least a part of the solvent contained in the composition.

The composition for forming a refractive index adjustment layer used in the coating method preferably contains a component (for example, a specific material, a specific polymer, a polymerizable compound, a polymerization initiator, and the like) constituting the refractive index adjustment layer and a solvent.

As the solvent, an organic solvent is preferable. The kind of the organic solvent is not particularly limited, and examples thereof include organic solvents exemplified as the organic solvent contained in the photosensitive composition.

The solvent can be used alone in 1, can also be used simultaneously more than 2.

When the composition for forming a refractive index adjustment layer contains a solvent, the total solid content of the composition for forming a refractive index adjustment layer is preferably 1 to 80% by mass, more preferably 3 to 40% by mass, and still more preferably 3 to 30% by mass, based on the total mass of the photosensitive composition.

The solid component is a component constituting the refractive index adjustment layer other than the solvent. The components constituting the refractive index adjustment layer are calculated as solid components even in a liquid state.

Examples of the coating method of the composition for forming a refractive index adjusting layer include a printing method, a spray coating method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method).

Examples of the drying method include natural drying, heat drying, and drying under reduced pressure. The above-described methods can be used alone or in combination of a plurality.

After the refractive index adjustment layer is formed, a protective film may be bonded to the refractive index adjustment layer as necessary.

The method of bonding the protective film to the refractive index adjustment layer is not particularly limited, and known methods may be used.

Examples of the apparatus for bonding the protective film to the refractive index adjustment layer include known laminators such as a vacuum laminator and an automatic cutting laminator.

The laminator is preferably provided with an optional heatable roller such as a rubber roller and can be pressurized and heated.

< use >

The transfer film of the present invention can be applied to various uses.

For example, the present invention can be applied to an electrode protection film, an insulating film, a planarizing film, a top coating film, a hard coating film, a passivation film, a partition wall, a spacer, a microlens, an optical filter, an antireflection film, a resist, a plated member, and the like. More specific examples thereof include a protective film or an insulating film for a touch panel electrode, a protective film or an insulating film for a printed wiring board, a protective film or an insulating film for a TFT substrate, a color filter, a top coat film for a color filter, a resist for forming wiring, and a sacrificial layer in plating.

In addition, the maximum width of the moire of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and further preferably 60 μm or less, from the viewpoint of suppressing the generation of bubbles in the bonding step described later. The lower limit of the maximum width of the corrugations is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more.

The maximum width of the moire of the transfer film is a value measured in the following order.

First, the transfer film was cut into a size of 20cm in the vertical direction by 20cm in the horizontal direction along the direction perpendicular to the main surface, thereby preparing a sample. Next, on a stage having a smooth and horizontal surface, the sample is left standing so that the surface of the temporary support body faces the stage. After standing, the surface of the sample is scanned by a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) within a range of 10cm square from the center of the sample to obtain a three-dimensional surface image, and the minimum depression height is subtracted from the maximum projection height observed in the obtained three-dimensional surface image. The above operation was performed on 10 samples, and the arithmetic average value thereof was taken as "maximum width of moire of transfer film".

< method for producing laminate >

By using the transfer film, the refractive index adjustment layer and the photosensitive composition layer can be transferred to an object to be transferred.

Among them, the transfer film of the present invention is preferably used for manufacturing a touch panel.

Among them, the method for producing a laminate of the present invention preferably includes:

a bonding step of bonding a substrate with a conductive layer, which has a substrate and a conductive layer disposed on the substrate, to the transfer film of the present invention to obtain a substrate with a photosensitive composition layer, which has the substrate, the conductive layer, a refractive index adjustment layer, the photosensitive composition layer, and a temporary support in this order;

an exposure step of pattern-exposing the refractive index adjustment layer and the photosensitive composition layer; and

the method further comprises a peeling step of peeling the temporary support from the substrate with the photosensitive composition layer between the bonding step and the exposure step or between the exposure step and the development step.

The sequence of the above steps will be described in detail below.

(bonding step)

The bonding step is a step of bonding a substrate with a conductive layer, which has a substrate and a conductive layer disposed on the substrate, to the transfer film of the present invention to obtain a substrate with a photosensitive composition layer, which has the substrate, the conductive layer, the refractive index adjustment layer, the photosensitive composition layer, and the temporary support in this order.

In the bonding, the conductive layer is preferably pressure-bonded so as to be in contact with a surface of the refractive index adjustment layer. In the above-described aspect, the pattern obtained after exposure and development can be preferably used as a resist when etching the conductive layer.

The pressure bonding method is not particularly limited, and known transfer methods and lamination methods can be used. Among them, it is preferable that the surface of the refractive index adjustment layer is overlapped on the substrate with the conductive layer, and is pressed and heated by a roller or the like.

The lamination can be performed using a known laminator such as a vacuum laminator and an automatic cutting laminator.

Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.

A preferred embodiment of the substrate is described in, for example, paragraph [0140] of international publication No. 2018/155193, which is incorporated herein by reference.

The conductive layer is preferably at least one layer selected from a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, from the viewpoint of conductivity and fine wire formability.

Further, only 1 conductive layer may be disposed on the substrate, or 2 or more conductive layers may be disposed on the substrate. When 2 or more conductive layers are arranged, conductive layers having different materials are preferable.

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

The substrate with a conductive layer is preferably a substrate having at least one of a transparent electrode and a wiring. Specifically, the substrate with a conductive layer is more preferably a substrate having at least one of an electrode for a touch panel and a wiring for a touch panel. 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) or IZO (indium zinc oxide), or a thin metal wire such as a metal mesh or a silver nanowire.

The metal thin wire may be a thin 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 (wiring for a touch panel), metal is preferable.

Examples of the metal as a material of the routing wire include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and an alloy composed of 2 or more of these metal elements. As a material of the routing wire, copper, molybdenum, aluminum, or titanium is preferable, and copper is particularly preferable.

The electrode protective film for a touch panel formed using the photosensitive composition layer in the transfer film of the present invention is preferably provided so as to cover the electrode or the like directly or via another layer 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).

(Exposure Process)

The exposure step is a step of pattern-exposing the refractive index adjustment layer and the photosensitive composition layer. Here, "pattern exposure" refers to exposure in a pattern-like exposure mode, that is, in a mode in which an exposed portion and a non-exposed portion are present.

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

The light source for pattern exposure may be appropriately selected as long as it can irradiate light (for example, 365nm or 405 nm) in at least the wavelength region of the curable refractive index adjustment layer and the photosensitive composition layer. Among them, the dominant wavelength of exposure light for pattern exposure is preferably 365nm. The dominant wavelength is a wavelength having the highest intensity.

Examples of the light source include various lasers, light Emitting Diodes (LEDs), ultra-high pressure mercury lamps, and metal halide lamps.

The exposure amount is preferably 5 to 200mJ/cm ² More preferably 10 to 200mJ/cm ² 。

Preferable examples of the light source, the exposure amount, and the exposure method used for the exposure include those described in paragraphs [0146] to [0147] of International publication No. 2018/155193, which are incorporated herein by reference.

(peeling step)

The peeling step is a step of peeling the temporary support from the substrate with the photosensitive composition layer between the bonding step and the exposure step or between the exposure step and a developing step described later.

The peeling method is not particularly limited, and the same mechanism as the film peeling mechanism described in paragraphs [0161] to [0162] of japanese patent application laid-open No. 2010-072589 can be used.

(developing step)

The developing step is a step of forming a pattern (film) by developing the exposed refractive index adjustment layer and the photosensitive composition layer.

The refractive index adjustment layer and the photosensitive composition layer can be developed using a developer.

As the developer, an alkaline aqueous solution is preferable. 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-hydroxyethyltrimethylammonium hydroxide).

Examples of the development method include spin immersion development, shower development, spin development, and immersion development.

The developer preferably used in the present invention includes, for example, the developer described in paragraph [0194] of international publication No. 2015/093271, and the developing method preferably used includes, for example, the developing method described in paragraph [0195] of international publication No. 2015/093271.

(post-exposure step and post-baking step ])

The method for producing the laminate may include a step of exposing the pattern obtained in the developing step (post-exposure step) and/or a step of heating the pattern obtained in the developing step (post-baking step).

When both the post-exposure step and the post-baking step are included, it is preferable to perform post-baking after the post-exposure.

(etching Process)

The method for producing a laminate may include an etching step of etching the conductive layer located in the region where no pattern is disposed in the obtained laminate.

In the etching step, the conductive layer is etched using a pattern formed of the refractive index adjustment layer and the photosensitive composition layer in the developing step as a resist.

As the etching treatment method, known methods such as the method described in paragraphs [0209] to [0210] of japanese patent application laid-open No. 2017-120435, the method described in paragraphs [0048] to [0054] of japanese patent application laid-open No. 2010-152155, and a method based on dry etching such as known plasma etching can be applied.

(removal step)

The method for manufacturing the laminate may include a removing step of removing the pattern.

The removal step can be performed as needed, and is preferably performed after the etching step.

The method for removing the pattern is not particularly limited, and a method for removing by a chemical treatment may be mentioned, and a removing solution is preferably used.

The method of removing the pattern includes a method of immersing the patterned laminate in a removing solution which is preferably stirred at 30to 80 ℃, more preferably at 50 to 80 ℃ for 1 to 30 minutes.

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

The removal liquid may be used for removal by a spray method, a shower method, a spin coating and immersion method, or the like.

(other steps)

The method for producing a laminate of the present invention may include any step (other step) other than the above.

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

The laminate produced by the method for producing a laminate of the present invention can be applied to various apparatuses. Examples of the device including the laminate include an input device, preferably a touch panel, and more preferably an electrostatic capacitance type touch panel. The input device can be applied to display devices such as organic electroluminescence display devices and liquid crystal display devices.

When the laminate is applied to a touch panel, the pattern formed from the photosensitive composition layer is preferably used as a protective film for an electrode for a touch panel. That is, the photosensitive composition layer included in the transfer film is preferably used for forming the electrode protection film for a touch panel.

Examples

The present invention will be described in further detail below with reference to examples. The materials, the amounts used, the ratios, the contents of the treatments, the procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below. Unless otherwise specified, "part" and "%" are based on mass.

In the following examples, the weight average molecular weight of the resin was determined by polystyrene conversion based on Gel Permeation Chromatography (GPC). Also, the acid value used is the theoretical acid value.

< Synthesis of Polymer >

(Synthesis of Polymer P-1)

Propylene glycol monomethyl ether (82.4 g, FUJIFILM Wako Pure Chemical Corporation) was added to the flask and heated to 90 ℃ under a stream of nitrogen gas. To this solution, a solution in which styrene (38.4 g, FUJIFIL Wako Pure Chemical Corporation), dicyclopentyl methacrylate (30.1 g, FACTRYL FA-513M, hitachi Chemical Co., ltd.) and methacrylic acid (34.0 g, FUJIFIL Wako Pure Chemical Corporation) were dissolved in propylene glycol monomethyl ether (20 g), and a solution in which a polymerization initiator V-601 (5.4 g, FUJIFIL Wako Pure Chemical Corporation) was dissolved in propylene glycol monomethyl ether acetate (43.6 g, FUJIFIL Wako Pure Chemical Corporation) were simultaneously dropped over 3 hours. After completion of the dropwise addition, V-601 (0.75 g) was added 3 times in total at 1 hour intervals. After that, the solution was allowed to react for further 3 hours. Thereafter, the obtained solution was diluted with propylene glycol monomethyl ether acetate (58.4 g) and propylene glycol monomethyl ether (11.7 g). The solution was warmed to 100 ℃ under a stream of air, and tetraethylammonium bromide (0.53g, FUJIFILM Wako Pure Chemical Corporation) and p-methoxyphenol (0.26g, FUJIFILM Wako Pure Chemical Corporation) were added. To the solution obtained, glycidyl methacrylate (25.5 g, NOF CORPORATION, BLEMMER GH) was added dropwise over 20 minutes. The obtained solution was reacted at 100 ℃ for 7 hours to obtain a solution of a polymer P-1. The solid content concentration of the obtained solution was 36.5 mass%. The weight average molecular weight in terms of standard polystyrene in GPC was 17000, the degree of dispersion was 2.4, and the acid value of the polymer was 94.5mgKOH/g. The amount of residual monomers was less than 0.1% by mass relative to the solid content of the polymer, among all the monomers, as measured by gas chromatography.

(Synthesis of polymers P-2 to P-4)

Polymers P-2 to P-4 were synthesized in the same manner as in the synthesis of polymer P-1 except that the types of the respective structural units and the contents of the respective structural units contained in the polymer were changed as shown in Table 1. All polymers were synthesized as a polymer solution, and the amount of the diluent (PGMEA) was adjusted to a polymer concentration (solid content concentration) in the polymer solution of 36.3 mass%.

(Synthesis of Polymer P' -1)

In a three-necked flask, hydroxyethyl methacrylate (169.2g, FUJIFILM Wako Pure Chemical Corporation), pyridine (108.4 g, FUJIFILM Wako Pure Chemical Corporation) and ethyl acetate (500g, FUJIFILM Wako Pure Chemical Corporation) were added and cooled to 5 ℃. To the obtained solution was added 2-bromoisobutyryl bromide (315g, FUJIFILM Wako Pure Chemical Corporation), and the obtained solution was stirred at room temperature for 3 hours. After the obtained solution was washed with ion-exchanged water (1000 g), p-methoxyphenol (0.09g, FUJIFILM Wako Pure Chemical Corporation) was added, and the solvent was removed under reduced pressure to 30Torr at 40 ℃ to obtain methacrylic acid precursor monomer A (355 g).

Dimethylacetamide (79.6 g) was added to a three-necked flask, and the temperature was raised to 95 ℃ under a nitrogen atmosphere. A solution to which methacrylic acid precursor monomer A (135.2 g), methacrylic acid (24.0 g, FUJIFILM Wako Pure Chemical Corporation), V-601 (6.15 g) and dimethylacetamide (79.6 g) were added was added dropwise over 2 hours to a solution in a three-necked flask maintained at a temperature in the range of 95 ℃. + -. 2 ℃. After the end of the dropwise addition, the obtained solution was stirred at a temperature in the range of 95 ℃. + -. 2 ℃ for 3 hours, whereby a precursor of the polymer P' -1 was obtained.

Then, diazabicyclo (153.4 g, FUJIFILM Wako Pure Chemical Corporation) and dibutylhydroxytoluene (0.12g, FUJIFILM Wako Pure Chemical Corporation) were added to the obtained solution, and after the temperature was raised to 40 ℃, the mixture was stirred for 3 hours. The obtained solution was cooled to 5 ℃ and concentrated hydrochloric acid (51.5 g, FUJIFILM Wako Pure Chemical Corporation) was added, followed by addition of distilled water (1000 g), whereby a solid precipitated. After the supernatant liquid was removed by decantation, the mixture was washed 3 times with distilled water (1000 g), and propylene glycol monomethyl ether (280 g) was added to obtain a propylene glycol monomethyl ether solution (solid content concentration: 25 mass%) of the polymer P' -1.

(Synthesis of Polymer P' -2)

Propylene glycol monomethyl ether (19.5 g) was charged into a three-necked flask, and the temperature was raised to 95 ℃ under a nitrogen atmosphere. A solution to which methacrylic acid (22.8 g), V-601 (3.04 g) and propylene glycol monomethyl ether (19.5 g) were added was added dropwise over 2 hours to a solution in a three-necked flask maintained at a temperature in the range of 95 ℃. + -. 2 ℃. After the end of the dropwise addition, the obtained solution was stirred at a temperature in the range of 95 ℃. + -. 2 ℃ for 3 hours, whereby a precursor of the polymer P' -2 was obtained.

Subsequently, propylene glycol monomethyl ether (32.3 g), dibutylhydroxytoluene (0.17 g), tetraethylammonium bromide (0.28 g) and glycidyl methacrylate (27.3 g) were added to the obtained solution, and after heating to 100 ℃, stirring was carried out for 8 hours, thereby obtaining a propylene glycol monomethyl ether solution (solid content concentration, 40 mass%) of the polymer P' -2.

(Synthesis of Polymer P' -3)

In a three-necked flask, hydroxyethyl methacrylate (180g, FUJIFILM Wako Pure Chemical Corporation) and dimethylacetamide (346 g) were added, and the mixture was cooled to 5 ℃. Next, 2-chloropropionyl chloride (193g, FUJIFILM Wako Pure Chemical Corporation) was added to the three-necked flask, and the obtained solution was stirred at room temperature for 1 hour. Subsequently, ethyl acetate (500g, FUJIFILM Wako Pure Chemical Corporation) was added to the solution to extract an organic phase, and the organic phase was washed with ion-exchanged water (300 g), saturated multi-layer water (300 g), and saturated brine (300 g) in this order. Subsequently, p-methoxyphenol (0.09 g) was added to the obtained solution, and the solvent was removed under reduced pressure of 30Torr at 40 ℃ to obtain an acrylic precursor monomer B (300 g).

Propylene glycol monomethyl ether (35.0 g) was charged into a three-necked flask, and the temperature was raised to 95 ℃ under a nitrogen atmosphere. A solution to which acrylic acid precursor monomer B (40.7 g), acrylic acid (6.0 g, FUJIFILM Wako Pure Chemical Corporation), V-601 (1.85 g) and propylene glycol monomethyl ether (35.0 g) were added was added dropwise over 2 hours to a solution in a three-necked flask maintained at a temperature range of 95 ℃. + -. 2 ℃. After the end of the dropwise addition, the obtained solution was stirred at a temperature in the range of 95 ℃. + -. 2 ℃ for 3 hours, whereby a precursor of the polymer P' -3 was obtained.

Then, triethylamine (36.4 g, FUJIFILM Wako Pure Chemical Corporation) and dibutylhydroxytoluene (0.04 g) were added to the obtained solution, and after the solution was warmed to 50 ℃, it was stirred for 3 hours. The obtained solution was cooled to 5 ℃, and after concentrated hydrochloric acid (17.7 g) was added to the solution, distilled water (400 g) was further added, whereby a solid precipitated. After the supernatant liquid was removed by decantation, the obtained solid content was washed 3 times with distilled water (400 g), and propylene glycol monomethyl ether (93 g) was added to the obtained solid content, thereby obtaining a propylene glycol monomethyl ether solution of the polymer P' -3 (solid content concentration of 25 mass%).

(Synthesis of Polymer P' -4)

Propylene glycol monomethyl ether (25.5 g) was charged into a three-necked flask, and the temperature was raised to 95 ℃ under a nitrogen atmosphere. A solution to which methacrylic acid (26.4 g), cyclohexyl methacrylate (4.7 g, FUJIFILM Wako Pure Chemical Corporation), V-601 (3.8 g) and propylene glycol monomethyl ether (25.5 g) were added was added dropwise over 2 hours to a solution in a three-necked flask maintained at a temperature in the range of 95 ℃. + -. 2 ℃. After the end of the dropwise addition, the obtained solution was stirred at a temperature in the range of 95 ℃. + -. 2 ℃ for 3 hours, whereby a precursor of the polymer P' -4 was obtained.

Subsequently, propylene glycol monomethyl ether (26.8 g), dibutylhydroxytoluene (0.22 g), tetraethylammonium bromide (0.35 g) and glycidyl methacrylate (24.0 g) were added to the obtained solution, and after heating to 100 ℃, stirring was carried out for 8 hours, thereby obtaining a propylene glycol monomethyl ether solution (solid content concentration: 40 mass%) of the polymer P' -4.

(Synthesis of Polymer P' -5)

Propylene glycol monomethyl ether (21.1 g) was charged into a three-necked flask, and the temperature was raised to 95 ℃ under a nitrogen atmosphere. A solution to which methacrylic acid (25.1 g), V-601 (4.0 g) and propylene glycol monomethyl ether (21.1 g) were added was added dropwise over 2 hours to a solution in a three-necked flask maintained at a temperature in the range of 95 ℃. + -. 2 ℃. After the end of the dropwise addition, the obtained solution was stirred at a temperature in the range of 95 ℃. + -. 2 ℃ for 3 hours, whereby a precursor of polymer P-5 was obtained.

Next, propylene glycol monomethyl ether (44.9 g), dibutylhydroxytoluene (0.19 g), tetraethylammonium bromide (0.31 g) and CYCLOMER M-100 (36.2g, daicel Corporation) were added to the obtained solution, and after heating to 100 ℃ and stirring was carried out for 8 hours, a propylene glycol monomethyl ether solution (solid content concentration: 40 mass%) of polymer P' -5 was obtained.

(Synthesis of Polymer P' -6)

Dimethylacetamide (61.6 g) was added to a three-necked flask, and the temperature was raised to 95 ℃ under a nitrogen atmosphere. A solution of methacrylic acid precursor monomer A (76.7 g), methacrylic acid (15.1 g), methyl methacrylate (31.3 g, FUJIFILM Wako Pure Chemical Corporation), V-601 (6.15 g) and dimethylacetamide (61.6 g) used in the synthesis of the polymer P' -1 was added dropwise to the solution in the three-necked flask maintained at a temperature in the range of 95 ℃. + -. 2 ℃ over 2 hours. After the end of the dropwise addition, the obtained solution was stirred at a temperature in the range of 95 ℃. + -. 2 ℃ for 3 hours, whereby a precursor of the polymer P' -6 was obtained.

Then, diazabicyclo (89.5 g) and dibutylhydroxytoluene (0.1 g) were added to the obtained solution, and after the temperature was raised to 40 ℃, the mixture was stirred for 3 hours. The obtained solution was cooled to 5 ℃, and after concentrated hydrochloric acid (30.7 g) was added to the solution, 700g of distilled water was further added, whereby a solid precipitated. After the supernatant liquid was removed by decantation, the obtained solid component was washed 3 times with a mixed solution of propylene glycol monomethyl ether (300 g) and distilled water (1000 g), and propylene glycol monomethyl ether (162 g) was added to the obtained solid component, whereby a propylene glycol monomethyl ether solution of the polymer P' -6 was obtained (solid component concentration of 25 mass%).

(Synthesis of Polymer P' -7)

Dimethylacetamide (55.4 g) was added to a three-necked flask, and the temperature was raised to 95 ℃ under a nitrogen atmosphere. A solution of methacrylic acid precursor monomer A (57.1 g), methacrylic acid (13.2 g), methyl methacrylate (40.6 g), V-601 (6.15 g) and dimethylacetamide (55.4 g) used for the synthesis of polymer P' -1 was added dropwise over 2 hours to a solution in a three-necked flask maintained at a temperature in the range of 95 ℃. + -. 2 ℃. After the end of the dropwise addition, the obtained solution was stirred at a temperature in the range of 95 ℃. + -. 2 ℃ for 3 hours, whereby a precursor of the polymer P' -7 was obtained.

Subsequently, diazabicyclo (70.1 g) and dibutylhydroxytoluene (0.1 g) were added to the obtained solution, and the mixture was heated to 40 ℃ and stirred for 3 hours. The obtained solution was cooled to 5 ℃, and after concentrated hydrochloric acid (24.7 g) was added to the solution, distilled water (700 g) was further added, whereby a solid precipitated. After the supernatant liquid was removed by decantation, the obtained solid content was washed 3 times with a mixed solution of propylene glycol monomethyl ether (300 g) and distilled water (1000 g), and propylene glycol monomethyl ether (125.5 g) was added to the obtained solid content, thereby obtaining a propylene glycol monomethyl ether solution of polymer P' -7 (solid content concentration of 25 mass%).

(Synthesis of Polymer P' -8)

Dimethylacetamide (91.5 g) was added to a three-necked flask, and the temperature was raised to 95 ℃ under a nitrogen atmosphere. A solution containing methacrylic acid precursor monomer A (169.6 g), methacrylic acid (13.4 g), V-601 (6.15 g) and dimethylacetamide (91.5 g) used for the synthesis of polymer P' -1 was added dropwise over 2 hours to a solution in a three-necked flask maintained at a temperature in the range of 95 ℃. + -. 2 ℃. After the end of the dropwise addition, the obtained solution was stirred at a temperature in the range of 95 ℃. + -. 2 ℃ for 3 hours, whereby a precursor of the polymer P' -8 was obtained.

Subsequently, diazabicyclo (162.4 g) and dibutylhydroxytoluene (0.1 g) were added to the obtained solution, and the mixture was stirred for 3 hours after being heated to 40 ℃. The obtained solution was cooled to 5 ℃, and concentrated hydrochloric acid (48.4 g) was added, followed by addition of distilled water (1000 g), whereby a solid precipitated. After the supernatant liquid was removed by decantation, the obtained solid was washed 3 times with a mixed solution of propylene glycol monomethyl ether (300 g) and distilled water (1000 g), and propylene glycol monomethyl ether (312.3 g) was added to the obtained solid, thereby obtaining a propylene glycol monomethyl ether solution of polymer P' -8 (solid concentration of 25 mass%).

(Synthesis of Polymer P' -9)

Dimethylacetamide (94.2 g) was added to a three-necked flask, and the temperature was raised to 95 ℃ under a nitrogen atmosphere. A solution containing methacrylic acid precursor monomer A (177.5 g), methacrylic acid (11.0 g), V-601 (6.15 g) and dimethylacetamide (94.2 g) used for the synthesis of polymer P' -1 was added dropwise over 2 hours to a solution in a three-necked flask maintained at a temperature in the range of 95 ℃. + -. 2 ℃. After the end of the dropwise addition, the obtained solution was stirred at a temperature in the range of 95 ℃. + -. 2 ℃ for 3 hours, whereby a precursor of the polymer P' -9 was obtained.

Then, diazabicyclo (164.6 g) and dibutylhydroxytoluene (0.15 g) were added to the obtained solution, and after the temperature was raised to 40 ℃, the solution was stirred for 3 hours. The obtained solution was cooled to 5 ℃, and after concentrated hydrochloric acid (47.7 g) was added to the solution, distilled water (1000 g) was further added, whereby a solid precipitated. After the supernatant liquid was removed by decantation, the obtained solid was washed 3 times with a mixed solution of propylene glycol monomethyl ether (300 g) and distilled water (1000 g), and propylene glycol monomethyl ether 319.6g was added to the obtained solid, thereby obtaining a propylene glycol monomethyl ether solution of polymer P' -9 (solid concentration of 25 mass%).

(Synthesis of Polymer P' -10)

Dimethylacetamide (106.5 g) was added to a three-necked flask, and the temperature was raised to 95 ℃ under a nitrogen atmosphere. A solution containing methacrylic acid precursor monomer A (213.0 g), V-601 (6.15 g) and dimethylacetamide (106.5 g) used for the synthesis of polymer P' -1 was added dropwise over 2 hours to a solution in a three-necked flask maintained at a temperature in the range of 95 ℃. + -. 2 ℃. After the end of the dropwise addition, the obtained solution was stirred at a temperature ranging from 95 ℃. + -. 2 ℃ for 3 hours, whereby a precursor of the polymer P' -10 was obtained.

Then, diazabicyclo (174.3 g) and dibutylhydroxytoluene (0.15 g) were added to the obtained solution, and after the temperature was raised to 40 ℃, the solution was stirred for 3 hours. The obtained solution was cooled to 5 ℃, and after concentrated hydrochloric acid (44.5 g) was added to the solution, distilled water (1100 g) was further added, whereby a solid precipitated. After removing the supernatant liquid by decantation, the obtained solid was washed 3 times with a mixed solution of propylene glycol monomethyl ether (300 g) and distilled water (1000 g), and propylene glycol monomethyl ether (352.9 g) was added to the obtained solid, thereby obtaining a propylene glycol monomethyl ether solution (solid concentration of 25 mass%) of the polymer P' -10.

(Synthesis of Polymer P' -11)

Propylene glycol monomethyl ether (37.5 g) was charged into a three-necked flask, and the temperature was raised to 90 ℃ under a nitrogen atmosphere. A solution to which methyl methacrylate (14.0 g), ethyl acrylate (28.95 g), acrylic acid (7.05 g), V-601 (2.43 g) and propylene glycol monomethyl ether (37.5 g) were added was added dropwise over 2 hours to a solution in a three-necked flask maintained at a temperature in the range of 90 ℃. + -. 2 ℃. After completion of the dropwise addition, the obtained solution was stirred at a temperature in the range of 90 ℃. + -. 2 ℃ for 2 hours, and propylene glycol monomethyl ether (41.7 g) was added to obtain a propylene glycol monomethyl ether solution of the polymer P' -11 (solid content concentration of 40 mass%).

(Synthesis of Polymer P' -12)

Propylene glycol monomethyl ether (270.0 g) was introduced into a three-necked flask, and the temperature was raised to 70 ℃ under a nitrogen stream while stirring. On the other hand, a dropping solution was prepared by dissolving allyl methacrylate (45.6 g, FUJIFILM Wako Pure Chemical Corporation) and methacrylic acid (14.4 g) in propylene glycol monomethyl ether (270.0 g), and further dissolving V-65 (3.94g, FUJIFILM Wako Pure Chemical Corporation), and was added dropwise to the flask over 2.5 hours. The obtained solution was kept in a stirred state and allowed to react for 2 hours. Thereafter, the temperature of the obtained solution was returned to room temperature, dropped into ion-exchanged water (2.7L) in a stirred state, and reprecipitation was carried out, thereby obtaining a suspension. The suspension was introduced into a suction filter with filter paper and filtered, and the filtrate was further washed with ion-exchanged water to obtain a wet powder. Subsequently, the polymer P '-12 was dried at 45 ℃ with air blowing, and was confirmed to be constant, and a powder of the polymer P' -12 was obtained at a yield of 70%.

In table 1, regarding structural units other than the structural unit having a (meth) acryloyl group, abbreviations of monomers used to form the respective structural units are given.

The structural unit having a (meth) acryloyl group is represented as an addition structure of a monomer and a monomer. For example, MAA-GMA is a structural unit obtained by adding glycidyl methacrylate to a structural unit derived from methacrylic acid.

[ Table 1]

TABLE 1

The abbreviations have the following meanings.

St: styrene (FUJIFILM Wako Pure Chemical Corporation)

MAA-GMA: structural unit obtained by adding glycidyl methacrylate to structural unit derived from methacrylic acid

MAA: methacrylic acid (FUJIFILM Wako Pure Chemical Corporation)

DCPMA: dicyclopentyl methacrylate (FANCRYL FA-513M, hitachi Chemical Co., ltd.)

CHMA: cyclohexyl methacrylate (CHMA, MITSUBISHI GAS CHEMICAL COMPANY, INC.)

MMA: methyl methacrylate (FUJIFILM Wako Pure Chemical Corporation)

EA: ethyl acrylate (FUJIFILM Wako Pure Chemical Corporation)

In table 2, the column "C = C valence" indicates the content of (meth) acryloyl groups in the polymer.

[ Table 2]

TABLE 2 (1)

[ Table 3]

TABLE 2 (its 2)

(Synthesis of blocked isocyanate Compound Q-1)

Butanone oxime (453g, idemitsu Kosan Co., ltd.) was dissolved in methyl ethyl ketone (700 g) under a nitrogen stream. 1,3-bis (isocyanotomethyl) cyclohexane (500 g, cis-trans isomer mixture, manufactured by Mitsui Chemicals, inc., manufactured by Takenate 600) was added dropwise thereto under ice-cooling over 1 hour, and the solution was further reacted for 1 hour after the dropwise addition. After that, the obtained solution was heated to 40 ℃ to react for 1 hour. By passing ¹ After completion of the reaction, H-NMR and HPLC confirmed that a methyl ethyl ketone solution of a blocked isocyanate compound Q-1 (the following structural formula) was obtained.

[ chemical formula 30]

< preparation of photosensitive composition >

In each of examples and comparative examples, materials A-1 to A-5, which were photosensitive compositions having the compositions shown in Table 3, were prepared. In Table 3, the numerical values of the respective components indicate the contents (parts by mass) of the respective components, and the amounts of the polymers P-1 to P-4 indicate the amounts of the polymer solutions (polymer concentration: 36.3% by mass).

[ Table 4]

TABLE 3

< preparation of composition for Forming refractive index adjustment layer >

Next, materials B-1 to B-17, which were compositions for forming a refractive index adjustment layer, were prepared in the compositions shown in Table 4 below.

[ Table 5]

TABLE 4 (its 1)

[ Table 6]

TABLE 4 (2)

[ Table 7]

TABLE 4 (its 3)

< production of transfer films of examples 1 to 19 and comparative examples 1 to 2 >

The coating amount was adjusted to a coating amount after drying so that the thickness became the thickness of table 5 by using a slit nozzle, and any one of the materials a-1 to a-5 of the photosensitive composition described in table 3 was coated on a temporary support of a polyethylene terephthalate film (manufactured by Lumirror 169440, toray industries, inc.) having a thickness of 16 μm, thereby forming a photosensitive composition layer.

After the solvent was evaporated from the photosensitive composition layer in the drying zone at 100 ℃, the refractive index adjusting layer was formed by using 1 of the materials B-1 to B-17 of the refractive index adjusting layer forming composition described in table 4 in combination of table 5 by a slit nozzle, adjusting the amount of application to the thickness after drying to the thickness described in table 5, applying the coating to the photosensitive composition layer, and then drying at a drying temperature of 80 ℃. Transfer films of examples 1 to 19 and comparative examples 1 to 2 were prepared by pressure-bonding a protective film (Lumirror 169440, toray industries, inc.) to the refractive index adjustment layer.

< preparation of transparent film substrate with refractive index adjusting layer >

(preparation of laminated film (substrate film/hard coat layer))

As a raw material of the curable composition for forming a hard coat layer, the following components (a), (B), (C), and (D) were first prepared.

(A) Synthesis of acrylic resin having polymerizable double bond (high-molecular acrylate)

An acrylic resin having an epoxy group derived from glycidyl methacrylate was synthesized by solution-polymerizing glycidyl methacrylate (80 parts by mass), methyl methacrylate (18 parts by mass), and ethyl acrylate (2 parts by mass) in methyl isobutyl ketone by a conventional method. By the reaction of the epoxy group of the obtained acrylic resin with acrylic acid, an acrylic resin (high molecular acrylate) having an acryloyloxy group is obtained. For 1 equivalent of glycidyl methacrylate used in the polymerization reaction, 1 equivalent of acrylic acid was used in the reaction. The weight-average molecular weight of the obtained high-molecular acrylic ester was 15000, and the double bond equivalent (molecular weight/number of polymerizable bonds in the same molecule) was 256.

(B) Polyfunctional polymerizable compound

B1: caprolactone-modified dipentaerythritol hexaacrylate (double bond equivalent: 135, nippon Kayaku Co., ltd., KAYARAD DPCA-20, hexa-functional)

B2: ethylene oxide-modified polyglycerol polyacrylate (double bond equivalent: 244, SHIN-NAKAMURA CHEMICAL Co., ltd., manufactured by Ltd., NK ECONOMER A-PG5027E, nine functions)

(C) Alkyleneoxy-modified bisphenol A diacrylate

EO-modified bisphenol A diacrylate (Hitachi Chemical Co., ltd., FANCRYL FA-323A, ltd.)

(D) Urethane acrylate

10 functional urethane acrylate (double bond equivalent: 116, hitachi Chemical Co., ltd., HITALOID HA7909-1 manufactured by Ltd.)

As the ratio of the solid components (components other than the solvent), 20 parts by mass of component (a), 20 parts by mass of component (B) B1, 52 parts by mass of component (B) B2, 15 parts by mass of component (C), 3 parts by mass of component (D), and methyl isobutyl ketone (150 parts by mass) as a solvent were mixed, and stirred at 40 ℃ for 1 hour to obtain a solution of the curable component.

The curable composition for coating was prepared by stirring and mixing a solution (100 parts by mass) of the curable component, a silica particle sol (40 parts by mass) (the amount of silica particles), a leveling agent (UV-3500 manufactured by BYK-Chemie GmbH) (0.5 parts by mass), and a photopolymerization initiator (IRGACURE 184, manufactured by BASF) (4 parts by mass) in methyl isobutyl ketone with a stirrer. As the silica particle sol, methyl ethyl ketone silica sol (MEK-ST-L manufactured by Nissan Chemical Corporation, number average particle diameter 0.056 μm, silica particle concentration 30 mass%, spherical) was used. The curable composition for forming a hard coat layer is used for producing a laminated film.

As the substrate film, a cyclic olefin resin film (product name: zeonorFilm ZF16, manufactured by Zeon Corporation, glass transition temperature: 163 ℃ C.) having a thickness of 100 μm was prepared. The curable composition for forming a hard coat layer was applied to one surface of the substrate film by a bar coater in a thickness of 2.5 μm. The coating film was dried by heating in a dryer for 1 minute. The dried coating was irradiated with 400mJ/cm using a transmission type high-pressure mercury lamp ² Light amount of ultraviolet rays. By ultraviolet irradiation, a cured film of the curable composition for forming a hard coat layer was formed, and a laminated film (substrate film/hard coat layer) was obtained. Irradiating ultraviolet raysIn this case, nitrogen gas is introduced so that the oxygen concentration becomes 10ppm by volume or less.

(production of transparent film substrate with refractive index adjusting layer (substrate film/hard coat layer/refractive index adjusting layer))

Zirconium oxide particles (30.0 g, daiichi Kigenno KAGAKU KOGYO CO., LTD., manufactured by UEP-100,1, average particle diameter of the secondary particles: 10 to 20 nm) were blended with 3-methacryloxypropyltrimethoxysilane (6.0 g, dow Corning Toray Co., manufactured by Ltd., Z6030) and methyl ethyl ketone (64.0 g), and dispersion treatment was performed under a bead mill condition at a peripheral speed of 8m/s for 30 minutes to recover a treatment liquid. Subsequently, 2-methacryloyloxyethyl isocyanate (2.0 g, manufactured by SHOWA DENKO K.K, karenz MOI) was added to the treatment liquid (100.0 g), and the mixture was dispersed for 1 hour by an ultrasonic disperser to obtain a dispersion containing 37 mass% of the surface-treated zirconia particles (Z-1).

The particle size distribution was measured by a dynamic light scattering particle size distribution measuring apparatus "LB-550" (manufactured by HORIBA, ltd.), and as a result, the cumulative 50% particle size (D50) of the zirconia particles (Z-1) was 24.2nm. The refractive index of the zirconia particles (Z-1) was measured by an Abbe refractometer (ATAGO CO., LTD., manufactured by LTD.; measurement wavelength: 589 nm), and was found to be 2.0.

In a vessel shielded from ultraviolet light, a dispersion (63 parts by mass) of zirconia particles (Z-1), ABPEF (5 parts by mass, SHIN-NAKAMURA CHEMICAL co., ltd.), a-DPH (10 parts by mass, SHIN-NAKAMURA CHEMICAL co., ltd.), and IRGACURE TPO (2 parts by mass, BASF Japan ltd., ltd.), were added to propylene glycol monomethyl ether (20.0 parts by mass), and stirred at room temperature for 2 hours, whereby a curable composition for forming a refractive index adjustment layer having a solid content concentration of 40 mass% was obtained.

The obtained curable composition for forming a refractive index adjustment layer was applied to the laminated film (substrate film/hard coat layer) prepared above using a bar coater. After the obtained coating film was dried at 80 ℃ for 2 minutes, the film was irradiated with an irradiation dose of 250mJ/cm under air using an electrodeless lamp system ² (UV Power Map, heraeus K.K., measuring wavelength UV-A) ultraviolet ray, and Sup>A cured film having Sup>A thickness of 100nm was formed as Sup>A transparent film substrate with Sup>A refractive index adjusting layerA material is provided.

< preparation of laminate for evaluation >

On the transparent film base with the refractive index adjustment layer prepared above, the protective films of the transfer films of examples and comparative examples were peeled off, and the exposed refractive index adjustment layer was laminated by adhering to the surface of the refractive index adjustment layer of the transparent film base, thereby forming a laminate a having a layer structure of a temporary support, a photosensitive composition layer, a refractive index adjustment layer, and a transparent film base with a refractive index adjustment layer. The lamination conditions at this time were set to a lamination roll temperature of 100 ℃, a linear pressure of 0.6MPa, and a carrying speed of 2 m/min.

< evaluation of undercut >

Using a proximity exposure machine (manufactured by Hitachi High-Tech Corporation) equipped with an ultra-High pressure mercury lamp, the temporary support was not peeled off, and the exposure amount was 120mJ/cm through a mask having a pattern of L/S =1000 μm/1000 μm ² (i-ray), the laminate A thus produced was exposed to light. After exposure, the temporary support was left to stand for 1 hour, and then peeled off, followed by development for 45 seconds using a 1 mass% aqueous solution of sodium carbonate (liquid temperature 33 ℃) to remove the refractive index adjustment layer and the photosensitive composition layer in the unexposed portion. Also, moisture is removed by blowing air.

After removing the refractive index adjusting layer and the photosensitive composition layer by development, the cross section was observed by SEM (scanning electron microscope), and undercut at the end of the 1000 μm line pattern was observed. From the observation results, undercutting was evaluated according to the following evaluation criteria.

Among the evaluation criteria described below, A, B, C is suitable for practical use, and a is most preferred. The evaluation results are shown in table 5. In addition, the distance of the undercut below refers to the distance of the undercut extending from the end portion of the pattern toward the central portion.

Evaluation criterion of development residue-

A: the distance of the undercut is less than 1 μm.

B: the distance of the undercut is 1 μm or more and less than 3 μm.

C: the distance of the undercut is 3 μm or more and less than 5 μm.

D: the distance of the undercut is 5 μm or more and less than 10 μm.

E: the distance of the undercut is 10 μm or more.

< evaluation of development residue >

The protective film was peeled off from the transfer films of the examples and comparative examples, and the transfer film from which the protective film was peeled was laminated on a cycloolefin resin film on which a copper foil was laminated under lamination conditions of a roll temperature of 100 ℃, a line pressure of 0.6MPa, and a carrying speed of 2 m/min, thereby transferring the refractive index adjustment layer and the photosensitive composition layer of the transfer film to the surface of the copper foil.

After the temporary support was peeled off from the laminate and left to stand for 24 hours after peeling, the refractive index adjusting layer and the photosensitive composition layer were removed by development for 45 seconds using a 1 mass% aqueous solution of sodium carbonate (liquid temperature 33 ℃ C.) as a developer. Also, moisture is removed by blowing air.

After the refractive index adjusting layer and the photosensitive composition layer were removed by development, the cross section was observed with a TEM (transmission electron microscope), and the development residue on the copper foil was confirmed. From the observation results, the development residue was evaluated according to the following evaluation criteria.

Among the evaluation criteria described below, A, B, C is suitable for practical use, and a is most preferred. The evaluation results are shown in table 5.

Evaluation criteria for development residues-

A: the thickness of the residue on the copper foil after the removal of the refractive index adjusting layer and the photosensitive composition layer by development is less than 10nm.

B: the thickness of the residue on the copper foil after the removal of the refractive index adjustment layer and the photosensitive composition layer by development is 10nm or more and less than 20nm.

C: the thickness of the residue on the copper foil after the removal of the refractive index adjustment layer and the photosensitive composition layer by development is 20nm or more and less than 30nm.

D: the thickness of the residue on the copper foil after the removal of the refractive index adjustment layer and the photosensitive composition layer by development is 30nm or more and less than 50nm.

E: the thickness of the residue on the copper foil after the removal of the refractive index adjusting layer and the photosensitive composition layer by development is 50nm or more.

< production of transparent electrode pattern film for producing laminate for evaluation of concealment of transparent electrode pattern >

(formation of film with transparent electrode layer)

The transparent film substrate with the refractive index adjusting layer obtained above was introduced into a vacuum chamber, and SnO was used ₂ An ITO target having a content of 10 mass% (indium: tin = 95: 5 (molar ratio)), and an ITO thin film having a thickness of 40nm and a refractive index of 1.82 was formed by Direct Current (DC) magnetron sputtering (conditions: temperature of the transparent film substrate was 150 ℃, argon partial pressure was 0.13Pa, and oxygen partial pressure was 0.01 Pa), thereby obtaining a film in which a transparent electrode layer was formed on the refractive index adjustment layer. The surface resistance of the ITO film was 80. Omega./m ² )。

(preparation of photosensitive film for etching E1)

A thermoplastic resin layer-forming composition consisting of the following formulation H1 was applied to a polyethylene terephthalate film temporary support having a thickness of 75 μm by means of a slit nozzle and dried. Next, an intermediate layer-forming composition composed of the following formulation P1 was applied and dried. A photocurable resin layer-forming composition for etching composed of the following formulation E1 was further applied and dried. By the above method, a laminate comprising a thermoplastic resin layer having a dry thickness of 15.1 μm, an intermediate layer having a dry thickness of 1.6 μm, and a photocurable resin layer for etching having a thickness of 2.0 μm was produced on the temporary support, and finally a protective film (polypropylene film having a thickness of 12 μm) was pressure-bonded. Thus, an etching photosensitive film E1, which is a transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the etching photocurable resin layer are integrated, was produced.

Composition for forming a photocurable resin layer for etching: formula E1-

Methyl methacrylate/styrene/methacrylic acid copolymer (copolymer composition (mass%): 31/40/29, weight average molecular weight 60,000, acid value 163 mgKOH/g): 16 parts by mass

Monomer 1 (trade name: BPE-500, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.): 5.6 parts by mass

0.5 mol adduct of tetracyclooxyethane monomethacrylate of hexamethylene diisocyanate: 7 parts by mass

Cyclohexane dimethanol monoacrylate as a compound having 1 polymerizable group in the molecule: 2.8 parts by mass

2-chloro-N-butylacridone: 0.42 part by mass

2,2-bis (o-chlorophenyl) -4,4',5,5' -tetraphenylbiimidazole: 2.17 parts by mass

Malachite green oxalate: 0.02 part by mass

Colorless crystal violet: 0.26 part by mass

Phenothiazine: 0.013 parts by mass

Surfactant (trade name: MEGAFACE F-780F, manufactured by DIC Corporation): 0.03 parts by mass

Methyl ethyl ketone: 40 parts by mass

1-methoxy-2-propanol: 20 parts by mass

The viscosity of the composition E1 for forming a photocurable resin layer for etching at 100 ℃ after removal of the solvent was 2,500pa · sec.

-composition for forming thermoplastic resin layer: formula H1-

Methanol: 11.1 parts by mass

Propylene glycol monomethyl ether acetate: 6.36 parts by mass

Methyl ethyl ketone: 52.4 parts by mass

Methyl methacrylate/2-ethylhexyl acrylate/benzyl methacrylate/methacrylic acid copolymer (copolymerization composition ratio (molar ratio) =55/11.7/4.5/28.8, molecular weight =10 ten thousand, glass transition temperature (Tg)

70 ℃): 5.83 parts by mass

Styrene/acrylic acid copolymer (copolymerization composition ratio (molar ratio) =63/37, weight average molecular weight =1 ten thousand, tg

100 ℃): 13.6 parts by mass

Monomer 1 (trade name: BPE-500, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.): 9.1 parts by mass

Fluorine-based polymer [ the following components ]: 0.54 parts by mass

Fluorine-based polymer: c ₆ F ₁₃ CH ₂ CH ₂ OCOCH＝CH ₂ (40 parts by mass), H (OCH (CH) ₃ )CH ₂ ) ₇ OCOCH＝CH ₂ (55 parts by mass) with H (OCHCH) ₂ ) ₇ OCOCH＝CH ₂ (5 parts by mass) of a copolymer (weight-average molecular weight: 3 ten thousand, 30% by mass solution of methyl ethyl ketone (trade name: MEGAFACE F F, manufactured by DIC Corporation))

-composition for intermediate layer formation: formula P1-

Polyvinyl alcohol (trade name: PVA205, KURARAY co., ltd., saponification degree =88%, polymerization degree 550): 32.2 parts by mass

Polyvinylpyrrolidone (trade name: K-30, ashland Japan. Co., manufactured by Ltd.): 14.9 parts by mass

Distilled water: 524 parts by mass

Methanol: 429 parts by mass

(formation of transparent electrode Pattern)

The photosensitive film E1 for etching from which the protective film was removed was laminated on the film having the transparent electrode layer formed on the refractive index adjustment layer prepared above. Temperature at the transparent film substrate: lamination was performed under lamination conditions of 130 ℃, rubber roll temperature 120 ℃, linear pressure 100N/cm, and carrying speed 2.2 m/min.

After the temporary support was peeled off, the distance between the surface of the exposure mask (quartz exposure mask having a transparent electrode pattern) and the above-mentioned photo-curable resin layer for etching was set to 200 μm, and the exposure amount was 50mJ/cm ² (i-ray) a pattern exposure was performed.

Subsequently, the substrate was treated with a triethanolamine-based developer (containing 30% by mass of triethanolamine, a liquid diluted 10-fold with pure water under the trade name of T-PD2 (manufactured by Fujifilm Corporation)) at 25 ℃ for 100 seconds, a cleaning liquid containing a surfactant (a liquid diluted 10-fold with pure water under the trade name of T-SD3 (manufactured by Fujifilm Corporation)) at 33 ℃ for 20 seconds, the residue was removed by a rotary brush or an ultrahigh pressure cleaning nozzle, and post-baking treatment was further performed at 130 ℃ for 30 minutes, thereby obtaining a film in which a transparent electrode layer and a photo-curable resin layer pattern for etching were formed on the refractive index adjustment layer of the transparent film substrate.

The film having the transparent electrode layer and the pattern of the photocurable resin layer for etching formed thereon was immersed in an etching bath containing an etching solution for ITO (hydrochloric acid, aqueous potassium chloride solution, liquid temperature 30 ℃) and treated for 100 seconds to dissolve and remove the transparent electrode layer in the region not covered with the photocurable resin layer for etching but exposed, thereby obtaining a film having a transparent electrode pattern having a pattern of the photocurable resin layer for etching.

Subsequently, the film with the transparent electrode pattern having the pattern of the photo-curable resin layer for etching was immersed in a resist stripping bath to which a resist stripping solution (N-methyl-2-pyrrolidone, monoethanolamine, and a surfactant (trade name: surfynol 465, manufactured by air Products and Chemicals, inc.) was added at a liquid temperature of 45 ℃ C.) and treated for 200 seconds to remove the photo-curable resin layer for etching, thereby obtaining a film having the transparent electrode pattern formed on the refractive index adjustment layer of the transparent film substrate.

< preparation of transparent laminate >

The transfer films of the examples and comparative examples, from which the protective film was peeled off, were used to transfer the refractive index adjustment layer and the transparent electrode pattern of the film, in which the transparent electrode pattern was formed on the refractive index adjustment layer of the transparent film base material, to the positions covered with the transfer film. As a result, the refractive index adjustment layer, the photosensitive composition layer, and the temporary support are sequentially transferred onto the refractive index adjustment layer and the transparent electrode pattern of the transparent film substrate by the transfer film. The transfer printing was performed using a vacuum laminator manufactured by LTD, MCK CO., under conditions of a transparent film substrate temperature of 40 ℃, a rubber roller temperature of 100 ℃, a line pressure of 3N/cm, and a carrying speed of 2 m/min.

Thereafter, the surface of the exposure mask (quartz exposure mask having a pattern for forming a top coat layer) was brought into close contact with the temporary support interposed therebetween by a proximity exposure machine (manufactured by Hitachi High-Tech Sokurations Corporation) equipped with an ultra-High pressure mercury lampA support body with an exposure of 100mJ/cm ² (i-ray) a pattern exposure was performed.

After the temporary support was peeled off, development treatment was performed at 32 ℃ for 60 seconds using a 1 mass% aqueous solution of sodium carbonate. Thereafter, the developed transparent film substrate was sprayed with ultrapure water from an ultrahigh pressure cleaning nozzle, thereby removing the residue. Subsequently, moisture on the transparent film substrate was removed by air blowing, and post-baking treatment was performed at 145 ℃ for 30 minutes to form a transparent laminate in which a refractive index adjusting layer, a transparent electrode pattern, and a pattern formed of a refractive index adjusting layer and a photosensitive composition layer were sequentially stacked on the transparent film substrate.

[ evaluation of transparent laminate ]

< evaluation of concealing Property of transparent electrode Pattern >

A transparent laminate, in which a refractive index adjustment layer, a transparent electrode pattern, and a pattern formed of a refractive index adjustment layer and a photosensitive composition layer are sequentially laminated, is bonded to a black PET material with a transparent adhesive Tape (product name: OCA Tape 8171CL, manufactured by 3M Japan Limited) on a transparent film substrate, thereby shielding the entire substrate from light.

The concealing property of the transparent electrode pattern was evaluated by the following method: in a darkroom, a fluorescent lamp (light source) and the manufactured substrate were irradiated with light from the glass surface side, and the reflected light from the glass surface was observed visually from an oblique direction. More preferably A or B, and especially preferably A.

Evaluation criteria

A: the transparent electrode pattern is not visible at all.

B: the transparent electrode pattern is visible (not readily discernible).

C: the transparent electrode pattern is clearly visible (easily resolved).

[ Table 8]

As shown in table 5, the transfer film of the present invention exhibited desired effects.

In particular, it was confirmed from comparison of examples 6 and 7 with the other examples that the occurrence of undercut was more suppressed in the case where the C = C valence was 2.50mmol/g or more (preferably 3.00mmol/g or more).

Further, from comparison of examples 9 and 10 with other examples, it was confirmed that the development residue was less likely to remain when the acid value was 60mgKOH/g or more.

Further, it was confirmed from the comparison between example 16 and other examples that the occurrence of undercut was more suppressed when the photosensitive composition layer contained an oxime ester compound or a phosphine oxide compound.

Claims

1. A transfer film comprising a temporary support, a photosensitive composition layer, and a refractive index adjustment layer in this order,

the refractive index adjustment layer contains at least one material selected from the group consisting of a metal oxide, a compound having a triazine ring, and a compound having a fluorene skeleton, and a polymer containing a structural unit having a (meth) acryloyl group.

2. The transfer film according to claim 1,

the content of (meth) acryloyl groups in the polymer is 2.50mmol/g or more.

3. The transfer film according to claim 1 or 2,

the polymer also comprises structural units having acid groups.

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

the acid value of the polymer is 60mgKOH/g or more.

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

the refractive index adjustment layer has a thickness of 500nm or less.

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

7. The transfer film according to any one of claims 1 to 6,

the content of the material is 50 mass% or more with respect to the total mass of the refractive index adjustment layer.

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

the refractive index of the refractive index adjustment layer is 1.60 or more.

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

the photosensitive composition layer includes a binder polymer, a polymerizable compound, and a polymerization initiator.

10. The transfer film according to claim 9,

the polymerization initiator includes at least one selected from an oxime ester compound and a phosphine oxide compound.

11. The transfer film according to any one of claims 1 to 10,

12. A method of manufacturing a laminate, comprising:

a bonding step of bonding a substrate with a conductive layer, which has a substrate and a conductive layer disposed on the substrate, to the transfer film according to any one of claims 1 to 11 to obtain a substrate with a photosensitive composition layer, which has the substrate, the conductive layer, the refractive index adjustment layer, the photosensitive composition layer, and the temporary support in this order;

a developing step of developing the exposed refractive index adjustment layer and the photosensitive composition layer to form a pattern,

the method for producing a laminate further comprises a peeling step of peeling the temporary support from the substrate with the photosensitive composition layer between the bonding step and the exposure step or between the exposure step and the development step.

13. The method for producing a laminate according to claim 12,

the substrate with the conductive layer is a substrate having at least one of an electrode for a touch panel and a wiring for a touch panel.