CN116149136A

CN116149136A - Photosensitive composition, laminate, pattern forming method, and patterned laminate

Info

Publication number: CN116149136A
Application number: CN202211431251.6A
Authority: CN
Inventors: 藤本进二; 有富隆志; 片山晃男
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2021-11-22
Filing date: 2022-11-15
Publication date: 2023-05-23
Also published as: JP2023076241A

Abstract

The invention provides a photosensitive composition, a laminate, a pattern forming method and a patterned laminate, wherein the photosensitive composition comprises a layer containing a metal nanomaterial capable of inhibiting migration and performing alkali development. In the photosensitive composition, the laminate, the pattern forming method, and the patterned laminate, the photosensitive composition contains a metal nanomaterial and an alkali-soluble compound.

Description

Photosensitive composition, laminate, pattern forming method, and patterned laminate

Technical Field

The invention relates to a photosensitive composition, a laminate, a pattern forming method and a patterned laminate.

Background

The layer containing a metal nanomaterial such as silver nanowires has high conductivity and transparency, and is therefore useful as a transparent conductive film. Further, a layer containing silver nanowires or the like can form a film having a higher strength than an inorganic transparent conductive film (for example, an ITO film, an IZO film or the like) which has been widely used conventionally, and therefore is expected to be used as a transparent conductive film for a flexible and foldable touch panel.

Techniques for forming a layer containing silver nanowires and a conductive pattern using the layer are disclosed in, for example, patent documents 1 to 6.

Patent document 1: japanese patent laid-open publication No. 2019-117794

Patent document 2: international publication No. 2010/021224

Patent document 3: japanese patent laid-open publication No. 2011-175972

Patent document 4: international publication No. 2014/196154

Patent document 5: international publication No. 2013/151052

Patent document 6: international publication No. 2015/049939

When a voltage is applied to a printed circuit board under an environmental condition where water (humidity) is large, so-called ion migration (hereinafter, simply referred to as "migration") is likely to occur, that is, a phenomenon in which metal of an anode of a conductive pattern (hereinafter, simply referred to as "pattern") is ionized and moved to an opposing cathode, and is generated again as metal at the cathode, and short circuit (short circuit) is likely to occur between wirings. In forming such a conductive pattern, for example, as disclosed in patent documents 1 to 6, the following steps are required: after forming the layer containing silver nanowires, other resin layers and the like are laminated and etching and the like are performed. However, this step tends to leave water on the pattern, and thus migration may be deteriorated.

Disclosure of Invention

The present invention has been made in view of such circumstances, and an object of an embodiment of the present invention is to provide a photosensitive composition for forming a layer containing a metal nanomaterial that suppresses migration and can be alkali-developed.

Another object of the present invention is to provide a laminate containing a metal nanomaterial that suppresses migration and can be alkali-developed.

Another object of the present invention is to provide a pattern forming method using the laminate.

Another object of the present invention is to provide a patterned laminate obtained from the laminate.

The present invention includes the following means.

<1> a photosensitive composition containing a metal nanomaterial and an alkali-soluble compound.

<2> the photosensitive composition according to <1>, which satisfies at least one of the following (1) and (2).

(1) Contains a photopolymerizable compound, and an alkali-soluble resin.

(2) The alkali-soluble compound is an alkali-soluble photopolymerizable compound.

<3> the photosensitive composition according to <2>, wherein the alkali-soluble resin is a carboxyl group-containing resin.

<4> the photosensitive composition according to <2> or <3>, wherein the alkali-soluble photopolymerizable compound is a carboxyl group-containing photopolymerizable compound.

<5> a laminate, which has, in order:

a substrate; a kind of electronic device with high-pressure air-conditioning system

A photosensitive layer containing a metal nanomaterial and an alkali-soluble compound.

<6> a laminate, which has, in order:

a substrate;

a layer containing metallic nanomaterial; a kind of electronic device with high-pressure air-conditioning system

A photosensitive layer containing an alkali-soluble compound.

<7> a laminate, which has, in order:

a substrate;

a photosensitive layer containing an alkali-soluble compound; a kind of electronic device with high-pressure air-conditioning system

A layer containing metallic nanomaterial.

<8> the laminate according to any one of <5> to <7>, which satisfies at least one of the following (1) and (2).

(1) Contains a photopolymerizable compound, and an alkali-soluble resin.

<9> the laminate according to <8>, wherein the alkali-soluble resin is a carboxyl group-containing resin.

<10> the laminate according to <8> or <9>, wherein the alkali-soluble photopolymerizable compound is a carboxyl group-containing photopolymerizable compound.

<11> the laminate according to any one of <5> to <10>, which has an oxygen barrier layer on the side of the photosensitive layer opposite to the side having the substrate.

<12> the laminate according to <11>, wherein the oxygen barrier layer contains one or more selected from the group consisting of polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, and polyamide-based resins.

<13> the laminate according to any one of <5> to <12>, which has photosensitive layers on both sides of the substrate,

the absorbance at 365nm of the substrate is 0.5 or more.

<14> a pattern forming method, comprising:

a step of preparing a laminate according to any one of <5> to <12 >;

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

And developing the pattern-exposed photosensitive layer.

<15> a pattern forming method, comprising:

a step of preparing a laminate having, in order, a first photosensitive layer containing a metal nanomaterial and an alkali-soluble compound, a substrate including a region having a transmittance for light of an exposure wavelength, and a second photosensitive layer containing a metal nanomaterial and an alkali-soluble compound;

exposing the first photosensitive layer;

exposing the second photosensitive layer;

developing the exposed first photosensitive layer to form a first resin pattern; a kind of electronic device with high-pressure air-conditioning system

Developing the exposed second photosensitive layer to form a second resin pattern,

a main wavelength lambda of an exposure wavelength in the step of exposing the first photosensitive layer ₁ Exposing the second photosensitive layerThe main wavelength lambda of the exposure wavelength in the step (2) ₂ Satisfy lambda ₁ ≠λ ₂ Is a relationship of (3).

<16> a pattern forming method, comprising:

a step of preparing a laminate having, in order, a layer containing a metal nanomaterial, a first photosensitive layer containing an alkali-soluble compound, a substrate including a region having transparency to light of an exposure wavelength, a layer containing a metal nanomaterial, and a second photosensitive layer containing an alkali-soluble compound;

exposing the first photosensitive layer;

exposing the second photosensitive layer;

a main wavelength lambda of an exposure wavelength in the step of exposing the first photosensitive layer ₁ And a main wavelength lambda of an exposure wavelength in the step of exposing the second photosensitive layer ₂ Satisfy lambda ₁ ≠λ ₂ Is a relationship of (3).

<17> a pattern forming method, comprising:

a step of preparing a laminate having, in order, a first photosensitive layer containing an alkali-soluble compound, a layer containing a metal nanomaterial, a substrate including a region having a transmittance for light of an exposure wavelength, a layer containing a metal nanomaterial, and a second photosensitive layer containing an alkali-soluble compound;

Exposing the first photosensitive layer;

exposing the second photosensitive layer;

<18> a pattern forming method, comprising:

a step of preparing a laminate having, in order, a layer containing a metal nanomaterial, a first photosensitive layer containing an alkali-soluble compound, a substrate including a region having a transmittance for light of an exposure wavelength, a second photosensitive layer containing an alkali-soluble compound, and a layer containing a metal nanomaterial;

exposing the first photosensitive layer;

exposing the second photosensitive layer;

<19> a pattern forming method, comprising:

a step of preparing a laminate having, in order, a first photosensitive layer containing an alkali-soluble compound, a layer containing a metal nanomaterial, a substrate including a region having a transmittance for light of an exposure wavelength, a second photosensitive layer containing an alkali-soluble compound, and a layer containing a metal nanomaterial;

exposing the first photosensitive layer;

exposing the second photosensitive layer;

exposure in the step of exposing the first photosensitive layerDominant wavelength lambda of light wavelength ₁ And a main wavelength lambda of an exposure wavelength in the step of exposing the second photosensitive layer ₂ Satisfy lambda ₁ ≠λ ₂ Is a relationship of (3).

The pattern forming method according to any one of <15> to <19>, wherein at least one of the first photosensitive layer and the second photosensitive layer satisfies at least one of the following (1) and (2).

(1) Contains a photopolymerizable compound, and an alkali-soluble resin.

<21> the pattern forming method according to <20>, wherein the alkali-soluble resin is a carboxyl group-containing resin.

<22> the pattern forming method according to <20> or <21>, wherein the alkali-soluble photopolymerizable compound is a carboxyl group-containing photopolymerizable compound.

<23> the pattern forming method according to any one of <15> to <22>, wherein in at least one of the first photosensitive layer and the second photosensitive layer, an oxygen barrier layer is provided on a side of the photosensitive layer opposite to a side having the substrate.

<24> the pattern forming method according to <23>, wherein the oxygen barrier layer contains one or more selected from the group consisting of polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin and polyamide-based resin.

The pattern formation method according to any one of <15> to <24>, wherein absorbance at 365nm of the substrate is 0.5 or more.

<26> a patterned laminate comprising:

A patterned resin layer containing a metal nanomaterial and an alkali-soluble compound.

<27> the patterned laminate according to <26>, wherein the alkali-soluble compound is an alkali-soluble resin.

<28> the patterned laminate according to <27>, wherein the alkali-soluble resin is a carboxyl group-containing resin.

Effects of the invention

According to one embodiment of the present invention, there is provided a photosensitive composition for forming a layer containing a metal nanomaterial that suppresses migration and is capable of alkali development.

According to another embodiment of the present invention, there is provided a laminate containing a metal nanomaterial that suppresses migration and is capable of alkali development.

According to another embodiment of the present invention, there is provided a pattern forming method using the above laminate.

According to another embodiment of the present invention, there is provided a patterned laminate obtained from the above laminate.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the present invention.

In the present invention, the numerical range indicated by "to" is a range including the numerical values before and after "to" as the lower limit value and the upper limit value. In the numerical ranges described in stages in the present invention, the upper limit or the lower limit described in a certain numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. In the numerical ranges described in the present invention, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value described in the embodiment.

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

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

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

In the expression of the group (radical) in the present invention, the expression not describing substitution and unsubstituted includes both a group (radical) having no substituent and a group (radical) having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

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

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

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

In the present invention, "solid component" means a component other than a solvent in the composition.

In the present invention, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured using a Gel Permeation Chromatography (GPC) analyzer (column: TSKgel GMHxL, TSKgel G4000HxL (manufactured by TOSOH CORPORATION) and TSKgel G2000HxL (manufactured by TOSOH CORPORATION)), a detector, a differential refractometer, and a solvent, tetrahydrofuran (THF)), and converted using polystyrene as a standard substance.

In the present invention, unless otherwise specified, a compound having a molecular weight distribution is simply referred to as a molecular weight, and is a weight average molecular weight.

In the present invention, unless otherwise specified, the composition ratio of the polymer is the mass ratio.

In the present invention, ordinal words (e.g., "first" and "second") are terms used to distinguish between constituent elements, and are not intended to limit the number of constituent elements or the advantages or disadvantages of the constituent elements.

In the present invention, the "exposure wavelength" means a wavelength of light reaching the photosensitive layer among light irradiated when the photosensitive layer is exposed. For example, when the photosensitive layer is exposed via a filter having wavelength selectivity, the wavelength of light before passing through the above filter does not correspond to the exposure wavelength. Here, "wavelength selectivity" means a property of transmitting light of a specific wavelength range. In the present invention, the wavelength of light and the intensity of light are measured using a known spectrometer (for example, RPS900-R, manufactured by International Light Technologies inc.).

In the present invention, the "dominant wavelength" refers to the wavelength of the strongest light among the wavelengths of light reaching the photosensitive layer (i.e., exposure wavelengths). For example, in the case of an exposure beam in which light reaching the photosensitive layer has a wavelength of 365nm and a wavelength of 405nm and the intensity of the wavelength of 365nm is greater than the intensity of the wavelength of 405nm, the main wavelength of the exposure beam is 365nm. In the present invention, the "exposure beam" means light for exposing the photosensitive layer.

< photosensitive composition >

The photosensitive composition of the present invention contains a metal nanomaterial and an alkali-soluble compound. Since the layer formed from the photosensitive composition contains an alkali-soluble compound, a pattern can be formed by alkali development after exposure. It is presumed that migration can be suppressed because the matrix material such as resin is not interposed between the patterns thus formed. The mechanism to be estimated is described above, but the scope of the present invention is not limited to the above estimation.

[ Metal nanomaterial ]

As a material of the metal nanomaterial, copper, silver, zinc, iron, chromium, molybdenum, nickel, aluminum, gold, platinum, palladium, an alloy of two or more of them, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide (Indium zinc Oxide)), conductive silica, and the like can be used, but copper, silver, nickel, aluminum, gold, platinum, palladium, or an alloy of them is preferable from the viewpoints of resistance value, cost, sintering temperature, and the like, silver, copper, or an alloy of them is more preferable, and silver or an alloy of silver is more preferable from the viewpoints of sintering temperature and oxidation resistance, and silver is particularly preferable. That is, the metal nanomaterial is particularly preferably a silver nanomaterial.

The shape of the metal nanomaterial is not particularly limited, and may be a known shape, and as the metal nanomaterial, metal nanoparticles or metal nanowires are preferable, and metal nanoparticles are more preferable.

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

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

The average primary particle diameter of the metal nanoparticles in the present invention can be obtained as follows: a scanning electron microscope (SEM image) of 100 particles was taken by a scanning electron microscope (for example, S-3700N, manufactured by Hitachi High-Tech Corporation), and the particle diameter was measured by an image processing measuring apparatus (LUZEX AP; manufactured by NIRECO CORPORATION), and an arithmetic average value was obtained. That is, the particle diameter in the present invention means the diameter when the projected shape of the particles is a circle, and the diameter when the particles are irregular other than a sphere is regarded as a circle having the same area as the projected area.

Further, as the metal nanoparticles, flat silver particles are preferably used, more preferably flat silver particles are used, and even more preferably flat silver particles in the shape of polygonal columns or cylinders are used.

The flat particles in the present invention include flat particles (for example, polygonal columnar particles, elliptic particles), elliptic particles, spindle particles, and the like.

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

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

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

The size (major axis length) of the flat metal particles is not particularly limited, and may be appropriately selected according to the purpose, and is preferably 10nm to 500nm, more preferably 20nm to 300nm, and even more preferably 50nm to 200nm in terms of average equivalent circle diameter.

The thickness T of the flat metal particles is preferably 20nm or less, more preferably 2nm to 15nm, particularly preferably 4nm to 12nm.

The particle thickness T can be measured by atomic force microscopy (Atomic Force Microscopo: AFM) or Transmission Electron Microscopy (TEM).

As a method for measuring the average particle thickness by AFM, for example, the following methods are mentioned: the particle dispersion containing the flat metal particles was dropped onto a glass substrate, dried, and the thickness of one particle was measured.

Examples of the method for measuring the average particle thickness by TEM include the following methods: a particle dispersion containing flat metal particles was dropped onto a silicon substrate, dried, subjected to a coating treatment by carbon vapor deposition or metal vapor deposition, and a cross-sectional slice was produced by Focused Ion Beam (FIB) processing, and the cross-section was observed by TEM to measure the thickness of the particles (hereinafter, also referred to as FIB-TEM.).

The metal nanomaterial may be used alone or in combination of two or more.

From the viewpoint of suppressing migration, the content of the metal nanomaterial is preferably 90 mass% or more, for example, 95 mass% or more, relative to the total mass of the solid components of the photosensitive composition.

[ alkali-soluble Compound ]

The alkali-soluble compound is not particularly limited, and may be, for example, an alkali-soluble resin, an alkali-soluble photopolymerizable compound, or the like.

In the present invention, "resin" means a polymer having a number average molecular weight of 2000 or more.

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

From the viewpoint of curability of a layer formed from the photosensitive composition (hereinafter, sometimes referred to as "photosensitive layer"), the photosensitive composition preferably satisfies at least one of the following (1) and (2).

(1) Contains a photopolymerizable compound, and an alkali-soluble resin.

From the viewpoint of developability, the alkali-soluble resin is preferably a carboxyl group-containing resin.

From the viewpoint of developability, the alkali-soluble photopolymerizable compound is preferably a carboxyl group-containing photopolymerizable compound.

The solubility of the photosensitive layer in the developer changes due to exposure. Examples of the photosensitive layer include a positive photosensitive layer whose solubility in a developing solution increases by exposure (hereinafter, sometimes simply referred to as a "positive photosensitive layer") and a negative photosensitive layer whose solubility in a developing solution decreases by exposure (hereinafter, sometimes simply referred to as a "negative photosensitive layer").

In the present invention, "solubility in a developing solution increases due to exposure" means that the solubility of an exposed portion in a developing solution becomes relatively larger than the solubility of a non-exposed portion in a developing solution.

In the present invention, "solubility in a developing solution decreases due to exposure" means that solubility of an exposed portion in a developing solution becomes relatively smaller than solubility of a non-exposed portion in a developing solution.

From the viewpoint of resolution, the photosensitive layer is preferably a positive type photosensitive layer whose solubility in a developer increases by exposure. From the viewpoints of strength, heat resistance, and chemical resistance of the obtained resin pattern, the photosensitive layer is preferably a negative photosensitive layer whose solubility in a developer is reduced by exposure.

Hereinafter, a positive photosensitive composition for forming a positive photosensitive layer and a negative photosensitive composition for forming a negative photosensitive layer will be described in detail as examples of the photosensitive composition according to the present invention.

[ Positive photosensitive composition ]

The positive photosensitive composition is not limited as long as it contains a metal nanomaterial and an alkali-soluble compound. The positive photosensitive composition preferably contains a polymer having a structural unit having an acid group protected by an acid-decomposable resin (i.e., an acid-decomposable group) and a photoacid generator. The positive photosensitive composition may contain a naphthoquinone diazide compound and a phenol novolac resin as a photoreaction initiator.

The positive photosensitive composition is more preferably a chemically amplified positive photosensitive composition containing a polymer having a structural unit having an acid group protected by an acid-decomposable group and a photoacid generator.

(Polymer having structural units having acid groups protected with acid-decomposable groups)

The positive photosensitive composition preferably contains a polymer (hereinafter, sometimes referred to as "polymer X") having a structural unit (hereinafter, sometimes referred to as "structural unit a") having an acid group protected by an acid-decomposable group. The positive photosensitive composition may contain one polymer X alone or two or more polymers X.

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

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

Structural units having acid groups protected by acid-decomposable groups

The polymer X preferably has a structural unit (structural unit a) having an acid group protected by an acid-decomposable group. The sensitivity of the positive photosensitive composition can be improved by having the structural unit a in the polymer X.

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

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

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

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

[ chemical formula 1]

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

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

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

In formula A3, R is ³¹ Or R is ³² In the case of an alkyl group, the number of carbon atoms is preferably 1 to 10.

In formula A3, R is ³¹ Or R is ³² In the case of aryl, phenyl is preferred.

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

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

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

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

In the formula A3, X ⁰ Preferably a single bond. Arylene groups may have substituents.

In A3From the viewpoint of further lowering the glass transition temperature (Tg) of the polymer X, R ³⁴ Preferably a hydrogen atom.

R in formula A3 ³⁴ The content of the structural unit which is a hydrogen atom is preferably 20 mass% or more with respect to the total mass of the structural unit a contained in the polymer X. R in formula A3 ³⁴ The content of the structural unit which is a hydrogen atom in the structural unit A can be confirmed by the intensity ratio of the peak intensities according to ¹³ C-Nuclear magnetic resonance Spectrometry (NMR) determination is calculated by conventional methods.

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

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

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

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

Structural units having acid groups

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

The structural unit B is a structural unit having an acid group not protected by an acid-decomposable group (i.e., an acid group having no protecting group). By having the structural unit B in the polymer X, the sensitivity at the time of patterning becomes good. In addition, since the developer is easily dissolved in an alkaline developer in a development step after exposure, the development time can be shortened.

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

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

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

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

Other structural units

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

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

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

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

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

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

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

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

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

The content of the structural unit C is preferably 90 mass% or less, more preferably 85 mass% or less, and particularly preferably 80 mass% or less, relative to the total mass of the polymer X. The content of the structural unit C is preferably 10 mass% or more, more preferably 20 mass% or more, relative to the total mass of the polymer X. The content of the structural unit C in the above range further improves resolution and adhesion to the substrate. In the case where the polymer X has two or more structural units C, the content of the above structural units C represents the total content of the two or more structural units C. Containing structural units C The amount can be confirmed by the intensity ratio of the peak intensities according to ¹³ The C-NMR measurement was calculated by a conventional method.

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

[ chemical formula 2]

Glass transition temperature-

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

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

Hereinafter, the FOX formula will be described by taking a copolymer having a first structural unit and a second structural unit as an example.

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

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

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

Acid number-

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

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

A＝56.11×Vs×0.1×f/w

A: acid value (mgKOH/g)

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

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

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

Weight average molecular weight-

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

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

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

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

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

As the column, a column was used in which one TSKgel (registered trademark) Super HZM-M (manufactured by 4.6mm ID. Times.15 cm, TOSOH CORPORATION), super HZ4000 (manufactured by 4.6mm ID. Times.15 cm, TOSOH CORPORATION), super HZ3000 (manufactured by 4.6mm ID. Times.15 cm, TOSOH CORPORATION) and Super HZ2000 (manufactured by 4.6mm ID. Times.15 cm, TOSOH CORPORATION) were connected in series.

As eluent THP (tetrahydrofuran) was used.

Regarding the measurement conditions, the sample concentration was set to 0.2 mass%, the flow rate was set to 0.35mL/min, the sample injection amount was set to 10. Mu.L, and the measurement temperature was set to 40 ℃.

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

The calibration curve was prepared using a "standard sample TSK standard, polystyrene", manufactured by TOSOH CORPORATION: any of the seven samples "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500" and "A-1000" were prepared.

Content-

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

Manufacturing method-

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

(other polymers)

In addition to the polymer X, the positive photosensitive composition may contain a polymer having no structural unit having an acid group protected by an acid-decomposable group (hereinafter, sometimes referred to as "other polymer").

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

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

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

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

The content of the polymer component is preferably 50 to 99.9 mass%, more preferably 70 to 98 mass% based on the total mass of the solid components of the positive photosensitive composition.

(photoacid generator)

The positive photosensitive composition contains a photosensitive compound. The positive photosensitive composition preferably contains a photoacid generator as a photosensitive compound. Photoacid generators are compounds that are capable of generating an acid upon irradiation with an activating light (e.g., ultraviolet, extreme ultraviolet, X-ray, and electron beam).

The photoacid generator is preferably a compound that generates an acid by sensing an activating light having a wavelength of 300nm or more (preferably, a wavelength of 300nm to 450 nm). The photoacid generator that does not directly sense the activating light having a wavelength of 300nm or more may be used in combination with a sensitizer, if it is a compound that generates an acid by sensing the activating light having a wavelength of 300nm or more together with the sensitizer.

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

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

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

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

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

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

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

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

As a preferable example of the photoacid generator, a photoacid generator having the following structure can be given.

[ chemical formula 3]

As the photoacid generator having absorption at a wavelength of 405nm, for example, ADEKA ARKLS (registered trademark) SP-601 (manufactured by ADEKA CORPORATION).

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

From the viewpoints of sensitivity and resolution, the content of the photoacid generator is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, relative to the total mass of the solid components of the positive photosensitive composition.

(other additives)

In addition to the above components, the positive photosensitive composition may contain known additives. Examples of the additive include a sensitizer, a basic compound, a heterocyclic compound, an alkoxysilane compound, and a surfactant.

Plasticizer-

The positive photosensitive composition may contain a plasticizer for the purpose of improving the plasticity.

From the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.

[ chemical formula 4]

In the above formula, R represents an alkylene group having 2 to 8 carbon atoms, n represents an integer of 1 to 50, and x represents a bonding site with another atom.

In addition, if the plasticity of the positive photosensitive layer containing the compound having the alkyleneoxy group having the above-described structure (hereinafter, referred to as "compound X"), the polymer X, and the photoacid generator is not improved over the plasticity of the positive photosensitive layer containing no compound X, the compound X does not correspond to the plasticizer in the present invention. Further, the surfactant to be used at random is not generally used in an amount capable of imparting plasticity to the positive photosensitive layer, and thus does not correspond to the plasticizer in the present invention.

Examples of the plasticizer include compounds having the following structures. However, the plasticizer is not limited to the following compounds.

[ chemical formula 5]

The weight average molecular weight of the plasticizer is preferably less than the weight average molecular weight of polymer X. From the viewpoint of imparting plasticity, the weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, particularly preferably 800 or more and less than 4,000.

The positive photosensitive composition may contain a single plasticizer or two or more plasticizers.

From the viewpoint of adhesion to a substrate, the content of the plasticizer is preferably 1 to 50 mass%, more preferably 2 to 20 mass% relative to the total mass of the solid components of the positive photosensitive composition.

Sensitizer-

The positive photosensitive composition preferably contains a sensitizer.

The sensitizer becomes an electron excited state by absorbing the activating light. The sensitizer in an electron excited state is brought into contact with the photoacid generator to cause electron transfer, energy transfer, heat generation, and the like. The photoacid generator generates acid under the above action. Therefore, the exposure sensitivity can be improved by containing the sensitizer in the positive photosensitive composition.

The sensitizer is preferably at least one compound selected from the group consisting of an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a basic styryl derivative, and a distyrylbenzene derivative, and more preferably an anthracene derivative.

The anthracene derivative is preferably anthracene, 9, 10-dibutoxyanthracene, 9, 10-dichloro anthracene, 2-ethyl-9, 10-dimethoxy anthracene, 9-hydroxymethyl anthracene, 9-bromo anthracene, 9-chloro anthracene, 9, 10-dibromoanthracene, 2-ethyl anthracene or 9, 10-dimethoxy anthracene.

Examples of the sensitizer include compounds described in paragraphs 0139 to 0141 of International publication No. 2015/093271.

The positive photosensitive composition may contain one kind of sensitizer, or may contain two or more kinds of sensitizers.

The content of the sensitizer is preferably 0 to 10 mass%, more preferably 0.1 to 10 mass%, based on the total mass of the solid components of the positive photosensitive composition.

Basic compounds

The positive photosensitive composition preferably contains an alkaline compound.

Examples of the basic compound include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples of the basic compound include compounds described in paragraphs 0204 to 0207 of Japanese patent application laid-open No. 2011-221494, the contents of which are incorporated herein by reference.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, and dicyclohexylamine.

Examples of the aromatic amine include aniline, benzylamine, N-dimethylaniline and diphenylamine.

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4, 5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1, 5-diazabicyclo [4.3.0] -5-nonene, and 1, 8-diazabicyclo [5.3.0] -7-undecene.

Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

Examples of the quaternary ammonium salt of carboxylic acid include tetramethyl ammonium acetate, tetramethyl ammonium benzoate, tetra-n-butyl ammonium acetate and tetra-n-butyl ammonium benzoate.

The basic compound is preferably a benzotriazole compound from the viewpoints of rust resistance of the metal nanomaterial and linearity of the conductive pattern.

The benzotriazole compound is not limited as long as it has a benzotriazole skeleton, and known benzotriazole compounds can be used. Examples of the benzotriazole compound include 1,2, 3-benzotriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] benzotriazole, 5-carboxybenzotriazole, 1- (hydroxymethyl) -1H-benzol, 1-acetyl-1H-benzol, 1-aminobenzol, 9- (1H-benzotriazol-1-ylmethyl) -9H-carbazole, 1-chloro-1H-benzol-triazole, 1- (2-pyridyl) benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-ethylbenzotriazole, 1- (1 ' -hydroxyethyl) benzotriazole, 1- (2 ' -hydroxyethyl) benzotriazole, 1-propylbenzotriazole, 1- (1 ' -hydroxypropyl) benzotriazole, 1- (2 ' -hydroxypropyl) benzotriazole, 1- (3 ' -hydroxypropyl) benzotriazole, 4-hydroxy-1H-benzol-benzotriazole, 5-methyl-1H-benzotriazol, methylbenzotriazole-5-benzotriazol-carboxylate, benzotriazole-5-ethyl-benzotriazol-5-carboxylate, and 1-methyl-1-benzotriazol-5-carboxylate, and 1-ethyl-benzotriazol-5-carboxylate 2-methyl-2H-benzotriazole and 2-ethyl-2H-benzotriazole.

The positive photosensitive composition may contain one kind of basic compound alone or two or more kinds of basic compounds.

The content of the alkaline compound is preferably 0.001 to 5% by mass, more preferably 0.005 to 3% by mass, based on the total mass of the solid components of the positive photosensitive composition.

Heterocyclic compounds

The positive photosensitive composition may contain a heterocyclic compound.

Examples of the heterocyclic compound include compounds having an epoxy group or an oxetane group in the molecule, heterocyclic compounds having an alkoxymethyl group, oxygen-containing heterocyclic compounds (for example, cyclic ethers and cyclic esters (for example, lactones)), and nitrogen-containing heterocyclic compounds (for example, cyclic amines and oxazolines). The heterocyclic compound may be a heterocyclic compound containing an element having an electron in the d-orbital (for example, silicon, sulfur, and phosphorus).

Examples of the compound having an epoxy group in a molecule include bisphenol a type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and aliphatic epoxy resin.

The compound having an epoxy group in a molecule is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin or an aliphatic epoxy resin, more preferably an aliphatic epoxy resin.

The compound having an epoxy group in the molecule can be obtained as a commercially available product. Examples of commercial products of compounds having an epoxy group in the molecule include JER828, JER1007, JER S157S 70 and JER S65 manufactured by Mitsubishi Chemical Corporation, and commercial products described in paragraph 0189 of japanese patent application laid-open publication No. 2011-221494.

Examples of commercial products other than those mentioned above include those produced by ADEKA CORPORATION, products ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S, nippon Kayaku Co., ltd. made NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502, DENACOL made Nagase ChemteX Corporation EX-611, EX-612, EX-614-B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214-L, EX-216L, EX-321-L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX-121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192, EX-NIPPON STEEL Chemical, material Co.; ltd, CELLOXIDE 2021P, 2081, 2000, 3000, EHPE3150, EPOLAD GT400, CELVENUS B0134 and B0177, manufactured by YH-300, YH-301, YH-302, YH-315, YH-324 and YH-325, and Daicel Corporation.

Examples of the compounds having an oxetanyl group in the molecule include TOAGOSEI CO. LTD. ARON OXETANE OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ and PNOX.

The compound having an oxetanyl group is preferably used alone or in combination with a compound having an epoxy group.

Among the above, the heterocyclic compound is preferably a compound having an epoxy group from the viewpoints of etching resistance and line width stability.

The positive photosensitive composition may contain a single heterocyclic compound or two or more heterocyclic compounds.

The content of the heterocyclic compound is preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 1 to 5% by mass, relative to the total mass of the solid components of the positive photosensitive composition, from the viewpoints of adhesion to a substrate and etching resistance.

Alkoxysilane compounds

The positive photosensitive composition may contain an alkoxysilane compound.

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

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

The positive photosensitive composition may contain one alkoxysilane compound alone or two or more alkoxysilane compounds.

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

Surfactant-containing compositions

From the viewpoint of uniformity of film thickness, the positive photosensitive composition preferably contains a surfactant.

Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants. The surfactant is preferably a nonionic surfactant.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyethylene glycol, silicone surfactants, and fluorine surfactants.

Examples of the commercial products of the nonionic surfactant include KP (Shin-Etsu Chemical Co., ltd.), POLYFLOW (KYOEISHA CHEMICAL CO., LTD.), EFTOP (JEM CO.), MEGAFACE (registered trademark), fluorine (Sumitomo 3M Limited), asahiguard (registered trademark) (AGC Inc.), surflon (registered trademark) (AGC SEIMI CHEMICAL CO., LTD.), polyFox (OMNOVA SOLUTIONS INC., ltd.), and SH-8400 (Dow Corning Toray Co., ltd.).

Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, and the like), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (made by BASF corporation), tetronic 304, 701, 704, 901, 904, 150R1 (made by BASF corporation), solsperse 20000 (made by Lubrizol Japan Limited) and the like), NCW-101, NCW-1001, NCW-1002 (made by PUJIPILM Wako Pure Chemical Corporation) and PIONIN D-6112, D-6112-W, D-6315 (made by Takey Ool and Pat Co, FID.sub.1010, lyn.400, ltde.400, and the like.

The surfactant is preferably a copolymer having a weight average molecular weight (Mw) of 1,000 to 10,000 in terms of polystyrene as measured by gel permeation chromatography using Tetrahydrofuran (THF) as a solvent, and containing a structural unit SA and a structural unit SB represented by the following formula I-1.

[ chemical formula 6]

In the formula (I-1), R ⁴⁰¹ R is R ⁴⁰³ Each independently represents a hydrogen atom or a methyl group, R ⁴⁰² Represents a linear alkylene group having 1 to 4 carbon atoms, R ⁴⁰⁴ Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, p represents a number of 10 to 80 mass%, q represents a value of 20 mass% or more and 90 mass% or less, r represents an integer of 1 or more and 18 or less, s represents an integer of 1 or more and 10 or less, and x represents a bonding site with another structure.

L is preferably a branched alkylene group represented by the following formula (I-2). R in formula (I-2) ⁴⁰⁵ Represents an alkyl group having 1 to 4 carbon atoms, and is compatible with each otherFrom the viewpoint of the properties, an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 2 or 3 carbon atoms is more preferable. The sum of p and q (p+q) is preferably p+q=100, i.e., 100 mass%.

[ chemical formula 7]

The weight average molecular weight (Mw) of the copolymer containing the structural units SA and SB represented by the above formula 1-1 is preferably 1,500 or more and 5,000 or less.

Commercial products of the fluorine-based surfactant, examples thereof include MEGAFACE 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, MFS-578, MFS-579, MFS-587, R-41-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (the above is DIC CORATN) Fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited above), surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc. above), polyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA SOLUTIONS INC. Above), ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730, LM 650AC, 681, 683 (manufactured by NEOS COMPANY LIMITED above), and the like.

As the fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group containing a fluorine atom and having a fluorine atom which volatilizes when a portion of the functional group containing a fluorine atom is cleaved upon heating can be preferably used. Examples of such a fluorine-based surfactant include the MEGAFACEDS series (The Chemical Daily (day 22 of 2016), nikkei Business Daily (day 23 of 2016) manufactured by DIC CORPORATION), and MEGAFACE DS-21.

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 preferably used.

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

As the fluorine-based surfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound having a fluorine atom and a structural unit derived from a (meth) acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) can be preferably used.

As the fluorine-based surfactant, a fluoropolymer having a group containing an ethylenically unsaturated bond in a side chain can also be used. Examples thereof include MEGAFACE RS-101, RS-102, RS-718K, RS-72-K (DIC CORPORATION).

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

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

Specific examples of Silicone surfactants include DOWSIL 8032 ADDITIVE, TORAY SILICONE DC PA, TORAY SILICONE SH7PA, TORAY SILICONE DC PA, TORAY SILICONE SH PA, TORAY SILICONE SH PA, TORAY SILICONE SH PA, TORAY SILICONE SH PA, TORAY SILICONE SH8400 (manufactured by Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (manufactured by Ltd. With respect to Shin-Etsu Silicone Co., above), F-43040, TSF-0, TSF-4445, TSF-4460, F-4452 (manufactured by Tb. With respect to Td. With respect to Tf-4300), KF-44In52 (manufactured by Tb. With respect to Tk. With respect to Tb. With respect to BY.

As the surfactant, the surfactants described in paragraphs 0017 to 0060 to 0071 of jp-a No. 4502784 and jp-a No. 2009-237362 can also be used.

The positive photosensitive composition may contain one kind of surfactant alone or two or more kinds of surfactants.

The content of the surfactant is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and particularly preferably 0.01% by mass to 3% by mass, based on the total mass of the solid components of the positive photosensitive composition.

Plasticizers, sensitizers, basic compounds, heterocyclic compounds, alkoxysilane compounds, and surfactants are also described in paragraphs 0097 to 0127 of International publication No. 2018/179640, respectively. The contents of which are incorporated by reference into this specification.

Other ingredients-

The positive photosensitive composition may contain components other than the above additives (hereinafter, sometimes referred to as "other components"). Examples of the other components include antioxidants, adhesion promoters, migration-preventing additives, dispersants, acid-proliferation agents, development promoters, conductive fibers, colorants, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic anti-settling agents. The preferred modes of the other components are described in paragraphs 0165 to 0184 of Japanese unexamined patent publication No. 2014-85643, respectively, the contents of which are incorporated herein by reference.

[ negative type photosensitive layer ]

The negative photosensitive composition is not limited as long as it contains a metal nanomaterial and an alkali-soluble compound. From the viewpoint of patterning, the negative photosensitive composition preferably contains a polymer having an acid group, a photopolymerizable compound, and a photopolymerization initiator. As a material of the negative photosensitive composition, for example, a material described in japanese patent application laid-open No. 2016-224162 can be used.

[ Polymer having acid groups ]

The negative photosensitive composition preferably contains a polymer having an acid group (hereinafter, sometimes referred to as "polymer Y"). Polymer Y is one mode of an alkali-soluble compound (in one mode, an alkali-soluble resin).

Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group, and a phosphonate group. The acid group is preferably a carboxyl group.

From the viewpoint of alkali developability, the polymer Y is preferably an alkali-soluble resin having an acid value of 60mgKOH/g or more, more preferably a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more.

Examples of the carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more include carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the polymer described in paragraph 0025 of JP 2011-95716, carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the polymers described in paragraphs 0033 to 0052 of JP 2010-237589, and carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the binder polymers described in paragraphs 0053 to 0068 of JP 2016-224162. Here, "acrylic resin" means a resin containing at least one of a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid ester. The content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester in the acrylic resin is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the total mass of the acrylic resin.

The content of the structural unit having an acid group in the polymer Y is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 12 to 30% by mass relative to the total mass of the polymer Y.

The polymer Y may have reactive groups. As the reactive group, a polymerizable group is preferable. Examples of the polymerizable group include an ethylenically unsaturated group, a polycondensable group (e.g., a hydroxyl group and a carboxyl group), and a polyaddition-reactive group (e.g., an epoxy group and an isocyanate group).

The acid value of the polymer Y is preferably 60 to 200mgKOH/g, more preferably 100 to 200mgKOH/g, particularly preferably 150 to 200mgKOH/g, from the viewpoint of alkali developability.

The weight average molecular weight of the polymer Y is preferably 1,000 or more, more preferably 10,000 or more, particularly preferably 20,000 ～ 100,000.

The polymer Y may have structural units derived from non-acidic monomers. Examples of the non-acidic monomer include (meth) acrylic acid esters, ester compounds of vinyl alcohol, (meth) acrylonitrile, and aromatic vinyl compounds.

Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate.

Examples of the ester compound of vinyl alcohol include vinyl acetate.

Examples of the aromatic vinyl compound include styrene and styrene derivatives.

The non-acidic monomer is preferably methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, a styrene derivative or benzyl (meth) acrylate. The non-acidic monomer is more preferably styrene, a styrene derivative or benzyl (meth) acrylate from the viewpoints of resolution, adhesion to a substrate, etching resistance and reduction of aggregates at the time of development.

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

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

Specific examples of the monomer having a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Further, a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms is exemplified. More specific examples thereof include (meth) acrylic acid (bicyclo [ 2.2.1] heptyl-2) ester, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 3-methyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyladamantanyl (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl (meth) acrylate, 3,5, 8-triethyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4, 7-menthol indene-5-yl (meth) acrylate, octahydro-4, 7-methyl-1-adamantyl (meth) acrylate, and (meth) acrylate, 1-menthyl (meth) acrylate 3-hydroxy-2, 6-trimethyl-bicyclo [ 3.1.1 ] heptyl (meth) acrylate, 3, 7-trimethyl-4-hydroxy-bicyclo [ 4.1.0 ] heptyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate. Among these (meth) acrylic esters, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl (meth) acrylate or tricyclodecyl (meth) acrylate is preferable, and cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate or tricyclodecyl (meth) acrylate is more preferable.

The negative photosensitive composition may contain one kind of polymer Y alone or two or more kinds of polymer Y.

From the viewpoint of photosensitivity, the content of the polymer Y is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, and particularly preferably 30 to 70 mass% with respect to the total mass of the solid components of the negative photosensitive composition.

[ photopolymerizable Compound ]

From the viewpoint of curability, the negative photosensitive composition preferably contains a photopolymerizable compound.

From the viewpoint of developability, the photopolymerizable compound preferably contains an acid group. The photopolymerizable compound containing an acid group is one embodiment of an alkali-soluble photopolymerizable compound.

The photopolymerizable compound is not limited, and a known photopolymerizable compound can be used. The photopolymerizable compound is preferably an ethylenically unsaturated compound. The ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups. The ethylenically unsaturated compound contributes to the photosensitivity (i.e., photocurability) of the negative photosensitive composition and the strength of the cured film.

The ethylenically unsaturated group is preferably a (meth) acryloyl group.

The ethylenically unsaturated compound is preferably a (meth) acrylate compound.

Examples of the ethylenically unsaturated compounds include caprolactone-modified (meth) acrylate compounds [ e.g., nippon Kayaku Co., ltd., KAYARAD (registered trademark) DPCA-20 and SHIN-NA KAMURA CHEMICAL CO, LTD., A-9300-1CL ], alkylene oxide-modified (meth) acrylate compounds [ e.g., nippon Kayaku Co., ltd., KAYARAD RP-1040, SHIN-NAKAMURA CHEMICAL CO, LTD, ATM-35E and A-9300, and DAICEL-ALLNEX LTD, EBECRYL (registered trademark) 135 ], ethoxylated glycerol triacrylates [ e.g., SHIN-NAKAMURA CHEMICAL CO, LTD. A-GLY-9E, ARONIX (registered trademark) TO-2349 (TOAGOSEI CO., LTD. Co.), ARONIX M-520 (TOAGOSEI CO., LTD. Co.), ARONIX M-510 (TOAGOSEI CO., LTD. Co.), and urethane (meth) acrylate compounds [ e.g., 8UX-015A (TAISEI FINE CHEMICAL CO,. LTD. Co., LTD.), UA-32P (SHIN-NAKAMURA CHEMICAL CO, LTD. Co., LTD.) and UA-1100H (SHIN-NAKAMURA CHEMICAL CO, LTD. Co.).

As the ethylenically unsaturated compound, a photopolymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 can be used.

The negative photosensitive composition preferably contains a compound having two or more ethylenically unsaturated groups as the ethylenically unsaturated compound. Hereinafter, an ethylenically unsaturated compound having X ethylenically unsaturated groups is sometimes referred to as "X-functional ethylenically unsaturated compound".

Examples of the 2-functional ethylenically unsaturated compound include tricyclodecane dimethanol diacrylate (A-DCP, SHIN-NAKAMURA CHEMICAL CO, manufactured by LTD.), tricyclodecane dimethanol dimethacrylate (DCP, SHIN-NAKAMURA CHEMICAL CO, manufactured by LTD.), 1, 9-nonanediol diacrylate (A-NOD-N, SHIN-NAKAMURA CHEMICAL CO, manufactured by LTD.), and 1, 6-hexanediol diacrylate (A-HD-N, SHIN-NAKAMURA CHEMICAL CO, manufactured by LTD.).

As 2-functional olefinically unsaturated compounds, preference is also given to using 2-functional olefinically unsaturated compounds having a bisphenol structure.

Examples of the 2-functional ethylenically unsaturated compound having a bisphenol structure include those described in paragraphs 0072 to 0080 of JP-A2016-224162. Further, as the 2-functional ethylenically unsaturated compound having a bisphenol structure, alkylene oxide-modified bisphenol a di (meth) acrylate is exemplified.

Examples of the alkylene oxide-modified bisphenol a di (meth) acrylate include ethylene glycol dimethacrylate obtained by adding an average of 5 moles of ethylene oxide to each of both ends of bisphenol a, ethylene glycol dimethacrylate obtained by adding an average of 2 moles of ethylene oxide to each of both ends of bisphenol a, ethylene glycol dimethacrylate obtained by adding an average of 5 moles of ethylene oxide to each of both ends of bisphenol a, alkylene glycol dimethacrylate obtained by adding an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide to each of both ends of bisphenol a, and alkylene glycol dimethacrylate obtained by adding an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol a.

Specific examples of the alkylene oxide-modified bisphenol A di (meth) acrylate include 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane and 2, 2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane.

As a commercial product of alkylene oxide-modified bisphenol A di (meth) acrylate, for example, BPE-500 (SHIN-NAKAMURA CHEMICAL CO, LTD. Co.).

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 glycerol tri (meth) acrylate.

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

The ethylenically unsaturated compound having 3 or more functions is preferably a tetramethyl acrylate obtained by adding an average of 9 moles of ethylene oxide to the terminal end of the hydroxyl group of pentaerythritol, a tetramethyl acrylate obtained by adding an average of 12 moles of ethylene oxide to the terminal end of the hydroxyl group of pentaerythritol, a tetramethyl acrylate obtained by adding an average of 15 moles of ethylene oxide to the terminal end of the hydroxyl group of pentaerythritol, a tetramethyl acrylate obtained by adding an average of 20 moles of ethylene oxide to the terminal end of the hydroxyl group of pentaerythritol, a tetramethyl acrylate obtained by adding an average of 28 moles of ethylene oxide to the terminal end of the hydroxyl group of pentaerythritol, or a tetramethyl acrylate obtained by adding an average of 35 moles of ethylene oxide to the terminal end of the hydroxyl group of pentaerythritol.

The molecular weight of the photopolymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200. In the case where the photopolymerizable compound is a compound having a molecular weight distribution (for example, a polymer), the weight average molecular weight (Mw) of the photopolymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

The negative photosensitive composition may contain one kind of photopolymerizable compound alone or two or more kinds of photopolymerizable compounds.

The content of the photopolymerizable compound is preferably 10 to 70 mass%, more preferably 20 to 60 mass%, and particularly preferably 20 to 50 mass% relative to the total mass of the solid components of the negative photosensitive composition.

[ photopolymerization initiator ]

The negative photosensitive composition contains a photosensitive compound. The negative photosensitive composition preferably contains a photopolymerization initiator as a photosensitive compound. The photopolymerization initiator initiates polymerization of the photopolymerizable compound by receiving activating light (e.g., ultraviolet rays and visible rays). The photopolymerization initiator is one of photoreaction initiators.

Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -aminoalkylbenzophenone structure, a photopolymerization initiator having an α -hydroxyalkylbenzophenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure. The photopolymerization initiator is preferably at least one selected from the group consisting of a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -aminoalkylbenzophenone structure, a photopolymerization initiator having an α -hydroxyalkylbenzophenone structure, and a photopolymerization initiator having an N-phenylglycine structure.

The photopolymerization initiator is also preferably at least one selected from the group consisting of 2,4, 5-triarylimidazole dimer and derivatives thereof, for example. In addition, in the 2,4, 5-triarylimidazole dimer and its derivative, the two 2,4, 5-triarylimidazole structures may be the same or different.

Preferred examples of the derivative of 2,4, 5-triarylimidazole dimer include 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer and 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer.

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

Examples of the photopolymerization initiator include 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, BASF Japan Ltd.), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetoxime) (trade name: IRGACURE OXE-02, BASF Japan Ltd.), IRGACURE OXE-03 (manufactured by BASF Japan Ltd.), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (trade name: omni 379EG, manufactured by IGM Resins B.V.), 2-methyl-1- (4-methylthiophenyl) -2-propanone (manufactured by BASF Japan Ltd.), 2- (Omni-4-morpholinyl) phenyl ] -1-hydroxy-3-yl } -2- (Omni-methyl-phenyl) -2- (Omni-p-one, and (manufactured by Omni-4-morpholinyl) phenyl ] -1-butanone (manufactured by BASF Japan Ltd.) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: omnirad 369, IGM Resins b.v.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (manufactured by Omnirad 184, manufactured by IGM Resins B.V.), 2-dimethoxy-1, 2-diphenylethan-1-one (manufactured by Omnirad 651, manufactured by IGM Resins B.V.), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by Omnirad TPO H, manufactured by IGM Resins B.V.), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (manufactured by Omnirad 819, manufactured by IGM Resins B.V.), oxime ester photopolymerization initiator (manufactured by DK holar 6, SH HoldLtd.), 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole (manufactured by Omnix 2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer (manufactured by Omnirad TPO H, manufactured by IGM Resins B.V.), bis (manufactured by Omnirad 819, manufactured by IGM Resins B.V.), oxime ester photopolymerization initiator (manufactured by Omnirad 6, DK. Manufactured by DK hold. Ltd), 2' -bis (2-chlorophenyl) -4, 5' -tetraphenylimidazole dimer (manufactured by Omnix 35 B.35B, manufactured by BCC).

Further, examples of commercial products of photopolymerization initiators include ADEKA ARKLS NCI-930, ADEKA ARKLS NCI-730, and ADEKA ARKLS N-1919T manufactured by ADEKA CORPORATION.

The negative photosensitive composition may contain one kind of photopolymerization initiator alone or two or more kinds of photopolymerization initiators.

The content of the photopolymerization initiator is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and particularly preferably 1.0 mass% or more, based on the total mass of the solid components of the negative photosensitive composition. The content of the photopolymerization initiator is preferably 10 mass% or less, more preferably 5 mass% or less, based on the total mass of the solid components of the negative photosensitive composition.

[ other additives ]

In addition to the above components, the negative photosensitive composition may contain known additives. Examples of the additive include a polymerization inhibitor, a plasticizer, a sensitizer, a hydrogen donor, a heterocyclic compound, and an Ultraviolet (UV) absorber.

(polymerization inhibitor)

The negative photosensitive composition may contain a polymerization inhibitor.

Examples of the polymerization inhibitor include thermal polymerization inhibitors described in paragraph 0018 of Japanese patent No. 4502784. The polymerization inhibitor is preferably phenothiazine, phenoxazine, hydroquinone, tetrachlorobenzoquinone, sodium phenoindophenol, m-aminophenol or 4-methoxyphenol.

The negative photosensitive composition may contain a single kind of polymerization inhibitor or two or more kinds of polymerization inhibitors.

The content of the polymerization inhibitor is preferably 0.01 to 3% by mass, more preferably 0.01 to 1% by mass, and particularly preferably 0.01 to 0.8% by mass, based on the total mass of the solid components of the negative photosensitive composition.

(plasticizer)

Examples of the plasticizer include the plasticizers described in the above positive photosensitive composition, and preferred plasticizers are also the same.

The negative photosensitive composition may contain a single plasticizer or two or more plasticizers.

From the viewpoint of adhesion to a substrate, the content of the plasticizer is preferably 1 to 50 mass%, more preferably 2 to 20 mass% relative to the total mass of the solid components of the negative photosensitive composition.

(sensitizer)

The negative photosensitive composition may contain a sensitizer.

Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, cyanine compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2, 4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

As the sensitizer, a dye or a pigment may be used. Examples of the dye or pigment include magenta, phthalocyanine GREEN, coumarin 6, coumarin 7, coumarin 102, DOC iodide, indocarbocyanine sodium, auramine, alkoxide GREEN S, paramagenta, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite GREEN (HODOGAYA CHEMICAL co., ltd. System, AIZEN (registered trademark) MALACHITE GREEN), basic blue 20, and DIAMOND GREEN (HODOGAYA CHEMICAL co., ltd. System, AIZEN (registered trademark) DIAMOND GREEN GH).

As the dye, a color-developing dye can be used. The color-developing dye is a compound having a function of developing color by irradiation with light. Examples of the color-developing dye include leuco dyes and fluoran dyes. The color-developing dye is preferably a leuco dye.

The negative photosensitive composition may contain one kind of sensitizer or two or more kinds of sensitizers.

The content of the sensitizer is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% relative to the total mass of the solid components of the negative photosensitive composition, from the viewpoint of improving the sensitivity to the light source and improving the curing speed by the balance between the polymerization speed and chain transfer.

(Hydrogen donor)

The negative photosensitive composition may contain a hydrogen donor. The hydrogen donor may supply hydrogen to the photopolymerization initiator.

Examples of the hydrogen donor include bis [4- (dimethylamino) phenyl ] methane, bis [4- (diethylamino) phenyl ] methane, thiol compounds, and colorless crystal violet.

The negative photosensitive composition may contain a single hydrogen donor or two or more hydrogen donors.

The content of the hydrogen donor is preferably 0.01 to 10 mass%, more preferably 0.05 to 5 mass%, and particularly preferably 0.1 to 2 mass% relative to the total mass of the negative photosensitive composition.

(heterocyclic Compound)

Examples of the heterocyclic compound include the heterocyclic compounds described in the above positive photosensitive composition, and the same is true for the preferred heterocyclic compounds.

The negative photosensitive composition may contain a single heterocyclic compound or two or more heterocyclic compounds.

The content of the heterocyclic compound is preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 1 to 5% by mass, relative to the total mass of the solid components of the negative photosensitive composition, from the viewpoints of adhesion to a substrate and etching resistance.

(ultraviolet (UV) absorber)

The negative photosensitive composition may contain a UV absorber within a range not departing from the gist of the present invention. The UV absorber can reduce the transmittance of the negative photosensitive layer to the exposure wavelength.

Examples of the UV absorber include benzophenone-based UV absorbers, benzotriazole-based UV absorbers, benzoate-based UV absorbers, salicylate-based UV absorbers, triazine-based UV absorbers, and cyanoacrylate-based UV absorbers. The UV absorber is preferably at least one UV absorber selected from benzotriazole-based UV absorbers and triazine-based UV absorbers.

Examples of the benzotriazole-based UV absorber include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylethyl) phenol, 2- [ 5-chloro (2H) -benzotriazol-2-yl ] -4-methyl-6- (t-butyl) phenol, 2- (2H-benzotriazol-yl) -4, 6-di-t-amylphenol, and 2- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol. The benzotriazole-based UV absorber may be a mixture, modified product, polymer or derivative of the above-mentioned compounds.

Examples of the triazine-based UV absorber include 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [ (hexyl) oxy ] -phenol, 2- [4- [ (2-hydroxy-3-dodecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [4- [ (2-hydroxy-3-tridecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, and 2, 4-bis (2, 4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -s-triazine. The triazine-based UV absorber may be a mixture, modified product, polymer or derivative of the above-mentioned compounds.

The negative photosensitive composition may contain one kind of UV absorber alone or two or more kinds of UV absorbers.

The content of the UV absorber is preferably 0.1 to 5 mass%, more preferably 0.1 to 3 mass%, and particularly preferably 0.1 to 2 mass% with respect to the total mass of the solid components of the negative photosensitive composition, from the viewpoint of suppressing the generation of exposure haze and resolution.

(other Components)

The negative photosensitive composition may contain components other than the above additives (hereinafter, sometimes referred to as "other components"). Examples of the other components include antioxidants, adhesion promoters, migration-preventing additives, dispersants, acid-proliferation agents, development promoters, colorants, thermal radical polymerization initiators, thermal acid generators, thickeners, crosslinking agents, and organic or inorganic anti-settling agents. A preferred embodiment of these components is described in paragraphs 0165 to 0184 of japanese unexamined patent publication No. 2014-85643, the contents of which are incorporated herein by reference.

The negative photosensitive composition may contain a resin other than the polymer Y. Preferable examples of the resin include polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin and polysiloxane resin. The resins other than the polymer Y contained in the negative photosensitive layer may be one kind or two or more kinds.

[ solvent ]

The photosensitive composition may contain water as a solvent, and may also contain an organic solvent.

Examples of the organic solvent include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. Examples of the organic solvent include those described in paragraphs 0174 to 0178 of JP 2011-221494 and those described in paragraphs 0092 to 0094 of International publication No. 2018/179640, the contents of which are incorporated herein by reference.

Benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate or propylene carbonate may be added to the above-mentioned organic solvent as required.

The organic solvent is preferably an organic solvent having a boiling point of 130 ℃ or more and less than 160 ℃, an organic solvent having a boiling point of 160 ℃ or more, or a mixture thereof.

Examples of the organic solvent having a boiling point of 130℃or higher and lower than 160℃include propylene glycol monomethyl ether acetate (boiling point 146 ℃), propylene glycol monoethyl ether acetate (boiling point 158 ℃), propylene glycol methyl n-butyl ether (boiling point 155 ℃) and propylene glycol methyl n-propyl ether (boiling point 131 ℃).

Examples of the organic solvent having a boiling point of 160℃or higher include ethyl 3-ethoxypropionate (boiling point 170 ℃), diethylene glycol methylether (boiling point 176 ℃), propylene glycol monomethyl ether propionate (boiling point 160 ℃), dipropylene glycol methyl ether acetate (boiling point 213 ℃), 3-methoxybutyl ether acetate (boiling point 171 ℃), diethylene glycol diethyl ether (boiling point 189 ℃), diethylene glycol dimethyl ether (boiling point 162 ℃), propylene glycol diacetate (boiling point 190 ℃), diethylene glycol monoethyl ether acetate (boiling point 220 ℃), dipropylene glycol dimethyl ether (boiling point 175 ℃) and 1, 3-butanediol diacetate (boiling point 232 ℃).

The photosensitive composition may contain a single solvent or two or more solvents.

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

[ impurity etc. ]

The photosensitive composition preferably contains less impurities in each layer described later.

Specific examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and ions thereof.

The content of impurities in each layer is preferably 80ppm or less, more preferably 10ppm or less, and further preferably 2ppm or less on a mass basis. The lower limit is not particularly limited, and the content of impurities in each layer may be 1ppb or more or 0.1ppm or more on a mass basis.

As a method for forming the impurity in the above range, a material having a small impurity content is selected as a material for each layer, and the impurity is prevented from being mixed in and removed by washing when forming each layer. In this way, the impurity amount can be made within the above range.

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

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

The water content in each 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.

< laminate >

As a laminate according to the present invention, a laminate according to the following modes 1 to 3 is given.

The laminate of embodiment 1 has, in order:

The laminate of embodiment 2 has, in order:

a substrate;

A photosensitive layer containing an alkali-soluble compound.

The laminate of embodiment 3 has, in order:

a substrate;

A layer containing metallic nanomaterial.

In the laminate of embodiment 1, the photosensitive layer contains a metal nanomaterial, whereas in the laminates of embodiment 2 and embodiment 3, the photosensitive layer contains a metal nanomaterial in a layer different from the photosensitive layer. In contrast to the laminate of embodiment 2 having a layer containing a metal nanomaterial between the substrate and the photosensitive layer, the laminate of embodiment 3 has a photosensitive layer between the substrate and the layer containing a metal nanomaterial.

The laminate according to the present invention can be preferably used for patterning described later, and a laminate having a different layer structure as in modes 1 to 3 can be suitably used in consideration of the application, process, and the like.

The laminated body according to each of embodiments 1 to 3 will be described in detail below. The laminated body according to any one of aspects 1 to 3 may be simply referred to as a "laminated body".

Laminate of mode 1 ]

[ photosensitive layer A ]

The laminate of embodiment 1 has a photosensitive layer (hereinafter, sometimes referred to as "photosensitive layer a") containing a metal nanomaterial and an alkali-soluble compound. Migration is suppressed by the photosensitive layer a, and alkali development is possible.

The photosensitive layer a may contain the above materials in the photosensitive composition.

Details of each material are as described above, but the "photosensitive composition" is modified to be "photosensitive layer a".

When the photosensitive layer a contains a solvent, the content of the solvent is preferably 2 mass% or less, more preferably 1 mass% or less, and particularly preferably 0.5 mass% or less, based on the total mass of the photosensitive layer a.

The thickness of the photosensitive layer a is not limited. The average thickness of the photosensitive layer a is preferably 0.05 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more, from the viewpoint of uniformity of film thickness. The average thickness of the photosensitive layer a is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less from the viewpoint of resolution. The average thickness of the photosensitive layer a is measured by a method based on the measurement method of the average thickness of the substrate described below.

Laminate of embodiment 2 and embodiment 3-

[ layer containing Metal nanomaterial ]

The laminate of modes 2 and 3 has a layer containing a metal nanomaterial (hereinafter, sometimes referred to as a "metal nanomaterial-containing layer").

The metal nanomaterial-containing layer may contain a material other than the metal nanomaterial and the photosensitive compound in the photosensitive composition.

Details of each material are as described above, but the "photosensitive composition" is modified to be "a metal nanomaterial-containing layer".

In the case where the metal-containing nanomaterial layer contains a solvent, the content of the solvent is preferably 2 mass% or less, more preferably 1 mass% or less, and particularly preferably 0.5 mass% or less, relative to the total mass of the metal-containing nanomaterial layer.

[ photosensitive layer B ]

The laminate of modes 2 and 3 has a photosensitive layer containing an alkali-soluble compound (hereinafter, sometimes referred to as "photosensitive layer B").

The photosensitive layer B may contain materials other than the above-mentioned metal nanomaterial in the photosensitive composition.

Details of each material are as described above, but the "photosensitive composition" is changed to "photosensitive layer B".

When the photosensitive layer B contains a solvent, the content of the solvent is preferably 2 mass% or less, more preferably 1 mass% or less, and particularly preferably 0.5 mass% or less, based on the total mass of the photosensitive layer B.

The thickness of the photosensitive layer B is not limited. The average thickness of the photosensitive layer B is preferably 0.05 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more, from the viewpoint of uniformity of film thickness. The average thickness of the photosensitive layer B is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less from the viewpoint of resolution. The average thickness of the photosensitive layer B is measured by a method based on the measurement method of the average thickness of the above-described substrate.

The thickness of the layer containing the metal nanomaterial is not limited. From the viewpoint of uniformity of film thickness, the average thickness of the metal-containing nanomaterial layer is preferably 0.05 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more. From the viewpoint of resolution, the average thickness of the metal-containing nanomaterial layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. The average thickness of the metal-containing nanomaterial layer is measured by a method based on the measurement method of the average thickness of the substrate described below.

The photosensitive layer B and the metal nanomaterial-containing layer are combined together to have the same function as the photosensitive layer a of the laminate of embodiment 1. That is, migration is suppressed by the photosensitive layer B and the metal nanomaterial-containing layer, and alkali development can be performed.

In one approach, in the case where the photosensitive layer B is in contact with the metal-nano-material-containing layer, the boundary between the two layers is not necessarily clear at times. In this case, the photosensitive layer B and the layer containing the metal nanomaterial may be combined together as one layer. In this embodiment, there is a possibility that the metal nanomaterial is present in a biased region in the layer regarded as one layer due to the metal nanomaterial-containing layer, and thus there is a possibility that the metal nanomaterial is unevenly distributed in the layer regarded as one layer.

Whether the boundary between the photosensitive layer B and the metal-containing nanomaterial layer is clear or not can be determined by, for example, observing a cross section of the photosensitive layer B and the metal-containing nanomaterial layer in a direction perpendicular to the in-plane direction using a Scanning Electron Microscope (SEM).

Modification of layer structure

The laminate according to the present invention may have photosensitive layers on both surfaces of the substrate. The photosensitive layers on the two sides may be the same or different. The photosensitive layer containing no metal nanomaterial is preferably used together with a layer containing a metal nanomaterial.

For example, the laminate of embodiment 1 may have the photosensitive layer a on the side opposite to the side having the photosensitive layer a, or may have the photosensitive layer B and the metal nanomaterial-containing layer on the side opposite to the side having the photosensitive layer a. The substrate, the photosensitive layer B, and the metal nanomaterial-containing layer may be provided in this order, or the substrate, the metal nanomaterial-containing layer, and the photosensitive layer B may be provided in this order.

The laminate of embodiments 2 and 3 may have the photosensitive layer a on the side of the substrate opposite to the side having the photosensitive layer B and the metal-containing nanomaterial, or may have the photosensitive layer B and the metal-containing nanomaterial on the side of the substrate opposite to the side having the photosensitive layer B and the metal-containing nanomaterial. The substrate, the photosensitive layer B, and the metal nanomaterial-containing layer may be provided in this order, or the substrate, the metal nanomaterial-containing layer, and the photosensitive layer B may be provided in this order.

In the laminate, the photosensitive layer present on one side of the substrate is sometimes referred to as a "first photosensitive layer", and the photosensitive layer present on the other side of the substrate is sometimes referred to as a "second photosensitive layer". The combination of the photosensitive layer a and the photosensitive layer B is sometimes simply referred to as a "photosensitive layer".

As a combination of the type of the first photosensitive layer and the type of the second photosensitive layer, for example, the following combination is given.

(1) The first photosensitive layer is a negative photosensitive layer, and the second photosensitive layer is a negative photosensitive layer.

(2) The first photosensitive layer is a positive photosensitive layer, and the second photosensitive layer is a positive photosensitive layer.

(3) The first photosensitive layer is a negative photosensitive layer, and the second photosensitive layer is a positive photosensitive layer.

(4) The first photosensitive layer is a positive photosensitive layer, and the second photosensitive layer is a negative photosensitive layer.

[ substrate ]

The laminate has a substrate including a region having a transmittance for light of an exposure wavelength.

In the present invention, the "region having transmittance to light of an exposure wavelength" means a region having transmittance of 30% or more at a dominant wavelength in the exposure wavelength. The transmittance is preferably 50% or more, more preferably 60% or more, further preferably 80% or more, and particularly preferably 90% or more. The upper limit of the transmittance is not limited. The transmittance may be determined, for example, in a range of 100% or less. The transmittance is measured using a known transmittance measuring instrument (for example, V-700series manufactured by JASCO Corporation).

The region having transmittance to light of the exposure wavelength may be disposed over the entire substrate or a part of the substrate. The region having transmittance to light of the exposure wavelength is preferably arranged at a portion corresponding to the exposure portion in the exposure step. The region having transmittance to light of the exposure wavelength is preferably disposed over the entire substrate. That is, the substrate is preferably a substrate transparent to the exposure wavelength.

Examples of the material of the substrate include a resin material and an inorganic material.

Examples of the resin material include polyesters (for example, polyethylene terephthalate and polyethylene naphthalate), polyether ether ketone, acrylic resins, cycloolefin polymers, and polycarbonates.

Examples of the inorganic material include glass and quartz.

The substrate is preferably a resin film, more preferably a polyethylene terephthalate film, a polyethylene naphthalate film or a cycloolefin polymer film.

The thickness of the substrate is not limited. The average thickness of the substrate is preferably 10 μm to 100 μm, more preferably 10 μm to 60 μm, from the viewpoints of transport property, electrical property and film forming property. The average thickness of the substrate was set to be an average value of the thickness at 10 points measured by observing a cross section of the substrate in a direction perpendicular to the in-plane direction using a Scanning Electron Microscope (SEM).

When the laminate has photosensitive layers on both surfaces, the absorbance of the substrate at 365nm is preferably 0.5 or more. Thus, for example, when the first photosensitive layer is exposed to 365nm light, 365nm light after transmitting the first photosensitive layer is absorbed by the substrate, and thus exposure of the second photosensitive layer to 365nm light via the substrate can be suppressed. Thus, patterns of different shapes are easily formed in the first photosensitive layer and the second photosensitive layer.

[ other layers ]

The laminate may have layers other than those described above (hereinafter, sometimes referred to as "other layers"). Examples of the other layer include a temporary support and a protective film.

The temporary support will be described below. As described later, the temporary support is, for example, a member used when a photosensitive layer is formed using a transfer material. In the case where the laminated body has a temporary support, the temporary support may be generally disposed on a surface of at least one of the laminated bodies. Specifically, the temporary support may be disposed on the outermost layer on the side on which the first photosensitive layer is disposed with respect to the substrate. The temporary support may be disposed on the outermost layer on the side where the second photosensitive layer is disposed with respect to the substrate.

Examples of the temporary support include a glass substrate, a resin film, and paper. The temporary support is preferably a resin film from the viewpoint of strength and flexibility. Examples of the resin film include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. The temporary support is preferably a polyethylene terephthalate film, more preferably a biaxially stretched polyethylene terephthalate film.

As the temporary support, a film which has flexibility and does not undergo significant deformation, shrinkage or elongation under pressure or under pressure and heat can be used. Examples of such a film include a polyethylene terephthalate film (for example, a biaxially stretched polyethylene terephthalate film), a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film. Among them, biaxially stretched polyethylene terephthalate film is particularly 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 highly transparent from the viewpoint of enabling pattern exposure via the temporary support. The transmittance at 365nm of the temporary support is preferably 60% or more, more preferably 70% or more.

The smaller the haze of the temporary support, the more preferable from the viewpoints of the pattern formability at the time of pattern exposure via the temporary support and the transparency of the temporary support. Specifically, the haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and particularly preferably 0.3% or less.

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

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

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

When the laminate has a protective film, the protective film may be disposed on at least one surface of the laminate. Specifically, the protective film may be disposed on the outermost layer on the side where the first photosensitive layer is disposed with respect to the substrate. The protective film may be disposed on the outermost layer on the side where the second photosensitive layer is disposed with respect to the substrate.

Hereinafter, the protective film will be described. Examples of the protective film include a resin film and paper. The protective film is preferably a resin film from the viewpoint of strength and flexibility. Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. The resin film is preferably a polyethylene film, a polypropylene film or a polyethylene terephthalate film.

The protective film preferably has light transmittance. The protective film has light transmittance, and thus exposure can be performed via the protective film.

The thickness of the protective film is not limited. The average thickness of the protective film may be determined, for example, in the range of 1 μm to 2 mm. The average thickness of the protective film is measured by a method based on the above-described method for measuring the average thickness of the substrate.

Examples of the other layer include a thermoplastic resin layer and an intermediate layer.

The thermoplastic resin layer will be described below. The thermoplastic resin layer contains a resin. Part or all of the resin is a thermoplastic resin. The thermoplastic resin layer preferably contains a thermoplastic resin.

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

As the alkali-soluble resin, an acrylic resin is preferable from the viewpoints of developability and adhesion to an adjacent layer. The acrylic resin means a resin having at least one structural unit selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylamide. In the acrylic resin, the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylamide is preferably 50 mass% or more with respect to the total mass of the acrylic resin. Wherein the total content of the structural units derived from (meth) acrylic acid and the structural units derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, relative to the total mass of the acrylic resin.

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

From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 40mgKOH/g or more, more preferably a carboxyl-containing acrylic resin having an acid value of 40mgKOH/g or more. The acid value of the alkali-soluble resin is preferably 300mgKOH/g or less, more preferably 250mgKOH/g or less, still more preferably 200mgKOH/g or less, particularly preferably 160mgKOH/g or less.

Examples of the carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more include alkali-soluble resins as carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the polymer described in paragraph 0025 of JP 2011-095716, carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the polymers described in paragraphs 0033 to 0052 of JP 2010-237589, and carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the binder polymers described in paragraphs 0053 to 0068 of JP 2016-224162. The copolymerization ratio of the structural unit having a carboxyl group in the carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 12 to 30% by mass relative to the total mass of the acrylic resin. As the alkali-soluble resin, an acrylic resin having a structural unit derived from (meth) acrylic acid is particularly preferable from the viewpoints of developability and adhesion to an adjacent layer.

The alkali-soluble resin may have a reactive group. Examples of the reactive group include an addition polymerizable group. Examples of the reactive group include an ethylenically unsaturated group polycondensation group (for example, hydroxyl group and carboxyl group) and a polyaddition reactive group (for example, epoxy group and (block) isocyanate group).

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

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

The content of the alkali-soluble resin is preferably 10 to 99 mass%, more preferably 20 to 90 mass%, even more preferably 40 to 80 mass%, and particularly preferably 50 to 75 mass% with respect to the total mass of the thermoplastic resin layer from the viewpoints of developability and adhesion to the adjacent layer.

The thermoplastic resin layer preferably contains a dye (hereinafter, sometimes referred to as "dye B") having a maximum absorption wavelength of 450nm or more and a maximum absorption wavelength that changes due to an acid, a base, or a radical in a wavelength range of 400nm to 780nm at the time of color development. From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid. From the viewpoint of visibility and resolution of the exposed portion and the non-exposed portion, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength of the dye B changes depending on the acid and a compound that generates an acid by light.

The pigment B may be used singly or in combination of two or more.

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

The content of the pigment B indicates the content of the pigment when all of the pigment B contained in the thermoplastic resin layer is in a color-developed state. Hereinafter, a method for determining the content of the dye B will be described by taking a dye developed by a radical as an example. A solution in which 0.001g of a dye was dissolved in 100mL of methyl ethyl ketone and a solution in which 0.01g of a dye was dissolved in 100mL of methyl ethyl ketone were prepared. To each of the obtained solutions, irgacure OXE01 (trade name, BASF Japan ltd.) as a photo radical polymerization initiator was added, and a radical was generated by irradiation with light of 365nm, thereby bringing all the pigments into a color development state. Then, the absorbance of each solution having a liquid temperature of 25℃was measured under an air atmosphere using a spectrophotometer (manufactured by UV3100, SHIMADZU CORPORATION), and a calibration curve was prepared. Next, the absorbance of the solution in which the pigment was completely developed was measured by the same method as described above except that 0.1g of the thermoplastic resin layer was dissolved in methyl ethyl ketone instead of the pigment. The amount of the pigment contained in the thermoplastic resin layer was calculated from the absorbance of the obtained solution containing the thermoplastic resin layer based on the calibration curve.

The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (hereinafter, sometimes referred to as "compound C"). The compound C is preferably a compound that generates an acid, a base, or a radical upon receiving an activating light such as ultraviolet rays or visible rays. As the compound C, a known photoacid generator, photobase generator, and photo radical polymerization initiator (photo radical generator) can be used.

From the viewpoint of resolution, the thermoplastic resin layer may contain a photoacid generator. Examples of the photoacid generator include photo-cationic polymerization initiators.

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

[ chemical formula 8]

The thermoplastic resin layer may contain a photo radical polymerization initiator. The photo radical polymerization initiator may be any of the photo radical polymerization initiators that the negative photosensitive layer may contain.

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

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

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

The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to an adjacent layer, and developability. The plasticizer preferably has a molecular weight (weight average molecular weight in the case of an oligomer or polymer and having a molecular weight distribution) smaller than that of the alkali-soluble resin. The molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000. The plasticizer is not particularly limited as long as it is a compound that exhibits plasticity by being compatible with the alkali-soluble resin, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and more preferably is a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

Further, the plasticizer preferably contains a (meth) acrylate compound from the viewpoints of resolution and storage stability. From the viewpoints of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound. The (meth) acrylate compound used as the plasticizer includes (meth) acrylate compounds described as photopolymerizable compounds contained in the negative photosensitive layer.

In the case where the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer, it is preferable that the (meth) acrylate compound does not polymerize even in the exposed portion that is exposed to light from the viewpoint of adhesion of the thermoplastic resin layer to the adjacent layer. Further, as the (meth) acrylate compound used as the plasticizer, a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule is preferable from the viewpoints of resolution of the thermoplastic resin layer, adhesion to an adjacent layer, and developability. Further, as the (meth) acrylate compound used as the plasticizer, a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound is also preferable.

One kind of plasticizer may be used alone, or two or more kinds may be used.

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

The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include those which the negative photosensitive layer may contain.

The sensitizer may be used singly or in combination of two or more.

The content of the sensitizer may be appropriately selected according to the purpose, but is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% relative to the total mass of the thermoplastic resin layer, from the viewpoint of improving the sensitivity to the light source and visibility of the exposed portion and the non-exposed portion.

In addition to the above components, the thermoplastic resin layer may contain a known additive such as a surfactant, if necessary. The thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese patent application laid-open No. 2014-085643, the contents of which are incorporated herein by reference.

From the viewpoint of adhesion to the adjacent layer, the thickness of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more. From the viewpoints of developability and resolution, the thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 8 μm or less.

Hereinafter, the intermediate layer will be described. As the intermediate layer, for example, a water-soluble resin layer containing a water-soluble resin is preferably used. Further, as the intermediate layer, for example, an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in Japanese patent application laid-open No. 5-072724 is also used. If the intermediate layer is an oxygen barrier layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved. The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers. Preferably an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (e.g., a 1 mass% aqueous solution of sodium carbonate at 22 ℃). In the case where the laminate has an oxygen barrier layer, the laminate preferably has an oxygen barrier layer on the side of the photosensitive layer opposite to the side having the substrate.

The intermediate layer is preferably disposed between the photosensitive layer and the thermoplastic resin layer.

The water-soluble resin layer as one of the intermediate layers contains a resin. Part or all of the resin is a water-soluble resin. Examples of the resin that can be used as the water-soluble resin include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, and polyamide resins. Further, as the water-soluble resin, for example, a copolymer of (meth) acrylic acid/vinyl compound can be mentioned. As the copolymer of (meth) acrylic acid/vinyl compound, a copolymer of (meth) acrylic acid/(meth) acrylic acid allyl ester is preferable, and a copolymer of methacrylic acid/methacrylic acid allyl ester is more preferable. When the water-soluble resin is a copolymer of (meth) acrylic acid and a vinyl compound, the composition ratio (mol%) is, for example, preferably 90/10 to 20/80, more preferably 80/20 to 30/70.

The oxygen barrier layer as one embodiment of the water-soluble resin layer preferably contains one or more selected from the group consisting of polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, and polyamide-based resin.

The weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and particularly preferably 10,000 or more. The weight average molecular weight of the water-soluble resin is preferably 200,000 or less, more preferably 100,000 or less, and particularly preferably 50,000 or less. The dispersity (Mw/Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.

From the viewpoint of further improving the interlayer mixing suppression capability of the water-soluble resin layer, the resin in the water-soluble resin layer is preferably a resin different from the resin contained in the layer disposed on one surface side of the water-soluble resin layer and the resin contained in the layer disposed on the other surface side.

From the viewpoint of further improving the oxygen barrier property and interlayer mixing inhibition ability, the water-soluble resin preferably contains polyvinyl alcohol, more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

The water-soluble resin may be used singly or in combination of two or more.

The content of the water-soluble resin is preferably 50 mass% or more, more preferably 70 mass% or more, still more preferably 80 mass% or more, and particularly preferably 90 mass% or more, relative to the total mass of the water-soluble resin layer, from the viewpoint of further improving the oxygen barrier property and interlayer mixing inhibition ability. The upper limit of the content of the water-soluble resin is not limited. The content of the water-soluble resin is preferably 99.9 mass% or less, more preferably 99.8 mass% or less, relative to the total mass of the water-soluble resin layer.

The intermediate layer may contain a known additive such as a surfactant, if necessary. Examples of the surfactant include those described in the above item "positive photosensitive layer".

The thickness of the intermediate layer is preferably 0.1 μm to 5. Mu.m, more preferably 0.5 μm to 3. Mu.m. When the thickness of the intermediate layer is within the above range, the interlayer mixing inhibition ability is excellent, but the oxygen barrier property is not lowered. In addition, an increase in the removal time of the intermediate layer during development can be suppressed.

< method of Forming Pattern >

As a pattern forming method according to the present invention, the pattern forming methods of the following modes 1 to 6 are exemplified.

The pattern forming method of embodiment 1 includes:

a step of preparing a laminate according to the present invention;

And developing the pattern-exposed photosensitive layer.

The pattern forming method of embodiment 2 includes:

exposing the first photosensitive layer;

Exposing the second photosensitive layer;

The pattern forming method of embodiment 3 includes:

exposing the first photosensitive layer;

exposing the second photosensitive layer;

main wavelength of exposure wavelength in the step of exposing the first photosensitive layerλ ₁ And a main wavelength lambda of an exposure wavelength in the step of exposing the second photosensitive layer ₂ Satisfy lambda ₁ ≠λ ₂ Is a relationship of (3).

The pattern forming method of embodiment 4 includes:

exposing the first photosensitive layer;

exposing the second photosensitive layer;

The pattern forming method of embodiment 5 includes:

Exposing the first photosensitive layer;

exposing the second photosensitive layer;

exposure wavelength in the step of exposing the first photosensitive layerDominant wavelength lambda ₁ And a main wavelength lambda of an exposure wavelength in the step of exposing the second photosensitive layer ₂ Satisfy lambda ₁ ≠λ ₂ Is a relationship of (3).

The pattern forming method of embodiment 6 includes:

exposing the first photosensitive layer;

exposing the second photosensitive layer;

The patterning method according to the present invention can be preferably used for patterning using the laminate, and patterning methods corresponding to various layer structures as in modes 1 to 6 can be suitably used in consideration of the layer structure of the laminate.

The pattern forming method according to embodiment 2 will be described in detail below by taking a typical example. The description of the pattern forming method according to embodiment 2 is also applicable to the pattern forming methods according to embodiments 3 to 6. The pattern forming method of embodiment 1 can be described as being applied to the pattern forming method of embodiment 2 in the same manner except for the configuration using the first photosensitive layer and the second photosensitive layer.

The pattern forming method of embodiment 2 includes:

a step of preparing a laminate having, in order, a first photosensitive layer containing a metal nanomaterial and an alkali-soluble compound, a substrate including a region having a transmittance to light of an exposure wavelength, and a second photosensitive layer containing a metal nanomaterial and an alkali-soluble compound (hereinafter, sometimes referred to as a "preparation step");

A step of exposing the first photosensitive layer (hereinafter, sometimes referred to as an "exposure step (1)");

a step of exposing the second photosensitive layer (hereinafter, sometimes referred to as an "exposure step (2)");

a step of developing the exposed first photosensitive layer to form a first resin pattern (hereinafter, sometimes referred to as a "developing step (1)"); a kind of electronic device with high-pressure air-conditioning system

A step of developing the exposed second photosensitive layer to form a second resin pattern (hereinafter, sometimes referred to as a "developing step (2)"),

a main wavelength lambda of an exposure wavelength in the step of exposing the first photosensitive layer ₁ And a main wavelength lambda of an exposure wavelength in the step of exposing the second photosensitive layer ₂ Satisfy lambda ₁ ≠λ ₂ (hereinafter, sometimes referred to as "specific exposure condition").

The pattern forming method according to embodiment 2 can form a resin pattern with excellent resolution by including the steps described above, and suppressing the generation of exposure mist. The reason why the pattern forming method of embodiment 2 exerts the above-described effects is presumed to be as follows. As described above, in order to suppress the generation of exposure mist, for example, if the optical density of the photosensitive layer is increased by using an ultraviolet absorbing material, the resolution of the obtained resin pattern may be deteriorated. On the other hand, the pattern forming method according to the present invention includes a preparation step, an exposure step (1), an exposure step (2), a development step (1) and a development step (2), wherein the exposure step (1) has a dominant wavelength λ of the exposure wavelength ₁ And a dominant wavelength lambda of the exposure wavelength in the exposure step (2) ₂ By this, the first photosensitive layer and the second photosensitive layer can be selectively or preferentially exposed. Therefore, the pattern forming method according to the present invention can suppress the generation of exposure mist, and can form a pattern having excellent resolutionAnd (3) a resin pattern.

Hereinafter, each step of the pattern forming method of the method 2 will be specifically described.

< preparation procedure >

The pattern forming method of embodiment 2 includes a step of preparing a laminate including, in order, a first photosensitive layer, a substrate (hereinafter, may be simply referred to as "substrate") including a region having a transmittance for light of an exposure wavelength, and a second photosensitive layer.

In the present invention, "preparing a laminate" means making the laminate usable, and includes preparing a laminate manufactured in advance and manufacturing the laminate unless otherwise specified. That is, the laminate used in the pattern forming method according to the present invention may be a laminate manufactured in advance or a laminate manufactured in a preparation process.

As the laminate, the pattern forming method of embodiment 2 can be preferably used.

[ sensitivity of photosensitive layer ]

Preferably, the first photosensitive layer and the second photosensitive layer each have a specific exposure sensitivity. This can effectively suppress the generation of exposure mist.

Specifically, when the sensitivities of the first photosensitive layer and the second photosensitive layer satisfy the following relationships 1 and 2, the generation of exposure mist can be effectively suppressed.

Relationship 1: e is more than or equal to 1.1 _1r /E ₂

Relationship 2: e is more than or equal to 1.1 _2r /E ₁

Here, E _1r Representing the passage of the light having the dominant wavelength lambda from the second photosensitive layer side of the laminate ₂ The highest exposure amount, E, of the first photosensitive layer not reacting when the light is exposed ₂ Indicating that the light passes through the light-sensitive film having a dominant wavelength lambda in the process of exposing the second photosensitive layer ₂ Exposure amount E when exposing the second photosensitive layer _2r Representing the first photosensitive layer side of the laminate passing through a light source having a dominant wavelength lambda ₁ The highest exposure amount, E, of the second photosensitive layer not reacting when the light is exposed ₁ Is shown in the pairIn the step of exposing the first photosensitive layer, the first photosensitive layer is exposed to light having a dominant wavelength lambda ₁ Is used for exposing the first photosensitive layer. The exposure amounts are the same. The unit of each exposure is, for example, mJ/cm ² 。

The above-described sensitivity conditions will be described in detail. In the process of exposing the first photosensitive layer and the second photosensitive layer facing each other across the substrate (i.e., the exposure step (1) and the exposure step (2)), the first photosensitive layer is formed by a substrate having a dominant wavelength λ ₁ Exposing the second photosensitive layer by an exposure beam having a dominant wavelength lambda ₂ Is exposed to an exposure beam of (a). Further, in the above process, the first photosensitive layer is located at a dominant wavelength lambda from the substrate side through which the second photosensitive layer and the substrate are transmitted ₂ The second photosensitive layer is in a state of being exposed by the exposure beam having a dominant wavelength lambda from the substrate side through which the first photosensitive layer and the substrate are transmitted ₁ Is exposed to the exposure beam.

Therefore, it is required that the first photosensitive layer and the second photosensitive layer do not react with the exposure light beam transmitted from the substrate side, that is, do not generate exposure mist with the exposure light beam transmitted from the substrate side. If the photosensitive layer reacts with the exposure beam transmitted through the substrate, for example, an undesired exposure pattern is formed, thereby adversely affecting the final wiring quality. In order to avoid exposure haze, in the case of the first photosensitive layer, the exposure dose E is the highest dose at which the first photosensitive layer does not react when exposed from the second photosensitive layer side _1r Higher exposure E than the second photosensitive layer ₂ The state of (2) is just required. This is also the same for the second photosensitive layer.

As E _1r /E ₂ Values of (E) and E _2r /E ₁ The value of (2) is preferably 1.1 or more, more preferably 1.15 or more, and particularly preferably 1.2 or more, respectively. By making E _1r /E ₂ 、E _2r /E ₁ By such a ratio, even if there is a slight process variation in the exposure amount, stable patterning can be performed without generating exposure mist. E (E) _1r /E ₂ E and E _2r /E ₁ The upper limit of (2) is not particularly limited as long asThe photosensitive layer may have an appropriate property and may be set to any value.

In order to E _1r /E ₂ E and E _2r /E ₁ At the ratio described above, the light-sensitive layer can be adjusted to the dominant wavelength lambda ₁ Dominant wavelength lambda ₂ The respective absorption coefficients. More specifically, by appropriately selecting a compound involved in photoreaction such as a photoreaction initiator, a sensitizer, a chain transfer agent, etc., for each photosensitive layer, a photosensitive layer having the above-described properties can be obtained.

For example, when the first photosensitive layer is exposed to light having a dominant wavelength of 405nm and the second photosensitive layer is exposed to light having a dominant wavelength of 365nm, the light absorption coefficient of the first photosensitive layer at 365nm is reduced, so that exposure mist generated by an exposure beam having a wavelength of 365nm transmitted through the second photosensitive layer and the substrate can be made less likely to be generated. Also, for example, a method of controlling the amount of light transmitted through the second photosensitive layer and the substrate by introducing a compound that absorbs light having a wavelength of 365nm into the second photosensitive layer may be used as a technical method for suppressing the generation of exposure mist in the first photosensitive layer. On the other hand, for example, by reducing the absorption coefficient of the second photosensitive layer to the wavelength of 405nm, the generation of exposure mist in the second photosensitive layer can be suppressed similarly to the first photosensitive layer.

The following relationships 3 and 4 are also preferably satisfied with respect to the respective sensitivities of the first photosensitive layer and the second photosensitive layer.

Relationship 3: s is more than or equal to 3 ₁₂ /S ₁₁

Relationship 4: s is more than or equal to 3 ₂₁ /S ₂₂

Here, S ₁₂ Representing the dominant wavelength lambda of the first photosensitive layer ₂ Spectral sensitivity of S ₁₁ Representing the dominant wavelength lambda of the first photosensitive layer ₁ Spectral sensitivity of S ₂₁ Representing the dominant wavelength lambda of the second photosensitive layer ₁ Spectral sensitivity of S ₂₂ Representing the dominant wavelength lambda of the second photosensitive layer ₂ Is a function of the spectral sensitivity of the sample. The units of the spectral sensitivities are the same. The unit of each spectral sensitivity is mJ/cm ² 。

Spectral sensitivity refers to the minimum exposure required for the photosensitive layer to react when exposed to light having a specific wavelength. The smaller the value of spectral sensitivity (i.e., the minimum exposure amount required for the photosensitive layer to react) in the present invention, the higher the sensitivity of the photosensitive layer. In general, the photosensitive layer has different absorption coefficients according to wavelengths, and the photoreaction initiator and sensitizer have different quantum yields according to wavelengths, so that the sensitivity of the photosensitive layer generally varies according to wavelengths. In order to suppress exposure haze, for example, the first photosensitive layer is preferably a light having a dominant wavelength lambda ₂ Spectral sensitivity (S) ₁₂ ) Large, i.e. low sensitivity. Through S ₁₂ /S ₁₁ S and S ₂₁ /S ₂₂ The ratio (2) is not less than a predetermined value, and the exposure light beam transmitted from the substrate side is not easily reacted, so that good patterning performance can be obtained.

As S ₁₂ /S ₁₁ Values of (2) and S ₂₁ /S ₂₂ The value of (2) is preferably 3 or more, more preferably 4 or more, and particularly preferably 5 or more, respectively. S is S ₁₂ /S ₁₁ Values of (2) and S ₂₁ /S ₂₂ The upper limit of the value of (c) is not particularly limited, and may be set to any value as long as the photosensitive layer has an appropriate performance. A photosensitive layer having such properties can be obtained by adjusting the dominant wavelength lambda of the photosensitive layer ₁ Dominant wavelength lambda ₂ The respective absorption coefficients are obtained by a method.

In measuring the spectral sensitivity, an exposure beam of a specific wavelength is irradiated to the photosensitive layer via an exposure ruler, followed by a developing operation. In the negative photosensitive layer, the lowest exposure amount remaining in the exposure portion may be set to the spectral sensitivity. On the other hand, in the positive photosensitive layer, the lowest exposure amount from which the exposure portion is removed may be set to the spectral sensitivity.

The first photosensitive layer and the second photosensitive layer preferably contain different photosensitive compounds. The first photosensitive layer and the second photosensitive layer contain different photosensitive compounds, so that the generation of exposure mist can be further suppressed.

In the present invention, the term "photosensitive compounds different from each other" means photosensitive compounds having different molar absorptivity values at the exposure wavelength. In the first photosensitive layer and the second photosensitive layer, for example, in the photosensitive compound contained in one photosensitive layer, the molar absorptivity at wavelength 365nm is preferably larger than the molar absorptivity at wavelength 405nm, and in the photosensitive compound contained in the other photosensitive layer, the molar absorptivity at wavelength 405nm is preferably larger than the molar absorptivity at wavelength 365 nm.

Regarding "the value of molar absorptivity at wavelength 365nm is larger than the value of molar absorptivity at wavelength 405 nm", preferred ranges are shown below. When the molar absorptivity at 365nm is set to 100%, the molar absorptivity at 405nm is preferably 80% or less, more preferably 50% or less, further preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less. The lower limit of the value of the molar absorptivity at the wavelength of 405nm is not limited. When the molar absorptivity at 365nm is set to 100%, the molar absorptivity at 405nm can be determined to be, for example, 0% or more.

Regarding "the value of molar absorptivity at wavelength 405nm is larger than the value of molar absorptivity at wavelength 365 nm", preferred ranges are shown below. When the molar absorptivity at the wavelength of 405nm is set to 100%, the molar absorptivity at the wavelength of 365nm is preferably 80% or less, more preferably 50% or less, further preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less. The lower limit of the value of the molar absorptivity at the wavelength of 365nm is not limited. When the molar absorptivity at the wavelength of 405nm is set to 100%, the molar absorptivity at the wavelength of 365nm can be determined within a range of 0% or more, for example.

For example, in the first photosensitive layer and the second photosensitive layer, it is preferable that the photosensitive layer exposed at an exposure wavelength having an intensity of 365nm greater than an intensity of 405nm contains a photosensitive compound having a molar absorptivity at 365nm greater than a molar absorptivity at 405nm, and the photosensitive layer exposed at an exposure wavelength having an intensity of 405nm greater than an intensity of 365nm contains a photosensitive compound having a molar absorptivity at 405nm greater than a molar absorptivity at 365 nm. The first photosensitive layer and the second photosensitive layer contain the photosensitive compound as described above, whereby the generation of exposure mist can be further suppressed.

[ light absorption Property ]

The first photosensitive layer preferably has an absorption dominant wavelength lambda ₂ Is a property of light of (a) a light source. In the step of exposing the second photosensitive layer (i.e., the exposure step (2)), for example, the exposure beam that has transmitted through the second photosensitive layer, the substrate, and the first photosensitive layer in this order may be reflected by a member such as a filter having wavelength selectivity and then reach the second photosensitive layer again. If the second photosensitive layer is re-exposed by the reflected exposure beam, the resolution may be degraded. On the other hand, has absorption dominant wavelength lambda ₂ The first photosensitive layer having the property of light and capable of absorbing and transmitting the dominant wavelength lambda after the second photosensitive layer and the substrate ₂ And a dominant wavelength lambda reflected by a wavelength-selective filter or the like ₂ Is a light source of a light. Therefore, a decrease in resolution caused by re-exposure of the second photosensitive layer can be suppressed.

The second photosensitive layer preferably has an absorption dominant wavelength lambda ₁ Is a property of light of (a) a light source. In the step of exposing the first photosensitive layer (i.e., the exposure step (1)), for example, the exposure beam that has transmitted the first photosensitive layer, the substrate, and the second photosensitive layer in this order may be reflected by a member such as a filter having wavelength selectivity and then reach the first photosensitive layer again. If the first photosensitive layer is re-exposed by the reflected exposure beam, the resolution may be degraded. On the other hand, has absorption dominant wavelength lambda ₁ The second photosensitive layer having the property of light and capable of absorbing and transmitting the dominant wavelength lambda after the first photosensitive layer and the substrate ₁ And a dominant wavelength lambda reflected by a wavelength-selective filter or the like ₁ Is a light source of a light. Therefore, a decrease in resolution caused by re-exposure of the first photosensitive layer can be suppressed.

From the standpoint of suppressing the degradation of resolution caused by re-exposure, in one embodiment,preferably, the first photosensitive layer contains an absorption dominant wavelength lambda ₂ Or the second photosensitive layer contains a substance that absorbs light of dominant wavelength lambda ₁ Is a light source of the above light source. The above embodiment includes the following (1) to (3). In the following (1) to (3), (3) is preferable.

(1) The first photosensitive layer contains an absorption dominant wavelength lambda ₂ Is a light source of the above light source.

(2) The second photosensitive layer contains an absorption dominant wavelength lambda ₁ Is a light source of the above light source.

(3) The first photosensitive layer contains an absorption dominant wavelength lambda ₂ And the second photosensitive layer contains a substance that absorbs light of dominant wavelength lambda ₁ Is a light source of the above light source.

The layer having a property of absorbing light of a specific dominant wavelength may be a layer other than the first photosensitive layer and the second photosensitive layer from the viewpoint of suppressing a decrease in resolution due to re-exposure. In one embodiment, the laminate preferably has a wavelength lambda having an absorption dominant wavelength lambda selected from the group consisting of those disposed between the substrate and the first photosensitive layer ₂ A layer of a substance having an absorption dominant wavelength lambda disposed on the substrate via the first photosensitive layer ₂ A layer of a substance containing an absorption dominant wavelength lambda disposed between the substrate and the second photosensitive layer ₁ A layer of a substance having an absorption dominant wavelength lambda disposed on the substrate via the second photosensitive layer ₁ At least one of the layers of the substance of the light of (a). As a component containing absorption dominant wavelength lambda ₁ Or dominant wavelength lambda ₂ Examples of the layer of the light-emitting substance of (a) include the layers described in the following "other layers". Containing absorption dominant wavelength lambda ₁ Or dominant wavelength lambda ₂ The layer of the light-emitting substance of (a) is preferably a thermoplastic resin layer or an intermediate layer, more preferably a thermoplastic resin layer.

As absorption dominant wavelength lambda ₁ Or dominant wavelength lambda ₂ Examples of the light-emitting substance include dyes and pigments. As absorption dominant wavelength lambda ₁ Or dominant wavelength lambda ₂ Examples of the light-emitting substance (b) include near ultraviolet absorbers. As absorption dominant wavelength lambda ₁ Or dominant wavelength lambda ₂ Examples of the light-emitting substance (b) include inorganic particles.

Preferably absorbs dominant wavelength lambda ₂ Is characterized by having a dominant wavelength lambda ₁ Any one of the substances having absorption in a wavelength region of 400nm or more. The exposure wavelength is actually selected, for example, with 400nm as a boundary, according to the spectral distribution of a light source such as a high-pressure mercury lamp. For example, the exposure wavelength in either one of the exposure step (1) and the exposure step (2) may be selected in a wavelength region of 400nm or more. When the exposure wavelength as described above is applied, absorption of the dominant wavelength lambda is particularly preferable ₂ Is characterized by having a dominant wavelength lambda ₁ Any one of the substances having absorption in a wavelength region of 400nm or more.

Examples of the substance having an absorption in a wavelength region of 400nm or more include a dye having an absorption in a wavelength region of 400nm or more and a pigment having an absorption in a wavelength region of 400nm or more. Examples of the dye having absorption in a wavelength region of 400nm or more include solvent yellow 4, solvent yellow 14, solvent yellow 56, methyl yellow, solvent green 3, acid yellow 23, acid yellow 36, acid yellow 73, basic yellow 1, basic yellow 2, basic yellow 7, acid green 1, acid green 3, acid green 27, acid green 50, acid green a, and basic green 1. Examples of pigments having an absorption in a wavelength region of 400nm or more include pigment yellow 1, pigment yellow 14, pigment yellow 34, pigment yellow 93, pigment yellow 138, pigment yellow 150, pigment green 7, pigment green 36, pigment green 50, and pigment green 58. Examples of the substance having an absorption in a wavelength region of 400nm or more include a near ultraviolet absorber having an absorption in a wavelength region of 400nm or more and inorganic particles having an absorption in a wavelength region of 400nm or more.

The substance having absorption in the wavelength region of 400nm or more preferably has a maximum absorption wavelength lambda in the wavelength region of 400nm or more _max Is a substance of (a).

Absorption of dominant wavelength lambda ₁ Or dominant wavelength lambda ₂ The preferable mode of the light source of (2) can be selected according to the following (1) to (4). The substance having the light absorption characteristic corresponding to the main wavelength of the subject can suppress a decrease in resolution caused by re-exposure.

(1) In the main waveLong lambda ₁ At 400nm or more, the absorption dominant wavelength lambda ₁ The light-absorbing material of (2) has absorption in a wavelength region of 400nm or more.

(2) At dominant wavelength lambda ₁ Below 400nm, absorption dominant wavelength lambda ₁ Has absorption in the wavelength region of less than 400 nm.

(3) At dominant wavelength lambda ₂ At 400nm or more, the absorption dominant wavelength lambda ₂ The light-absorbing material of (2) has absorption in a wavelength region of 400nm or more.

(4) At dominant wavelength lambda ₂ Below 400nm, absorption dominant wavelength lambda ₂ Has absorption in the wavelength region of less than 400 nm.

Absorption of dominant wavelength lambda ₁ Or dominant wavelength lambda ₂ The content of the light-emitting substance in (a) is preferably 30 mass% or less relative to the total mass of the layer containing the substance. By absorption of dominant wavelength lambda ₁ Or dominant wavelength lambda ₂ The content of the light-emitting substance is minimized, and the deterioration of the original functions of the layer containing the substance can be suppressed. Absorption of dominant wavelength lambda ₁ Or dominant wavelength lambda ₂ The lower limit of the content of the substance of the light of (a) can be determined from the amount of light at which the reflected exposure beam reaches the photosensitive layer again (hereinafter referred to as "reflected light amount" in this paragraph). Preferably will absorb the dominant wavelength lambda ₁ Or dominant wavelength lambda ₂ The content of the substance of the light is adjusted so that the ratio of the amount of reflected light to the amount of exposure light incident on the target photosensitive layer is 50% or less (preferably 20% or less, more preferably 10% or less). Calculation of the reflected light amount is based on, for example, absorbance and reflectance of the photosensitive layer, absorbance and reflectance of the substrate, absorbance and reflectance of the photomask, and absorption dominant wavelength λ ₁ Or dominant wavelength lambda ₂ The absorbance of the substance of the light of (a) is measured.

[ method for producing laminate ]

The method for producing the laminate is not limited, and a known method can be used. For example, the following methods are mentioned: a first photosensitive layer is formed on one surface of the substrate, and then a second photosensitive layer is formed on the other surface of the substrate. The first photosensitive layer and the second photosensitive layer may be formed simultaneously or separately. Hereinafter, the first photosensitive layer and the second photosensitive layer may be collectively referred to as a "photosensitive layer". Unless otherwise indicated, the term "photosensitive layer" includes a first photosensitive layer, a second photosensitive layer, or both the first photosensitive layer and the second photosensitive layer.

The method for forming the photosensitive layer is not limited, and a known method can be used. Examples of the method for forming the photosensitive layer include a coating method and a method using a transfer material.

The methods of forming the first photosensitive layer and the second photosensitive layer may be the same or different. For example, the first photosensitive layer and the second photosensitive layer may be formed by a coating method or a method using a transfer material. One of the first photosensitive layer and the second photosensitive layer may be formed by a coating method, and the other photosensitive layer may be formed using a transfer material. In the case of the pattern forming methods of aspects 3 to 6, a photosensitive composition for forming the photosensitive layer B (i.e., a photosensitive layer containing an alkali-soluble compound) and a composition containing a metal nanomaterial for forming a metal nanomaterial-containing layer may be prepared, and a coating method, a transfer material, or the like may be appropriately used.

(coating method)

The coating method is not limited, and a known method can be used. For example, the photosensitive layer may be formed by coating a photosensitive composition onto a substrate. The photosensitive layer-forming composition applied to the substrate may be dried by a known method as required.

Examples of the method for producing the photosensitive composition include a method in which a raw material of the target photosensitive layer and a solvent are mixed in an arbitrary ratio. The mixing method is not limited, and a known method can be used. The photosensitive layer-forming composition may be filtered using a filter or the like having a pore size of 0.2 μm.

Examples of the method for coating the photosensitive composition include slit coating, spin coating, curtain coating, and inkjet coating. The method of coating the photosensitive layer forming composition is preferably slot coating.

(transfer step)

Examples of the method using the transfer material include a method of bonding a substrate and a transfer material. For example, the first photosensitive layer may be transferred onto the substrate by attaching a transfer material having a temporary support and the first photosensitive layer onto the substrate.

The bonding of the substrate and the transfer material is preferably performed while pressing and heating using a roller or the like. The pressure can be determined, for example, in the range of 1,000N/m to 10,000N/m. The temperature can be determined, for example, in the range from 40℃to 130 ℃. If at least one of the pressure and the temperature is lower than the above range, air involved in lamination may not be sufficiently squeezed out from between the substrate and the photosensitive layer. In the case where the pressure is higher than the above range, there is a possibility that the photosensitive layer may be deformed. When the temperature is higher than the above range, the photosensitive layer may be decomposed or deteriorated by heat, and this may be an undesirable form.

For example, a laminator, a vacuum laminator, and an automatic cutting laminator that can further improve productivity can be used for bonding the substrate and the transfer material. The bonding of the substrate and the transfer material may be performed by roll-to-roll processing depending on the material of the substrate.

The transfer of the first photosensitive layer on the substrate and the transfer of the second photosensitive layer on the substrate may be performed simultaneously or separately.

The transfer material may form the photosensitive layer by, for example, applying the photosensitive layer forming composition to a temporary support. The photosensitive layer-forming composition applied to the temporary support may be dried by a known method as required. As the temporary support, the temporary support described in the above item "other layer" can be mentioned, and the same is preferable.

In the case where the transfer material has a temporary support and a photosensitive layer, a protective film may be disposed on a surface of the photosensitive layer opposite to the surface on which the temporary support is disposed. As the protective film, the protective film described in the above item "other layer" can be mentioned, and the same is preferable.

Exposure Process (1)

The pattern formation method of embodiment 2 includes a step of exposing the first photosensitive layer (exposure step (1)). In the exposure step (1), the solubility of the exposed first photosensitive layer (i.e., the exposed portion) in the developer is changed. For example, in the case where the first photosensitive layer is a positive type photosensitive layer, the solubility of the exposed portion of the first photosensitive layer in a developer increases as compared with the unexposed portion. For example, in the case where the first photosensitive layer is a negative type photosensitive layer, the solubility of the exposed portion of the first photosensitive layer in a developer is reduced as compared with the unexposed portion.

As a method of exposing the first photosensitive layer, for example, a method using a photomask can be cited. For example, by disposing a photomask between the first photosensitive layer and the light source, the first photosensitive layer can be exposed in a pattern through the photomask. By pattern-exposing the first photosensitive layer, an exposed portion and an unexposed portion can be formed in the first photosensitive layer.

In the exposure step (1), the first photosensitive layer is preferably exposed by contacting the first photosensitive layer with a photomask. The resolution can be improved by exposing the first photosensitive layer in contact with a photomask (also referred to as "contact exposure").

In addition to the contact exposure, the exposure step (1) may be appropriately selected from a short-distance exposure method, a lens-based or mirror-based projection exposure method, and a direct exposure method using an exposure laser or the like. In the case of the projection exposure system of the lens system, an exposure machine having an appropriate lens Numerical Aperture (NA) can be used depending on the required resolution and focal depth. In the case of the direct exposure method, the photosensitive layer may be directly drawn, or the photosensitive layer may be subjected to reduced projection exposure via a lens. The exposure may be performed not only under the atmosphere but also under reduced pressure or vacuum, and may be performed by interposing a liquid such as water between the light source and the photosensitive layer.

In the case where a protective film is disposed on the first photosensitive layer, the first photosensitive layer may be exposed via the protective film. In the case of exposing the first photosensitive layer by contact exposure, it is preferable to expose the first photosensitive layer via a protective film from the viewpoint of preventing contamination of the photomask and influence of foreign matter adhering to the photomask on exposure. In the case of exposing the first photosensitive layer via the protective film, the development step (1) described later is preferably performed after the removal of the protective film.

The protective film used when exposing the first photosensitive layer through the protective film is preferably a film that transmits light irradiated at the time of exposure. As the protective film, for example, a protective film which transmits light irradiated at the time of exposure among the protective films described in the above item of "other layer" can be used.

In the case of exposing the first photosensitive layer via the protective film, the protective film may be disposed on the first photosensitive layer at least before the first exposure step (1).

In the case where the temporary support is disposed on the first photosensitive layer, the first photosensitive layer may be exposed via the temporary support, or the first photosensitive layer may be exposed after the temporary support is removed from the first photosensitive layer. In the case of exposing the first photosensitive layer by contact exposure, it is preferable to expose the first photosensitive layer via a temporary support from the viewpoint of preventing contamination of the photomask and influence of foreign matter adhering to the photomask on exposure. In the case of exposing the first photosensitive layer via the temporary support, the development step (1) described later is preferably performed after removing the temporary support.

The temporary support used when exposing the first photosensitive layer via the temporary support is preferably a film that transmits light irradiated at the time of exposure. As the temporary support, for example, a temporary support that transmits light irradiated at the time of exposure among the temporary supports described in the above item of "other layers" can be used.

The light source for exposure is not limited as long as it is a light source capable of irradiating light in a wavelength region (for example, 365nm or 405 nm) capable of changing the solubility of the first photosensitive layer in the developer. Examples of the light source for exposure include an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a Light Emitting Diode (LED).

As described above, the main wavelength λ of the exposure wavelength in the exposure step (1) ₁ So long as it is exposed to lightThe main wavelength lambda of the exposure wavelength in step (2) ₂ Different materials are needed. Exposure wavelength and dominant wavelength lambda in exposure step (1) ₁ For example, it can be determined in a wavelength region of 10nm to 450 nm. Dominant wavelength lambda ₁ For example, it is preferable to be in the range of 300nm to 400nm or 370nm to 450nm, and more preferable to be in the range of 300nm to 380nm or 390nm to 450 nm.

The exposure wavelength in the exposure step (1) preferably does not include 365nm. In the present invention, "not including the wavelength 365nm" means that the intensity at the wavelength 365nm is 30% or less when the maximum value of the intensity (i.e., the intensity of the dominant wavelength) in the entire exposure wavelength region is set to 100%. When the maximum value of the intensity in the entire exposure wavelength region is set to 100%, the intensity at 365nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. The lower limit of the intensity at 365nm is not limited. When the maximum value of the intensity in the entire exposure wavelength region is set to 100%, the intensity of 365nm wavelength can be determined in a range of 0% or more, for example.

In the case where the exposure wavelength in the exposure step (1) does not include 365nm, it is preferable that the exposure wavelength in the exposure step (1) includes a dominant wavelength in a wavelength region of 370nm to 450nm, and in the case where the intensity of the dominant wavelength is set to 100%, the intensity of 365nm is 30% or less, more preferably 380nm to 430nm, and in the case where the intensity of the dominant wavelength is set to 100%, the intensity of 365nm is 30% or less, particularly preferably 390nm to 420nm, and in the case where the intensity of the dominant wavelength is set to 100%, the intensity of 365nm is 30% or less. When the intensity of the dominant wavelength is 100%, the intensity at 365nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. The lower limit of the intensity at 365nm is not limited. When the intensity of the dominant wavelength is set to 100%, the intensity of 365nm can be determined within a range of 0% or more, for example.

The exposure wavelength in the exposure step (1) preferably does not include 405nm. In the present invention, "excluding the wavelength 405nm" means that the intensity at the wavelength 405nm is 30% or less when the maximum value of the intensity in the entire exposure wavelength region is set to 100%. When the maximum value of the intensity in the entire exposure wavelength region is set to 100%, the intensity at 405nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. The lower limit of the intensity at the wavelength of 405nm is not limited. When the maximum value of the intensity in the entire exposure wavelength region is set to 100%, the intensity of 405nm can be determined in a range of 0% or more, for example.

In the case where the exposure wavelength in the exposure step (1) does not include the wavelength 405nm, it is preferable that the exposure wavelength in the exposure step (1) includes the dominant wavelength in the wavelength region of 300nm to 400nm, and in the case where the intensity of the dominant wavelength is set to 100%, the intensity of the wavelength 405nm is 30% or less, more preferably the intensity of the dominant wavelength is set to 300nm to 380nm, and in the case where the intensity of the dominant wavelength is set to 100%, the intensity of the wavelength 405nm is 30% or less, particularly preferably the dominant wavelength is included in the wavelength region of 350nm to 380nm, and in the case where the intensity of the dominant wavelength is set to 100%, the intensity of the wavelength 405nm is 30% or less. When the intensity of the dominant wavelength is 100%, the intensity at 405nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. The lower limit of the intensity at the wavelength of 405nm is not limited. When the intensity of the dominant wavelength is set to 100%, the intensity of 405nm can be determined within a range of 0% or more, for example.

In one embodiment, the exposure wavelength in the exposure step (1) is preferably an exposure wavelength having an intensity of 365nm greater than an intensity of 405nm (hereinafter, referred to as "condition (1-1)") or an exposure wavelength having an intensity of 405nm greater than an intensity of 365nm (hereinafter, referred to as "condition (1-2)") in this paragraph. When the intensity of 365nm is 100% in the condition (1-1), the intensity of 405nm is preferably 80% or less, more preferably 50% or less, further preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less. The lower limit of the intensity of 405nm in the condition (1-1) is not limited. When the intensity of 365nm is 100% in condition (1-1), the intensity of 405nm can be determined to be, for example, 0% or more. On the other hand, in the case where the intensity of 405nm is 100% in the condition (1-2), the intensity of 365nm is preferably 80% or less, more preferably 50% or less, further preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less. The lower limit of the intensity of 365nm wavelength in condition (1-2) is not limited. When the intensity of 405nm is 100% in the condition (1-2), the intensity of 365nm can be determined within a range of 0% or more, for example.

Examples of the method for adjusting the exposure wavelength in the exposure step (1) include a method using a filter having wavelength selectivity and a method using a light source capable of irradiating light having a specific wavelength. For example, by exposing the first photosensitive layer via a filter having wavelength selectivity, the wavelength of light reaching the first photosensitive layer can be adjusted within a specific range.

The exposure is preferably 5mJ/cm ² ～1,000mJ/cm ² More preferably 10mJ/cm ² ～500mJ/cm ² Particularly preferably 10mJ/cm ² ～200mJ/cm ² . The exposure amount is determined according to the illuminance of the light source and the exposure time. Also, the exposure amount may be measured using a light meter.

In the exposure step (1), the first photosensitive layer may be exposed without using a photomask. In the case where the first photosensitive layer is exposed without using a photomask (hereinafter, sometimes referred to as "maskless exposure"), the first photosensitive layer may be exposed using a direct drawing apparatus, for example. The direct rendering device may directly render an image using active energy rays. Examples of the light source used in maskless exposure include a laser (e.g., a semiconductor laser, a gas laser, and a solid state laser) capable of irradiating light having a wavelength of 350nm to 410nmLaser) and mercury short arc lamps (e.g., ultra-high pressure mercury lamps). Dominant wavelength lambda of exposure wavelength in maskless exposure ₁ As long as the main wavelength lambda is equal to the exposure wavelength in the exposure step (2) ₂ Different, there is no limitation. The preferred ranges of exposure wavelengths are described above. The exposure amount depends on the illuminance of the light source and the moving speed of the laminate. The drawing pattern may be computer controlled.

In the exposure step (1), the first photosensitive layer may be exposed from the side where the first photosensitive layer is arranged with reference to the substrate, or the first photosensitive layer may be exposed from the side where the second photosensitive layer is arranged with reference to the substrate. In the exposure step (1), the first photosensitive layer is preferably exposed from the side where the first photosensitive layer is disposed with reference to the substrate, from the viewpoint of suppressing exposure haze.

Exposure Process (2)

The pattern formation method of embodiment 2 includes a step of exposing the second photosensitive layer (exposure step (2)). In the exposure step (2), the solubility of the exposed second photosensitive layer (exposed portion) in the developer is changed. For example, in the case where the second photosensitive layer is a positive type photosensitive layer, the solubility of the exposed portion of the second photosensitive layer in a developer increases as compared with the unexposed portion. For example, in the case where the second photosensitive layer is a negative type photosensitive layer, the solubility of the exposed portion of the second photosensitive layer in the developer is reduced as compared with the unexposed portion.

As a method of exposing the second photosensitive layer, for example, a method using a photomask can be cited. For example, by disposing a photomask between the second photosensitive layer and the light source, the second photosensitive layer can be exposed in a pattern through the photomask. By pattern-exposing the second photosensitive layer, an exposed portion and an unexposed portion can be formed in the second photosensitive layer.

In the exposure step (2), the laminate is preferably exposed by contacting the laminate with a photomask. The resolution can be improved by exposing the laminate in contact with a photomask (also referred to as "contact exposure").

In the case where a protective film is disposed on the second photosensitive layer, the second photosensitive layer may be exposed via the protective film. In the case where the second photosensitive layer is exposed by contact exposure, the second photosensitive layer is preferably exposed via a protective film from the viewpoint of preventing contamination of the photomask and influence of foreign matter attached to the photomask on exposure. In the case of exposing the second photosensitive layer through the protective film, the development step (2) described later is preferably performed after the removal of the protective film.

The protective film used for exposing the second photosensitive layer through the protective film is not limited as long as it is a film that transmits light irradiated during exposure. As the protective film, for example, a protective film which transmits light irradiated at the time of exposure among the protective films described in the above item of "other layer" can be used.

In the case where the temporary support is disposed on the second photosensitive layer, the second photosensitive layer may be exposed via the temporary support, or the second photosensitive layer may be exposed after the temporary support is removed from the second photosensitive layer. In the case of exposing the second photosensitive layer by contact exposure, it is preferable to expose the second photosensitive layer via a temporary support from the viewpoint of preventing contamination of the photomask and influence of foreign matter adhering to the photomask on exposure. In the case of exposing the second photosensitive layer via the temporary support, the development step (2) described later is preferably performed after removing the temporary support.

The temporary support used when exposing the second photosensitive layer via the temporary support is preferably a film that transmits light irradiated at the time of exposure. As the temporary support, for example, a temporary support that transmits light irradiated at the time of exposure among the temporary supports described in the above item of "other layers" can be used.

The light source for exposure is not limited as long as it is a light source capable of irradiating light in a wavelength region (for example, 365nm or 405 nm) capable of changing the solubility of the second photosensitive layer in the developer. Examples of the light source for exposure include an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a Light Emitting Diode (LED).

As described above, the main wavelength λ of the exposure wavelength in the exposure step (2) ₂ As long as the exposure process is%1) Main wavelength lambda of exposure wavelength in (a) ₁ Different materials are needed. Exposure wavelength and dominant wavelength lambda in exposure step (2) ₂ For example, it can be determined in a wavelength region of 10nm to 410 nm. Dominant wavelength lambda ₂ For example, it is preferable to be in the range of 300nm to 400nm or 370nm to 450 nm. More preferably in the range of 300nm to 380nm or 390nm to 450 nm. For example, the dominant wavelength λ in the exposure step (1) ₁ In the case of a wavelength of 300nm to 400nm (preferably 300nm to 380 nm), the dominant wavelength lambda in the exposure step (2) ₂ Preferably in the range of 370nm to 450nm (preferably 390nm to 450 nm). For example, the dominant wavelength λ in the exposure step (1) ₁ In the case of a wavelength in the range of 370nm to 450nm (preferably 390nm to 450 nm), the dominant wavelength lambda in the exposure step (2) ₂ Preferably in the range of 300nm to 400nm (preferably 300nm to 380 nm).

When the exposure wavelength in the exposure step (1) does not include 365nm, the exposure wavelength in the exposure step (2) preferably does not include 405nm. By using the exposure wavelength described above in the exposure step (1) and the exposure step (2), a specific photosensitive layer can be exposed more selectively. When the maximum value of the intensity in the entire exposure wavelength region is set to 100%, the intensity at 405nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. The lower limit of the intensity at the wavelength of 405nm is not limited. When the maximum value of the intensity in the entire exposure wavelength region is set to 100%, the intensity of 405nm can be determined in a range of 0% or more, for example.

In the case where the exposure wavelength in the exposure step (2) does not include the wavelength 405nm, it is preferable that the exposure wavelength in the exposure step (2) includes the main wavelength in a wavelength region of 300nm to 400nm, and in the case where the intensity of the main wavelength is set to 100%, the intensity of the wavelength 405nm is 30% or less, more preferably, the intensity of the main wavelength is set to 300nm to 380nm, and in the case where the intensity of the main wavelength is set to 100%, the intensity of the wavelength 405nm is 30% or less, particularly preferably, the main wavelength is included in a wavelength region of 350nm to 380nm, and in the case where the intensity of the main wavelength is set to 100%, the intensity of the wavelength 405nm is 30% or less. When the intensity of the dominant wavelength is 100%, the intensity at 405nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. The lower limit of the intensity at the wavelength of 405nm is not limited. When the intensity of the dominant wavelength is set to 100%, the intensity of 405nm can be determined within a range of 0% or more, for example.

When the exposure wavelength in the exposure step (1) does not include the wavelength 405nm, the exposure wavelength in the exposure step (2) preferably does not include the wavelength 365nm. By using the exposure wavelength described above in the exposure step (1) and the exposure step (2), a specific photosensitive layer can be exposed more selectively. When the maximum value of the intensity in the entire exposure wavelength region is set to 100%, the intensity at 365nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. The lower limit of the intensity at 365nm is not limited. When the maximum value of the intensity in the entire exposure wavelength region is set to 100%, the intensity of 365nm wavelength can be determined in a range of 0% or more, for example.

In the case where the exposure wavelength in the exposure step (2) does not include 365nm, it is preferable that the exposure wavelength in the exposure step (2) includes a dominant wavelength in a wavelength region of 370nm to 450nm, and in the case where the intensity of the dominant wavelength is set to 100%, the intensity of 365nm is 30% or less, more preferably 380nm to 430nm, and in the case where the intensity of the dominant wavelength is set to 100%, the intensity of 365nm is 30% or less, particularly preferably 390nm to 420nm, and in the case where the intensity of the dominant wavelength is set to 100%, the intensity of 365nm is 30% or less. When the intensity of the dominant wavelength is 100%, the intensity at 365nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. The lower limit of the intensity at 365nm is not limited. When the intensity of the dominant wavelength is set to 100%, the intensity of 365nm can be determined within a range of 0% or more, for example.

When the exposure wavelength in the exposure step (1) is "the exposure wavelength having an intensity of 365nm greater than an intensity of 405 nm", the exposure wavelength in the exposure step (2) is preferably an exposure wavelength having an intensity of 405nm greater than an intensity of 365nm (hereinafter, referred to as "condition (2-1)"). The preferable mode of the condition (2-1) is the same as the preferable mode of the condition (1-2) described in the item "exposure step (1)". On the other hand, when the exposure wavelength in the exposure step (1) is "the exposure wavelength having an intensity of 405nm greater than an intensity of 365nm, the exposure wavelength in the exposure step (2) is preferably an exposure wavelength having an intensity of 365nm greater than an intensity of 405nm (hereinafter, referred to as" condition (2-2) ") in this paragraph. The preferable mode of the condition (2-2) is the same as the preferable mode of the condition (1-1) described in the item "exposure step (1)".

Examples of the method for adjusting the exposure wavelength in the exposure step (2) include a method using a filter having wavelength selectivity and a method using a light source capable of irradiating light having a specific wavelength. For example, by exposing the second photosensitive layer via a filter having wavelength selectivity, the wavelength of light reaching the second photosensitive layer can be adjusted within a specific range.

Wherein the dominant wavelength lambda ₁ The dominant wavelength lambda ₂ The following is preferable.

From the viewpoint of suppressing exposure mist, the above-mentioned dominant wavelength lambda ₁ Preferably in the range of more than 395nm and 500nm or less, more preferably in the range of 396nm or more and 456nm or less.

From the viewpoint of suppressing exposure mist, the above-mentioned dominant wavelength lambda ₂ Preferably in the range of 250nm to 395nm, more preferably in the range of 335nm to 395 nm.

Further, from the viewpoint of suppressing exposure mist, the above-mentioned dominant wavelength λ is more preferable ₁ Within a range exceeding 395nm and 500nm or less and the above dominant wavelength lambda ₂ In the range of 250nm to 395nm, the above dominant wavelength lambda is particularly preferred ₁ Within a range of 396nm to 456nm inclusive and the above dominant wavelength lambda ₂ In the range of 335nm to 395 nm.

In the pattern forming method according to embodiment 2, the exposure amount in the exposure step (1) and the exposure amount in the exposure step (2) may be the same or different.

In the exposure step (2), the second photosensitive layer may be exposed without using a photomask. In the case where the first photosensitive layer is exposed without using a photomask (hereinafter, sometimes referred to as "maskless exposure"), the first photosensitive layer may be exposed using a direct drawing apparatus, for example. The direct rendering device may directly render an image using active energy rays. Examples of the light source used in maskless exposure include a laser (for example, a semiconductor laser, a gas laser, and a solid state laser) capable of irradiating light having a wavelength of 350nm to 410nm, and a mercury short arc lamp (for example, an ultra-high pressure mercury lamp). Dominant wavelength lambda of exposure wavelength in maskless exposure ₂ As long as the dominant wavelength lambda is equal to the exposure wavelength in the exposure step (1) ₁ Different, there is no limitation. The preferred ranges of exposure wavelengths are described above. The exposure amount depends on the illuminance of the light source and the moving speed of the laminate. The drawing pattern may be computer controlled.

In the exposure step (2), the second photosensitive layer may be exposed from the side where the second photosensitive layer is arranged with reference to the substrate, or the second photosensitive layer may be exposed from the side where the first photosensitive layer is arranged with reference to the substrate. The irradiation direction of light in the exposure step (1) and the irradiation direction of light in the exposure step (2) may be the same or different. In the exposure step (2), the second photosensitive layer is preferably exposed from the side where the second photosensitive layer is disposed with reference to the substrate, from the viewpoint of suppressing exposure haze.

In one embodiment, the absorption dominant wavelength lambda is preferably arranged between the first photosensitive layer and a light source for exposing the first photosensitive layer ₂ Is arranged between the second photosensitive layer and the light source for exposing the second photosensitive layer ₁ Is a light component of (a). According to the above embodiment, as described in the above "light absorption characteristics", degradation of resolution due to re-exposure can be suppressed. That is, the absorption dominant wavelength lambda arranged between the first photosensitive layer and the light source for exposing the first photosensitive layer ₂ The component of light of (2) can absorb and transmit the dominant wavelength lambda after the second photosensitive layer and the substrate ₂ And a dominant wavelength lambda reflected by a wavelength-selective filter or the like ₂ Is a light source of a light. Therefore, a decrease in resolution caused by re-exposure of the second photosensitive layer can be suppressed. On the other hand, absorption dominant wavelength lambda arranged between the second photosensitive layer and the light source for exposing the second photosensitive layer ₁ The component of light of (2) can absorb and transmit the dominant wavelength lambda after the first photosensitive layer and the substrate ₁ And a dominant wavelength lambda reflected by a wavelength-selective filter or the like ₁ Is a light source of a light. Therefore, a decrease in resolution caused by re-exposure of the first photosensitive layer can be suppressed. The above embodiment includes the following (1) to (3). In the following (1) to (3), (3) is preferable.

(1) An absorption dominant wavelength lambda is arranged between the first photosensitive layer and a light source for exposing the first photosensitive layer ₂ Is a light component of (a).

(2) An absorption dominant wavelength lambda is arranged between the second photosensitive layer and a light source for exposing the second photosensitive layer ₁ Is a light component of (a).

(3) An absorption dominant wavelength lambda is arranged between the first photosensitive layer and a light source for exposing the first photosensitive layer ₂ Is arranged between the second photosensitive layer and a light source for exposing the second photosensitive layer and absorbs the dominant wavelength lambda ₁ Is a light component of (a).

Absorption of dominant wavelength lambda ₁ Preferably the component of (2) comprises an absorberDominant wavelength lambda ₁ Is a light source of the above light source. Absorption of dominant wavelength lambda ₂ Preferably the component of light of (2) contains an absorption dominant wavelength lambda ₂ Is a light source of the above light source. As absorption dominant wavelength lambda ₁ Or dominant wavelength lambda ₂ Examples of the light-emitting substance (B) include the absorption dominant wavelength lambda described in the above item of "light absorption characteristics ₁ Or dominant wavelength lambda ₂ Is a light source of the above light source. Absorption of dominant wavelength lambda ₁ Or dominant wavelength lambda ₂ The preferred mode of the light-emitting substance of (2) is the absorption dominant wavelength lambda as described in the above item of "light absorption characteristics ₁ Or dominant wavelength lambda ₂ The preferred manner of the light-emitting substances of (a) is the same. Further, absorb dominant wavelength lambda ₂ Is a component of light of (a) and absorbs a dominant wavelength lambda ₁ Any of the members containing a substance having absorption in a wavelength region of 400nm or more is preferable. Examples of the substance having an absorption in a wavelength region of 400nm or more include the substances having an absorption in a wavelength region of 400nm or more described in the above item of "light absorption characteristics". The preferable mode of the substance having absorption in the wavelength region of 400nm or more is the same as the preferable mode of the substance having absorption in the wavelength region of 400nm or more described in the above item of "light absorption characteristics".

Absorption of dominant wavelength lambda ₁ Or dominant wavelength lambda ₂ The content of the substance of the light of (2) is determined, for example, within a range that does not affect the exposure sensitivity. Absorption of dominant wavelength lambda ₁ Or dominant wavelength lambda ₂ The lower limit of the content of the substance of the light of (a) is determined, for example, within the range described in the above item of "light absorption characteristics".

In the pattern forming method according to embodiment 2, the exposure step (1) and the exposure step (2) may be performed simultaneously. The exposure step (1) and the exposure step (2) may be performed separately. The exposure step (2) may be performed before the exposure step (1). The exposure step (2) may be performed after the exposure step (1). From the viewpoint of productivity, the exposure step (1) and the exposure step (2) are preferably performed simultaneously.

In the present invention, "the step of simultaneously exposing the first photosensitive layer (exposure step (1)) and the step of exposing the second photosensitive layer (exposure step (2))" is not limited to the case of completely simultaneously exposing the first photosensitive layer and the second photosensitive layer, and includes the case where the period of exposing the first photosensitive layer and the period of exposing the second photosensitive layer are repeated.

In the present invention, "the step of exposing the first photosensitive layer alone (exposure step (1)) and the step of exposing the second photosensitive layer (exposure step (2))" means that the first photosensitive layer and the second photosensitive layer are exposed to light within a range where the period of exposing the first photosensitive layer and the period of exposing the second photosensitive layer do not overlap.

Developing Process (1)

The pattern forming method of embodiment 2 includes a step of developing the exposed first photosensitive layer to form a first resin pattern (developing step (1)). In the developing process (1), the first resin pattern may be formed by removing a portion of the exposed first photosensitive layer where the solubility in the developing solution is relatively large, for example.

In the present invention, the "exposed first photosensitive layer" means the first photosensitive layer subjected to the exposure step (1), and is not limited to the exposed portion of the first photosensitive layer.

The developing method is not limited, and a known method can be used. For example, the first photosensitive layer may be developed using a developer.

The developer is not limited, and a known developer can be used. Examples of the developer include those described in JP-A-5-72724. Examples of the preferable developer include the developer described in paragraph 0194 of International publication No. 2015/093271.

The developer is preferably an aqueous alkali developer containing a compound having a pKa of 7 to 13. In the above aqueous alkali developer, the concentration of the compound having a pKa of 7 to 13 is preferably 0.05mol/L to 5mol/L.

The developer may contain, for example, an organic solvent miscible with water and a surfactant as components other than those described above.

The temperature of the developer is preferably 20 to 40 ℃.

The development method is not limited, and a known method can be used. Examples of the development method include spin-coating immersion development, shower development, spin development, and immersion development.

As an example of the development method, the shower development will be described. For example, in the case where the first photosensitive layer is a negative type photosensitive layer, the unexposed portion of the first photosensitive layer can be removed by spraying a developer to the exposed first photosensitive layer using a shower. After development, it is preferable to remove the development residue while spraying a cleaning agent or the like by a shower and wiping with a brush or the like.

The developing process (1) may include a process of heat-treating the first resin pattern (also referred to as "post baking").

The heat treatment is preferably performed in an atmosphere of 8.1kPa to 121.6kPa, more preferably in an atmosphere of 8.1kPa to 114.6kPa, and particularly preferably in an atmosphere of 8.1kPa to 101.3 kPa.

The temperature of the heat treatment is preferably 20 to 250 ℃, more preferably 30 to 170 ℃, particularly preferably 50 to 150 ℃.

The time of the heat treatment is preferably 1 to 30 minutes, more preferably 2 to 10 minutes, and particularly preferably 2 to 4 minutes.

The heat treatment may be performed in an air atmosphere or in a nitrogen substitution atmosphere.

Developing Process (2)

The pattern forming method of embodiment 2 includes a step of developing the exposed second photosensitive layer to form a second resin pattern (developing step (2)). In the developing process (2), the second resin pattern may be formed by removing a portion of the exposed second photosensitive layer where the solubility in the developing solution is relatively large, for example.

In the present invention, the "exposed second photosensitive layer" means the second photosensitive layer subjected to the exposure step (2), and is not limited to the exposed portion of the second photosensitive layer.

The developing method is not limited, and a known method can be used. For example, the second photosensitive layer may be developed using a developer.

The temperature of the developer is preferably 20 to 40 ℃.

As an example of the development method, the shower development will be described. For example, in the case where the second photosensitive layer is a negative type photosensitive layer, the unexposed portion of the second photosensitive layer can be removed by spraying a developer to the exposed second photosensitive layer using a shower. After development, it is preferable to remove the development residue while spraying a cleaning agent or the like by a shower and wiping with a brush or the like.

The developing process (2) may include a process of heat-treating the second resin pattern (also referred to as "post baking").

In the pattern forming method according to embodiment 2, the developing step (1) and the developing step (2) may be performed simultaneously. The developing step (1) and the developing step (2) may be performed separately. The developing step (2) may be performed before the developing step (1). The developing step (2) may be performed after the developing step (1). From the viewpoint of productivity, the developing step (1) and the developing step (2) are preferably performed simultaneously.

In the present invention, "the step of developing the exposed first photosensitive layer to form the first resin pattern (developing step (1)) and the step of developing the exposed second photosensitive layer to form the second resin pattern (developing step (2))" are not limited to the case where the development of the first photosensitive layer and the development of the second photosensitive layer are performed completely at the same time, and include the case where the period of developing the first photosensitive layer and the period of developing the second photosensitive layer are repeated.

In the present invention, "the step of developing the exposed first photosensitive layer alone to form the first resin pattern (developing step (1)) and the step of developing the exposed second photosensitive layer to form the second resin pattern (developing step (2))" means that the first photosensitive layer and the second photosensitive layer are developed within a range where the period of developing the first photosensitive layer and the period of developing the second photosensitive layer do not overlap.

In one embodiment, it is preferable that the exposure step (1) and the exposure step (2) are performed simultaneously, and the development step (1) and the development step (2) are performed simultaneously. By simultaneously performing the exposure step (1) and the exposure step (2) and simultaneously performing the development step (1) and the development step (2), the time and environment from the exposure to the start of development can be made the same, and the product quality can be easily stabilized, and in addition, the process time can be shortened, thereby reducing the process cost. On the other hand, in one embodiment, it is preferable to perform the exposure step (1) and the exposure step (2) alone or to perform the development step (1) and the development step (2) alone. For example, when the reaction progress speeds after exposure are greatly different for the first photosensitive layer and the second photosensitive layer, or when it is necessary to dispose different exposure light sources away from the photosensitive layers, the exposure step (1) and the exposure step (2) are preferably performed separately. For example, when the developing solution for developing the first photosensitive layer and the developing solution for developing the second photosensitive layer are different, the developing step (1) and the developing step (2) are preferably performed separately.

Cleaning procedure and drying procedure ]

The pattern forming method of embodiment 2 may include a cleaning step and a drying step as needed after the developing step (2) from the viewpoint of preventing contamination of the production line.

In the cleaning step, the substrate may be cleaned with pure water at room temperature (e.g., 25 ℃). The cleaning time can be appropriately set in the range of 10 seconds to 300 seconds, for example.

In the drying step, the substrate may be dried using, for example, a blower. The blower pressure is preferably 0.1kg/cm ² ～5kg/cm ² 。

< full-face exposure procedure >

The pattern forming method according to the present invention may include a step of performing a blanket exposure on at least one of the first resin pattern and the second resin pattern (hereinafter, may be referred to as a "blanket exposure step"). The entire exposure step is preferably performed before a removal step described later. The pattern forming method according to the present invention includes the entire surface exposure step, and can improve the removability of the resin pattern in the removal step described later and further improve the reactivity of the pattern remaining after development. For example, the removal performance in a removal process described later can be further improved by performing full-face exposure using a resin pattern formed by a positive photosensitive layer. For example, the resin pattern formed using the negative photosensitive layer is subjected to exposure to the entire surface, and curing proceeds further, whereby the resistance of the resin pattern to the process can be improved.

In the entire exposure step, at least one of the first resin pattern and the second resin pattern may be exposed. For example, in the case of performing full-face exposure of the first resin pattern, the portion where the first resin pattern is not arranged may be exposed or may not be exposed. In the case of performing the entire exposure of the second resin pattern, the portion where the second resin pattern is not disposed may be exposed or may not be exposed.

In the entire exposure step, the entire surface of the substrate is preferably exposed from the viewpoint of convenience.

The light source for exposure is not limited, and a known light source can be used. Examples of the light source for exposure include an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a Light Emitting Diode (LED).

From the viewpoint of removability, the exposure wavelength preferably includes a wavelength of 365nm or 405nm.

From the viewpoint of removability, the exposure amount is preferably 5mJ/cm ² ～1,000mJ/cm ² More preferably 10mJ/cm ² ～800mJ/cm ² Particularly preferably 100mJ/cm ² ～500mJ/cm ² 。

From the viewpoint of removability, the exposure amount is preferably at least one of the exposure steps (1) and (2), and more preferably greater than at least one of the exposure steps (1) and (2).

The exposure illuminance is preferably 5mW/cm ² ～25,000mW/cm ² More preferably 20mW/cm ² ～20,000mW/cm ² Particularly preferably 30mW/cm ² ～15,000mW/cm ² . By increasing the illuminance, the time required for the entire exposure can be shortened.

Heating procedure-

The pattern forming method according to embodiment 2 may include a step of heating at least one of the first resin pattern and the second resin pattern (hereinafter, may be referred to as a "heating step") between the surface-mount exposure step and before the surface-mount exposure step and the removal step described later. The pattern forming method according to embodiment 2 includes a heating step, and can easily remove the first resin pattern and the second resin pattern. For example, in a resin pattern formed using a positive photosensitive layer, the reaction rate of a photoacid generator and the reaction rate of the generated acid and the positive photosensitive composition can be improved, and thus the removal performance can be improved.

The heating device is not limited, and a known heating device can be used. Examples of the heating device include an infrared heater, a hot air blower, and a convection oven.

The heating temperature is preferably 30 to 100 ℃, more preferably 30 to 80 ℃, and particularly preferably 30 to 60 ℃ from the viewpoint of removability.

From the viewpoint of removability, the heating time is preferably 1 second to 600 seconds, more preferably 1 second to 120 seconds, and particularly preferably 5 seconds to 60 seconds. Here, the term "heating time" means a time from when the substrate surface reaches the set temperature, excluding a time during which the temperature is raised.

The heating atmosphere is preferably air (relative humidity: 10% RH to 90% RH). The heating atmosphere may be an inert gas (e.g., nitrogen and argon).

The pressure is preferably atmospheric pressure.

When a large amount of water adheres to the substrate, a step of blowing off the excessive water by an air knife or the like may be combined at least in one of the period of time before and during the heating step, from the viewpoint of improving the heating efficiency.

Volume-to-volume manner-

The pattern forming method of embodiment 2 is preferably performed in a roll-to-roll manner. The roll-to-roll system is not limited, and a known roll-to-roll system can be used. For example, in the pattern forming method according to the present invention, processing can be performed while conveying the substrate by providing at least a step of unwinding the substrate and at least a step of winding the substrate before and after at least one step, respectively.

< other procedures >

The pattern formation method of embodiment 2 may include steps other than the above. Examples of the steps other than the above steps include the following steps.

[ procedure for reducing visible ray reflectance ]

In the case where the substrate has a conductive layer, the pattern formation method of embodiment 2 may include a step of performing a treatment for reducing the visible light reflectance of a part or the entire conductive layer.

As the treatment for reducing the reflectance of visible light, for example, an oxidation treatment is given. For example, in the case where the conductive layer contains copper, copper oxide may be formed by subjecting copper to oxidation treatment to reduce the visible ray reflectance of the conductive layer.

A preferred embodiment of the treatment for reducing the reflectance of visible light is described in paragraphs 0017 to 0025 of jp 2014-150118 a and paragraphs 0041, 0042, 0048 and 0058 of jp 2013-206315 a, the contents of which are incorporated herein by reference.

The pattern forming method according to the present invention will be described by taking the pattern forming method according to embodiment 2 as a representative example.

From the viewpoint of being applied to the pattern forming method described above, the laminate used in the pattern forming methods of aspects 2 to 6 preferably has the following characteristics a and B.

Characteristic A: when the maximum sensitivity wavelength of the first photosensitive layer is set to lambda _m1 Setting the maximum sensitivity wavelength of the second photosensitive layer to lambda _m2 When meeting lambda _m1 ≠λ _m2 Is a relationship of (3). The maximum sensitivity wavelength is the wavelength at which the minimum exposure amount in the case where the minimum exposure amount of the photosensitive layer reaction is obtained as the spectral sensitivity for each wavelength of light.

Characteristic B: the substrate is opposite to the wavelength lambda _m1 Lambda (lambda) _m2 Has a transmittance of at least 50% or more.

In addition, the maximum sensitivity wavelength can be determined as follows, for example. When the photosensitive layer is irradiated with light of a specific wavelength through the Stouffer4105 exposure ruler, the lowest exposure amount at which the photosensitive material reacts is set to Emin. By changing the irradiation wavelength, a spectral sensitivity curve can be obtained. Since Emin varies depending on the wavelength, the wavelength having the smallest value becomes the wavelength of maximum sensitivity.

In the negative photosensitive layer, the minimum exposure amount remaining in the exposure portion may be set to Emin. On the other hand, in the positive photosensitive layer, the minimum exposure amount at which the exposure portion is removed may be set to Emin.

In addition, when the light source light has a discrete light quantity distribution (such as g-ray, h-ray, i-ray) as in the case of a high-pressure mercury lamp, or when the wavelength of the irradiation light is controlled by using a filter or the like, the wavelength with the highest sensitivity among the light actually irradiated to the photosensitive material is set to the maximum sensitivity wavelength. For example, it is assumed that in the spectral sensitivity curve of a certain photosensitive material, the minimum value is at 290nm, and the 2 nd minimum value is at 365nm (i-ray). Since the high-pressure mercury lamp emits substantially little light of 290nm, 365nm becomes the maximum sensitivity wavelength in the case of exposing the photosensitive material with the high-pressure mercury lamp.

The layered body used in the pattern forming methods of aspects 2 to 6 is the above-described aspect, whereby the generation of exposure mist can be suppressed, and a resin pattern with excellent resolution can be formed.

The reason why the laminate used in the pattern forming method of aspects 2 to 6 exhibits the above-described effects is presumed to be as follows. As described above, in order to suppress the generation of exposure mist, for example, if the optical density of the photosensitive layer is increased by using an ultraviolet absorbing material, the resolution of the obtained resin pattern may be deteriorated. On the other hand, the pattern forming method according to any one of aspects 2 to 6 includes a preparation step, an exposure step (1), an exposure step (2), and a development step (1), and the maximum sensitivity wavelength λ of the first photosensitive layer _m1 Maximum sensitivity wavelength lambda with the second photosensitive layer _m2 Are different from each other, and therefore even if the substrate is aligned with the wavelength lambda _m1 Lambda (lambda) _m2 The first photosensitive layer and the second photosensitive layer can be selectively or preferentially exposed, respectively, with a transmittance of at least 50% or more. Therefore, the laminate of the present invention can suppress the generation of exposure mist, and can form a resin pattern with excellent resolution.

The preferred modes of the first photosensitive layer, the substrate, and the second photosensitive layer in the laminate are the same as the preferred modes of the first photosensitive layer, the substrate, and the second photosensitive layer in the pattern forming method, respectively, except for those described later.

The wavelength λ in the laminate is, in addition to the following _m1 Lambda (lambda) _m2 Respectively with the dominant wavelength lambda in the pattern forming method ₁ Lambda (lambda) ₂ In a preferred mode of (a) the dominant wavelength lambda ₁ Lambda (lambda) ₂ Replaced by the wavelength lambda _m1 Lambda (lambda) _m2 The same is preferable.

From the viewpoint of suppressing exposure haze, the wavelength λ _m1 Preferably in the range of more than 395nm and 500nm or less, more preferably in the range of 396nm or more and 456nm or less.

From the viewpoint of suppressing exposure haze, the wavelength λ _m2 Preferably in the range of 250nm to 395nm, more preferably in the range of 335nm to 395 nm.

Further, from the viewpoint of suppressing exposure mist, the wavelength λ is more preferable _m1 The wavelength lambda is within a range of more than 395nm and less than 500nm _m2 In the range of 250nm to 395nm, the wavelength lambda is particularly preferable _m1 The wavelength lambda is within a range of 396nm to 456nm _m2 In the range of 335nm to 395 nm.

The first photosensitive layer preferably contains a light absorbing component that absorbs the wavelength lambda from the viewpoint of suppression of exposure haze and resolution _m2 Is a light source of the above light source.

From the viewpoint of suppression of exposure haze and resolution, the wavelength λ in the first photosensitive layer _m2 The light transmittance of (2) is preferably 70% or less, more preferably 50% or less, further preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less. The lower limit of the transmittance is 0%.

The second photosensitive layer preferably contains a light absorbing layer that absorbs the wavelength lambda from the viewpoint of suppression of exposure fog and resolution _m1 Is a light source of the above light source.

From the viewpoint of suppression of exposure haze and resolution, the wavelength λ in the second photosensitive layer _m1 The transmittance of the light of (2) is preferably 70% or less, more preferably 50% or lessMore preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less. The lower limit of the transmittance is 0%.

As a means for absorbing the above-mentioned wavelength lambda _m2 Is a substance that absorbs light of the wavelength lambda _m1 Respectively, and absorbs the above dominant wavelength lambda ₂ Is a substance that absorbs light of the dominant wavelength lambda ₁ The same is preferable for the same substance of the light.

The first photosensitive layer and the second photosensitive layer preferably satisfy the following relationship C and relationship D from the viewpoint of suppression of exposure haze and resolution.

Relationship C:3 is less than or equal to (S) _m12 /S _m11 )

Relationship D:3 is less than or equal to (S) _m21 /S _m22 )

Here, S _m12 Representing the wavelength lambda of the first photosensitive layer _m2 Spectral sensitivity of S _m11 Representing the wavelength lambda of the first photosensitive layer _m1 Spectral sensitivity of S _m21 Representing the wavelength lambda of the second photosensitive layer _m1 Spectral sensitivity of S _m22 Representing the wavelength lambda of the second photosensitive layer _m2 Is a function of the spectral sensitivity of the sample.

As S _m12 /S _m11 Values of (2) and S _m21 /S _m22 The value of (2) is preferably 3 or more, more preferably 4 or more, and particularly preferably 5 or more, respectively. S is S _m12 /S _m11 Values of (2) and S _m21 /S _m22 The upper limit of the value of (c) is not particularly limited, and may be set to any value as long as the photosensitive layer has an appropriate performance. A photosensitive layer having such properties can be obtained by adjusting the wavelength lambda of the photosensitive layer to the above-mentioned wavelength lambda _m1 The wavelength lambda _m2 The respective absorption coefficients are obtained by a method.

< layered body with Pattern >

The patterned laminate according to the present invention comprises:

The method for producing the patterned laminate is not particularly limited, and can be suitably produced by the patterning method according to the present invention. Details of the materials are as described above.

The patterned laminate can be suitably used as, for example, a printed wiring board, a touch panel sensor, or the like.

Examples

The present invention will be described in detail with reference to examples. Unless otherwise specified, "parts" and "%" are based on mass.

< term >

The following abbreviations represent the following compounds, respectively.

"St": styrene (FUJIFILM Wako Pure Chemical Corporation system)

"AA": acrylic acid (Tokyo Chemical Industry Co., ltd.)

"PGME": propylene glycol monomethyl ether (Showa Denko K.K.)

"V-601": dimethyl 2,2' -azobis (2-methylpropionate) (FUJIFILM Wako Pure Chemical Corporation)

< Synthesis of alkali-soluble resin 1 >

Propylene glycol monomethyl ether (PGME, showa Denko k.k., 116.5 parts by mass) was placed in a three-necked flask, and the temperature was raised to 90 ℃ under a nitrogen atmosphere. To the three-necked flask solution maintained at 90.+ -. 2 ℃ was added dropwise a solution containing St (71.0 parts by mass), AA (29.0 parts by mass), V-601 (4.0 parts by mass) and PGME (116.5 parts by mass) over 2 hours. After completion of the dropwise addition, alkali-soluble resin 1 (solid content: 30% by mass, molecular weight: 10,000, glass transition temperature: 102 ℃ C., acid value: 229 mgKOH/g) was obtained by stirring at 90.+ -. 2 ℃ C. For 2 hours.

< Synthesis of silver nanowire >

The following materials were mixed and reacted at 190℃for 30 minutes. After the reaction was precipitated, ethylene glycol was removed as a supernatant, sun-dried, and redispersed in 5L of deionized water. The dispersion was filtered through a glass filter (diameter: 5 μm, manufactured by SPG technology co., ltd) and dried in the sun to obtain silver nanowires (metal nanomaterial).

AgNO ₃ (0.1M ethylene glycol solution) 0.5L

PVP (polyvinylpyrrolidone) (0.15M ethylene glycol solution) 0.5L

TBAC (tetrabutylammonium chloride in 0.001M glycol) 0.5L

< preparation of substrate 1 >

The polyethylene terephthalate resin chips were dried in a Henschel mixer and a paddle dryer until the water content became 50ppm or less. Then, the chip material is melted in an extruder having a heater temperature set to 280 to 300 ℃. The molten polyester resin was discharged from the die part onto a cooling roll to which static electricity was applied, to obtain an amorphous matrix. After stretching the amorphous substrate at a stretching ratio of 3.3 times in the substrate advancing direction, stretching was performed at a stretching ratio of 3.6 times in the substrate width direction, to obtain a film having a thickness of 97 μm.+ -. 2. Mu.m. The absorbance at 365nm was 0.1.

< preparation of substrate 2 >

The ultraviolet absorber, CONFOGUARD UV-001 (manufactured by FUJIFILM Holdings Corporation), was kneaded into a polyethylene terephthalate resin in advance to be in the form of chips, and mixed with chips of a general polyethylene terephthalate resin. The ultraviolet absorber was adjusted to a net content of 0.4 mass% with respect to all polyester resins. These chip materials were dried in a henschel mixer and a paddle dryer to a water content of 50ppm or less, and then melted in an extruder at a heater temperature of 280 to 300 ℃. The molten polyester resin was discharged from the die part onto a cooling roll to which static electricity was applied, to obtain an amorphous matrix. After stretching the amorphous substrate at a stretching ratio of 3.3 times in the substrate advancing direction, stretching was performed at a stretching ratio of 3.9 times in the substrate width direction, to obtain a film having a thickness of 97 μm.+ -. 2. Mu.m. The absorbance at 365nm was 2.0.

< preparation of composition >

Compositions 1 to 11 were prepared by mixing the components in the proportions (parts by mass) shown in tables 1 to 4.

Details of the respective components described in tables 1 to 4 are shown below.

(solvent)

"PGME": propylene glycol monomethyl ether (Showa Denko K.K.)

"PGMEA": propylene glycol monomethyl ether acetate (Daicel Corporation)

(alkali-soluble Compound)

"alkali-soluble resin 1": copolymers of styrene and acrylic acid (71/29 mass%, acid value: 226mgKOH/g, solid content: 30%, PGME solution)

"alkali-soluble photopolymerizable compound 1": ARONIX TO-2349 (TOAGOSEI CO., LTD.)

"alkali-soluble resin 2": HOA-MS (N) (KYOEISHA CHEMICAL co., ltd.,) manufactured by ltd

(other matrix materials)

"resin 1": HPMC (TOMOE Engineering Co., ltd.)

"photopolymerizable compound 1": NK ESTER A-400 (SHIN-NAKAMURA CHEMICAL CO, LTD.)

"photopolymerizable compound 2": 2-ethylhexyl acrylate (Mitsubishi Chemical Corporation)

"photopolymerizable compound 3": trimethylolpropane triacrylate (A-TMPT, SHIN-NAKAMURA CHEMICAL CO, LTD.)

(photopolymerization initiator)

"photopolymerization initiator 1": IRGACURE OXE-01 (manufactured by BASF Japan Ltd.)

"photopolymerization initiator 2":2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer (Hampford Research Inc.. Manufactured by Ohwi et al.)

"photopolymerization initiator 3": omnirad 754 (manufactured by IGM Resins B.V.)

(sensitizer)

"sensitizer 1": EAB-F (HODOGAYA CHEMICAL CO., LTD.)

"sensitizer 2": coumarin 7 (Tokyo Chemical Industry co., ltd. Manufactured)

(chain transfer agent)

"chain transfer agent 1": N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation)

(polymerization inhibitor)

"polymerization inhibitor 1": phenothiazine (FUJIFILM Wako Pure Chemical Corporation system)

(surfactant)

"surfactant 1": triton X-100 (Sigma-Aldrich Co.LLC)

"surfactant 2": MEGAFACE F552 (DIC CORPORATION)

"surfactant 3": MEGAFACE F444 (DIC CORPORATION)

(other additives)

"adhesion promoter 1": sliquest A1100 GE (Momentive performance Materials Inc. manufactured)

"antioxidant 1": irganox 1010ff (manufactured by BASF Japan Ltd.)

"migration inhibitor 1":1,2, 4-triazole (Tokyo Chemical Industry co., ltd. & gt)

(resin)

"PVA-205": polyvinyl alcohol resin (KURARAY co., ltd.)

"PVP-K30": polyvinylpyrrolidone resin (Tokyo Chemical Industry co., ltd.)

TABLE 1

TABLE 2

TABLE 3

TABLE 4

< examples 1 to 14, comparative example 1>

Resin patterns are formed on one side of the substrate by the following methods, respectively.

[ production of transfer Material ]

The compositions shown in tables 1 to 4 were applied to a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) using a slit nozzle. The composition on the temporary support was dried in a convection oven at 100 ℃ for 2 minutes to form a layer. A protective film (polypropylene film, thickness: 12 μm, haze: 0.2%) was laminated on the layer to prepare a transfer material.

[ production of laminate ]

After cutting the transfer material selected according to the descriptions in tables 5 and 6 to 50cm square, the protective film was peeled off from the transfer material. Next, the transfer material was bonded to one side of a substrate (polyethylene terephthalate film, thickness: 40 μm) under lamination conditions of a roll temperature of 90℃and a line pressure of 0.8MPa and a line speed of 3.0 m/min. Specifically, a transfer material for forming the layer (1) is bonded to one surface of a substrate.

With examples 4 to 14, the transfer material for forming the layer (2) was attached to the layer (1). In examples 8 to 14, the transfer material for forming the layer (3) was bonded to the layer (2). Layers (1) to (3) are sometimes collectively referred to as "transfer layers". According to the above steps, laminates of examples 1 to 14 and comparative example 1 were produced.

[ Pattern formation ]

A glass mask having two parallel wiring patterns each having a line width of 50 μm and a space width of 50 μm and a length of 15mm and a lead wiring pattern 10mm in front of the two wiring patterns was brought into close contact with the laminate without peeling the temporary support, and exposure was performed.

The exposure conditions were set as the following exposure amounts: after exposure under the "exposure condition excluding 405 nm", the remaining line pattern width was set to be in the range of 49.0 μm to 51.0 μm when development was performed for 1 hour.

"exposure conditions excluding 405 nm": the exposure was performed by using an ultra-high pressure mercury lamp (manufactured by USH-2004MB, manufactured by USHIO inc.) through a band-pass filter for mercury exposure (model: HB0365, center wavelength: 365nm, manufactured by Asahi Spectra co., ltd.). The dominant wavelength was 365nm. When the intensity of the dominant wavelength is 100%, the intensity at 405nm is 0.5% or less.

After exposure for 1 hour, a conductive wiring pattern was formed by development. Development was performed by spray development using a 1.0% aqueous potassium carbonate solution (developer) at 28 ℃ for 30 seconds. Through the above steps, patterned laminates of examples 1 to 14 and comparative example 1 were produced.

< evaluation >

Migration was evaluated using the patterned laminates produced in examples 1 to 14 and comparative example 1. The evaluation results are shown in tables 5 and 6.

[ initial migration ]

The patterned laminate was covered with an OCA film (MO-T015-LINTEC Corporation) on the wiring pattern portion, and a carbon double-sided tape (Nisshin-EM) for SEM was attached to the lead wiring portion, and dried at room temperature for one day to prepare an evaluation substrate. The conductivity between wirings was measured using a contact resistance measuring device RM3548 (manufactured by HIOKI e.e. corporation), and the initial conductivity was measured using a needle-shaped lead (manufactured by HIOKI e.e. corporation, 9772) and a 2-terminal probe.

The initial surface resistivity was evaluated based on the following criteria, and substrates satisfying the criteria a to D were judged to be practically usable.

(reference)

A: the wiring portion has a resistance value of 40 Ω or less, and the non-wiring portion is insulated.

B: the wiring portion has a resistance value exceeding 40Ω and 60deg.Ω or less, and the non-wiring portion is insulated.

C: the wiring portion has a resistance value exceeding 60 omega and 80 omega or less, and the non-wiring portion is insulated.

D: the wiring portion has a resistance value exceeding 80 Ω and 100 Ω or less, and the non-wiring portion is insulated.

E: the wiring portion has a resistance value exceeding 100deg.C, or the non-wiring portion is not insulated.

[ migration after the moist Heat resistance test ]

The conductivity after the wet heat resistance test was performed for 72 hours at 65℃under an atmosphere of 95% RH in a state where a voltage of 5V was applied to the lead wiring portion of the patterned laminate was measured by using a needle-shaped lead (9772) in a contact resistance measuring device RM3548 (manufactured by HIOKI E.E. CORPORATION). Then, the presence or absence of ion migration was confirmed by a microscope.

The resistivity rise was evaluated based on the following criteria, and substrates satisfying the criteria a to D were judged to be practically usable.

(reference)

A: the rate of rise in the resistance value of the wiring portion was 5% or less, and ion migration was not confirmed.

B: the rate of increase in the resistance value of the wiring portion was more than 5% and 10% or less, and ion migration was not confirmed.

C: the rate of increase in the resistance value of the wiring portion was more than 10% and 20% or less, or ion migration of 10 μm or less was confirmed.

D: the rate of increase in the resistance value of the wiring portion was more than 20% and 50% or less, or ion migration was confirmed to be more than 10 μm and 40 μm or less.

E: the wiring portion resistance value exceeded 50%, or ion migration exceeding 40 μm was confirmed.

TABLE 5

TABLE 6

< examples 15 to 27, comparative example 2>

Resin patterns are formed on both sides of the substrate, respectively, by the following method.

[ production of transfer Material ]

[ production of laminate ]

After cutting the transfer material selected according to the descriptions in tables 7 and 8 to 50cm square, the protective film was peeled off from the transfer material. Then, the transfer material was bonded to both surfaces of a substrate (polyethylene terephthalate film, thickness: 40 μm) under lamination conditions of a roll temperature of 90℃and a line pressure of 0.8MPa and a line speed of 3.0 m/min. Specifically, the transfer material for forming the layer (4) is attached to one surface (1 st surface) of the substrate, and then the transfer material for forming the layer (7) is attached to the other surface (2 nd surface) of the substrate.

With examples 18 to 27, the transfer material for the formation layer (5) was attached to the layer (4), and the transfer material for the formation layer (8) was attached to the layer (7). In examples 21 to 27, the transfer material for forming the layer (6) was bonded to the layer (5), and the transfer material for forming the layer (9) was bonded to the layer (8). Layers (4) to (9) are sometimes collectively referred to as "transfer layers". According to the above steps, laminates of examples 15 to 27 and comparative example 2 were produced.

[ Pattern formation ]

A glass mask (duty ratio 1:1) having a line width of 3-40 μm and a space pattern was brought into close contact with the transfer layer of the laminate without peeling the temporary support. The glass masks are arranged on both surfaces of the laminate so that the line patterns of the glass masks are orthogonal to each other in a plan view. Then, the first photosensitive layer and the second photosensitive layer are simultaneously exposed. When the first photosensitive layer and the second photosensitive layer are simultaneously exposed, the first photosensitive layer is exposed from the side where the first photosensitive layer is arranged with reference to the substrate, and the second photosensitive layer is exposed from the side where the second photosensitive layer is arranged with reference to the substrate.

The exposure conditions of the respective layers were determined as follows.

A first photosensitive layer: the first photosensitive layer was exposed to light through the glass mask under exposure conditions not including 365nm for 1 hour, and then developed, so that the residual pattern width was in the range of 49.0 μm to 51.0 μm in the line 50 μm/space 50 μm pattern portion.

A second photosensitive layer: the second photosensitive layer was exposed to light through the glass mask under exposure conditions excluding 405nm, and then left for 1 hour, and developed, so that the residual pattern width was in the range of 49.0 μm to 51.0 μm in the line 50 μm/space 50 μm pattern portion.

The meaning of the description of "exposure condition not including 365 nm" and "exposure condition not including 405 nm" are as follows.

"exposure conditions excluding 365 nm": the exposure was performed using an ultra-high pressure mercury lamp (USH-2004 MB, manufactured by USHIO inc.) via a short wavelength cut-off filter (model: LUO400, cut-off wavelength: 400nm, manufactured by Asahi Spectra co., ltd.). The dominant wavelength was 405nm. When the intensity of the dominant wavelength is 100%, the intensity at 365nm is 0.5% or less.

When the 365nm exposure condition is not included, the exposure amount is measured by attaching a 405nm light receiver (UVD-C405, manufactured by USHIO INC.) to an illuminometer (UIT-250, manufactured by USHIO INC.) via the LU0400 cut-off filter. When the exposure condition of 405nm was not included, the exposure amount was measured by attaching a 365nm light receiver (UVD-C365, manufactured by USHIO INC.) to an illuminometer and passing through the band pass filter (HB 0365).

After exposure for 1 hour, a conductive wiring pattern was formed by development. Development was performed by spray development using a 1.0% aqueous potassium carbonate solution (developer) at 28 ℃ for 30 seconds.

The development is performed simultaneously on the first photosensitive layer and the second photosensitive layer. Through the above steps, patterned laminates of examples 15 to 27 and comparative example 2 were produced.

< evaluation >

The patterned laminates produced in examples 15 to 27 and comparative example 2 were used to evaluate exposure haze. The evaluation results are shown in tables 7 and 8.

[ Exposure fog ]

The non-exposed portion (only the portion where the substrate surface on the opposite side to the non-exposed portion is the exposed portion) of the surface of the patterned laminate was observed. When the exposure mist is generated, residues originating from the photosensitive layer are observed in the non-exposed portion. The substrate satisfying the criterion a is determined to be practically usable.

(reference)

A: when observed with an optical microscope having a magnification of 50 times, no residue was observed on either the side on which the first photosensitive layer was disposed with reference to the substrate or the side on which the second photosensitive layer was disposed with reference to the substrate.

B: when observed with an optical microscope having a magnification of 50 times, residues were observed on at least one of the side on which the first photosensitive layer was disposed with reference to the substrate and the side on which the second photosensitive layer was disposed with reference to the substrate.

TABLE 7

TABLE 8

/>

Claims

1. A photosensitive composition contains a metal nanomaterial and an alkali-soluble compound.

2. The photosensitive composition according to claim 1, which satisfies at least one of the following (1) and (2),

(1) Comprising a photopolymerizable compound, the alkali-soluble compound being an alkali-soluble resin,

3. The photosensitive composition according to claim 2, wherein,

the alkali-soluble resin is carboxyl-containing resin.

4. A photosensitive composition according to claim 2 or 3, wherein,

the alkali-soluble photopolymerizable compound is a carboxyl group-containing photopolymerizable compound.

5. A laminated body, which has, in order:

6. A laminated body, which has, in order:

a substrate;

A photosensitive layer containing an alkali-soluble compound.

7. A laminated body, which has, in order:

a substrate;

A layer containing metallic nanomaterial.

8. The laminate according to any one of claim 5 to 7, which satisfies at least one of the following (1) and (2),

9. The laminate according to claim 8, wherein,

the alkali-soluble resin is carboxyl-containing resin.

10. The laminate according to claim 8, wherein,

11. The laminate according to any one of claims 5 to 7, which has an oxygen barrier layer on a side of the photosensitive layer opposite to a side having a substrate.

12. The laminate according to claim 11, wherein,

the oxygen barrier layer contains one or more selected from polyvinyl alcohol resin, polyvinylpyrrolidone resin, cellulose resin, acrylamide resin, polyethylene oxide resin, gelatin, vinyl ether resin and polyamide resin.

13. The laminate according to any one of claim 5 to 7, which has the photosensitive layers on both sides of the substrate,

the substrate has an absorbance at 365nm of 0.5 or more.

14. A pattern forming method, comprising:

a step of preparing the laminate according to any one of claims 5 to 12;

a step of performing pattern exposure on the photosensitive layer; a kind of electronic device with high-pressure air-conditioning system

And developing the photosensitive layer exposed by the pattern.

15. A pattern forming method, comprising:

exposing the first photosensitive layer;

exposing the second photosensitive layer;

A step of developing the exposed second photosensitive layer to form a second resin pattern,

16. A pattern forming method, comprising:

exposing the first photosensitive layer;

exposing the second photosensitive layer;

17. A pattern forming method, comprising:

a step of preparing a laminate having, in order, a first photosensitive layer containing an alkali-soluble compound, a layer containing a metal nanomaterial, a substrate including a region having transparency to light of an exposure wavelength, a layer containing a metal nanomaterial, and a second photosensitive layer containing an alkali-soluble compound;

Exposing the first photosensitive layer;

exposing the second photosensitive layer;

18. A pattern forming method, comprising:

a step of preparing a laminate having, in order, a layer containing a metal nanomaterial, a first photosensitive layer containing an alkali-soluble compound, a substrate including a region having transparency to light of an exposure wavelength, a second photosensitive layer containing an alkali-soluble compound, and a layer containing a metal nanomaterial;

exposing the first photosensitive layer;

exposing the second photosensitive layer;

A main wavelength lambda of an exposure wavelength in the step of exposing the first photosensitive layer ₁ Exposing the second photosensitive layerMain wavelength lambda of exposure wavelength in light process ₂ Satisfy lambda ₁ ≠λ ₂ Is a relationship of (3).

19. A pattern forming method, comprising:

exposing the first photosensitive layer;

exposing the second photosensitive layer;

20. The pattern forming method according to any one of claims 15 to 19, wherein,

At least one of the first photosensitive layer and the second photosensitive layer satisfies at least one of the following (1) and (2),

21. The pattern forming method as claimed in claim 20, wherein,

the alkali-soluble resin is carboxyl-containing resin.

22. The pattern forming method as claimed in claim 20, wherein,

23. The pattern forming method according to any one of claims 15 to 19, wherein,

in at least one of the first photosensitive layer and the second photosensitive layer, an oxygen barrier layer is provided on a side of the photosensitive layer opposite to a side having a substrate.

24. The pattern forming method as claimed in claim 23, wherein,

25. The pattern forming method according to any one of claims 15 to 19, wherein,

The substrate has an absorbance at 365nm of 0.5 or more.

26. A patterned laminate, comprising:

27. The patterned laminate of claim 26, wherein,

the alkali-soluble compound is an alkali-soluble resin.

28. The patterned laminate of claim 27, wherein,

the alkali-soluble resin is carboxyl-containing resin.