TW202309662A - Photosensitive composition, photosensitive composition layer, transfer film, method for producing laminate having a conductive pattern - Google Patents

Abstract

The present invention provides a photosensitive composition capable of forming a resist pattern that is excellent in releasability and excellent in shape when used after storage for a predetermined period. Furthermore, a photosensitive composition layer, a transfer film, and a method for manufacturing a laminate having a conductive pattern are provided. A photosensitive composition comprises a polymer A1, a polymerizable compound B, a photopolymerization initiator C, and a photoacid generator D, or comprises a polymer A2, the aforementioned polymerizable compound B, the aforementioned photopolymerization initiator C, the aforementioned photoacid generator D and a compound E, wherein the polymer A1 is a polymer comprising a structural unit A1a having an acid-decomposable group X that is decomposed by the action of an acid to generate an acid group, and a structural unit A1b having a carboxyl group. The polymer A2 is a resin comprising a structural unit A1c having a carboxyl group. The compound E is a compound having the above-mentioned acid decomposable group X. The photoacid generator D is one or more photoacid generators selected from a group including onium salt compounds, oxime sulfonate compounds, triazine compounds, nitrobenzylsulfonate compounds, disulfone compounds and bissulfonyl diazomethane compounds.

Description

Method for producing photosensitive composition, photosensitive composition layer, transfer film, laminate with conductor pattern

The present invention relates to a method for manufacturing a photosensitive composition, a photosensitive composition layer, a transfer film and a laminated body with a conductor pattern.

In the field of manufacturing printed wiring boards, photosensitive compositions or layers to be formed of the photosensitive compositions (hereinafter also referred to as "photosensitive compositions") are widely used as photoresist materials used in etching and plating. Layer".) It is arranged on a pseudo-support to make a transfer film of a laminate. For example, in Patent Document 1, it is disclosed that "a photosensitive resin composition contains (A) an unsaturated compound having a bond that can be decomposed by the action of an acid and/or heat at 130°C to 250°C. It is composed of a free radical polymerizable polymer, (B) a photopolymerizable compound and (C) a photopolymerization initiator." In the Example column of Patent Document 1, as the above-mentioned (A) component, a radically polymerizable polymer comprising a constituent unit formed of tertiary butyl methacrylate and a radically polymerizable polymer comprising a unit formed of tetrahydropyranyl methacrylate are disclosed. A free-radically polymerizable polymer of constituent units formed. Also, in the Example column of Patent Document 1, N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide as a photoacid generator is blended in the in the composition.

[Patent Document 1] Japanese Patent Laid-Open No. 2009-003000

The inventors of the present invention tried to form a conductive pattern (especially a semi-additive method) using a resist (negative resist) formed of the photosensitive composition described in Patent Document 1, which As a result, it was found that the peelability of the photoresist pattern after the etching step or the plating treatment step was good, but when the photosensitive composition was used after a predetermined period of storage, the shape of the formed photoresist pattern might deteriorate (becoming curled shape). When the shape of the photoresist pattern deteriorates due to aging of the photosensitive composition, it may also affect the shape of the formed conductor pattern. That is, it was clarified that there is room for further improvement in terms of maintaining the excellent peelability after the etching step or the plating treatment step, and suppressing the deterioration of the shape of the photoresist pattern caused by the deterioration of the photosensitive composition over time.

Therefore, an object of the present invention is to provide a photosensitive composition capable of forming a photoresist pattern that is excellent in releasability and excellent in shape when used after storage for a predetermined period. Moreover, the subject of this invention is providing the manufacturing method of the laminated body which has a photosensitive composition layer, a transfer film, and a conductor pattern.

As a result of intensive studies on the above-mentioned problems, the inventors of the present invention found that the above-mentioned problems can be solved by the following configurations. [1] A photosensitive composition comprising polymer A1, polymerizable compound B, photopolymerization initiator C, and photoacid generator D, or comprising polymer A2, the aforementioned polymerizable compound B, the aforementioned photopolymerizable initiator Agent C, the above-mentioned photoacid generator D and compound E, wherein The above-mentioned polymer A1 is a polymer comprising a structural unit A1a having an acid-decomposable group X that is decomposed by the action of an acid to generate an acid group, and a structural unit A1b having a carboxyl group, The above-mentioned polymer A2 is a resin comprising a structural unit A1c having a carboxyl group, The above-mentioned compound E is a compound having the above-mentioned acid decomposable group X, The above-mentioned photoacid generator D is selected from the group consisting of onium salt compounds, oxime sulfonate compounds, trisulphonate compounds, nitrobenzyl sulfonate compounds, disulfide compounds and bissulfonyldiazomethane compounds. More than one photoacid generator. [2] The photosensitive composition according to [1], wherein The above-mentioned acid-decomposable group X has a structure in which an acid group is protected by a protecting group decomposed by the action of an acid. [3] The photosensitive composition as described in [1] or [2], wherein The acid-decomposable group X has a tertiary ester structure or an acetal structure. [4] The photosensitive composition according to any one of [1] to [3], wherein In said polymer A1, content of the said structural unit A1a is 5-40 mass % with respect to all structural units, and content of the said structural unit A1b is 10-30 mass % with respect to all structural units. [5] The photosensitive composition according to any one of [1] to [4], wherein The acid value derived from the carboxyl group of the said polymer A1 is 150 mgKOH/g or less. [6] The photosensitive composition according to any one of [1] to [5], wherein The total value of the acid value derived from the carboxyl group of the above-mentioned polymer A1 and the acid value derived from the acid group generated from the above-mentioned acid-decomposable group X when the above-mentioned acid-decomposable group X is completely decomposed by the action of an acid is 230 mgKOH/g or less . [7] The photosensitive composition according to [1], wherein The above-mentioned compound E is a compound having two or more of the above-mentioned acid-decomposable groups X. [8] The photosensitive composition according to [1] or [7], wherein The above compound E is a polymer. [9] A photosensitive composition layer formed of the photosensitive composition described in any one of [1] to [8]. [10] A transfer film comprising: a pseudo-support; and a photosensitive composition layer formed of the photosensitive composition described in any one of [1] to [8]. [11] The transfer film according to [10], wherein An intermediate layer is further provided between the dummy support and the photosensitive composition layer. [12] The transfer film according to [11], wherein The above-mentioned intermediate layer contains a water-soluble resin. [13] The transfer film according to [12], wherein The water-soluble resin is at least one selected from the group consisting of water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyethers, phenol derivatives, and amide compounds. [14] A method for producing a laminate with a conductive pattern, using the transfer film described in any one of [10] to [13], the method for producing a laminate with a conductive pattern comprising: Bonding step, bonding the transfer film and the above-mentioned substrate in such a way that the surface of the above-mentioned transfer film opposite to the side of the dummy support is in contact with the above-mentioned conductive layer of the substrate having a conductive layer on the surface; Exposure step, performing pattern exposure on the photosensitive composition layer; A photoresist pattern forming step, performing a development treatment on the exposed photosensitive composition layer to form a photoresist pattern; an etching treatment step or an electroplating treatment step, performing etching treatment or electroplating treatment on the above-mentioned conductive layer located in the area where the above-mentioned photoresist pattern is not arranged; and a photoresist pattern stripping step, stripping the above photoresist pattern, When having the above-mentioned electroplating treatment step, there is further a removal step of removing the above-mentioned conductive layer exposed by the above-mentioned photoresist pattern stripping step and forming a conductive pattern on the above-mentioned substrate, wherein Between the bonding step and the exposing step or between the exposing step and the developing step, there is further a dummy support peeling step for peeling off the dummy support. [15] The method for producing a laminate having a conductor pattern according to [14], wherein A heating step is further provided between the photoresist pattern forming step and the photoresist pattern stripping step. [16] The method for producing a laminate having a conductor pattern according to [14] or [15], wherein The pH of the stripping liquid used in the stripping step of the photoresist pattern is above 13. [17] The method for producing a laminate having a conductor pattern according to any one of [14] to [16], wherein The pH of the developer used in the above photoresist pattern forming step was less than 13. [18] The method for producing a laminate having a conductor pattern according to any one of [14] to [17], wherein The value obtained by subtracting the pH of the developing solution used in the resist pattern forming step from the pH of the stripping solution used in the resist pattern stripping step is 1 or more. [19] The method for producing a laminate having a conductor pattern according to any one of [14] to [18], wherein A value obtained by subtracting the temperature of the developing solution used in the resist pattern forming step from the temperature of the stripping solution used in the resist pattern stripping step is 10° C. or more. [20] The method for producing a laminate having a conductor pattern according to any one of [14] to [19], wherein The exposure method in the above exposure step is any one of mask exposure, direct imaging exposure and projection exposure. [21] The method for producing a laminate having a conductor pattern according to any one of [14] to [20], wherein The thickness of the above pseudo-support is less than 16 μm. [22] The method for producing a laminate having a conductor pattern according to any one of [14] to [21], wherein The dummy support peeling step is provided between the bonding step and the exposing step. [23] The method for producing a laminate having a conductor pattern according to any one of [14] to [22], wherein The transfer film includes an intermediate layer between the dummy support and the photosensitive composition layer, There is the step of peeling off the dummy support between the step of laminating and the step of exposing, The exposure step is a step of exposing the intermediate layer exposed in the dummy support peeling step to a mask. [Invention effect]

According to the present invention, it is possible to provide a photosensitive composition capable of forming a photoresist pattern that is excellent in releasability and excellent in shape when used after storage for a predetermined period. Moreover, according to this invention, the manufacturing method of the laminated body which has a photosensitive composition layer, a transfer film, and a conductor pattern can also be provided.

Hereinafter, the present invention will be described in detail. The meanings of the following symbols in this specification are shown. The numerical range represented by "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In numerical ranges stated step by step, the upper limit or lower limit stated in a certain numerical range may be replaced with the upper limit or lower limit of other numerical ranges stated stepwise. In addition, in the numerical range described in this specification, the upper limit or the lower limit described in a certain numerical range may be replaced with the value shown in an Example. "Step" not only includes an independent step, but also includes in this term as long as the intended purpose of the step can be achieved even if it cannot be clearly distinguished from other steps. Unless otherwise specified, "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more. The average transmittance of visible light is a value measured using a spectrophotometer, for example, can be measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd. Unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm. Unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by MINOLTA).

Unless otherwise specified, TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are trade names manufactured by TOSOH CORPORATION) are used as columns and eluents for weight average molecular weight (Mw) and number average molecular weight (Mn). THF (tetrahydrofuran), using a differential refractometer as a detector, and using polystyrene as a standard substance, is a value in terms of polystyrene using a standard substance measured with a gel permeation chromatography (GPC) analyzer. Unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight (Mw). Unless otherwise specified, the content of metal elements is the value measured using an inductively coupled plasma (ICP: Inductively Coupled Plasma) spectroscopic analyzer. "(Meth)acryl" is a concept that includes both acryl and methacryl, and "(meth)acryloxy" is a concept that includes both acryloxy and methacryloxy. The concept, "(meth)acrylate" is a concept including both acrylate and methacrylate. "Alkali solubility" means that the solubility with respect to 100 g of 1 mass % aqueous solutions of sodium carbonate at 22 degreeC is 0.1 g or more. That is, "alkali-soluble resin" refers to a resin satisfying the above solubility. "Water solubility" means that the solubility to 100 g of water of pH 7.0 at a liquid temperature of 22° C. is 0.1 g or more. That is, "water-soluble resin" refers to a resin satisfying the above-mentioned solubility.

The "solid content" of a composition (such as a photosensitive composition, etc.) means a component that forms a composition layer (such as a photosensitive composition layer, etc.) formed using the composition. When the composition contains a solvent (such as an organic solvent and water, etc.), it refers to all components except solvents. Moreover, as long as it is a component which forms a composition layer (for example, a photosensitive composition layer etc.), a liquid component is also considered as a solid component.

[Photosensitive composition] The photosensitive composition of the present invention contains polymer A1, polymerizable compound B, photopolymerization initiator C, and photoacid generator D, or polymer A2, the above-mentioned polymerizable compound B, and the above-mentioned photopolymerization initiator C . The photosensitive composition of the above-mentioned photoacid generator D and compound E, wherein The above-mentioned polymer A1 is composed of a structural unit A1a (hereinafter, sometimes abbreviated as "acid decomposable group X") having an acid decomposable group X (hereinafter, sometimes abbreviated as "acid decomposable group X") having an acid group that is decomposed by the action of an acid. Abbreviated as "constituent unit A1a.") and a polymer having a carboxyl group-constituent unit A1b (hereinafter, sometimes abbreviated as "constituent unit A1b".), The above-mentioned polymer A2 is a resin containing a structural unit A1c (hereinafter, sometimes abbreviated as "structural unit A1c") having a carboxyl group, The above-mentioned compound E is a compound having the above-mentioned acid decomposable group X, The above-mentioned photoacid generator D is selected from the group consisting of onium salt compounds, oxime sulfonate compounds, trisulphonate compounds, nitrobenzyl sulfonate compounds, disulfide compounds and bissulfonyldiazomethane compounds (hereinafter, the etc. are collectively referred to as "specific photoacid generators".) One or more photoacid generators in the group.

That is, the photosensitive composition of this invention is the photosensitive composition of the following 1st embodiment, or it is the photosensitive composition of the following 2nd embodiment. <<Photosensitive composition of the first embodiment>> A photosensitive composition comprising a polymer A1, a polymerizable compound B, a photopolymerization initiator C and a photoacid generator D, The above-mentioned polymer A1 is a polymer comprising a structural unit A1a having an acid-decomposable group X and a structural unit A1b having a carboxyl group, The above photoacid generator D is one or more photoacid generators selected from the group including specific photoacid generators. <<Photosensitive composition of the second embodiment>> A photosensitive composition comprising polymer A2, polymerizable compound B, photopolymerization initiator C, photoacid generator D and compound E, The above-mentioned polymer A2 is a resin comprising a structural unit A1c having a carboxyl group, The above-mentioned compound E is a compound having an acid decomposable group X, The above photoacid generator D is one or more photoacid generators selected from the group including specific photoacid generators.

According to the photosensitive composition of this invention which has such a structure, the photoresist pattern which is excellent in releasability and excellent in formability even when it is used after storage for a predetermined period can be formed.

The details of the action mechanism by which the photosensitive composition of the present invention exhibits the desired effect are not clear, but the inventors of the present invention presume as follows. The said photosensitive composition is what is called a negative photosensitive composition, and is suitable for alkali image development. The photosensitive composition layer formed of the above-mentioned photosensitive composition has the following structure: the exposed part is hardened to reduce the solubility of the alkali developer, and on the other hand, the unexposed part is formed by the structural unit of the polymer A1 The presence of A1b or the constituent unit A1c contained in the polymer A2 makes it easy to dissolve in an alkaline developing solution. As a result, a dissolution contrast is generated between the exposed portion and the unexposed portion, whereby a resist pattern can be formed. Here, the said photosensitive composition contains a specific photoacid generator. The specific photoacid generator can be cleaved at a given exposure wavelength to generate acid. The generated acid is usually able to diffuse under the action of heat to decompose the acid decomposable group X during any heat treatment (baking treatment) performed after exposure, thereby converting it into an acid group. Thereby, the amount of acid groups in the photoresist pattern increases, and the solubility of the photoresist pattern to the stripping solution is improved. For example, when the hardening reaction of the polymerizable compound B in the photosensitive composition and the photosensitive cleavage/acid generation of the specific acid generator are carried out under light of approximately the same exposure wavelength, after forming a photoresist pattern, for example It is preferable to heat-treat (baking) the resist pattern to decompose by the acid-generating acid-decomposable group X after the etching step or after the plating step and before stripping the resist pattern. Also, when the hardening reaction of the polymerizable compound B in the photosensitive composition and the photosensitive cleavage/acid generation of the specific acid generator do not proceed under light of approximately the same exposure wavelength (in other words, when the photosensitive composition The hardening reaction of the polymerizable compound B in the light of the exposure wavelength does not generate a specific acid generator based on photolysis/acid generation), after forming a photoresist pattern, such as after an etching step or a plating treatment step Before stripping the photoresist pattern, it is preferable to decompose the photoresist pattern by the acid-generating acid-decomposable group X by fully exposing the photoresist pattern at the photosensitive wavelength of a specific photoacid generator and performing heat treatment (baking treatment).

Furthermore, according to the studies of the present inventors, it has been clarified that when a specific photoacid generator is used as the photoacid generator, it is possible to form a pattern with excellent shape even after storing the photosensitive composition for a predetermined period of time. (Hereinafter, it is also referred to as "excellent shape stability over time".). This is from the comparison of Examples and Comparative Example 1 (using N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide as a photoacid generator.) in the Example column of this specification can also be specified.

Hereinafter, the more excellent peelability of the resist pattern and/or the more excellent time-lapse shape stability of the photosensitive composition are also referred to as "more excellent effects of the present invention".

[Photosensitive composition of the first embodiment] Hereinafter, the photosensitive composition of 1st Embodiment is demonstrated. It is preferable that the photosensitive composition of 1st Embodiment is a negative photosensitive composition. The photosensitive composition of 1st Embodiment contains polymer A1. Hereinafter, polymer A1 will be described first.

＜Polymer A1＞ Polymer A1 is a polymer including a structural unit A1a having an acid-decomposable group X and a structural unit A1b having a carboxyl group. Polymer A1 is preferably an alkali-soluble resin.

(acid decomposable group X) The acid-decomposable group X is a group that is decomposed by the action of an acid to generate an acid group. By including the acid-decomposable group X, the polymer A1 can be decomposed by the action of an acid to increase its polarity. As the acid decomposable group X, a structure in which an acid group is protected by a protecting group that is decomposed (including detachment) by the action of an acid is preferable.

As the acid group, an alkali-soluble group is preferable, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonimide group, an (alkylsulfonyl group) )(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis( Acidic groups such as alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tris(alkylcarbonyl)methylene and tris(alkylsulfonyl)methylene, and alcoholic Hydroxy etc. Among these, a carboxyl group or a phenolic hydroxyl group is preferable as an acidic group.

Examples of the protecting group decomposed by the action of an acid (a detachment group detached by the action of an acid) include groups represented by formulas (Y1) to (Y4). Formula (Y1): -C (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) Formula (Y2): -C (=O)OC (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) Formula (Y3): -C (R ₃₆ )(R ₃₇ )(OR ₃₈ ) Formula (Y4): -Si(Rx ₁ )(Rx ₂ )(Rx ₃ )

In formula (Y1), formula (Y2) and formula (Y4), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched), cycloalkyl (monocyclic or polycyclic), alkenyl (linear or branched) or aryl (monocyclic or polycyclic). In addition, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), at least two of Rx ₁ to Rx ₃ are preferably methyl groups. Among them, Rx ₁ to Rx ₃ each independently represent a straight-chain or branched alkyl group is preferable, and Rx ₁ to Rx ₃ each independently represent a straight-chain alkyl group is more preferable. Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic or polycyclic ring. As the alkyl group of Rx ₁ to Rx ₃ , an alkyl group having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tertiary butyl group is preferable. Cycloalkyl groups for Rx ₁ to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkanes such as norbornyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl base is better. As the aryl group for Rx ₁ to Rx ₃ , an aryl group having 6 to 10 carbon atoms is preferable, and examples thereof include phenyl, naphthyl, and anthracenyl. As the alkenyl group for Rx ₁ to Rx ₃ , a vinyl group is preferable. A cycloalkyl group is preferable as a ring formed by bonding two of Rx ₁ to Rx ₃ . Cycloalkyl formed as two bonds among Rx ₁ to Rx ₃ , monocyclic cycloalkyl such as cyclopentyl or cyclohexyl, or norbornyl, tetracyclodecanyl, tetracyclododecyl or Polycyclic cycloalkyl groups such as adamantyl groups are preferred, and monocyclic cycloalkyl groups having 5 to 6 carbon atoms are more preferred. In the cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ , for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or vinylidene base substitution. In addition, in these cycloalkyl groups, one or more ethylidene groups constituting the cycloalkane ring may be substituted with vinylidene groups. As an example of a preferred aspect of the groups represented by formula (Y1), formula (Y2) and formula (Y4), Rx ₁ is a methyl or ethyl group and Rx ₂ and Rx ₃ are bonded to form the above-mentioned Forms of cycloalkyl groups.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may be bonded to each other to form a ring. As a monovalent organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned. R ₃₆ is also preferably a hydrogen atom. In addition, the above-mentioned alkyl group, cycloalkyl group, aryl group and aralkyl group may contain a heteroatom such as an oxygen atom and/or a group having a heteroatom such as a carbonyl group. For example, among the above-mentioned alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, for example, one or more methylene groups may be substituted with a heteroatom such as an oxygen atom and/or a group having a heteroatom such as a carbonyl group.

As the formula (Y3), a group represented by the following formula (Y3-1) is preferable.

[chemical formula 1]

Wherein, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof (for example, a combination of an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group that may contain heteroatoms, a cycloalkyl group that may contain heteroatoms, an aryl group that may contain heteroatoms, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination thereof ( For example, a combination of an alkyl group and a cycloalkyl group). In an alkyl group and a cycloalkyl group, for example, one of the methylene groups may be substituted with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group. In addition, it is preferable that one of L ₁ and L ₂ is a hydrogen atom and the other is an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group. At least two _of Q, M and L may be bonded to form a ring (preferably a 5-membered or 6-membered ring). From the viewpoint of pattern miniaturization, L ₂ is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of the secondary alkyl group include isopropyl, cyclohexyl, and norbornyl, and examples of the tertiary alkyl group include tertiary butyl or adamantyl.

As the acid decomposable group X, from the viewpoint of more excellent effect of the present invention, the carboxyl group or phenolic hydroxyl group is preferably protected by any protecting group represented by the above formula (Y1) to formula (Y4), and the carboxyl group is protected by The structure protected by any protecting group represented by formula (Y1) and formula (Y3), or the structure in which the phenolic hydroxyl group is protected by any protecting group represented by formula (Y1) to formula (Y4) is more preferable. Also, for example, when the carboxyl group is protected by a protecting group represented by formula (Y1), the acid-decomposable group X includes a tertiary ester structure. Also, when the carboxyl group is protected by a protecting group represented by formula (Y3) or the phenolic hydroxyl group is protected by a protecting group represented by formula (Y3), the acid-decomposable group X includes an acetal structure.

As the acid-decomposable group X, those having a tertiary ester structure or an acetal structure are also preferable from the viewpoint of more excellent effects of the present invention.

(Constituent unit A1a) Polymer A1 includes a structural unit A1a having the above-mentioned acid-decomposable group X. It does not specifically limit as structural unit A1a, For example, the structural unit represented by following formula (A1a-1) - a formula (A1a-3) is mentioned.

[chemical formula 2]

In formula (A1a-1) to formula (A1a-3), Ra and Rb each independently represent a hydrogen atom or a substituent. Ya represents any one of the protecting groups represented by the above formula (Y1) to formula (Y4). p represents an integer of 0-4. Xa represents an oxygen atom or NRc. Rc represents a hydrogen atom or a substituent. La represents a single bond or a divalent linking group.

As a substituent represented by Ra, a halogen atom, an alkyl group, etc. are mentioned, for example. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Moreover, as carbon number of an alkyl group, 1-12 are preferable, 1-6 are more preferable, 1-3 are still more preferable. The alkyl group may be any of linear, branched and cyclic. Moreover, an alkyl group may further have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an acyl group having 5 or less carbon atoms, an alkoxy group having 5 or less carbon atoms, and the like. As Ra, a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group is preferable.

The substituent represented by Rb is not particularly limited, and examples thereof include an alkyl group (1 to 4 carbons), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbons), a carboxyl group, and an alkoxycarbonyl group (carbon number 2-6), etc.

p is preferably from 0 to 2, more preferably 0 or 1, and still more preferably 0.

Examples of the substituent represented by Rc include alkyl groups having 1 to 6 carbon atoms (preferably linear or branched) and the like. An alkyl group may further have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an acyl group having 5 or less carbon atoms, an alkoxy group having 5 or less carbon atoms, and the like. As Rc, a hydrogen atom, a methyl group or an ethyl group is preferable.

The divalent linking group represented by La is not particularly limited, for example -CO-, -O-, -SO-, -SO ₂ -, -NR ^A -, alkylene (preferably The carbon number is 1-6. It can be straight chain or branched), cycloalkyl (preferably 3-15 carbon), aryl (preferably 6-10 membered ring, 6-membered A ring is further preferred.) and a divalent linking group formed by combining a plurality of these. In addition, the above-mentioned alkylene group, the above-mentioned cycloalkylene group, and arylylene group may have a substituent. As a substituent, a halogen atom (preferably a fluorine atom), a hydroxyl group, etc. are mentioned, for example. Examples of R ^A include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Although the specific example of the structural unit represented by Formula (A1a-1) is shown below, it is not limited to this. In addition, Ra is as described above.

[chemical formula 3]

Although the specific example of the structural unit represented by formula (A1a-2) or formula (A1a-3) is shown below, it is not limited to this. In addition, Ra is as described above.

[chemical formula 4]

Polymer A1 may contain one kind of structural unit A1a, or may contain two or more kinds. In the polymer A1, the content of the structural unit A1a (total content when plural types are included) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, relative to all the structural units of the polymer A1, 5-40 mass % is still more preferable.

(Constituent unit A1b) Polymer A1 contains structural unit A1b having a carboxyl group. In addition, the structural unit A1b does not contain the above-mentioned acid decomposable group X. The monomer forming the constituent unit A1b is not particularly limited as long as it has a carboxyl group in the molecule. Examples of the aforementioned monomers include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, and 4-vinylbenzoic acid, among which (meth)acrylic acid is preferred.

Polymer A1 may contain one type of structural unit A1b, or may contain two or more types. In the polymer A1, the content of the structural unit A1b (total content when plural types are included) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, relative to all the structural units of the polymer A1, 10-30 mass % is still more preferable.

(other constituent units) Polymer A1 may contain other structural units other than the aforementioned structural unit A1a and structural unit A1b.

It is preferable that polymer A1 contains a structural unit derived from a monomer having an aromatic hydrocarbon group from the viewpoint of suppressing deterioration of line width and resolution when the focal position shifts during exposure. In addition, the structural unit derived from a monomer having an aromatic hydrocarbon group does not include the above-mentioned structural unit A1a and structural unit A1b. As said aromatic hydrocarbon group, the phenyl group which may have a substituent, and the aralkyl group which may have a substituent are mentioned, for example. The content of the structural unit derived from a monomer having an aromatic hydrocarbon group is preferably at least 10% by mass, more preferably at least 20% by mass, and still more preferably at least 25% by mass, based on all the structural units of the polymer A1. The upper limit is preferably 80% by mass or less, more preferably 60% by mass or less, and still more preferably 55% by mass or less with respect to all the constituent units of the polymer A1. When the photosensitive composition contains a plurality of polymers A1, it is preferable that the mass average value of the content of the constituent unit derived from the monomer having an aromatic hydrocarbon group is within the above-mentioned range.

As monomers having an aromatic hydrocarbon group, for example, monomers having an aralkyl group, styrene and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tertiary butoxystyrene , Acetyloxystyrene, styrene dimer and styrene trimer, etc.), monomers with aralkyl groups or styrene are preferred, and styrene is more preferred. When the monomer having an aromatic hydrocarbon group is styrene, the content of the structural units derived from styrene is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, relative to all the structural units of the polymer A1, 25-55 mass % is still more preferable. When the photosensitive composition contains a plurality of polymers A1, it is preferable that the mass average value of the content of the constituent unit derived from the monomer having an aromatic hydrocarbon group is within the above-mentioned range.

Examples of the aralkyl group include a phenylalkyl group which may have a substituent (except for a benzyl group) and a benzyl group which may have a substituent, and a benzyl group which may have a substituent is preferable.

As a monomer which has a phenylalkyl group, phenyl ethyl (meth)acrylate is mentioned, for example.

Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group such as benzyl (meth)acrylate and benzyl chloride (meth)acrylate; vinylbenzyl chloride and vinylbenzyl alcohol Among vinyl monomers having a benzyl group, benzyl (meth)acrylate is preferred, and benzyl (meth)acrylate is more preferred. When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of constituent units derived from benzyl (meth)acrylate is preferably 10 to 90% by mass relative to all constituent units of polymer A1 , 20-80 mass % is more preferable, and 30-70 mass % is still more preferable.

Polymer A1 preferably contains a constituent unit derived from a non-acidic monomer having a polymerizable group in the molecule. In addition, the meaning of a polymeric group is the same as the polymeric group which the polymeric compound B mentioned later has, and a preferable aspect is also the same. Examples of the aforementioned monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate (meth)acrylic acid esters such as esters, 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; (meth)acrylonitrile. Among them, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate or n-butyl (meth)acrylate are preferred, methyl (meth)acrylate or Ethyl (meth)acrylate is more preferred. The content of the structural units derived from the above monomers is preferably from 1 to 80% by mass, more preferably from 1 to 60% by mass, and still more preferably from 1 to 50% by mass, based on all the structural units of the polymer A1.

Polymer A1 may have any of a linear structure, a branched structure, and an alicyclic structure in a side chain. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A1. The group having an alicyclic structure may be either monocyclic or polycyclic. "Side chain" refers to a group of atoms branching from the main chain. "Main chain" refers to the relatively longest bonded chain in the molecules of the polymer compound constituting the resin. Examples of monomers containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, (meth)acrylate ) tertiary butyl acrylate, isopentyl (meth) acrylate, tertiary pentyl (meth) acrylate, secondary pentyl (meth) acrylate, 2-octyl (meth) acrylate, (meth) 3-octyl acrylate and tertiary octyl (meth)acrylate. Among them, isopropyl (meth)acrylate, isobutyl (meth)acrylate or tertiary butyl methacrylate is preferred, and isopropyl methacrylate or tertiary butyl methacrylate is more preferred. As a monomer containing the group which has an alicyclic structure in a side chain, the monomer which has a monocyclic aliphatic hydrocarbon group, and the monomer which has a polycyclic aliphatic hydrocarbon group are mentioned, for example. Moreover, (meth)acrylate which has an alicyclic hydrocarbon group with 5-20 carbon atoms is mentioned. Specifically, (meth)acrylate (bicyclo[2.2.1]heptyl-2), (meth)acrylate-1-adamantyl, (meth)acrylate-2-adamantyl Esters, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyl (meth)acrylate Adamantyl ester, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate ester, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, (meth)acrylic acid 2-Ethyl-2-adamantyl ester, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-methanoinden-5-yl (meth)acrylate ester, octahydro-4,7-inden-1-ylmethyl (meth)acrylate, 1-menthol (meth)acrylate, tricyclodecane (meth)acrylate, (methyl ) Acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl ester, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1. 0) Heptyl ester, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fecundyl (meth)acrylate, 2,2,5-trimethyl (meth)acrylate Cyclohexyl and cyclohexyl (meth)acrylate. Among them, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (meth) 2-adamantyl acrylate, fenzyl (meth)acrylate, 1-menthol (meth)acrylate or tricyclodecane (meth)acrylate are preferred, cyclohexyl (meth)acrylate (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are more preferable.

As a preferable aspect of polymer A1, the aspect which has a polymeric group is mentioned. Such polymer A1 preferably includes a structural unit having a polymerizable group, and more preferably includes a structural unit having an ethylenically unsaturated group in a side chain. Examples of the polymerizable group include those possessed by the polymerizable compound B described later, preferably an ethylenically unsaturated group, and more preferably an acryl group or a methacryl group. Furthermore, it is also preferable that the polymerizable group is a polymerizable group capable of a polymerization reaction with the polymerizable group of the polymerizable compound B.

Polymer A1 containing a structural unit having a polymerizable group is preferably obtained by reacting a structural unit A1b or a hydroxyl group-containing polymer with the following monomer (hereinafter also referred to as "monomer X").

The monomer X is a monomer having two or more polymerizable groups in the molecule, more preferably a monomer having two polymerizable groups in the molecule. As a polymeric group, the polymeric group which the polymeric compound B mentioned later has is mentioned, for example. Among them, the monomer X preferably has two kinds of polymerizable groups, more preferably has an ethylenically unsaturated group and a cationic polymerizable group, and is still more preferably has an acryl group or a methacryl group and an epoxy group.

Examples of the monomer X include glycidyl (meth)acrylate, allyl (meth)acrylate, and the like.

As a structural unit having a polymerizable group, a structural unit represented by formula (P) is preferable.

[chemical formula 5]

In the formula (P), R ^P represents a hydrogen atom or a methyl group. ^LP represents a divalent linking group. P represents a polymerizable group.

R ^P represents a hydrogen atom or a methyl group. As R ^P , a hydrogen atom is preferable.

^LP represents a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO ₂ -, -NR ^N -, hydrocarbon groups, and combinations thereof. R ^N represents a hydrogen atom or a substituent. As said hydrocarbon group, an alkylene group, a cycloalkylene group, and an arylylene group are mentioned, for example. The above-mentioned alkylene group may be either linear or branched. The number of carbon atoms in the alkylene group is preferably 1-10, more preferably 2-8, and still more preferably 3-5. The above-mentioned alkylene group may have a heteroatom, and the methylene group in the above-mentioned alkylene group may be substituted with a heteroatom. As the above-mentioned hetero atom, an oxygen atom, a sulfur atom or a nitrogen atom is preferable, and an oxygen atom is more preferable. The above-mentioned cycloalkylene group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkylene group is preferably from 3 to 20, more preferably from 5 to 10, and still more preferably from 6 to 8. The aforementioned aryl group may be either monocyclic or polycyclic. The number of carbon atoms in the arylylene group is preferably from 6 to 20, more preferably from 6 to 15, and still more preferably from 6 to 10. A phenylene group is preferable as the above-mentioned arylylene group. The above-mentioned cycloalkylene group and the above-mentioned arylylene group may have a hetero atom as a ring member atom. As the above-mentioned hetero atom, an oxygen atom, a sulfur atom or a nitrogen atom is preferable, and an oxygen atom is more preferable. The above-mentioned hydrocarbon group may further have a substituent. Examples of the above-mentioned substituents include halogen atoms (for example, fluorine atoms, etc.), hydroxyl groups, nitro groups, cyano groups, alkyl groups, alkoxy groups, alkoxycarbonyl groups, and alkenyl groups, with hydroxyl groups being preferred. As L ^P , an alkylene group which may have a heteroatom is preferable.

P represents a polymerizable group. The aforementioned polymerizable group is as described above.

As a structural unit which has a polymeric group, the following structural units are mentioned, for example. In addition, in the following formulae, Rx and Ry each independently represent a hydrogen atom or a methyl group.

[chemical formula 6]

When the polymer A1 contains a structural unit having a polymerizable group, the content of the structural unit having a polymeric group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, relative to all the structural units of the polymer A1. , 15 to 40% by mass is still more preferable.

As a method for introducing a polymerizable group into polymer A1, for example, an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinylidene compound, an aldehyde compound, a methylol compound, and a carboxylic acid anhydride are mixed with polymer A1. The method of reacting the carboxyl group and the optionally included hydroxyl group, carboxyl group, primary amino group, secondary amino group, acetoacetyl group and sulfo group. As a preferable aspect of the method of introducing a polymerizable group into polymer A1, for example, the following method can be mentioned: After polymer A1 including constituent unit A1a and constituent unit A1b is synthesized by polymerization reaction, monomer X ( A (meth)acrylate having an epoxy group such as glycidyl (meth)acrylate) reacts with a part of the carboxyl group of the constituent unit A1b of the obtained polymer A1 to polymerize the polymerizable group (preferably ( meth)acryloxy) was introduced into polymer A1. As another method, the following method can be mentioned: After synthesizing the polymer having the structural unit A1a, the structural unit A1b and the hydroxyl group by polymerization reaction, the (meth)acrylic acid ester having the isocyanate group and the polymer reaction are used. A part of the hydroxyl groups of the obtained polymer is reacted to introduce (meth)acryloyloxy groups into the polymer. The reaction temperature of the above polymer reaction is preferably 80-110°C. It is better to use a catalyst in the above polymer reaction, and it is more preferable to use an ammonium salt (tetraethylammonium bromide). The reaction temperature of the above polymerization reaction is preferably 70-100°C, more preferably 80-90°C. It is better to use a polymerization initiator in the above-mentioned polymerization reaction. As a polymerization initiator, it is more preferable to use an azo initiator. As a polymerization initiator, V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) or V- 65 (manufactured by FUJIFILM Wako Pure Chemical Corporation) is further preferred.

As an example of a preferable aspect of the polymer A1, a structural unit derived from a structural unit A1a, a structural unit A1b, a structural unit derived from styrene, a structural unit derived from benzyl methacrylate, and a polymer derived from methyl methacrylate can be mentioned. A polymer of constituent units. In addition, as another example of a preferable aspect of the polymer A1, there can be mentioned the constituent units including the constituent unit A1a, the constituent unit A1b, the constituent unit derived from styrene, or the constituent unit derived from benzyl methacrylate, the constituent unit derived from the A polymer comprising a monomer having a branched structure group in the side chain or a monomer having an alicyclic structure group in the side chain. In addition, as another example of a preferable aspect of the polymer A1, there may be mentioned polymeric polymers containing a structural unit A1a, a structural unit A1b, a structural unit derived from styrene, or a structural unit derived from benzyl methacrylate, and having a polymerizable group. A polymer of constituent units. Moreover, as another example of a preferable aspect of polymer A1, the polymer which consists of two types of structural unit A1a and structural unit A1b is mentioned.

The Tg of the polymer A1 is preferably from 30 to 180°C, more preferably from 40 to 150°C, and still more preferably from 50 to 120°C.

From the viewpoint of more excellent effects of the present invention, the acid value of polymer A1 is preferably 220 mgKOH/g or less, more preferably 200 mgKOH/g or less, still more preferably 190 mgKOH/g or less, and especially 170 mgKOH/g or less. Good, below 150mgKOH/g is the best. From the standpoint of more excellent effects of the present invention, the lower limit is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 80 mgKOH/g or more, and particularly preferably 90 mgKOH/g or more.

The acid value of polymer A1 was calculated from the charge value at the time of synthesis of polymer A1. In addition, the structural unit which has an acidic group is also called "structural unit Ac" below. When there is only one kind of structural unit Ac in polymer A1, calculate it by formula (1); when there are two or more structural units Ac in polymer A1, calculate according to formula (1) for each structural unit Ac Acid value and calculate its total value. Equation (1): {(the charge ratio of raw material monomers constituting unit Ac to all raw material monomers (mass %))/(molecular weight of raw material monomers constituting unit Ac)}×10×56.1 The acid value of a polymer can be adjusted by the kind of structural unit which a polymer has, and/or content of the structural unit containing an acid group.

When the photosensitive composition contains two or more polymers A1, the content of the polymer A1 satisfying the range of the above-mentioned acid value is preferably 10-100% by mass, 60-100% by mass relative to the total content of the polymer A1 It is more preferable, and 90-100 mass % is more preferable.

From the standpoint of more excellent effects of the present invention, the acid value derived from the carboxyl group of polymer A1 is preferably 220 mgKOH/g or less, more preferably 200 mgKOH/g or less, more preferably 190 mgKOH/g or less, and 170 mgKOH/g or less. It is especially good if it is less than g, and the best is less than 150mgKOH/g. From the standpoint of more excellent effects of the present invention, the lower limit is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 80 mgKOH/g or more, and particularly preferably 90 mgKOH/g or more. The acid value derived from the carboxyl group of the polymer A1 can be calculated from the formula in which "constituent unit Ac" is replaced with "constituent unit having a carboxyl group" in the above formula (1).

In addition, from the viewpoint that the effect of the present invention is more excellent, when the acid value derived from the carboxyl group of the polymer A1 and the acid decomposable group X derived from the structural unit A1a are all decomposed by the action of an acid, the acid value decomposable group X The total value of the acid value of the generated acid groups is, for example, 265 mgKOH/g or less, preferably 230 mgKOH/g or less, more preferably 220 mgKOH/g or less, and 200 mgKOH/g or less from the viewpoint of more excellent effects of the present invention. Further better. From the standpoint of more excellent effects of the present invention, the lower limit is preferably 90 mgKOH/g or more, more preferably 100 mgKOH/g or more, still more preferably 110 mgKOH/g or more, and particularly preferably 120 mgKOH/g or more. The acid value of the acid group generated from the acid decomposable group X when the acid decomposable group X in the constituent unit A1a is completely decomposed by the action of an acid is calculated from the loaded value at the time of synthesis of the polymer A1. When there is only one kind of constituent unit A1a in polymer A1, it can be calculated by formula (2); when there are more than two kinds of constituent units A1a in polymer A1, it can be calculated according to formula (2) for each constituent unit A1a. When the acid decomposable group X is completely decomposed by the action of acid, the acid value of the acid group generated from the acid decomposable group X is calculated and the total value thereof is obtained. Equation (2): {(the charge ratio of raw material monomers constituting unit A1a to all raw material monomers (mass %))/(molecular weight of raw material monomers constituting unit A1a)}×10×56.1

In addition, from the viewpoint of more excellent effects of the present invention, the acid value of the polymer A1 derived from the acid group generated from the acid decomposable group X when all the acid decomposable groups X in the constituent unit A1a are decomposed by the action of an acid For example, it is preferably 15 to 170 mgKOH/g, more preferably 15 to 130 mgKOH/g.

The weight average molecular weight of the polymer A1 is preferably at most 500,000, more preferably at most 100,000, and still more preferably at most 50,000. The weight average molecular weight of polymer A1 is preferably at least 3,000, more preferably at least 4,000, still more preferably at least 5,000, and particularly preferably at least 10,000. When the weight average molecular weight is 500,000 or less, resolution and developability can be improved. Moreover, when the weight average molecular weight is 3,000 or more, the property of the image development aggregate and the property of an unexposed film, such as the edge melting property of a transfer film, and chipping property, can be controlled. "Edge meltability" refers to the ease with which the photosensitive composition layer protrudes from the end surface of the roll when the transfer film is wound up into a roll. "Cutting property" refers to the ease with which shavings are scattered when the unexposed film is cut with a cutter. If this swarf adheres to the upper surface of the transfer film, etc., it will be transferred to a mask (reticle) in the subsequent exposure process etc., and will become a cause of defective products. The degree of dispersion of polymer A1 is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0. When the photosensitive composition contains two or more polymers A1, the content of the polymer A1 satisfying the range of the above-mentioned weight average molecular weight and/or degree of dispersion is preferably 10 to 100% by mass relative to the total content of the polymer A1 , 60-100 mass % is more preferable, and 90-100 mass % is still more preferable.

One type of polymer A1 may be used alone, or two or more types may be used. When two or more polymers A1 are used, two polymers A1 containing constituent units derived from monomers having an aromatic hydrocarbon group are used in combination, or polymers containing constituent units derived from monomers having an aromatic hydrocarbon group are used in combination. The substance A1 and the polymer A1 which does not contain the structural unit derived from the monomer which has an aromatic hydrocarbon group are preferable. In the latter case, the content of the polymer A1 containing structural units derived from monomers having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, based on all the structural units of the polymer A1. , 80% by mass or more is further preferred, and 90% by mass or more is particularly preferred. The upper limit is preferably 100% by mass or less with respect to all the constituent units of the polymer A1.

The content of the polymer A1 is preferably 10.0 to 90.0% by mass, more preferably 20.0 to 80.0% by mass, more preferably 30.0 to 70.0% by mass, and still more preferably 40.0 to 60.0% by mass, based on the total solid content of the photosensitive composition. Excellent. When content of polymer A1 is 90.0 mass % or less with respect to the total solid content of a photosensitive composition, developing time can be controlled. Moreover, when content of polymer A1 is 10.0 mass % or more with respect to the total solid content of a photosensitive composition, edge melting resistance can be improved.

As a synthesis method of the polymer A1, for example, a method of adding an appropriate amount of a radical polymerization initiator to a solution obtained by diluting the raw material monomers of each constituent unit of the polymer A1 with a solvent, followed by heating and stirring is mentioned. It is also possible to synthesize while adding a part of the mixture dropwise to the reaction liquid. Moreover, after completion|finish of reaction, you may further add a solvent and adjust to desired density|concentration. As a synthesis method of the polymer A1, in addition to the above, block polymerization, suspension polymerization, and emulsion polymerization are mentioned, for example.

The photosensitive composition may contain other resins other than the above-mentioned polymer A1. Examples of other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formaldehyde, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxy Styrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine and polyalkylene glycol.

＜Polymerizable compound B＞ The photosensitive composition contains a polymerizable compound. The "polymerizable compound" means a compound different from the above-mentioned polymer A1 which has a polymerizable group and polymerizes under the action of the photopolymerization initiator C described later.

The polymerizable group possessed by the polymerizable compound may be any group as long as it participates in the polymerization reaction, and examples thereof include vinyl, acryl, methacryl, styryl, and maleimide groups. Groups with ethylenically unsaturated groups such as epoxy groups and oxetanyl groups with cationic polymerizable groups, preferably groups with ethylenically unsaturated groups, acryl or methacryl groups for better.

As a polymerizable compound, a compound having one or more ethylenically unsaturated groups in the molecule (hereinafter also referred to as "ethylenically unsaturated compound") is preferable from the viewpoint of further improving photosensitivity. Compounds having two or more ethylenically unsaturated groups (hereinafter also referred to as "polyfunctional ethylenically unsaturated compounds") are more preferred. Also, from the standpoint of better resolving properties and exfoliation properties, the number of ethylenically unsaturated groups in the molecule of the ethylenically unsaturated compound is 1 or more, preferably 1-6, and more preferably 1-3. 2 to 3 are further preferred.

The polymerizable compound may have an alkyleneoxy group. As the above-mentioned alkyleneoxy group, ethoxyl or propoxyl is preferable, and ethoxyl is more preferable. The number of additions of the alkyleneoxy groups added to the polymerizable compound is preferably 2-30 per molecule, more preferably 2-20.

From the standpoint of a better balance between photosensitivity, resolving power, and peelability of the photosensitive composition, the polymerizable compound contains bifunctional or trifunctional ethylenically unsaturated groups having 2 or 3 ethylenically unsaturated groups in the molecule. compounds are preferred.

From the viewpoint of excellent releasability, the content of the bifunctional ethylenically unsaturated compound is preferably 20.0% by mass or more, more preferably 40.0% by mass or more, and still more preferably 50.0% by mass or more, relative to the total mass of the polymerizable compound. good. The upper limit is preferably at most 100.0 mass %, more preferably at most 80.0 mass %. That is, all polymeric compounds contained in the photosensitive composition may be bifunctional ethylenically unsaturated compounds. The content of the trifunctional ethylenically unsaturated compound is preferably at least 10.0% by mass, more preferably at least 15.0% by mass, based on the total mass of the polymerizable compound. The upper limit is preferably at most 100.0 mass %, more preferably at most 80.0 mass %, and still more preferably at most 50.0 mass %. That is, all polymeric compounds contained in the photosensitive composition may be trifunctional ethylenically unsaturated compounds. Also, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryl group as a polymerizable group is preferable.

(polymerizable compound B1) As the polymerizable compound, it is also preferable to include a polymerizable compound B1 having one or more aromatic rings and two ethylenically unsaturated groups. Examples of the polymerizable compound B1 include bifunctional ethylenically unsaturated compounds having one or more aromatic rings among the above-mentioned polymerizable compounds.

Examples of the aromatic ring possessed by the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings; aromatic rings such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings; Heterocyclic ring; the condensed ring formed by combining these rings is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring. The above-mentioned aromatic ring may further have a substituent.

It is preferable that the polymerizable compound B1 has a bisphenol structure from the viewpoint of improving resolution by suppressing swelling of the photosensitive composition layer by a developer. As the bisphenol structure, for example, the bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl) phenyl)methane) and bisphenol B structure from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), bisphenol A structure is better.

Examples of the polymerizable compound B1 having a bisphenol structure include those having a bisphenol structure and two polymerizable groups (preferably (meth)acryl groups) bonded to both ends of the bisphenol structure. compound. Both ends of the bisphenol structure may be directly bonded to the polymerizable group, or may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy group which can be added to both ends of the bisphenol structure, an ethoxyl group or a propoxyl group is preferable, and an ethoxyl group is more preferable. The number of alkyleneoxy groups (preferably ethoxylate groups) added to the bisphenol structure is preferably 2 to 30 per molecule, more preferably 2 to 20. Examples of the polymerizable compound B1 having a bisphenol structure include paragraphs [0072] to [0080] of JP-A-2016-224162, and these contents are incorporated in the present specification.

As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is better. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy) yl)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane and 2, Ethoxylated bisphenol A dimethacrylate such as 2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE series, manufactured by Shin-Nakamura Chemical Co., Ltd.) , 2,2-bis(4-(methacryloxydodecyloxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and ethoxylated ( 10) Bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

As the polymerizable compound B1, a compound represented by the formula (B1) is also preferable.

[chemical formula 7]

In formula (B1), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group. A represents an ethylene group. B represents a propylene group. n1 and n3 each independently represent the integer of 1-39. n1+n3 represents the integer of 2-40. n2 and n4 each independently represent the integer of 0-29. n2+n4 represents an integer of 0-30. The arrangement of the constituent units of -(AO)- and -(BO)- may be either random or block. In the case of a block, any of -(AO)- and -(BO)- may be on the side of a bisphenyl group. As n1+n2+n3+n4, 2-20 are preferable, 2-16 are more preferable, 4-12 are still more preferable. Also, n2+n4 is preferably 0-10, more preferably 0-4, still more preferably 0-2, and particularly preferably 0.

From the standpoint of better resolution, the content of the polymerizable compound B1 is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, and still more preferably 25.0% by mass or more, relative to the total solid content of the photosensitive composition. good. From the viewpoint of transferability and edge melting (a phenomenon in which the photosensitive composition bleeds from the end of the transfer member), the upper limit is preferably 70.0% by mass or less, 60.0% by mass relative to the total solid content of the photosensitive composition Below % is better.

From the viewpoint of better resolution, the content of the polymerizable compound B1 is preferably 40.0% by mass or more, more preferably 45.0% by mass or more, and still more preferably 50.0% by mass or more, based on the total mass of the polymerizable compound. From the viewpoint of detachability, the upper limit is preferably 100.0% by mass or less, more preferably 99.0% by mass or less, still more preferably 95.0% by mass or less, and particularly preferably 90.0% by mass or less with respect to the total mass of the polymerizable compound. , below 85.0% by mass is the best.

(other polymeric compounds) The photosensitive composition may contain other polymerizable compounds in addition to the above. As another polymeric compound, a well-known polymeric compound is mentioned, for example. Specifically, compounds having one ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compound), bifunctional ethylenically unsaturated compounds not having an aromatic ring, and trifunctional or more functional ethylenically unsaturated compounds include saturated compounds.

Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloxyethylsuccinate, polyethylene glycol Alcohol Mono(meth)acrylate, Polypropylene Glycol Mono(meth)acrylate and Phenoxyethyl(meth)acrylate.

Examples of bifunctional ethylenically unsaturated compounds not having an aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and urethane di(meth)acrylate. base) acrylate and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol Dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1 , 6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl Glycol di(meth)acrylate. Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. Acrylate. Examples of the urethane di(meth)acrylate include propylene oxide modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide modified urethane di(meth)acrylate. Moreover, examples of commercially available urethane di(meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.) and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

Examples of ethylenically unsaturated compounds having a trifunctional or higher function include diperythritol (tri/tetra/penta/hexa)(meth)acrylate, neopentylthritol (tri/tetra)(meth)acrylic acid ester, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate Meth)acrylate, glycerol tri(meth)acrylate and their alkylene oxide modified substances. "(Three/four/five/six) (meth)acrylates" include tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates and hexa(meth)acrylates concept. Also, "(tri/tetra)(meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate.

Examples of alkylene oxide modified products of trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (for example, KAYARAD (registered trademark) manufactured by Nippon Kayaku Co., Ltd. DPCA-20 and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide modified (meth)acrylate compounds (for example, KAYARAD RP- 1040, ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., SR454 manufactured by TOMOE Engineering Co., Ltd., etc.), ethoxy Glyceryl triacrylate (for example, A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), ARONIX (registered trademark) series (for example, TO-2349 manufactured by TOAGOSEI CO., LTD., M -270, M-520 and M-510, etc.).

The polymeric compound may be a polymeric compound having an acid group (eg, carboxyl group, etc.). The above-mentioned acid groups may form groups derived from acid anhydrides. Examples of the polymerizable compound having an acid group include ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-520 (manufactured by TOAGOSEI CO., LTD.) and ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI CO., LTD.). Examples of the polymerizable compound having an acid group include those described in paragraphs [0025] to [0030] of JP-A-2004-239942.

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

A polymeric compound can be used individually by 1 type or in 2 or more types. The content of the polymerizable compound is preferably from 10.0 to 70.0% by mass, more preferably from 15.0 to 70.0% by mass, and still more preferably from 20.0 to 70.0% by mass, relative to the total solid content of the photosensitive composition.

＜Photopolymerization initiator C＞ The photosensitive composition contains a photopolymerization initiator. The photopolymerization initiator is a compound that initiates the polymerization of the above-mentioned polymerizable compound B by receiving active rays such as ultraviolet rays, visible rays, and X-rays. As a photopolymerization initiator, a well-known photoradical polymerization initiator is mentioned, for example.

Examples of photoradical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, and photopolymerization initiators having an α-hydroxyalkylphenone structure. A photopolymerization initiator, a photopolymerization initiator with an acyl phosphine oxide structure, and a photopolymerization initiator with an N-phenylglycine structure.

From the viewpoints of photosensitivity, visibility and resolution of exposed and non-exposed parts, the photoradical polymerization initiator is selected from the group consisting of 2,4,5-triaryl imidazole dimers and derivatives thereof. At least one of the group is preferred. In addition, the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of derivatives of 2,4,5-triaryl imidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl) -4,5-bis(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.

Examples of photoradical polymerization initiators include those described in paragraphs [0031] to [0042] of JP-A-2011-095716 and paragraphs [0064]-[0081] of JP-A-2015-014783. Recorded photoradical polymerization initiator.

Examples of photoradical polymerization initiators include dimethylaminobenzoic acid ethyl ester (DBE), benzoin methyl ether, (p,p'-dimethoxybenzyl) anisyl ester, TAZ-110 (manufactured by Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (manufactured by Midori Kagaku Co., Ltd.), 1- [4-(Phenylthio)]-1,2-octanedione-2-(O-benzoyl oxime) (IRGACURE (registered trademark) OXE-01, manufactured by BASF Corporation), 1-[9-ethyl -6-(2-Methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF Corporation), IRGACURE OXE-04 (manufactured by BASF Corporation), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Endolinyl)phenyl]-1-butanone (Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-enderinylpropan-1- Ketone (Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropane- 1-keto (Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-portolinylphenyl)butanone-1 (Omnirad 369, manufactured by IGM Resins B.V. company), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, manufactured by IGM Resins B.V. ), 2,2-dimethoxy-1,2-diphenylethan-1-one (Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide (Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819, manufactured by IGM Resins B.V.), oxime ester-based Photopolymerization initiator (Lunar 6, manufactured by DKSH Japan K.K.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (2-(2- Chlorophenyl)-4,5-diphenylimidazole dimer) (B-CIM, manufactured by Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (BCTB, Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) ( TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)- 9H-carbazol-3-yl]-,2-(O-acetyloxime) (TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.) and 3-cyclohexyl-1-(6- (2-(Benzyloxyimino)hexyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.).

One kind of polymerization initiator may be used alone, or two or more kinds may be used. The content of the polymerization initiator is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, based on the total solid content of the photosensitive composition. The upper limit is preferably at most 20 mass %, more preferably at most 15.0 mass %, and still more preferably at most 10.0 mass %, with respect to the total solid content of the photosensitive composition.

＜Photoacid generator D＞ The photosensitive composition contains a photoacid generator. Photoacid generators are selected from the group consisting of onium salt compounds, oxime sulfonate compounds, trioxane compounds, nitrobenzylsulfonate compounds, disulfide compounds and bissulfonyl diazomethane compounds (collectively referred to as specific photoacid generators). one or more photoacid generators in the group of agents).

Known compounds can be used as the specific photoacid generator. Examples of onium salts include percite salts, iodonium salts, diazonium salts, etc., preferably permeium salts or iodonium salts, and examples thereof include compounds represented by the following formula (D1) or formula (D2). Examples of the oxime sulfonate compound include compounds represented by the following formula (D3). The compound represented by the following formula (D7) is mentioned as a trioxane compound. Examples of the nitrobenzylsulfonate compound include compounds represented by the following formula (D4). Examples of disulfide compounds include compounds represented by the following formula (D6). Examples of the bissulfonyldiazomethane compound include compounds represented by the following formula (D5). As the specific photoacid generator, a permeic acid salt or an oxime sulfonate is preferable from the viewpoint that the effect of the present invention is more excellent.

[chemical formula 8]

Rd ₁ to Rd ₁₅ each independently represent an organic group. m represents an integer of 0-2. X ^- indicates relative anion. Rd ₁₆ and Rd ₁₇ each independently represent a hydrogen atom or an alkyl group. In the formula (D1), Rd ₁ to Rd ₃ are each independently an aryl group or an alkyl group (any of linear, branched and cyclic may be possible.) It is preferable. In addition, two or more of Rd ₁ to Rd ₃ may be bonded to each other to form a ring.

The aryl group may be monocyclic or polycyclic. As the aryl group, phenyl or naphthyl is preferable, and phenyl is more preferable. The aryl group may have a substituent. Examples of substituents include alkyl (eg, 1 to 15 carbons), cycloalkyl (eg, 3 to 15 carbons), aryl (eg, 6 to 14 carbons), alkoxy (eg, 1 to 15 carbons), ~15), halogen atom, hydroxyl group, phenylthio group and -S ⁺ ( _RA ) ( _RB ), etc. R _A and R _B have the same meanings as Rd ₁ to Rd ₃ , and preferred embodiments are also the same.

The alkyl group may be any of linear, branched and cyclic, for example, a linear alkyl group having 1 to 15 carbons, a branched alkyl group having 3 to 15 carbons, or a carbon Cycloalkyl groups with a number of 3 to 15, specifically, methyl, ethyl, propyl, n-butyl, secondary butyl, tertiary butyl, cyclopropyl, cyclobutyl, and cyclohexyl, etc. . In addition, CH ₂ in the alkyl group may be substituted with a heteroatom such as an oxygen atom or a heteroatom group such as a carbonyl group. An alkyl group may have a substituent. Examples of substituents include aryl groups (eg, having 6 to 14 carbon atoms), alkoxy groups (eg, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and thiophenyl groups.

In addition, the ring formed by bonding two or more of Rd ₁ to Rd ₃ to each other may be any of an aromatic ring and an alicyclic ring, and may be a monocyclic ring or a polycyclic ring. The number of ring members is, for example, 3 to 10, preferably 4 to 8, more preferably 5 or 6. In addition, the above-mentioned ring may contain an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, or an amide bond.

X ^- is not particularly limited, and examples include BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , AsF ₆ ^- , substituted or unsubstituted alkanesulfonate anions (for example, CF ₃ SO ₂ ^- , C ₃ F ₇ SO ₃ ^- , C ₄ F ₉ SO ₃ ^- and camphorsulfonic acid anion, etc.), substituted benzenesulfonic acid anions (such as p-toluenesulfonic acid anion and mesitylenesulfonic acid anion, etc.) and disulfonic acid anion Imide anion (for example, bis(trifluoromethanesulfonylimide anion, cyclohexafluoropropane-1,3-bis(sulfonyl)imide anion, etc.), etc.

Specific examples of the photoacid generator represented by the formula (D1) are shown below. In the following specific examples, tBu represents a tertiary butyl group, and Ph represents a phenyl group. In addition, X ^- represents an ion selected from BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , AsF ₆ ^- , substituted or unsubstituted alkanesulfonic acid anions (for example, CF ₃ SO ₂ ^- , C ₃ F ₇ SO ₃ ^- , C ₄ F ₉ SO ₃ ^- and camphorsulfonic acid anions, etc.), substituted benzenesulfonic acid anions (such as p-toluenesulfonic acid anions and mesitylenesulfonic acid anions, etc.) and bissulfonimide anions (such as , the relative anion in the group of bis(trifluoromethanesulfonylimide anion and cyclohexafluoropropane-1,3-bis(sulfonyl)imide anion, etc.).

[chemical formula 9]

In the formula (D2), Rd ₄ and Rd ₅ have the same meanings as Rd ₁ to Rd ₃ , and preferred embodiments are also the same. As Rd ₄ and Rd ₅ , a substituted or unsubstituted aryl group is preferred, and a substituted or unsubstituted phenyl group is more preferred.

Specific examples of the photoacid generator represented by the formula (D2) are shown below. In the following specific examples, X ^- represents an ion selected from BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , AsF ₆ ^- , substituted or unsubstituted alkanesulfonate anions (for example, CF ₃ SO ₂ ^- , C ₃ F ₇ SO ₃ ^- , C ₄ F ₉ SO ₃ ^- and camphorsulfonic acid anion, etc.), substituted benzenesulfonic acid anion (for example, p-toluenesulfonic acid anion and mesitylenesulfonic acid anion, etc.) and bissulfonyl A counter anion in the group of iminium anions (for example, bis(trifluoromethanesulfonylimide anion and cyclohexafluoropropane-1,3-bis(sulfonyl)imide anion, etc.).

[chemical formula 10]

In the formula (D3), Rd ₆ has the same meaning as Rd ₁ to Rd ₃ , and preferred embodiments are also the same. An aryl group is preferable as Rd ₇ . The aryl group may be either monocyclic or polycyclic, and the number of ring member atoms is preferably 6-20, more preferably 6-15. Specific examples of the aryl group include phenyl, naphthyl, anthracenyl, and perylene. The aryl group may have a substituent. Examples of substituents include alkyl (eg, 1 to 15 carbons), cycloalkyl (eg, 3 to 15 carbons), aryl (eg, 6 to 14 carbons), alkoxy (eg, 1 to 15 carbons), ~15), halogen atoms and hydroxyl groups, etc.

As Rd ₈ , an aryl group, an alkyl group or a cyano group is preferable. Examples of the aryl group represented by Rd ₈ include the same ones as those represented by Rd ₇ . The alkyl group represented by Rd ₈ may be linear, branched, or cyclic, and examples include linear alkyl groups having 1 to 15 carbons and branched alkyl groups having 3 to 15 carbons. Alkyl groups or cycloalkyl groups with 3 to 15 carbon atoms, specifically, methyl, ethyl, propyl, n-butyl, secondary butyl, tertiary butyl, cyclopropyl, cyclobutyl base and cyclohexyl etc. In addition, CH ₂ in the alkyl group may be substituted with a heteroatom such as an oxygen atom or a heteroatom group such as a carbonyl group. An alkyl group may have a substituent. Examples of substituents include aryl groups (eg, having 6 to 14 carbon atoms), alkoxy groups (eg, having 1 to 15 carbon atoms), halogen atoms (preferably fluorine atoms), hydroxyl groups, and the like. In addition, it is also preferable that the alkyl group is a perfluoroalkyl group. In addition, the ring formed by bonding Rd ₇ and Rd ₈ to each other may be any of an aromatic ring and an alicyclic ring, and may be a monocyclic ring or a polycyclic ring. The number of ring members is, for example, 3 to 20, preferably 4 to 15, more preferably 6 to 15. In addition, the above-mentioned ring may contain an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, or an amide bond.

Specific examples of the photoacid generator represented by the formula (D3) are shown below.

[chemical formula 11]

In formula (D4), an alkyl group or an aryl group is preferable as Rd ₁₀ . The alkyl group and aryl group represented by Rd ₁₀ are the same as the alkyl group and aryl group represented by Rd ₆ , and preferred embodiments are also the same. As Rd ₉ , an alkyl group or a nitro group is preferable. Examples of the alkyl group represented by Rd ₉ include the same ones as those represented by Rd ₁ to Rd ₃ . Rd ₁₆ and Rd ₁₇ each independently represent a hydrogen atom or an alkyl group. Examples of the alkyl group represented by Rd ₁₆ and Rd ₁₇ include the same ones as those represented by Rd ₁ to Rd ₃ . As Rd ₁₆ and Rd ₁₇ , hydrogen atoms are preferred. Specific examples of the photoacid generator represented by the formula (D4) are shown below.

[chemical formula 12]

In formula (D5), Rd ₁₁ and Rd ₁₂ are preferably alkyl or aryl. The alkyl group and aryl group represented by Rd ₁₁ and Rd ₁₂ are the same as the alkyl group and aryl group represented by Rd ₆ , and preferred embodiments are also the same. Specific examples of the photoacid generator represented by the formula (D5) are shown below.

[chemical formula 13]

In formula (D6), Rd ₁₃ and Rd ₁₄ are preferably aryl groups. The aryl group represented by Rd ₁₃ and Rd ₁₄ is the same as the aryl group represented by Rd ₆ , and the preferred embodiment is also the same. Specific examples of the photoacid generator represented by the formula (D6) are shown below.

[chemical formula 14]

In formula (D7), Rd ₁₅ is preferably a group represented by *-L _X1 -Rd _X1 . L _X1 represents a single bond or a divalent linking group. Rd _X1 includes an aromatic hydrocarbon ring group or an aromatic heterocyclic group. Examples of the divalent linking group represented by L _X1 include -CO-, -O-, -SO-, -SO ₂ -, -NR ^A -, alkylene (preferably having 1 to 6 carbon atoms) It can be linear or branched), alkenyl (preferably carbon number 2 to 6. It can be linear or branched), alkynyl (preferably carbon The number is 2 to 6. It may be a straight chain or a branched chain) and a divalent linking group formed by combining a plurality of these. Moreover, the above-mentioned alkylene group, alkenylene group and alkynylene group may have a substituent. As a substituent, a halogen atom (preferably a fluorine atom), a hydroxyl group, etc. are mentioned, for example. Examples of R ^A include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among them, L _X1 is preferably a single bond or an alkenylene group, more preferably a single bond or an alkenylene group having 2 to 4 carbon atoms. Examples of the aromatic hydrocarbon ring group represented by Rd _X1 include phenyl and naphthyl. The aromatic heterocyclic group represented by Rd _X1 includes pyrrole ring group, furan ring group, thiophene ring group, indole ring group, benzofuran ring group and benzothiophene furan ring group, etc., wherein the furan ring group is better. The aromatic hydrocarbon ring group and aromatic heterocyclic group represented by Rd _X1 may further have a substituent. Examples of substituents include alkyl (eg, 1 to 15 carbons), cycloalkyl (eg, 3 to 15 carbons), aryl (eg, 6 to 14 carbons), alkoxy (eg, 1 to 15 carbons), ~15), halogen atoms and hydroxyl groups, etc. Specific examples of the photoacid generator represented by the formula (D7) are shown below.

[chemical formula 15]

A photoacid generator may be used individually by 1 type, and may use 2 or more types. The content of the photoacid generator is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, based on the total solid content of the photosensitive composition. The upper limit is preferably at most 10.0 mass %, more preferably at most 8.0 mass %, and still more preferably at most 6.0 mass %, with respect to the total solid content of the photosensitive composition.

＜Pigment＞ From the viewpoint of the visibility of the exposed portion and the non-exposed portion, and the pattern visibility and resolution after development, the photosensitive composition may contain a color having a maximum absorption wavelength of 450 nm or more and a maximum absorption wavelength of 400 nm to 780 nm during color development. A dye whose absorption wavelength is changed by acid, alkali, or free radicals (hereinafter also referred to as "dye N"). When the dye N is contained, although the detailed mechanism is not clear, the adhesiveness with the adjacent layer (for example, the intermediate layer) improves and resolution becomes more excellent.

The "maximum absorption wavelength of the pigment is changed by acid, alkali or free radical" can refer to the state that the pigment in the color development state is decolorized by acid, alkali or free radical, and the pigment in the decolorized state is decolorized by acid or alkali. Any of the state in which the color is developed by free radicals and the state in which the pigment in the color state changes to another color state. Specifically, the dye N may be any of a compound that develops color by changing from a decolorized state by exposure and a compound that decolorizes by changing from a color-developed state by exposure. In the above case, it may be a pigment that generates acid, alkali, or free radicals in the photosensitive composition layer by exposure, and these acts to change the state of color development or decolorization, or it may be a photosensitive composition. A pigment in which the state (for example, pH, etc.) in the material layer is changed to develop or decolorize due to changes in acid, alkali, or free radicals. In addition, it may be a pigment that undergoes a change in the state of color development or decolorization by directly being stimulated by an acid, an alkali, or a free radical without exposure to light.

Among them, from the viewpoint of the visibility and resolution of the exposed part and the non-exposed part, dye N is a dye whose maximum absorption wavelength is changed by acid or free radicals, and the maximum absorption wavelength is generated by free radicals. Varying pigments are more preferred. From the viewpoint of the visibility and resolution of the exposed part and the non-exposed part, the photosensitive composition contains a dye whose maximum absorption wavelength is changed by radicals as a dye N and a photoradical polymerization initiator. better. Moreover, it is preferable that dye N is a dye which develops color by acid, alkali, or a radical from the viewpoint of the visibility of an exposure part and a non-exposure part.

As the color development mechanism of the dye N, for example, a radical-reactive dye, an acid-reactive dye, or an alkali-reactive dye (for example, a leuco dye, etc.) , photocationic polymerization initiator (photoacid generator) or photobase generator and free radicals, acids or bases generated by photoradical polymerization initiators, photocationic polymerization initiators or photobase generators after exposure And the appearance of color.

From the viewpoint of the visibility of the exposed part and the non-exposed part, as the maximum absorption wavelength in the wavelength range of 400 to 780 nm in the color development of the dye N, a wavelength of 550 nm or more is preferable, and a wavelength of 550 to 700 nm is more preferable. 550-650 nm is still more preferable. In addition, the dye N may have one or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm for color development. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm for color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be at least 450 nm.

The maximum absorption wavelength of pigment N can be measured by measuring the transmission spectrum of a solution (liquid temperature 25° C.) containing pigment N in the wavelength range of 400 to 780 nm and detecting the intensity of light by using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric environment. Intensity is measured at an extremely small wavelength (maximum absorption wavelength).

As a coloring matter which develops or decolorizes by exposure, a colorless compound is mentioned, for example. Examples of dyes that decolorize by exposure include leuco compounds, diarylmethane-based dyes, 㗁𠯤-based dyes, Kuchi Yamaguchi-based dyes, iminonaphthoquinone-based dyes, azomethine-based dyes, and anthracene-based dyes. Quinone pigments. As the dye N, a colorless compound is preferable from the viewpoint of the visibility of the exposed portion and the non-exposed portion.

As the colorless compound, for example, a colorless compound having a triarylmethane skeleton (triarylmethane dye), a colorless compound having a helicopyran skeleton (helicopyran dye), and a colorless compound having a fluorescent yellow mother skeleton ( Fluorescent yellow parent system pigment), colorless compound with diarylmethane skeleton (diarylmethane pigment), colorless compound with rhodamine lactam skeleton (rhodamine lactamide pigment), indolyl A colorless compound with a phthalide skeleton (indolylphthalide pigment) and a colorless compound with a colorless aureamine skeleton (colorless aureamine pigment). Among them, triarylmethane-based pigments or fluorescent yellow parent system pigments are preferred, and colorless compounds (triphenylmethane-based pigments) with triphenylmethane skeletons or fluorescent yellow parent system pigments are more preferred.

The colorless compound preferably has a lactone ring, a sultone ring, or a sultone ring from the viewpoint of the visibility of the exposed portion and the non-exposed portion. Thereby, the lactone ring, sultone ring or sultone ring of the colorless compound can be reacted with the free radical generated by the photoradical polymerization initiator or the acid generated by the photocationic polymerization initiator Decolorize a colorless compound by closing its ring, or develop a color by opening its ring. As a colorless compound, a compound having a lactone ring, a sultone ring or a sultone ring and the lactone ring, a sultone ring or a sultone ring is colored by free radicals or acid ring opening is preferable , a compound that has a lactone ring and the lactone ring is opened by free radicals or acid to develop color is more preferred.

Examples of the dye N include dyes and colorless compounds. Examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal Rose bengal, metanil yellow, thymol sulfonphthalein, xylenol blue, methyl orange, p-methyl red, Congo red, benzorubin (benzopurpurine) 4B, α-naphthyl red, nile blue (nile blue) 2B, nile blue A, methyl violet, malachite green, parafuchsin, victoria pure blue )-Naphthalenesulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Industries Co., Ltd. .), oil red 5B (manufactured by Orient Chemical Industries Co., Ltd.), oil scarlet (oil scarlet) #308 (manufactured by Orient Chemical Industries Co., Ltd.), oil red OG (manufactured by Orient Chemical Industries Co., Ltd. .), oil red RR (manufactured by Orient Chemical Industries Co., Ltd.), oil green #502 (manufactured by Orient Chemical Industries Co., Ltd.), spilon red (manufactured by Orient Chemical Industries Co., Ltd.) BEH special (Hodogaya Chemical Co., Ltd. Manufactured), m-cresyl violet, cresyl red, rhodamine B, rhodamine 6G, sulforhodamine B, auretamine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino -4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone , 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylene Amino-5-pyrazolone.

Examples of colorless compounds include p,p',p"-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green Lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)amino fluorescent yellow precursor, 2-anilino -3-Methyl-6-(N-ethyl-p-toluidyl) fluorescent yellow precursor, 3,6-dimethoxy fluorescent yellow precursor, 3-(N,N-diethylamino) -5-methyl-7-(N,N-dibenzylamino) fluorescent yellow precursor, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorescent Luminous yellow precursor, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorescent yellow precursor, 3-(N,N-diethylamino)-6-methyl -7-stibamidofluorescent yellow precursor, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorescent yellow precursor, 3-(N,N-diethylamino )-6-methoxy-7-amino fluorescent yellow precursor, 3-(N,N-diethylamino)-7-(4-chloroanilino) fluorescent yellow precursor, 3-(N, N-diethylamino)-7-chlorofluorescent yellow precursor, 3-(N,N-diethylamino)-7-benzylamino fluorescent yellow precursor, 3-(N,N-di Ethylamino)-7,8-benzofluorescent yellow precursor, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorescent yellow precursor, 3-(N, N-dibutylamino)-6-methyl-7-stibamidofluorescent yellow precursor, 3-piperidinyl-6-methyl-7-anilinyl fluorescent yellow precursor, 3-pyrrolidinyl- 6-Methyl-7-anilinofluorescent yellow precursor, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl -2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-di Ethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethyl Aminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1 (3H), 9'-[9H]koukousing-3-one.

As the dye N, a dye whose maximum absorption wavelength is changed by radicals is preferable from the viewpoint of the visibility of the exposed part and the non-exposed part, the visibility of the pattern after development, and the resolution. And the color pigment is better. As the dye N, leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalenesulfonate are preferable.

Pigment N can be used alone or in combination of two or more. From the viewpoint of the visibility of the exposed portion and the non-exposed portion, and the pattern visibility and resolution after development, the content of the pigment N is preferably 0.1% by mass or more with respect to the total solid content of the photosensitive composition, and 0.1% by mass is preferable. -10.0 mass % is more preferable, 0.1-5.0 mass % is still more preferable, and 0.1-1.0 mass % is especially preferable.

The content of the dye N means the content of the dye when all the dye N contained in the total solid content of the photosensitive composition is in a colored state. Hereinafter, a method for quantifying the content of the dye N will be described by taking a dye that develops color by radicals as an example. A solution obtained by dissolving dye N (0.001 g) in methyl ethyl ketone (100 mL) and a solution obtained by dissolving dye N (0.01 g) were prepared. A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan Ltd.) was added to each of the obtained solutions, and irradiated with light having a wavelength of 365 nm, thereby generating radicals and bringing all the dyes N into a colored state. Then, under an atmospheric environment, the absorbance of each solution at a liquid temperature of 25° C. was measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve was prepared. Next, except that the total solid content (3 g) of the photosensitive composition was dissolved in methyl ethyl ketone instead of the dye N, the absorbance of the solution in which all the dye was developed was measured by the same method as above. Based on the calibration curve, the content of the dye N contained in the total solid content (3 g) of the photosensitive composition was calculated from the absorbance of the obtained solution containing the total solid content (3 g) of the photosensitive composition. The "total solid content (3 g) of the photosensitive composition" has the same meaning as that of the photosensitive composition layer 3 g.

＜Heat-crosslinkable compound＞ From the viewpoint of the strength of the cured film to be obtained and the adhesiveness of the uncured film to be obtained, the photosensitive composition may contain a heat-crosslinkable compound. The heat-crosslinkable compound which has an ethylenically unsaturated group mentioned later is handled not as a polymeric compound, but as a heat-crosslinkable compound. Examples of thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds, and blocked isocyanate compounds are preferred from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. good. The blocked isocyanate compound reacts with the hydroxyl group and the carboxyl group. Therefore, for example, when the resin and/or the polymerizable compound has at least one of the hydroxyl group and the carboxyl group, the hydrophilicity of the film formed will decrease, which will harden the photosensitive composition layer. The resulting film tends to enhance its function when used as a hardened film. "Blocked isocyanate compound" means a compound having a structure in which the isocyanate group of isocyanate is protected by a blocking agent.

The dissociation temperature of the blocked isocyanate compound is preferably from 100 to 160°C, more preferably from 130 to 150°C. As a method of measuring the dissociation temperature of the blocked isocyanate compound, for example, using a differential scanning calorimeter (for example, DSC6200, manufactured by Seiko Instruments Inc., etc.), by DSC (Differential scanning calorimetry: differential scanning calorimetry) analysis, The temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate compound was used as a measure of the degree of dissociation.

As a terminal blocking agent whose dissociation temperature is 100-160 degreeC, active methylene compounds, such as malonate diester, and an oxime compound are mentioned, for example. Examples of the malonate diester include dimethyl malonate, diethyl malonate, di-n-butyl malonate and di-2-ethylhexyl malonate. Examples of oxime compounds include compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketone oxime, and cyclohexanone oxime. . Among them, an oxime compound is preferred as a terminal blocking agent having a dissociation temperature of 100 to 160° C. from the viewpoint of storage stability.

It is preferable that the blocked isocyanate compound has an isocyanurate structure from the viewpoint of improving the brittleness of the film and improving the adhesive force with the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among them, as a blocked isocyanate compound having an isocyanurate structure, there are oxime compounds having Compounds with an oxime structure used as a blocking agent are preferred.

The blocked isocyanate compound may have a polymerizable group. As a polymeric group, the meaning is the same as the polymeric group which the said polymeric compound has, for example, and a preferable aspect is also the same.

Examples of blocked isocyanate compounds include Karenz series (registered trademarks) such as AOI-BM, MOI-BM, and MOI-BP (manufactured by SHOWA DENKO K.K.); blocked duranate series such as TPA-B80E and WT32-B75P ( registered trademark) (manufactured by Asahi Kasei Chemicals Corporation). As the blocked isocyanate compound, the following compounds are preferred.

[chemical formula 16]

The heat-crosslinkable compound can be used individually by 1 type, or may use 2 or more types. The content of the heat-crosslinkable compound is preferably 1.0 to 50.0% by mass, more preferably 5.0 to 30.0% by mass, relative to the total solid content of the photosensitive composition.

＜Pigment＞ The photosensitive composition may contain a pigment. When the photosensitive composition contains a pigment, the photosensitive composition layer corresponds to the colored resin layer. In recent years, a cover glass having a black frame-shaped light-shielding layer formed on the back peripheral portion of a transparent glass substrate or the like may be attached to a liquid crystal display window of an electronic device in order to protect the liquid crystal display window. In order to form such a light-shielding layer, a colored resin layer can be used. As a pigment, what is necessary is just to select suitably according to a desired hue, For example, black pigment, a white pigment, and color pigments other than black and white are mentioned. When forming a black pattern, a black pigment is preferable as a pigment.

(black pigment) As a black pigment, a well-known black pigment (for example, an organic pigment, an inorganic pigment, etc.) is mentioned, for example. Among these, carbon black, titanium oxide, titanium carbide, iron oxide, or graphite are preferred as the black pigment, and carbon black is more preferred, from the viewpoint of optical density. As the carbon black, a surface-modified carbon black in which at least a part of the surface is covered with a resin is preferable from the viewpoint of surface resistance.

From the viewpoint of dispersion stability, the particle diameter (number average particle diameter) of the black pigment is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm. "Particle size" refers to the diameter of a circle when the area of the pigment particle is calculated from a photographic image of the pigment particle taken with an electron microscope and a circle having the same area as the area of the pigment particle is considered. In addition, the "number average particle diameter" means the average value obtained by obtaining the said particle diameter for arbitrary 100 particles, and averaging the obtained 100 particle diameters.

Examples of white pigments include inorganic pigments and white pigments described in paragraphs [0015] and [0114] of JP-A-2005-007765. As the inorganic pigment, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide or barium sulfate are preferred, titanium oxide or zinc oxide is more preferred, titanium oxide is further preferred , rutile-type or anatase-type titanium oxide is particularly preferred, and rutile-type titanium oxide is most preferred. In addition, the surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or organic matter, or two or more of these treatments may be performed. Thereby, the catalytic activity of titanium oxide is suppressed, and heat resistance and delustering properties can be improved. From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, it is preferable to perform at least one of alumina treatment and zirconia treatment as the surface treatment on the surface of titanium oxide, and to perform alumina treatment and zirconium dioxide treatment are both better.

When the photosensitive composition layer is used as the colored resin layer, it is also preferable that the photosensitive composition contains color pigments other than black pigments and white pigments from the viewpoint of transferability. The particle size (number average particle size) of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of better dispersibility. The lower limit is preferably at least 10 nm. Examples of color pigments include Victoria Pure Blue BO (Color Index (Color Index) (hereinafter, also referred to as "C.I.") 42595), auretamine (C.I. 41000), fat black (fat black) HB (C.I. 26150 ), monolight yellow GT (C.I. Pigment Yellow 12), permanent yellow GR (C.I. Pigment Yellow 17), permanent yellow HR (C.I. Pigment Yellow 83), permanent carmine (permanent carmine) FBB (C.I. Pigment Red 146), Hestaperm Red (hostaperm red) ESB (C.I. Pigment Violet 19), Permanent Ruby (permanent ruby) FBH (C.I. Pigment Red 11), Fastel Pink (pastel pink) B Supura (C.I. Pigment Red 81), monastral fast blue (C.I. Pigment Blue 15), Monolette Fast Black B (C.I. Pigment Black 1) and Carbon, C.I. Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:4, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64, C.I. Pigment Violet 23, and C.I. Pigment Red 177 are preferred.

One kind of pigment may be used alone, or two or more kinds may be used. The content of the pigment is preferably more than 3.0% by mass and not more than 40.0% by mass relative to the total solid content of the photosensitive composition, more preferably more than 3.0% by mass and not more than 35.0% by mass, and more preferably more than 5.0% by mass and not more than 35.0% by mass. More preferably, 10.0 to 35.0% by mass is particularly preferred.

When the photosensitive composition contains pigments other than black pigments (for example, white pigments and color pigments, etc.), the content of pigments other than black pigments is preferably 30.0% by mass or less relative to the total mass of black pigments, and 1.0～ 20.0 mass % is more preferable, and 3.0-15.0 mass % is further more preferable.

When the photosensitive composition contains a black pigment, it is preferred that the black pigment (preferably carbon black) be introduced into the photosensitive composition in the form of a pigment dispersion. The dispersion liquid may be prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent (or vehicle) and dispersing with a disperser. What is necessary is just to select a pigment dispersant according to a pigment and a solvent, For example, a commercially available dispersant can be used. "Vehicle" refers to the part of the medium that disperses the pigment when preparing the pigment dispersion. The above-mentioned vehicle is liquid and contains a binder component that maintains the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

Examples of the dispersing machine include known dispersing machines such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. In addition, fine pulverization can also be carried out by mechanical grinding using frictional force. Examples of the disperser and fine pulverization include the descriptions in "Paint Dictionary" (by Kunizo Asakura, first edition, Asakura Shoten, 2000, pages 438 and 310).

＜Other additives＞ The photosensitive composition may contain other additives as needed in addition to the above components. As other additives, for example, resins other than polymer A1, radical polymerization inhibitors, antioxidants (for example, phenidone, etc.), rust inhibitors (for example, benzotriazoles and carboxybenzotriazoles, etc.) class, etc.), sensitizers, surfactants, plasticizers, heterocyclic compounds (e.g., triazoles, etc.), pyridines (e.g., isonicotinamide, etc.), and purine bases (e.g., adenine, etc.) . In addition, examples of other additives include metal oxide particles, chain transfer agents, antioxidants, dispersants, acid multiplying agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, organic or inorganic precipitation inhibitors and paragraphs [0165] to [0184] of JP-A-2014-085643, the contents of which are incorporated in this specification. Other additives may be used alone or in combination of two or more.

＜Radical polymerization inhibitor＞ Examples of radical polymerization inhibitors include thermal polymerization inhibitors described in paragraph [0018] of Japanese Patent No. 4502784, among which phenthiazine, phenanthrene, or 4-methoxyphenol are preferable. Examples of radical polymerization inhibitors include naphthylamine, copper (I) chloride, nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosoamine, from the viewpoint of not impairing the sensitivity of the photosensitive composition For this purpose, aluminum salt of nitrosophenylhydroxylamine is preferred. The content of the radical polymerization inhibitor is preferably from 0.001 to 5.0% by mass, more preferably from 0.01 to 3.0% by mass, and still more preferably from 0.02 to 2.0% by mass, relative to the total solid content of the photosensitive composition. The content of the radical polymerization inhibitor is preferably from 0.005 to 5.0% by mass, more preferably from 0.01 to 3.0% by mass, and still more preferably from 0.01 to 1.0% by mass, based on the total mass of the polymerizable compound.

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

(Carboxybenzotriazoles) Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di -2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole and N-(N,N - Di-2-ethylhexyl)aminoethylenylcarboxybenzotriazole. As a commercial item of carboxybenzotriazoles, CBT-1 (made by JOHOKU CHEMICAL CO., LTD.) is mentioned, for example.

The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably from 0.01 to 3.0% by mass, more preferably from 0.05 to 1.0% by mass, based on the total solid content of the photosensitive composition. When the said total content is 0.01 mass % or more, the storage stability of a photosensitive composition becomes more excellent. On the other hand, when the above-mentioned total content is 3.0% by mass or less, the maintenance of sensitivity and the suppression of decolorization of the dye are more excellent.

(sensitizer) As a sensitizer, a well-known sensitizer, dye, and a pigment are mentioned, for example. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone (xanthone) compounds, thioxanthone (thioxanthone) compounds, Pyridone compound, oxazole compound, benzoxazole compound, thiazole compound, benzothiazole compound, triazole compound (for example, 1,2,4-triazole, etc.), stilbene compound, trioxazole compound, thiophene compound, naphthalene Diformimide compounds, triarylamine compounds and aminoacridine compounds.

From the standpoint of improving the sensitivity to the light source and improving the hardening speed by balancing the polymerization speed and chain transfer, the content of the sensitizer is preferably 0.01 to 5.0% by mass relative to the total solid content of the photosensitive composition, and 0.05 ~1.0% by mass is more preferable.

(surfactant) Examples of the surfactant include those described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of Japanese Patent Application Laid-Open No. 2009-237362.

As the surfactant, a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant is preferable. Examples of fluorine-based surfactants 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-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94 and DS-21 (the above are DIC Corporation); Fluorad FC430, FC431, and FC171 (the above are manufactured by Sumitomo 3M Limited); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC -383, S-393 and KH-40 (manufactured by AGC Inc. above); PolyFox PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA Solutions Inc. above); Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (manufactured by Neos Corporation).

Also, as the fluorine-based surfactant, an acrylic compound having a molecular structure containing a functional group containing a fluorine atom, wherein the functional group containing a fluorine atom is partially broken when heat is applied, and the fluorine atom volatilizes is also preferable. Examples of such fluorine-based surfactants include MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016) and Nikkei Sangyo Shimbun (February 23, 2016)). Furthermore, it is also preferable to use a copolymer 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 as the fluorine-based surfactant. As the fluorine-based surfactant, a blocked polymer can also be used. As a fluorine-based surfactant, a fluorine-containing polymer compound is also preferred, and the fluorine-containing polymer compound includes a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structure unit derived from a (meth)acrylate compound having two or more (preferably It is a constituent unit of (meth)acrylate compound having 5 or more) alkoxyl groups (preferably ethoxyl groups, propoxyl groups). In addition, examples of fluorine-based surfactants include fluorine-containing polymers having ethylenically unsaturated groups in side chains, such as MEGAFACE RS-101, RS-102, RS-718K, and RS-72- K (the above are manufactured by DIC Corporation).

From the viewpoint of improving environmental suitability, fluorine-based surfactants are derived from compounds having a linear perfluoroalkyl group with 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). The surfactant of the alternative material is preferred.

Examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerin propoxylate and glycerol ethyl oxides, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol Dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF Corporation); Tetronic 304, 701, 704, 901, 904 and 150R1 (the above are manufactured by BASF Corporation); Solsperse 20000 (the above are manufactured by Lubrizol Japan Limited); NCW-101, NCW-1001 and NCW-1002 (the above are manufactured by FUJIFILM Wako Pure Chemical Corporation Manufactured); PIONIN D-6112, D-6112-W and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd. above); Olfine E1010, Surfynol 104, 400 and 440 (manufactured by Nissin Chemical Co., Ltd. .manufacture).

Examples of silicone-based surfactants include linear polymers formed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains and/or terminals.

Examples of silicone-based surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400. (The above are manufactured by Dow Corning Toray Co., Ltd.); X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002 (the above are manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.); BYK307, BYK323, and BYK330 (the above are manufactured by BYK Chemie).

The content of the surfactant is preferably from 0.01 to 3.0% by mass, more preferably from 0.01 to 1.0% by mass, and still more preferably from 0.05 to 0.8% by mass, relative to the total solid content of the photosensitive composition.

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

＜Impurities＞ The photosensitive composition may contain impurities. Examples of impurities include metal impurities or ions thereof, halide ions, residual organic solvents, residual monomers, and water.

(Metal impurities and halide ions) Examples of metal impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and their ions and halide ions. Among these, sodium ions, potassium ions, and halide ions are preferably contained at the following contents from the viewpoint of easy mixing. The metal impurities are compounds different from the above-mentioned particles (for example, metal oxide particles) that may be contained in the transfer film.

The content of metal impurities is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and still more preferably 2 mass ppm or less with respect to the total solid content of the photosensitive composition. The lower limit is preferably at least 1 mass ppb with respect to the total solid content of the photosensitive composition, more preferably at least 0.1 mass ppm.

As a method of adjusting the content of impurities, for example, a method of selecting a material with a low content of impurities as a raw material of the photosensitive composition, a method of preventing contamination of impurities when forming a photosensitive composition, and a method of washing and removing them can be mentioned. The content of impurities can be quantified by known methods such as ICP emission spectrometry, atomic absorption spectrometry, and ion chromatography, for example.

(residual monomer) The photosensitive composition may contain residual monomers derived from each structural unit of the polymer (resin) contained in the photosensitive composition. From the viewpoint of patternability and reliability, the residual monomer content is preferably at most 5,000 mass ppm, more preferably at most 2,000 mass ppm, and still more preferably at most 500 mass ppm, based on the total mass of the polymer. The lower limit is preferably at least 1 mass ppm with respect to the total mass of the polymer, more preferably at least 10 mass ppm. From the viewpoint of patternability and reliability, the residual monomer derived from each constituent unit of the polymer is preferably 3000 mass ppm or less, more preferably 600 mass ppm or less, based on the total solid content of the photosensitive composition , 100 mass ppm or less is still more preferable. The lower limit is preferably 0.1 mass ppm or more with respect to the total solid content of the photosensitive composition, more preferably 1 mass ppm or more. As a method of adjusting the content of residual monomers, for example, a method of adjusting the content of the above-mentioned impurities is mentioned. The content of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

[Photosensitive composition of the second embodiment] Hereinafter, the photosensitive composition of 2nd Embodiment is demonstrated. It is preferable that the photosensitive composition of 2nd Embodiment is a negative photosensitive composition. The photosensitive composition of 2nd Embodiment can be made into the same composition as the photosensitive composition of 1st Embodiment already described except the point which used polymer A2 instead of polymer A1, and the point which further contains compound E. Therefore, only polymer A2 and compound E will be described below.

＜Polymer A2＞ The photosensitive composition contains polymer A2. Polymer A2 is resin containing structural unit A1c which has a carboxyl group. As structural unit A1c which has a carboxyl group, the structural unit derived from the 1st monomer mentioned later is mentioned specifically,. As the polymer A2, alkali-soluble resins are preferred.

It is preferable that polymer A2 contains a structural unit derived from a monomer having an aromatic hydrocarbon group from the viewpoint of suppressing deterioration of line width and resolution when the focal position shifts during exposure. As said aromatic hydrocarbon group, the phenyl group which may have a substituent, and the aralkyl group which may have a substituent are mentioned, for example. The content of the structural unit derived from a monomer having an aromatic hydrocarbon group is preferably at least 10% by mass, more preferably at least 20% by mass, and still more preferably at least 30% by mass, based on all the structural units of the polymer A2. The upper limit is preferably 80% by mass or less, more preferably 60% by mass or less, and still more preferably 55% by mass or less with respect to all the constituent units of the polymer A2. When the photosensitive composition contains several kinds of polymers A2, it is preferable that the mass average value of the content of the structural unit derived from the monomer which has an aromatic hydrocarbon group exists in the said range.

As monomers having an aromatic hydrocarbon group, for example, monomers having an aralkyl group, styrene and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tertiary butoxystyrene , Acetyloxystyrene, 4-vinylbenzoic acid, styrene dimer and styrene trimer, etc.), monomers with aralkyl groups or styrene are preferred, and styrene is more preferred. When the monomer having an aromatic hydrocarbon group is styrene, the content of the structural units derived from styrene is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, relative to all the structural units of the polymer A2, 30-55 mass % is more preferable. When the photosensitive composition contains several kinds of polymers A2, it is preferable that the mass average value of the content of the structural unit derived from the monomer which has an aromatic hydrocarbon group exists in the said range.

Examples of the aralkyl group include a phenylalkyl group which may have a substituent (except for a benzyl group) and a benzyl group which may have a substituent, and a benzyl group which may have a substituent is preferable.

As a monomer which has a phenylalkyl group, phenyl ethyl (meth)acrylate is mentioned, for example.

Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group such as benzyl (meth)acrylate and benzyl chloride (meth)acrylate; vinylbenzyl chloride and vinylbenzyl alcohol Among vinyl monomers having a benzyl group, benzyl (meth)acrylate is preferred, and benzyl (meth)acrylate is more preferred. When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of constituent units derived from benzyl (meth)acrylate is preferably 10 to 90% by mass relative to all constituent units of polymer A2 , 20-80 mass % is more preferable, and 30-70 mass % is still more preferable.

When the polymer A2 includes a constituent unit derived from a monomer having an aromatic hydrocarbon group, as the polymer A2, a polymer obtained by polymerizing a monomer having an aromatic hydrocarbon group and at least one first monomer described later or A polymer obtained by polymerizing a monomer having an aromatic hydrocarbon group, at least one first monomer described below, and at least one second monomer described below is preferred.

When the polymer A2 does not contain a constituent unit derived from a monomer having an aromatic hydrocarbon group, it is preferable that the polymer A2 is obtained by polymerizing at least one first monomer described later, by making at least one first monomer It is more preferable that the monomer is obtained by polymerizing at least one second monomer described later.

The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid. Half ester, (meth)acrylic acid is preferred. The content of the structural unit derived from the first monomer is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 10 to 30% by mass, based on all the structural units of the polymer A2. When the above content is 5% by mass or more, excellent developability, control of edge melting properties, and the like can be achieved. When the above-mentioned content is 50% by mass or less, high resolution of the photoresist pattern, control of bead shape, and high chemical resistance of the photoresist pattern can be realized.

The second monomer is a non-acidic monomer having a polymerizable group in the molecule. The meaning of the polymerizable group is the same as that of the polymerizable group described later in the polymerizable compound, and the preferred aspects are also the same. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, Butyl ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ring (meth)acrylate (Meth)acrylates such as hexyl ester and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile, etc. Among them, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate or n-butyl (meth)acrylate are preferred, methyl (meth)acrylate or Ethyl (meth)acrylate is more preferred. The content of the structural units derived from the above-mentioned monomers is preferably 1 to 80% by mass, more preferably 1 to 60% by mass, and still more preferably 1 to 50% by mass, based on all the structural units of the polymer A2.

Polymer A2 may have any of a linear structure, a branched structure, and an alicyclic structure in a side chain. For example, by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of polymer A2 middle. The group having an alicyclic structure may be either monocyclic or polycyclic. "Side chain" refers to a group of atoms branching from the main chain. "Main chain" refers to the relatively longest bonded chain in the molecules of the polymer compound constituting the resin. Examples of monomers containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, (meth)acrylate ) tertiary butyl acrylate, isopentyl (meth) acrylate, tertiary pentyl (meth) acrylate, secondary pentyl (meth) acrylate, 2-octyl (meth) acrylate, (meth) 3-octyl acrylate and tertiary octyl (meth)acrylate. Among them, isopropyl (meth)acrylate, isobutyl (meth)acrylate or tertiary butyl methacrylate is preferred, and isopropyl methacrylate or tertiary butyl methacrylate is more preferred. As a monomer containing the group which has an alicyclic structure in a side chain, the monomer which has a monocyclic aliphatic hydrocarbon group, and the monomer which has a polycyclic aliphatic hydrocarbon group are mentioned, for example. Moreover, (meth)acrylate which has an alicyclic hydrocarbon group with 5-20 carbon atoms is mentioned. Specifically, (meth)acrylate (bicyclo[2.2.1]heptyl-2), (meth)acrylate-1-adamantyl, (meth)acrylate-2-adamantyl Esters, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyl (meth)acrylate Adamantyl ester, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate ester, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, (meth)acrylic acid 2-Ethyl-2-adamantyl ester, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-inden-5-yl (meth)acrylate, ( Octahydro-4,7-inden-1-ylmethyl methacrylate, 1-menthol (meth)acrylate, tricyclodecane (meth)acrylate, (meth)acrylate- 3-Hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl ester, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl Esters, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fecundyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate and cyclohexyl (meth)acrylate. Among them, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (meth) 2-adamantyl acrylate, fenzyl (meth)acrylate, 1-menthol (meth)acrylate or tricyclodecane (meth)acrylate are preferred, cyclohexyl (meth)acrylate (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are more preferable.

From the standpoint of more excellent effect of the present invention, it is preferable that polymer A2 has a polymerizable group, and it is more preferably composed of a constituent unit having a polymerizable group, and the constituent unit containing an ethylenically unsaturated group in a side chain is Further better. As the structural unit having a polymeric group in the polymer A2, preferably the structural unit having a polymeric group mentioned in the polymer A1 is mentioned.

The Tg of the polymer A2 is preferably from 30 to 180°C, more preferably from 40 to 150°C, and still more preferably from 50 to 120°C.

From the viewpoint of more excellent effects of the present invention, the acid value of polymer A2 is preferably 220 mgKOH/g or less, more preferably 200 mgKOH/g or less, still more preferably 190 mgKOH/g or less, and especially 170 mgKOH/g or less. Good, below 150mgKOH/g is the best. From the standpoint of more excellent effects of the present invention, the lower limit is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 80 mgKOH/g or more, and particularly preferably 90 mgKOH/g or more. Also, from the viewpoint of more excellent effect of the present invention, the acid value derived from the carboxyl group of the polymer A2 is preferably 220 mgKOH/g or less, more preferably 200 mgKOH/g or less, and still more preferably 190 mgKOH/g or less. Below 170mgKOH/g is especially preferred, and below 150mgKOH/g is the best. From the standpoint of more excellent effects of the present invention, the lower limit is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 80 mgKOH/g or more, and particularly preferably 90 mgKOH/g or more. The acid value of the above-mentioned polymer A2 and the acid value derived from the carboxyl group in the polymer A2 can be calculated by the same method as the acid value of the above-mentioned polymer A1 and the acid value derived from the carboxyl group in the polymer A1. The acid value of polymer A2 can be adjusted by the kind of the structural unit which polymer A2 has, and/or content of the structural unit containing an acid group.

When the photosensitive composition contains two or more polymers A2, the content of the polymer A2 satisfying the range of the above-mentioned acid value is preferably 10 to 100% by mass, more preferably 60 to 100% by mass, based on all the polymers A2. Preferably, 90 to 100% by mass is more preferably.

The weight average molecular weight of the polymer A2 is preferably at most 500,000, more preferably at most 100,000, still more preferably at most 50,000, and particularly preferably at most 30,000. The weight average molecular weight of the polymer A2 is preferably at least 3,000, more preferably at least 4,000, still more preferably at least 5,000, and particularly preferably at least 10,000. When the weight average molecular weight is 500,000 or less, resolution and developability can be improved. Moreover, when the weight average molecular weight is 3,000 or more, the property of the image development aggregate and the property of an unexposed film, such as the edge melting property of a transfer film, and chipping property, can be controlled. The degree of dispersion of the polymer A2 is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. It is also preferable that the polymer A2 which satisfies the ranges of the above-mentioned weight average molecular weight and/or dispersity further satisfies the above-mentioned or hereinafter-mentioned preferable requirements. When the photosensitive composition contains two or more polymers A2, the content of the polymer A2 satisfying the above range of weight average molecular weight and/or dispersity is preferably 10 to 100% by mass relative to all the polymers A2, 60 -100 mass % is more preferable, and 90-100 mass % is still more preferable.

One type of polymer A2 may be used alone, or two or more types may be used. When two or more polymers A2 are used, two polymers A2 containing constituent units derived from monomers having an aromatic hydrocarbon group are used in combination, or polymers containing constituent units derived from monomers having an aromatic hydrocarbon group are used in combination. The substance A2 and the polymer A2 which does not contain the structural unit derived from the monomer which has an aromatic hydrocarbon group are preferable. In the latter case, the content of the polymer A2 containing structural units derived from monomers having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, based on all the structural units of the polymer A2. , 80% by mass or more is further preferred, and 90% by mass or more is particularly preferred. The upper limit is preferably 100% by mass or less with respect to all the constituent units of the polymer A2.

The content of the polymer A2 is preferably 10.0 to 90.0% by mass, more preferably 20.0 to 80.0% by mass, still more preferably 30.0 to 70.0% by mass, and still more preferably 40.0 to 60.0% by mass, based on the total solid content of the photosensitive composition. Excellent. When content of polymer A2 is 90.0 mass % or less with respect to the total solid content of a photosensitive composition, developing time can be controlled. Moreover, when content of polymer A2 is 10.0 mass % or more with respect to the total solid content of a photosensitive composition, edge melting resistance can be improved.

As a synthesis method of polymer A2, the method of adding an appropriate amount of radical polymerization initiator to the solution which diluted the said monomer with a solvent, and heating and stirring is mentioned, for example. It is also possible to synthesize while adding a part of the mixture dropwise to the reaction liquid. Moreover, after completion|finish of reaction, you may further add a solvent and adjust to desired density|concentration. As a synthesis method of the polymer A2, in addition to the above, block polymerization, suspension polymerization, and emulsion polymerization are mentioned, for example.

＜Compound E＞ Compound E is a compound having an acid decomposable group X. The acid-decomposable group X is as already described. Compound E may be a low-molecular compound or a high-molecular compound (polymer). When the compound E is a low molecular weight compound, the molecular weight is preferably 3000 or less, more preferably 500-3000, and still more preferably 1000-2500.

(Compound E as a low-molecular compound) The number of acid-decomposable groups X in compound E which is a low-molecular compound is not particularly limited, for example, two or more are preferable. As an upper limit, it is 20 or less, for example.

Regarding a preferred aspect of Compound E as a low-molecular compound, it can be mentioned that a part or all of the hydroxyl groups of polyphenol compounds are selected from the group consisting of acetal, tertiary butoxycarbonyl and tertiary alkoxycarbonylmethyl A compound substituted with a group in the group group, and a tertiary ester compound in which a part or all of the carboxyl groups of the polycarboxylic acid is tertiary esterified. Moreover, the compound represented by following formula (E1) is also mentioned about a preferable aspect of the compound E which is a low molecular weight compound, for example. Formula (E1): M-(Ya)q In the formula, M represents a q-valent linking group. Ya represents an acid decomposable group X. q represents the integer of 2-20.

In formula (E1), as M, it is preferable to represent the integer of 2-10, and it is more preferable to represent the integer of 2-6.

Specific examples of M include m2-valent linking groups represented by C(R _T ) _m1 (-L _T -*) _m2 and _n2 represented by Ph(R _T ) _n1 (-L _T -*) n2 Valence linking base, etc. However, m1+m2 represents 4, m1 represents an integer of 0-2, and m2 represents an integer of 2-4. Moreover, n1+n2 represents 6, m1 represents the integer of 0-4, and n2 represents the integer of 2-6. R _T represents a hydrogen atom or a substituent. The substituent represented by R _T is not particularly limited, and represents hydroxyl, alkyl, alkoxy, acyl, acyloxy, aryl, aryloxy, aralkyl, aralkyloxy, halogen atom , nitro, carboxyl, cyano and substituted or unsubstituted amino, etc. L _T represents a single bond or a divalent linking group. As the divalent linking group represented by L _T , for example, an alkylene group (preferably having 1 to 20 carbon atoms. It may be linear or branched.), a cycloalkylene group (preferably It is a carbon number of 6 to 20), an aryl group (preferably an aromatic ring group with a ring member of 6 to 10), and a divalent linking group formed by combining a plurality of these. The methylene group in the alkylene group and the methylene group forming the ring in the cycloalkylene group can be replaced by heteroatoms such as -O-, -NR ^A - and -S-, and >C (=O) and -SO ₂ - etc. are substituted with heteroatom groups. Moreover, an alkylene group, a cycloalkylene group, and an arylylene group may have a substituent further. As a substituent, a halogen atom (preferably a fluorine atom), a hydroxyl group, etc. are mentioned, for example. Examples of R ^A include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The number of atoms of the divalent linking group represented by L _T is, for example, preferably 1 to 100, more preferably 1 to 50, and still more preferably 1 to 30.

Ph represents a benzene ring. The ring member atoms of the benzene ring have n1 R _Ts and n2 -L _T -*.

* represents a bond with the acid-decomposable group X represented by Ya.

Examples of the compound represented by the formula (E1) include compounds represented by the following formula (EX).

[chemical formula 17]

The presence of a plurality of Ya each independently represents an acid-decomposable group X. R _T1 to R _T4 each independently represent a substituent. When a plurality of R _T1 exists, each of the plurality of R _T1 may be the same or different. When there are plural R _T2s , the plural R _T2s may be the same or different. When a plurality of R _T3 exists, each of the plurality of R _T3 may be the same or different. When a plurality of R _T4 exists, each of the plurality of R _T4 may be the same or different. j1, k1, and l1 each independently represent the integer of 0-5. Moreover, m1 represents the integer of 0-3. However, the total number of j1, k1, l1, and m1 is 2 or more. It is preferable that j1, k1, and l1 are integers of 0-2, and 1 is more preferable. Moreover, it is preferable that m1 is an integer of 0-2, and 0 is more preferable. j2, k2, and l2 each independently represent the integer of 0-5. Moreover, m2 represents the integer of 0-3. L _T1 to L _T3 each independently represent an alkylene group. The alkylene group is preferably linear or branched. The number of carbon atoms in the alkylene group is preferably 1-12, more preferably 1-6.

As the compound E which is a low molecular weight compound, for example, compounds described in paragraphs [0028] to [0063] of JP-A-8-123031 can also be used.

(Compound E as a polymer compound) When the compound E is a polymer compound, it is preferable that the compound E is a polymer different from the polymer A1 already described, and contains a structural unit comprising an acid-decomposable group X (corresponding to the structure of the polymer A1 already described. Unit A1a.) and a polymer that does not contain a structural unit containing a carboxyl group (corresponding to the structural unit A1b of the polymer A1 already described) is preferred.

Specific examples of the compound E as a high molecular compound include polymers having the same configuration as the polymer A1 described above except for not including a structural unit including a carboxyl group. Moreover, also about content of each structural unit in this polymer, it is the same as content of each structural unit in polymer A1.

As an example of a preferable aspect of Compound E as a high molecular compound, there can be mentioned a constituent unit derived from structural unit A1a, a constituent unit derived from styrene, a constituent unit derived from benzyl methacrylate, and a constituent unit derived from methyl methacrylate. A polymer of constituent units. In addition, as another example of a preferable aspect of Compound E as a polymer compound, a structural unit derived from styrene or benzyl methacrylate comprising a structural unit A1a, and a structural unit derived from a compound contained in A polymer comprising a monomer having a branched structure group in the side chain or a monomer having an alicyclic structure group in the side chain. In addition, as another example of a preferable aspect of Compound E as a polymer compound, it is possible to include structural units including structural units A1a, structural units derived from styrene, or structural units derived from benzyl methacrylate and polymerizable groups. A polymer of constituent units. Moreover, as another example of the preferable aspect of the compound E which is a high molecular compound, the polymer which consists only of structural unit A1a is mentioned.

The weight average molecular weight of Compound E which is a polymer compound is preferably at most 100,000, more preferably at most 80,000, still more preferably at most 50,000, and particularly preferably at most 30,000. The weight average molecular weight of Compound E which is a polymer compound is preferably 5,000 or more, more preferably 6,000 or more, still more preferably 8,000 or more, and particularly preferably 10,000 or more.

The content of Compound E is preferably 1.0 to 50.0% by mass, more preferably 2.0 to 40.0% by mass, still more preferably 3.0 to 30.0% by mass, particularly preferably 5.0 to 20.0% by mass, based on the total solid content of the photosensitive composition. good.

[Transfer film] The invention also relates to transfer films. The transfer film of the present invention has a pseudo-support and a photosensitive composition layer formed of the above-described photosensitive composition.

The transfer film may have other layers other than the photosensitive composition layer described later. As another layer, the intermediate|middle layer mentioned later is mentioned, for example. Moreover, the transfer film may have other members (for example, a protective film etc.) mentioned later.

As an embodiment of the transfer film, for example, the following constitution (1) or (2) can be mentioned, and constitution (2) is preferable. (1) "pseudo-support/photosensitive composition layer/protective film" (2) "pseudo-support/intermediate layer/photosensitive composition layer/protective film" It is preferable that the transfer film has an intermediate layer.

From the viewpoint of suppressing generation of air bubbles in a bonding step described later, the maximum width of the ripples of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and still more preferably 60 μm or less. The lower limit is preferably at least 0 μm, more preferably at least 0.1 μm, and still more preferably at least 1 μm. The maximum width of the ripples of the transfer film is a value measured by the following procedure. The transfer film was cut into a size of 20 cm in length x 20 cm in width in a direction perpendicular to the main surface to prepare a test sample. In addition, when the transfer film has a protective film, the protective film is peeled from the transfer film. Next, the above-mentioned test sample was left still on a table with a smooth and horizontal surface so that the surface of the dummy support faced the table. After standing still, scan the surface of the test sample with a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) to obtain a three-dimensional surface image of the center of the test sample within a 10 cm square area. From the obtained three-dimensional surface image The height of the largest convexity minus the height of the lowest concave. The above-mentioned operation was performed on 10 test samples, and the arithmetic mean thereof was used as the maximum corrugation width of the transfer film.

In the photosensitive composition layer of the transfer film, when there are further composition layers (for example, a photosensitive composition layer and an intermediate layer, etc.) on the surface of the photosensitive composition layer opposite to the dummy support , The total thickness of the other composition layers is preferably 0.1 to 30%, more preferably 0.1 to 20%, of the thickness of the photosensitive composition layer.

From the viewpoint of better adhesion, the transmittance of light having a wavelength of 365 nm of the photosensitive composition layer is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more. The upper limit is preferably 99.9% or less, more preferably 99.0% or less.

An example of embodiment of the transfer film will be described. The transfer film 10 shown in FIG. 1 has a dummy support 11 , a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15 , and a protective film 19 in this order. Although the transfer film 10 shown in FIG. 1 has the intermediate layer 13 and the protective film 19, it does not need to have the intermediate layer 13 and the protective film 19. In FIG. 1 , each layer (for example, a photosensitive composition layer, an intermediate layer, etc.) that can be disposed on the dummy support 11 other than the protective film 19 is also referred to as a “composition layer”.

Hereinafter, with regard to the transfer film, each member and each component will be described in detail. In addition, the description of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

〔Pseudo-support body〕 The transfer film has a pseudo-support. The member of the pseudo support system supporting the photosensitive composition layer is finally removed by peeling treatment.

The pseudo-support may be any of a single-layer structure and a multi-layer structure. As the pseudo-support, a thin film is preferable, and a resin thin film is more preferable. Also, as a pseudo-support, a film that is flexible and does not undergo significant deformation, shrinkage or elongation under pressure or under pressure and heat is also preferred, and a film without deformation such as wrinkles and scratches is also preferred. better. Examples of films include polyethylene terephthalate films (for example, biaxially stretched polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films , polyimide film and polycarbonate film, polyethylene terephthalate film is preferred.

From the viewpoint of enabling pattern exposure through the dummy support, it is preferable that the dummy support has high transparency. Specifically, the transmittance of the pseudo-support at a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more. It is better if the upper limit is less than 100%. It is preferable that the haze of the dummy support is small from the viewpoint of the pattern formability at the time of pattern exposure through the dummy support and the transparency of the dummy support. Specifically, the haze of the pseudo-support is preferably 2% or less, more preferably 0.5% or less, and still more preferably 0.1% or less. The lower limit is preferably 0% or more.

It is preferable that the number of fine particles, foreign matter, and defects in the dummy support is small from the viewpoint of pattern formation properties during pattern exposure through the dummy support and transparency of the dummy support. Specifically, the number of particles (for example, particles with a diameter of 1 μm), foreign matter and defects in the pseudo-support is preferably 50 pieces/10mm ² or less, more preferably 10 pieces/10mm ² or less, and 3 pieces/10mm ² The following are more preferable, and less than 1 piece/10mm ² is particularly preferable. The lower limit is preferably 0 piece/10mm ² or more.

The thickness of the dummy support is preferably 5 μm or more, more preferably 10 μm or more. The upper limit is preferably 200 μm or less, more preferably 150 μm or less, more preferably 50 μm or less, particularly preferably 25 μm or less, and most preferably less than 16 μm from the viewpoint of ease of handling and versatility. The thickness of the pseudo-support was calculated as an average value of arbitrary five points measured by cross-sectional observation with SEM (Scanning Electron Microscope).

From the viewpoint of handleability, the pseudo-support may have a layer (lubricant layer) containing fine particles on one or both surfaces of the pseudo-support. The fine particles contained in the lubricant layer preferably have a diameter of 0.05 to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

From the viewpoint of improving the adhesiveness between the dummy support and the photosensitive composition layer, the surface of the dummy support that is in contact with the photosensitive composition layer may be subjected to a surface modification treatment. Examples of the surface modification treatment include treatment using UV irradiation, corona discharge, and plasma. The exposure amount in UV irradiation is preferably 10 to 2000 mJ/cm ² , more preferably 50 to 1000 mJ/cm ² . As long as the exposure amount is within the above-mentioned range, the lamp output and the illuminance are not particularly limited. Examples of light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and luminescent lamps that emit light in the 150-450 nm wavelength band. Diodes (LEDs).

Examples of pseudo-supports include biaxially stretched polyethylene terephthalate film with a thickness of 16 μm, biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, and biaxially stretched polyethylene terephthalate film with a thickness of 9 μm. Ethylene phthalate film. In addition, as the pseudo-support, for example, paragraphs [0017] to [0018] of JP-A 2014-085643, paragraphs [0019]-[0026] of JP-A 2016-027363, international publications Paragraphs [0041] to [0057] of No. 2012/081680 and paragraphs [0029] to [0040] of International Publication No. 2018/179370 are incorporated into this specification. Examples of commercially available pseudo-supports include registered trademark LUMIRROR 16KS40 and registered trademark LUMIRROR 16FB40 (the above are manufactured by TORAY INDUSTRIES, INC.); Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (the above are Toyobo Co., Ltd. manufacture).

〔Photosensitive composition layer〕 The transfer film has a photosensitive composition layer. The photosensitive composition layer is a layer formed of the above-mentioned photosensitive composition.

The thickness (film thickness) of the photosensitive composition layer is often 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, still more preferably 0.5 to 30 μm, and particularly preferably 1 to 20 μm. Thereby, the developability of a photosensitive composition layer improves and resolution can be improved.

＜Residual organic solvents＞ The photosensitive composition layer may contain residual organic solvents. Examples of residual organic solvents include benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethyl Acetamide and hexane. The content of the residual organic solvent is preferably at most 100 mass ppm with respect to the total mass of the photosensitive composition layer, more preferably at most 20 mass ppm, still more preferably at most 4 mass ppm. The lower limit is preferably at least 10 mass ppb with respect to the total mass of the photosensitive composition layer, more preferably at least 100 mass ppb. As a method of adjusting content of a residual organic solvent, the method of adjusting the drying process conditions in the manufacturing method of the transfer film mentioned later is mentioned. Moreover, content of a residual organic solvent can be quantified by a well-known method, such as a gas chromatography analysis, for example.

〔middle layer〕 The transfer film may have an intermediate layer between the dummy support and the photosensitive composition layer. Examples of the intermediate layer include a water-soluble resin layer and an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in JP-A-5-072724. As an intermediate layer, an oxygen barrier layer is preferable from the standpoint of improving the sensitivity during exposure and reducing the time load of the exposure machine, thereby improving productivity. It exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (22 1 mass % aqueous solution of sodium carbonate at ℃) the oxygen barrier layer is more preferable. Hereinafter, each component which may be contained in an intermediate|middle layer is demonstrated.

＜Water-soluble resin＞ The intermediate layer may contain a water-soluble resin. Examples of water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, polyether-based resins, gelatin, and polyamide resins. The water-soluble resin comprises polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, and polyamide At least one of the group of resins is preferred.

Examples of cellulose-based resins include water-soluble cellulose derivatives. Examples of water-soluble cellulose derivatives include hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose.

Examples of polyether-based resins include polyethylene glycol, polypropylene glycol, and their alkylene oxide adducts, and vinyl ether-based resins. Examples of polyamide resins include acrylamide resins, vinylamide resins, and allylamide resins.

Examples of water-soluble resins include (meth)acrylic acid/vinyl compound copolymers, preferably (meth)acrylic acid and allyl (meth)acrylate copolymers, and methacrylic acid and methacrylic acid copolymers. Copolymers of allyl acrylate are more preferred. When the water-soluble resin is a copolymer of (meth)acrylic acid and vinyl compound, as each composition ratio (mol% of (meth)acrylic acid/mol% of vinyl compound), 90/10 to 20/80 is relatively Good, 80/20～30/70 is better.

The weight average molecular weight of the water-soluble resin is preferably at least 5,000, more preferably at least 7,000, and still more preferably at least 10,000. The upper limit is preferably at most 200,000, more preferably at most 100,000, and further preferably at most 50,000. The degree of dispersion of the water-soluble resin is preferably 1-10, more preferably 1-5, and still more preferably 1-3.

The water-soluble resins may be used alone or in combination of two or more. From the viewpoint of further improving the oxygen barrier properties and interlayer mixing suppression ability, the content of the water-soluble resin is preferably 50.0% by mass or more, more preferably 70.0% by mass or more, and furthermore 80.0% by mass or more with respect to the total mass of the intermediate layer. Preferably, 90.0% by mass or more is particularly preferred. The upper limit is preferably 100% by mass or less, more preferably 99.9% by mass or less, still more preferably 99.8% by mass or less, and particularly preferably 99.0% by mass or less with respect to the total mass of the intermediate layer.

＜Other ingredients＞ The intermediate layer may contain other components in addition to the above-mentioned water-soluble resin.

As other components, polyols, alkylene oxide adducts of polyols, phenol derivatives, or amide compounds are preferable, and polyols, phenol derivatives, or amide compounds are more preferable. Moreover, as another component, a well-known surfactant is also mentioned, for example.

Examples of polyhydric alcohols include glycerin, diglycerin, and diethylene glycol. As the number of the hydroxyl groups which polyols have, 2-10 are preferable. Examples of the alkylene oxide adducts of polyols include compounds in which ethoxyl groups, propoxyl groups, and the like are added to the above polyols. The average addition number of alkyleneoxy groups is preferably from 1 to 100, more preferably from 2 to 50, and still more preferably from 2 to 20. As a phenol derivative, bisphenol A and bisphenol S are mentioned, for example. As an amide compound, N-methylpyrrolidone is mentioned, for example.

The intermediate layer preferably contains at least one selected from the group consisting of water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyether resins, phenol derivatives, and amide compounds.

The molecular weight of other components is preferably not more than 5,000, more preferably not more than 4,000, still more preferably not more than 3,000, particularly preferably not more than 2,000, and most preferably not more than 1,500. The lower limit is preferably 60 or more.

The other components may be used alone or in combination of two or more. The content of other components is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, and still more preferably at least 1.0% by mass, based on the total mass of the intermediate layer. The upper limit is preferably less than 30.0 mass %, more preferably 10.0 mass % or less, and still more preferably 5.0 mass % or less.

＜Impurities＞ The intermediate layer may contain impurities. As an impurity, the impurity contained in the said photosensitive composition layer is mentioned, for example.

The thickness of the intermediate layer is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the intermediate layer is within the above range, the oxygen barrier property is not lowered, and the interlayer mixing suppression ability is excellent. In addition, the intermediate layer removal time during development can be further shortened.

[other components] The transfer film may have other members in addition to the above-mentioned members. As another member, a protective film is mentioned, for example.

As a protective film, the resin film which has heat resistance and solvent resistance is mentioned, for example. Specifically, polyolefin films, such as a polypropylene film and a polyethylene film, polyester films, such as a polyethylene terephthalate film, a polycarbonate film, and a polystyrene film are mentioned. In addition, as the protective film, a resin film made of the same material as the dummy support described above can be used. Among them, as the protective film, a polyolefin film is preferable, and a polypropylene film or a polyethylene film is more preferable.

The thickness of the protective film is preferably from 1 to 100 μm, more preferably from 5 to 50 μm, still more preferably from 5 to 40 μm, and particularly preferably from 15 to 30 μm. From the viewpoint of excellent mechanical strength, the thickness of the protective film is preferably 1 μm or more, and from the viewpoint of relatively low cost, it is preferably 100 μm or less.

The number of fisheyes with a diameter of 80 μm or more included in the protective film is preferably 5 or less/m ² . The lower limit is preferably 0 piece/m ² or more. "Fish eye" means that when the material is thermally melted, kneaded, extruded, and produced by biaxial stretching and casting methods, foreign matter, undissolved matter, and oxidative deterioration of the material are taken in. Those in the film.

The number of particles with a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm ² or less, more preferably 10 particles/mm ² or less, still more preferably 5 particles/mm ² or less. The lower limit is preferably 0 piece/mm ² or more. When it is in the said range, the defect which arises by transcribe|transferring the unevenness|corrugation by the particle|grains contained in a protective film to a photosensitive composition layer or a conductive layer can be suppressed.

From the viewpoint of imparting windability, the surface of the protective film opposite to the surface in contact with the photosensitive composition layer or the contact surface has an arithmetic average roughness Ra of 0.01 μm or more, preferably 0.02 μm or more More preferably, 0.03 μm or more is still more preferable. The upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, and still more preferably 0.30 μm or less.

[Manufacturing method of transfer film] It does not specifically limit as a manufacturing method of a transfer film, A well-known method is mentioned. As a method for producing the above-mentioned transfer film 10, for example, a method including the steps of applying a composition for forming an intermediate layer on the surface of the dummy support 11 to form a coating film, and further drying the coating film to form an intermediate layer The step of layer 13; and the step of coating the photosensitive composition on the surface of the intermediate layer 13 to form a coating film, and further drying the coating film to form the photosensitive composition layer 15.

When the transfer film 10 has the protective film 19, the protective film 19 can be crimped on the composition layer 17 of the transfer film 10 manufactured by the above-mentioned manufacturing method. As a method of manufacturing the transfer film 10, a process including a dummy support 11, an intermediate layer, and a process including the step of providing the protective film 19 in contact with the surface of the composition layer 17 opposite to the dummy support 11 is provided. 13. The photosensitive composition layer 15 and the transfer film 10 of the protective film 19 are preferred. After the transfer film 10 is produced by the above-mentioned production method, the transfer film in roll form can be produced and stored by winding up the transfer film 10 . The transfer film 10 in the form of a roll can be provided as it is in the step of bonding to a substrate by a roll-to-roll system described later.

In addition, the method of manufacturing the transfer film 10 described above may be a method of forming the composition layer 17 on the protective film 19 .

<Method for forming water-soluble resin composition and intermediate layer (water-soluble resin layer)> The water-soluble resin composition preferably contains various components and a solvent that form the above-mentioned intermediate layer (water-soluble resin layer). In addition, in the water-soluble resin composition, the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the above-mentioned water-soluble resin layer. The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin. At least one selected from the group consisting of water and water-miscible organic solvents is preferred. Water or a mixture of water and water-miscible organic solvents A solvent is more preferred. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, and alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol is more preferred. One kind of solvent may be used alone, or two or more kinds may be used. The content of the solvent is preferably from 50 to 2,500 parts by mass, more preferably from 50 to 1,900 parts by mass, and still more preferably from 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

The formation method of the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer comprising the above-mentioned components, for example, known coating methods (such as slit coating, spin coating, curtain coating and inkjet coating) coating, etc.).

<Formation method of photosensitive composition and photosensitive composition layer> As a photosensitive composition, it is as above-mentioned. From the viewpoint of excellent productivity, it is preferable to use the photosensitive composition described above and form it by a coating method. As a method for producing a transfer film, specifically, a method of coating a photosensitive composition on an intermediate layer to form a coating film, and drying the coating film at a predetermined temperature to form a photosensitive composition layer is relatively good.

Examples of coating methods for the photosensitive composition include printing, spray coating, roll coating, bar coating, curtain coating, spin coating, and die coating (ie, slit coating).

As a method of drying the coating film of the photosensitive composition, heat drying and reduced-pressure drying are preferable. The drying temperature is preferably 80°C or higher, more preferably 90°C or higher. The upper limit is preferably 130°C or lower, more preferably 120°C or lower. Also, the drying time is preferably at least 20 seconds, more preferably at least 40 seconds, and still more preferably at least 60 seconds. The upper limit is preferably 600 seconds or less, more preferably 300 seconds or less.

Furthermore, a transfer film can be manufactured by bonding a protective film to a photosensitive composition layer. As a method of bonding a protective film to a photosensitive composition layer, a well-known method is mentioned, for example. As an apparatus which bonds a protective film to a photosensitive composition layer, well-known laminators, such as a vacuum laminator and an automatic cutting laminator, are mentioned, for example. The laminator is preferably equipped with any heatable roll such as a rubber roll, and is capable of pressurization and heating.

[Manufacturing method of laminated body having conductive pattern] By using the above transfer film, it is also possible to manufacture a laminate having a conductor pattern. The method of manufacturing the layered body having a conductive pattern is not particularly limited as long as it is a method of manufacturing a layered body having a conductive pattern using the transfer film described above. Among them, the method for manufacturing a laminate with a conductor pattern of the present invention is preferably the following method for manufacturing a laminate with a conductor pattern, which has: A bonding step, bonding the transfer film and the substrate in such a way that the surface of the transfer film opposite to the side of the dummy support is in contact with the conductive layer of the substrate having a conductive layer on the surface; Exposure step, pattern exposure of the photosensitive composition layer; Photoresist pattern forming step, performing development treatment on the exposed photosensitive composition layer to form a photoresist pattern; Etching step or electroplating treatment step, performing etching treatment or electroplating treatment on the conductive layer located in the area where the photoresist pattern is not arranged; and a photoresist pattern stripping step, stripping the photoresist pattern, When there is an electroplating treatment step, there is further a removal step of removing the conductive layer exposed due to the photoresist pattern stripping step and forming a conductive pattern on the substrate, wherein Between the bonding step and the exposure step or between the exposure step and the development step, there is further a dummy support peeling step for peeling off the dummy support. In addition, the method for manufacturing a laminate having a conductive pattern includes the above lamination step, the above exposure step, the above photoresist pattern formation step, the above etching step or the above plating treatment step, the above photoresist pattern stripping step, and the above removal step ( When having the above electroplating treatment step) is preferred.

In addition, in the method of manufacturing a laminate having a conductive pattern, between the photoresist pattern forming step and the photoresist pattern stripping step, acid decomposition of the acid-decomposable group X based on the diffusion of a specific photoacid generator is performed. It is preferable to further have a heating step. The heating step is not particularly limited as long as it is performed between the photoresist pattern forming step and the photoresist pattern stripping step, and it is preferably performed between the etching step or the electroplating step and the photoresist pattern stripping step.

Hereinafter, each step of the manufacturing method of the laminated body which has a conductor pattern is demonstrated.

＜Fitting procedure＞ The bonding step is as follows: For the transfer film having a pseudo-support and a photosensitive composition layer, the transfer film and The above substrates are bonded together. When the transfer film has a protective film described later, it is preferable to carry out the bonding step after peeling the protective film. It is also preferable that the transfer film further has an intermediate layer between the dummy support and the photosensitive composition layer. About the transfer film, it is as above-mentioned.

In bonding, it is preferable to press-bond the photosensitive composition layer side (the surface opposite to the dummy support side) of the transfer film in contact with the conductive layer on the substrate. As the pressure-bonding method, for example, a known transfer method and a lamination method can be mentioned. The surface of the photosensitive composition layer of the transfer film on the side opposite to the dummy support is superimposed on the substrate and applied with a roller or the like. The methods of pressing and heating are preferred. As a bonding method, the method of using a well-known laminator, such as a vacuum laminator and an automatic cutting laminator, is mentioned, for example. The lamination temperature is preferably 70-130°C.

A substrate having a conductive layer on its surface (a substrate with a conductive layer) has a substrate and a conductive layer arranged on the surface of the substrate. Substrate with conductive layer Any layer other than the above-mentioned conductive layer may be formed on the substrate as needed. That is, it is preferable that the substrate with a conductive layer has at least a substrate and a conductive layer arranged on the surface of the substrate. Examples of the substrate include resin substrates, glass substrates, ceramic substrates, and semiconductor substrates, and the substrates described in paragraph [0140] of International Publication No. 2018/155193 are preferred. As the material of the resin substrate, polyethylene terephthalate, cycloolefin polymer, or polyimide is preferable. The thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm.

As the conductive layer, at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphite layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoint of conductivity and thin line formability is better. In addition, only one conductive layer may be arranged on the substrate, or two or more layers may be arranged. When disposing two or more conductive layers, conductive layers having different materials are preferred. As a preferred aspect of the conductive layer, for example, it is described in paragraph [0141] of International Publication No. 2018/155193, and the content thereof is incorporated in this specification.

The conductive layer is preferably a metal layer. The metal layer is a layer containing metal, and the metal is not particularly limited, and known metals can be used. Examples of the main component (so-called main metal) of the metal layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. In addition, the "main component" refers to the metal with the largest content among the metals contained in the metal layer.

The method of forming the metal layer is not particularly limited, and examples thereof include known methods such as a method of applying a dispersion liquid in which fine metal particles are dispersed and firing the coating film, sputtering, and vapor deposition.

The thickness of the metal layer is not particularly limited, and is preferably greater than 50 nm, more preferably greater than 100 nm. The upper limit is preferably 2 μm or less.

One or more metal layers may be disposed on the substrate. When two or more metal layers are arranged, the two or more metal layers may be the same or different from each other, and metal layers of different materials are preferred.

The substrate having a conductive layer may be a substrate having at least one of transparent electrodes and wiring. Such a substrate can be suitably used as a substrate for a touch panel. A transparent electrode can function preferably as an electrode for touch panels. The transparent electrodes are preferably composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), and thin metal wires such as metal meshes and metal nanowires. Examples of thin metal wires include thin wires of silver, copper, and the like. Among them, silver conductive materials such as silver mesh and silver nanowires are preferred.

As a material for laying out wiring, metal is preferable. The metal used as the material of the wiring includes gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese, and alloys of two or more of these metal elements. As a material for laying out wiring, copper, molybdenum, aluminum or titanium are preferable, and copper is particularly preferable.

＜Exposure steps＞ The exposure step is a step of exposing the photosensitive composition layer, preferably a step of pattern exposure. "Pattern exposure" means exposure in a patterned form, and refers to exposure in a form in which exposed parts and unexposed parts exist. The positional relationship between the exposed part (exposed area) and the unexposed part (unexposed area) in pattern exposure can be adjusted suitably. Regarding the exposure direction, exposure may be performed from the side of the photosensitive composition layer or the side (substrate side) opposite to the side of the photosensitive composition layer. Examples of the exposure method in the exposure step include mask exposure, direct imaging exposure, and projection exposure, and mask exposure is preferred.

When the dummy support peeling step described later is carried out between the bonding step and the exposure step, as the exposure step, the side of the layered body from which the dummy support has been peeled off in the dummy support peeling step is made to be opposite to the substrate side The exposure step of performing pattern exposure by contacting one surface with a mask is preferable. In other words, the exposure of the photosensitive composition layer by bringing the exposed surface (the surface of the photosensitive layer, the surface of the intermediate layer, etc.) steps are better. In addition, as the above-mentioned exposed surface, when the transfer film is composed of two layers of a dummy support and a photosensitive composition layer, the surface of the photosensitive composition layer corresponds to this, and when the transfer film is a dummy support, an intermediate layer In the case of a three-layer constitution of the photosensitive composition layer, the surface of the intermediate layer corresponds to this. If this exposure step is adopted, a higher-definition photoresist pattern can be obtained, and a higher-definition conductor pattern can be finally obtained. In particular, it is preferable to use such an exposure step when the dummy support peeling step described later is performed between the bonding step and the exposure step.

In the exposure step of performing pattern exposure as described above, a curing reaction of components contained in the photosensitive composition layer may occur in the exposed region (region corresponding to the opening of the mask) of the photosensitive composition layer. By performing a developing step after exposure, unexposed regions of the photosensitive composition layer are removed to form a pattern.

It is also preferable to have a mask stripping step of stripping the mask used in the exposure step between the exposure step and the development treatment. As a mask peeling process, a well-known peeling process can be mentioned, for example.

As a light source for pattern exposure, any light in the wavelength range capable of curing the photosensitive composition layer (for example, light with a wavelength of 365 nm or 405 nm) can be irradiated, and the dominant wavelength is preferably 365 nm. "Dominant wavelength" means the wavelength of highest intensity.

Examples of light sources include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure amount is preferably 5 to 200 mJ/cm ² , more preferably 10 to 200 mJ/cm ² . Examples of the light source, exposure amount, and exposure method include paragraphs [0146] to [0147] of International Publication No. 2018/155193, and these contents are incorporated in this specification.

<Pseudo-support stripping step> The dummy support stripping step is performed between the bonding step and the exposure step or between the exposure step and the development step. Among them, it is preferable to have a peeling step between the bonding step and the exposing step. The peeling step is a step of peeling off the dummy support from the laminate of the transfer film and the substrate with the conductive layer. As the method of peeling off the pseudo-support, for example, known peeling methods can be mentioned. Specifically, there may be mentioned the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589.

＜Resist pattern formation process＞ The step of forming a photoresist pattern is a step of performing a development process on the exposed photosensitive composition layer to form a photoresist pattern. It is preferable to carry out the development process using a developer. By developing using the above-mentioned developing solution, the unexposed region of the photosensitive composition layer is removed, and a resist pattern having the openings of the mask as protrusions is formed.

As a developing solution, an alkaline aqueous solution containing an alkali metal salt is preferable. The alkali metal salt contained in the developer is preferably a compound that dissolves in water and exhibits basicity. Examples of alkali metal salts include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate. The developer may contain a compound that dissolves in water and exhibits basicity other than alkali metal salts. As the above compound, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide ).

As for the liquid temperature of the developer at the time of developing processing, 10-50 degreeC is preferable, 15-40 degreeC is more preferable, 20-35 degreeC is still more preferable. The pH of the developer at the time of developing is preferably 9 or higher, more preferably 10 or higher, and still more preferably 11 or higher. The upper limit is preferably 14 or less, more preferably less than 13. pH can be measured by the method based on JIS Z8802-1984 using a well-known pH meter. The measurement temperature of pH was set at 25°C.

The content of water in the developer is preferably at least 50.0% by mass and less than 100% by mass, more preferably at least 90.0% by mass and less than 100% by mass, based on the total mass of the developer. In the developer, the content of the alkali metal salt is preferably 0.01 to 20.0% by mass, more preferably 0.1 to 10.0% by mass, based on the total mass of the developer.

As an image development method, a well-known image development method is mentioned, for example. Specifically, spin-on-dip image development, shower image development, spin image development, and immersion image development are mentioned. As a developing method, the developing method described in paragraph [0195] of International Publication No. 2015/093271 is preferable.

It is also preferable to perform a rinsing process for removing the developing solution remaining on the substrate with the conductive layer after the development and before transferring to the next step. Water or the like can be used for the rinsing treatment. After the developing and/or rinsing process, a drying process may be performed to remove excess liquid from the substrate with the conductive layer.

The position and size of the photoresist pattern formed on the substrate with the conductive layer are not particularly limited, but a thin line shape is preferred. Specifically, the line width of the photoresist pattern is preferably 20 μm or less, more preferably 15 μm or less, further preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is often 1.0 μm or more.

<Post-exposure step> A step of further exposing the photoresist pattern obtained on the substrate with a conductive layer (hereinafter also referred to as "post-exposure step") may be provided between the development step and the etching step described later. The exposure amount in the post-exposure step is preferably 100 to 5000 mJ/cm ² , more preferably 200 to 3000 mJ/cm ² .

＜Etching step＞ The etching step is a step of etching the above-mentioned conductive layer in the region where the photoresist pattern is not arranged. Specifically, in an etching process, it is a process of performing an etching process on a conductive layer using the photoresist pattern obtained up to the said process as an etching resist. If the etching step is performed, the conductive layer will be removed at the opening of the photoresist pattern, and the conductive layer will have the same pattern shape as the photoresist pattern.

As a method of the etching treatment, for example, a known etching method can be mentioned. Specifically, the method described in paragraphs [0209] to [0210] of JP-A-2017-120435 and the method described in paragraphs [0048]-[0054] of JP-A-2010-152155 can be mentioned. method, wet etching immersed in etching solution, and dry etching such as plasma etching.

As the etchant used for wet etching, an acidic or alkaline etchant can be appropriately selected according to the object to be etched. Examples of the acidic etching solution include an acidic aqueous solution containing at least one acidic compound and an acidic mixed aqueous solution of an acidic compound and at least one selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate. At least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid is preferred as the acidic compound (a compound that dissolves in water and exhibits acidity) contained in the acidic aqueous solution. Examples of the alkaline etching solution include an alkaline aqueous solution containing at least one alkaline compound and an alkaline mixed aqueous solution of an alkaline compound and a salt (for example, potassium permanganate, etc.). As the basic compound contained in the alkaline aqueous solution (a compound that dissolves in water and exhibits basicity), for example, it is selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (for example, hydroxide At least one of the group of tetramethylammonium, etc.) is preferred. It is preferable that the etching solution does not dissolve the photoresist pattern. The developing solution used in the developing step can also be used as an etching solution for etching. In this case, the developing step and the etching step may be performed simultaneously.

It is also preferable to perform a rinsing process for removing the etching solution remaining on the substrate with the conductive layer after the etching process and before transferring to the next step. Water or the like can be used for the rinsing treatment. After the etching process and/or the rinsing process, a drying process may be performed to remove excess liquid from the substrate with the conductive layer.

＜Plating treatment steps＞ The electroplating treatment step is the following step; an electroplating layer is formed by electroplating treatment on the conductive layer (conductive layer exposed on the surface due to the development step) located in the area where the photoresist pattern is not arranged. As a method of electroplating treatment, an electrolytic plating method and an electroless plating method are mentioned, for example, The electrolytic plating method is preferable from a viewpoint of productivity. If the electroplating step is performed, an electroplating layer having the same pattern shape as the region (opening of the photoresist pattern) on which the photoresist pattern is not arranged on the substrate with the conductive layer can be obtained.

As a metal contained in a plating layer, a well-known metal is mentioned, for example. Specifically, metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, and alloys of these metals are mentioned. Among these, it is preferable that the electroplating layer contains copper or its alloy from the viewpoint that the electroconductivity of a conductive pattern is more excellent. Moreover, it is preferable that an electroplating layer contains copper as a main component from a viewpoint of the electroconductivity of a conductive pattern being more excellent.

The thickness of the plating layer is preferably at least 0.1 μm, more preferably 1 μm. The upper limit is preferably 20 μm or less.

＜Protective layer formation process＞ It is also preferable to have a protective layer forming step between the plating treatment step and the resist pattern stripping step described later. The protective layer forming step is a step of forming a protective layer on the plating layer. As a material of the protective layer, a material having resistance to the stripping liquid and/or etching liquid in the resist pattern stripping step and/or removing step is preferable. Examples thereof include metals such as nickel, chromium, tin, zinc, magnesium, gold, and silver, alloys thereof, and resins, with nickel or chromium being preferred.

As a method of forming the protective layer, for example, an electroless plating method, an electroplating method, etc. are mentioned, and an electroplating method is preferable.

The thickness of the protective layer is preferably at least 0.3 μm, more preferably at least 0.5 μm. The upper limit is preferably 3.0 μm or less, more preferably 2.0 μm or less.

<Exposure Step After Etching Step or Plating Step> After the etching step or plating step and before carrying out the peeling step described later (in other words, between the etching step or plating step and the peeling step described later), there may be A step of exposing the photoresist pattern obtained on the substrate of the conductive layer (preferably a step of performing full-scale exposure). The exposure wavelength after the etching step or the plating step is the photosensitive wavelength of the specific photoacid generator contained in the photoresist pattern and is a wavelength capable of cleaving the specific acid generator to generate acid (for example, wavelength 254nm, 313nm, 365nm) is better. Examples of light sources include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure amount in the above exposure step is preferably 100-5000 mJ/cm ² , more preferably 200-3000 mJ/cm ² . In particular, in photoresist pattern formation, when the hardening reaction of the polymerizable compound in the photosensitive composition layer and the photosensitive cleavage/acid generation of a specific acid generator do not proceed under light of approximately the same exposure wavelength (in other words , when the photosensitive cleavage/acid generation of the specific acid generator does not occur under the light of the exposure wavelength for the hardening reaction of the polymerizable compound in the photosensitive composition layer), it is preferable to have this exposure step.

<Heating step after etching step or plating step> After the etching step or the electroplating step and before the stripping step described later (in other words, between the etching step or the electroplating step and the stripping step described later), it is possible to carry out the photoresist pattern obtained on the substrate with the conductive layer. Step of heat treatment (baking treatment). In addition, when the exposure step after the above-mentioned etching step or plating step is performed, it is preferably performed after the above-mentioned exposure step. The baking temperature is preferably 60 to 200°C, more preferably 80 to 180°C, and still more preferably 90 to 150°C. The baking time is preferably 20 seconds to 10 minutes, more preferably 30 seconds to 5 minutes, and still more preferably 30 seconds to 2 minutes. By performing this heating step, the generated acid generated by the specific acid generator diffuses to generate an acid group based on the decomposition of the acid decomposable group X. As a result, the resist pattern is easily peeled from the substrate in the subsequent resist pattern peeling step.

<Resist Pattern Stripping Step> The photoresist pattern stripping step is a step of removing the photoresist pattern remaining after the etching step. As a method of removing the remaining photoresist pattern, for example, a method of removing by chemical treatment is mentioned, and a method of removing using a stripper is preferable. As a method of removing the remaining photoresist pattern, for example, a method of removing by a known method such as a spray method, a shower method, and a spin-on-dip method using a stripping liquid is mentioned.

As a stripping liquid, for example, a stripping liquid obtained by dissolving a basic compound in at least one selected from the group consisting of water, dimethylsulfoxide, and N-methylpyrrolidone is mentioned. Examples of basic compounds (compounds that dissolve in water and exhibit basicity) include basic inorganic compounds such as sodium hydroxide and potassium hydroxide, primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary amine compounds. Basic organic compounds such as ammonium salt compounds.

As a preferable aspect of the removal method, a method of immersing a substrate having a pattern to be removed in a stripping liquid having a liquid temperature of 50 to 80° C. under stirring for 1 to 30 minutes is mentioned. It is also preferable that the stripping solution does not dissolve the conductive layer.

The liquid temperature of the stripping liquid at the time of performing the stripping treatment is preferably 30 to 80°C, more preferably 50 to 80°C. The pH of the stripping liquid at the time of the stripping treatment is preferably 11 or higher, more preferably 12 or higher, and still more preferably 13 or higher. The upper limit is preferably 14 or less, more preferably 13.8 or less. pH can be measured by the method based on JIS Z8802-1984 using a well-known pH meter. The measurement temperature of pH was set at 25°C. It is preferable that the liquid temperature °C of the stripping solution when performing the stripping treatment is higher than the liquid temperature °C of the developing solution when performing the developing treatment. Specifically, the value obtained by subtracting the liquid temperature °C of the above-mentioned developer from the liquid temperature °C of the above-mentioned stripping liquid (the liquid temperature °C of the above-mentioned stripping liquid-the liquid temperature °C of the above-mentioned developer) is preferably 10 °C or more, and 20 °C The above is better. The upper limit is preferably 100°C or lower, more preferably 80°C or lower. It is preferable that the pH of the stripping solution when performing the stripping treatment is higher than the pH of the developing solution when performing the developing treatment. Specifically, the value obtained by subtracting the pH of the developer from the pH of the stripping solution (pH of the stripping solution−pH of the developer) is preferably 1 or more, more preferably 1.5 or more. The upper limit is preferably 5 or less, more preferably 4 or less.

After stripping the photoresist pattern with the stripping solution, it is also preferable to perform a rinse process for removing the stripping solution remaining on the substrate. Water or the like can be used for the rinsing treatment. After the stripping and/or rinsing process of the photoresist pattern by the stripping liquid, a drying process for removing excess liquid from the substrate may be performed.

＜Removal procedure＞ When the method of manufacturing a laminate having a conductor pattern has a plating treatment step, the method of manufacturing a laminate having a conductor pattern has a removal step. The removing step is a step of removing the conductive layer exposed by the stripping step of the photoresist pattern to obtain a conductive pattern on the substrate. In addition, in the removal step, etching treatment of the conductive layer located in the non-pattern formation region (in other words, the region not protected by the plating layer) is performed using the plating layer formed by the plating step as an etching resist.

The method of removing a part of the conductive layer is not particularly limited, and it is preferable to use a known etching solution. Examples of known etching solutions include ferric chloride solution, copper chloride solution, ammonia-alkali solution, sulfuric acid-hydrogen peroxide mixed solution, phosphoric acid-hydrogen peroxide mixed solution, and the like.

When the removal step is performed, the conductive layer exposed on the surface is removed from the substrate, and the plated layer (conductor pattern) having a pattern shape remains, so that a laminate having a conductor pattern can be obtained.

The line width of the formed conductor pattern is preferably 8 μm or less, more preferably 6 μm or less. The lower limit is often 1 μm or more.

＜Other steps＞ The method of manufacturing a laminate having a conductor pattern may include other steps in addition to the above-mentioned steps. As other steps, for example, the step of reducing the reflectance of visible light described in paragraph [0172] of International Publication No. 2019/022089 and the step of reducing the reflectance of visible light described in paragraph [0172] of International Publication No. The step of forming a new conductive layer on the surface of the film.

(Steps to reduce reflectance of visible light) The manufacturing method of the laminated body which has a conductor pattern may have the process of performing the process which reduces the visible light reflectance of a part or all of the conductor pattern which a laminated body has. As a treatment for lowering the reflectance of visible light, for example, an oxidation treatment is mentioned. When the laminate has a conductor pattern made of copper, the visible light reflectance of the laminate can be reduced by oxidizing the copper to become copper oxide and blackening the conductor pattern. As a treatment for reducing the reflectance of visible light, for example, paragraphs [0017] to [0025] of JP-A-2014-150118 and paragraphs [0041], [0042], and [0048] of JP-A-2013-206315 can be cited. ] and [0058] paragraphs, which are incorporated into this specification.

(The step of forming an insulating film, the step of forming a new conductive layer on the surface of the insulating film) The method of manufacturing a laminate having a conductive pattern may include a step of forming an insulating film on the surface of the laminate having a conductive pattern and a step of forming a new conductive layer (conductive pattern, etc.) on the surface of the insulating film. Through the above steps, the first electrode pattern and the insulated second electrode pattern can be formed. As a step of forming an insulating film, for example, a method of forming a known permanent film can be mentioned. In addition, an insulating film having a desired pattern can also be formed by photolithography using a photosensitive composition having insulating properties. As a step of forming a new conductive layer on the surface of the insulating film, for example, a photosensitive composition having conductivity can be used to form a new conductive layer of a desired pattern by photolithography.

In the method of manufacturing a laminate with a conductor pattern, a substrate having a plurality of conductive layers (conductive layers, etc.) is used on both surfaces of the laminate, and a conductor pattern is formed sequentially or simultaneously using the conductive layers formed on both surfaces of the substrate Also better. With the above configuration, it is possible to form circuit wiring for a touch panel in which the first conductive pattern is formed on one substrate surface and the second conductive pattern is formed on the other substrate surface. Moreover, it is also preferable to form the circuit wiring for touch panels of the said structure from both surfaces of a board|substrate in a roll-to-roll system.

[Applications of laminates having conductor patterns] The laminated body having a conductor pattern manufactured by the above-mentioned manufacturing method is preferably used for a semiconductor package, a printed circuit board, and a process film of an interposer rewiring layer, for example. As a device provided with a layered body having a conductive pattern manufactured by the above-mentioned manufacturing method, for example, an input device is mentioned, and a touch panel is preferable, and a capacitive type touch panel is more preferable. In addition, the input device described above can be applied to display devices such as organic EL display devices and liquid crystal display devices. [Example]

Hereinafter, the present invention will be described in further detail based on examples. Materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed unless departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the Examples shown below.

[Synthesis of Polymer] [Synthesis of Polymer A1-1] 9.7 g of propylene glycol monomethyl ether and 9.7 g of propylene glycol monomethyl ether acetate were put into a flask, and it heated to 90 degreeC under nitrogen stream. To this liquid, 26.9 g of styrene, 6.7 g of methyl methacrylate, 11.9 g of methacrylic acid, 6.2 g of tertiary butyl methacrylate, and polymerization initiator V-601 (FUJIFILM A solution prepared by dissolving 1.7 g of propylene glycol monomethyl ether and 5 g of propylene glycol monomethyl ether acetate and 1.7 g of polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) dissolved in propylene glycol A solution of 9.7 g of monomethyl ether and 9.7 g of propylene glycol monomethyl ether acetate. After the dropwise addition was completed, 0.6 g of V-601 was added three times every hour. Thereafter, it was further reacted for 3 hours. Next, the obtained reaction liquid was diluted with propylene glycol monomethyl ether acetate to obtain a solution of polymer A1-1 having a solid content concentration of 30%. The weight average molecular weight in terms of standard polystyrene in GPC was 23,000, the degree of dispersion was 2.3, and the acid value of the polymer was 150 mgKOH/g. The amount of residual monomers measured by gas chromatography did not reach 0.1% by mass with respect to the polymer solid content in any of the monomers.

[Synthesis of polymers A1-2 to A1-5, A1-8, A1-9, A2-1 and A2-2] Polymers A1-2 to A1-5, A1-8, A1-9, A2-1, and A2-2 were synthesized by the same method as that of polymer A1-1. The amount of residual monomers measured by gas chromatography did not reach 0.1% by mass with respect to the polymer solid content in any of the monomers. In addition, polymers A1-2 to A1-5, A1-8, A1-9, A2-1, and A2-2 were also obtained as a polymer solution having a solid content concentration of 30%.

[Synthesis of Polymer A1-6] 38.6 g of propylene glycol monomethyl ether was put into the flask, and it heated to 90 degreeC under nitrogen flow. To this liquid, 53.8 g of styrene, 6.1 g of tert-butyl methacrylate, 38.0 g of methacrylic acid, and 9.2 g of polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) were added dropwise over 3 hours. A solution obtained by dissolving 29.8 g of propylene glycol monomethyl ether. After the dropwise addition was completed, 0.8 g of V-601 was added three times every hour. Thereafter, it was further reacted for 3 hours. Thereafter, it was diluted with 54.5 g of propylene glycol monomethyl ether acetate and 79.0 g of propylene glycol monomethyl ether. Under air flow, the temperature of the reaction liquid was raised to 100° C., and 0.59 g of tetraethylammonium bromide and 0.11 g of p-methoxyphenol were added thereto. 24.4 g of glycidyl methacrylate (BLEMMER G manufactured by NOF CORPORATION) was added dropwise thereto over 20 minutes. It was made to react at 100 degreeC for 7 hours, after that, it diluted with propylene glycol monomethyl ether acetate, and obtained the solution of polymer A1-6 with a solid content concentration of 30%. The amount of residual monomers measured by gas chromatography did not reach 0.1% by mass with respect to the polymer solid content in any of the monomers.

[Synthesis of Polymer A1-7 and Polymer A2-3] Polymer A1-7 and polymer A2-3 were synthesized by the same method as polymer A1-6. The amount of residual monomers measured by gas chromatography did not reach 0.1% by mass with respect to the polymer solid content in any of the monomers. In addition, polymer A1-7 and polymer A2-3 were also obtained as a polymer solution having a solid content concentration of 30%.

[chemical formula 18]

[chemical formula 19]

The weight average molecular weight, degree of dispersion, and acid value of each polymer are shown below. The acid value 1 represents the acid value (mgKOH/g) of the polymer in the state before the acid-decomposable group X is acid-decomposed by the action of an acid, and represents a value measured by the method already described. Acid value 2 represents the acid value (mgKOH/g) derived from the acid group generated from the above-mentioned acid-decomposable group X when the acid-decomposable group X is completely decomposed by the action of acid, and represents the value measured by the method described .

[Table 1] polymer Weight average molecular weight Dispersion Acid value1 (mgKOH/g) Acid value 2 (mgKOH/g) (Acid value derived from the acid group generated by the decomposition of the acid decomposable group X) Total value of acid value 1 and acid value 2 (mgKOH/g) A1-1 23000 2.3 150 47 197 A1-2 27000 2.8 130 97 227 A1-3 40000 2.5 98 126 224 A1-4 46000 2.6 137 45 182 A1-5 12000 2.1 150 64 214 A1-6 24000 2.8 101 20 121 A1-7 24000 2.8 124 98 222 A1-8 23000 2.3 163 66 229 A1-9 23000 2.3 163 75 262 A2-1 22000 2.1 150 - - A2-2 22000 2.1 190 - - A2-3 18000 2.6 124 - -

[Photosensitive Compositions of Examples and Comparative Examples] [Preparation of photosensitive composition] The photosensitive composition layer which the transfer film has was formed using the photosensitive composition. The components used in the preparation of the photosensitive composition are as follows, and the respective components shown below were mixed in the formulation shown in Table 2 shown in the following paragraph to obtain the respective photosensitive compositions used in Examples or Comparative Examples.

[Components of photosensitive composition] Various components used for preparation of the photosensitive composition are shown below.

＜Polymer A1/A2＞ The polymer synthesized in the synthesis example column of the above paragraph was used. In addition, when blending, it is added to the composition in the form of a polymer solution.

＜Photoacid generator D＞ The photoacid generator D used is shown below.

[chemical formula 20]

＜Compound E＞ Compound E used is shown below. E-1: Poly(tertiary butyl methacrylate) E-2: The following compound (synthesized by the method described in JP-A-8-123031.)

[chemical formula 21]

＜Polymerizable compound B＞ The polymerizable compound B used is shown below. SR454: Ethoxylated (3) trimethylolpropane trimethacrylate, manufactured by TOMOE Engineering Co., Ltd. ・BPE-500: Ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. ・BPE-100: Ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. ・M-270: ARONIX M-270, polypropylene glycol diacrylate (n≈12), manufactured by TOAGOSEI CO.,LTD. 4G: NK Ester 4G, polyethylene glycol #200 dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

＜Photopolymerization initiator C＞ The polymerizable compound C used is shown below. ·2-(o-chlorophenyl)-4,5-diphenylimidazole dimer

＜Other blends＞ Other blends used are shown below. (sensitizer) 4,4′-bis(diethylamino)benzophenone

(polymerization inhibitor) · Phenothiophene 𠯤

(Antioxidants) ·Phenidone

(Reagent) · Colorless crystal violet: manufactured by Tokyo Chemical Industry Co., Ltd.

(Rust inhibitor) ・CBT-1: carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO.,LTD.

(surfactant) ・F552: MEGAFACE F-552, manufactured by DIC Corporation

(solvent) MMPGAc: 1-methoxy-2-propyl acetate MEK: methyl ethyl ketone

[Production and Evaluation of Transfer Film-1] 〔Composition for intermediate layer formation〕 The intermediate layer which the transfer film has was formed using the composition for intermediate layer formation. The components used in the preparation of the composition for forming an intermediate layer are as follows, and each component for forming an intermediate layer used in an example or a comparative example was obtained by mixing the components shown below in the formulation shown in Table 2 in the latter paragraph. Composition.

[Components of the intermediate layer forming composition] ＜Resin＞ ・PVA: Polyvinyl alcohol, product name "KURARAY POVAL PVA-205", manufactured by Kuraray Co., Ltd. ・PVP: Polyvinylpyrrolidone, product name "Polyvinylpyrrolidone K-30", manufactured by NIPPON SHOKUBAI CO.,LTD. ・HPMC: hydroxypropyl methylcellulose, product name "METOLOSE 60SH-03", manufactured by Shin-Etsu Chemical Co., Ltd.

＜Surfactant＞ ・F444: MEGAFACE F444, fluorine-based surfactant, manufactured by DIC Corporation

<Solvent> ·water · Methanol

〔Production and evaluation of transfer film〕 Using the photosensitive composition and the composition for intermediate layer formation mentioned above, the transfer film was produced according to the following procedure according to the structure shown in Table 2.

＜Preparation of transfer film＞ Each transfer film composed of a dummy support, an intermediate layer and a photosensitive composition layer was produced. details as follows. First, an intermediate layer is formed by applying a bar coater on a dummy support (polyethylene terephthalate film with a thickness of 16 μm (LUMIRROR 16KS40, manufactured by TORAY INDUSTRIES, INC.)) so that the thickness after drying becomes 1.0 μm. Using the composition, an intermediate layer was formed at 90° C. using an oven. Furthermore, a photosensitive composition was coated on the intermediate layer with a bar coater so that the thickness after drying became 3.0 μm, and dried at 80° C. using an oven to form a photosensitive composition layer (negative photosensitive composition layer). On the obtained photosensitive composition layer, polyethylene terephthalate (16KS40, manufactured by TORAY INDUSTRIES, INC.) with a thickness of 16 μm was crimped as a protective film, and the transfer film used in each example or comparative example was produced. .

＜Test procedures (laminate production, 1st pattern formation) and various evaluations＞ A PET substrate with a copper layer in which a copper layer with a thickness of 500 nm was formed on a PET film (polyethylene terephthalate film) with a thickness of 188 μm by sputtering was used. Cut the produced transfer film into 50cm squares, peel off the protective film, and make the photosensitive composition layer contact with the copper layer on the surface of the PET substrate, at a roller temperature of 90°C, a line pressure of 0.8MPa, and a line speed of 3.0m/ The laminated body was obtained by laminating on a PET substrate with a copper layer under lamination conditions of min. At this point, the laminate has a configuration of "PET film-copper layer-photosensitive composition layer-intermediate layer-dummy support". Let the present be the stage of producing laminates. For bonding, the dummy support is peeled off from the obtained laminate to expose the intermediate layer on the surface of the laminate. The ratio of line (μm)/space (μm) is 1/1 and a photomask having a line width of 1 to 10 μm in steps of 1 μm is brought into close contact with the intermediate layer exposed on the surface of the laminate. Light was irradiated using an ultra-high pressure mercury lamp exposure machine (main wavelength: 365 nm). The exposure amount was set as the exposure amount for reproducing a 5 μm line-and-space shape in the resist pattern obtained after development. Then, image development was performed using 28 degreeC 1.0% sodium carbonate aqueous solution (pH=11.4) as a developing solution. Specifically, after performing shower processing for 30 seconds during image development and performing air knife (Air Knife) processing to shake off the developing solution, shower processing was performed with pure water for 30 seconds and further air knife processing was performed. Thereby, a laminate having a resist pattern in a line and space shape with line width:space width=1:1 was obtained. Let the up to now be the first pattern formation stage. At this point, the laminate has a configuration of "PET film-copper layer-photoresist pattern".

(Evaluation of resist resolution (minimum resolution line width) and resist pattern shape) The smallest line width that can be formed without causing pattern collapse or the like is set as the minimum analysis line width. Also, the cross-sectional shape of the resist pattern was observed with a scanning electron microscope (SEM), and the presence or absence of curling at the minimum analytical line width was evaluated. A: Pattern shape without curling B: Slightly curled C: curled shape The results are shown in Table 2.

(Evaluation of Conductor Pattern Formation and Resist Pattern Removal by Electroplating and Conductor Pattern Formation (Copper Pattern) Shape) The above-mentioned laminate (a substrate with a resist pattern (with The layered body of the photoresist pattern)) was placed in a copper sulfate plating solution (copper sulfate 75g/L, sulfuric acid 190g/L, chloride ion 50 mass ppm, manufactured by Meltex Inc., "Copper Glyme PCM", 5mL/L), in Under the condition of 1A/dm ² , the copper electroplating treatment was carried out. After washing with water and drying the said laminated body after copper electroplating process, it heated for 2 minutes in the oven of 120 degreeC. In addition, in the evaluation of compositions containing D1-1, D2-1, D4-1, D5-1, and D6-1 as photoacid generators, a high-pressure mercury lamp ( Dominant wavelengths 254nm, 313nm) were fully exposed at an exposure amount of 50mJ/cm ² . These photoacid generators do not have absorption at 365 nm, and therefore do not generate acid in the first patterning stage, but generate acid in the overall exposure. The photoresist pattern was peeled off by immersing in 50 degreeC 1 mass % potassium hydroxide aqueous solution (pH=13.5). The peeling was performed while changing the peeling time, and the time for the resist to be peeled in a 5 μm line-and-space pattern was evaluated as follows. The shorter the time, the better the detachability. The results are shown in Table 2. A: Less than 30 seconds B: More than 30 seconds and less than 60 seconds C: More than 60 seconds and less than 120 seconds D: More than 120 seconds

Then, the copper layer (seed layer) which the laminated body had was removed with the aqueous solution containing 0.1 mass % of sulfuric acid and 0.1 mass % of hydrogen peroxide, and the conductor pattern (copper pattern) was obtained. The cross-sectional shape of the conductor pattern was observed with a scanning electron microscope (SEM), and the presence or absence of undercut at the bottom of the conductor pattern in the 5 μm pattern was evaluated. The results are shown in Table 2. A: Pattern shape without undercut B: Slightly undercut shape C: undercut shape

(Conductor Pattern Formation by Etching and Conductor Pattern Linearity (LWR) Evaluation) The same procedure was carried out up to the first pattern formation stage to obtain a substrate on which a resist pattern was formed (a laminate having a resist pattern). The laminated body with the photoresist pattern above was etched with a copper etchant (Cu-02: manufactured by Kanto Chemical Co., Inc.) at 23°C for 30 seconds, heated in an oven at 120°C for 2 minutes, and then monoethanolamine was used to An aqueous solution-based stripping solution (pH=13.1) was used to strip the photoresist pattern at 40°C to obtain a substrate on which copper wiring was patterned (a laminate with a conductor pattern). In addition, in the evaluation of compositions containing D1-1, D2-1, D4-1, D5-1, and D6-1 as photoacid generators, a high-pressure mercury lamp ( Dominant wavelengths 254nm, 313nm) were fully exposed at an exposure amount of 50mJ/cm ² . These photoacid generators do not have absorption at 365 nm, and therefore do not generate acid in the first patterning stage, but generate acid in the overall exposure. The measurement was performed at 100 locations about the line widths at locations randomly selected from the 5 μm line-and-space copper wiring pattern. The standard deviation (unit: nm) of the obtained line width was obtained, and the value of the standard deviation was defined as LWR (Line Width Roughness: line width roughness). The obtained LWR values were classified according to the following classification, and the linearity of the conductor pattern was evaluated. The smaller the LWR is, the smaller the variation in the line width is, which is preferable. The results are shown in Table 2. A: LWR is less than 150nm B: LWR is more than 150nm and less than 200nm C: LWR is more than 200nm and less than 300nm D: LWR is more than 300nm

＜Evaluation over time＞ The produced transfer film was allowed to pass for 10 days under the conditions of temperature 50° C./humidity 50%. Next, various evaluation tests (resist resolution (minimum resolution line width) and resist Evaluation of pattern shape; conductor pattern formation based on electroplating and photoresist pattern peelability and conductor pattern shape evaluation; conductor pattern formation based on etching and conductor pattern linearity (LWR) evaluation). The results are shown in Table 2.

Table 2 is shown below.

[Table 2] Table 2 Composition (blending amount: parts by mass) Example 1 2 3 4 5 6 7 8 9 photosensitive composition Polymer A1/A2 (30% by mass solution) A1-1 25.2 25.2 25.2 25.2 25.2 25.2 25.2 A1-2 A1-3 A1-4 A1-5 A1-6 A1-7 A1-8 A1-9 A2-1 A2-2 23.2 A2-3 23.2 photoacid generator D D1-1 0.2 D2-1 0.2 D3-1 0.2 0.2 0.2 D4-1 0.2 D5-1 0.2 D6-1 0.2 D7-1 0.2 DX (for comparison) Compound E E-1 2 E-2 2 polymeric compound B SR454 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 BPE500 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 BPE100 M270 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 4G Photopolymerization initiator C 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer 1 1 1 1 1 1 1 1 1 Sensitizer 4,4'-Bis(diethylamino)benzophenone 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 polymerization inhibitor phenothiophene 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 Antioxidants Phenidone 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 pigment colorless crystal violet 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 Rust inhibitor CBT-1 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Surfactant F552 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 solvent MMPGAc 37.3 37.3 37.3 37.3 37.3 37.3 37.3 37.3 37.3 MEK 30 30 30 30 30 30 30 30 30 Composition for intermediate layer formation resin PVA 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 pvp 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 HPMC 1 1 1 1 1 1 1 1 1 Surfactant F444 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 solvent Methanol 630 630 630 630 630 630 630 630 630 water 270 270 270 270 270 270 270 270 270 Minimum analytical line width (μm) 1 2 1 2 2 2 2 1 1 Minimum analytical line width (μm) after time 1 2 1 2 2 2 2 1 1 Photoresist pattern shape A A A A A A A A A Photoresist pattern shape after time A A A A A A A A A Stripping A A A A A A A B B Conductor pattern shape A A A A A A A A A Conductor pattern shape after time A A A A A A A A A Conductor pattern LWR (nm) A A A A A A A A A Conductor pattern LWR (nm) after time A A A A A A A A A

[table 3] Table 2 (continued) Composition (blending amount: parts by mass) Example comparative example 10 11 12 13 14 15 16 17 18 19 1 2 photosensitive composition Polymer A1/A2 (30% by mass solution) A1-1 25.2 25.2 25.2 A1-2 25.2 A1-3 25.2 A1-4 25.2 A1-5 25.2 A1-6 25.2 A1-7 25.2 A1-8 25.2 A1-9 25.2 A2-1 25.2 A2-2 A2-3 photoacid generator D D1-1 0.2 0.2 D2-1 D3-1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 D4-1 D5-1 D6-1 D7-1 DX (for comparison) 0.2 Compound E E-1 E-2 polymeric compound B SR454 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 BPE500 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 BPE100 2.8 2.8 M270 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 4G 2.8 Photopolymerization initiator C 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer 1 1 1 1 1 1 1 1 1 1 1 1 Sensitizer 4,4'-Bis(diethylamino)benzophenone 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 polymerization inhibitor phenothiophene 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 Antioxidants Phenidone 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 pigment colorless crystal violet 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 Rust inhibitor CBT-1 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Surfactant F552 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 solvent MMPGAc 37.3 37.3 37.3 37.3 37.3 37.3 37.3 37.3 37.3 37.3 37.3 37.3 MEK 30 30 30 30 30 30 30 30 30 30 30 30 Composition for intermediate layer formation resin PVA 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 pvp 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 HPMC 1 1 1 1 1 1 1 1 1 1 1 1 Surfactant F444 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 solvent Methanol 630 630 630 630 630 630 630 630 630 630 630 630 water 270 270 270 270 270 270 270 270 270 270 270 270 Minimum analytical line width (μm) 1 1 1 1 1 1 2 2 1 1 2 2 Minimum analytical line width (μm) after time 1 1 1 1 1 1 2 2 1 1 3 2 Photoresist pattern shape A A A A A A B B A A B B Photoresist pattern shape after time A A A A A A B B A A C B Stripping A A A A A A A A A A B D. Conductor pattern shape A A A A A A A B A A C B Conductor pattern shape after time A A A A A A A B A A C B Conductor pattern LWR (nm) A A A A A A A B A A C B Conductor pattern LWR (nm) after time A A A A A A A B A A D. B

From the results in Table 2, it was confirmed that according to the photosensitive composition of the present invention, a photoresist pattern having excellent releasability and excellent formability can be formed even after storage for a predetermined period of time. Also, from the comparison of the Examples (for example, the comparison of Examples 1 to 7), it has been confirmed that when the photoacid generator D is a columium salt or an oxime sulfonate, the minimum analytical line width before and after the passage of time changes. smaller. Also, from the comparison of the examples (for example, the comparison of Examples 4, 10 to 17 and Examples 8 and 9), it was confirmed that the photosensitive composition of the first embodiment was more effective than the photosensitive composition of the second embodiment. The peelability of the material is more excellent. Also, from the comparison of Examples (for example, the comparison of Examples 4, 10-15 and Examples 16 and 17), it is confirmed that when the acid value derived from the carboxyl group in Polymer A1 is 150 mgKOH/g or less (preferably When the acid value derived from the carboxyl group is 150 mgKOH/g or less and the acid value derived from the carboxyl group and the acid value derived from the acid group generated from the acid decomposable group X when the acid decomposable group X is completely decomposed by the action of an acid When the total value is 230mgKOH/g or less), the minimum analytical line width before and after aging becomes smaller, and the shape of the photoresist pattern before and after aging, and the conductor before and after aging The pattern shape and its LWR performance are more excellent.

[Production of transfer film-2] The dummy support was produced in the same manner as in Examples 1 to 19, except that the polyester film (thickness: 6.9 μm) described in Example 1 of JP-A-2000-309650 was used. As a result of carrying out the above-mentioned evaluation on the transfer film and the obtained transfer film, all evaluation results were good results equivalent to Examples 1-19.

10: transfer film 11: Pseudo-support 13: middle layer 15: Photosensitive composition layer 17: Composition layer 19: Protective film

FIG. 1 is a schematic diagram showing an example of the structure of a transfer film.

10: transfer film

11: Pseudo-support

13: Intermediate

15: Photosensitive composition layer

17: Composition layer

19: Protective film

Claims (23)

A photosensitive composition comprising a polymer A1, a polymerizable compound B, a photopolymerization initiator C, and a photoacid generator D, or comprising a polymer A2, the aforementioned polymerizable compound B, the aforementioned photopolymerization initiator C, The aforementioned photoacid generator D and compound E, wherein The aforementioned polymer A1 is a polymer comprising a structural unit A1a having an acid decomposable group X that is decomposed by the action of an acid to generate an acid group, and a structural unit A1b having a carboxyl group, The aforementioned polymer A2 is a resin comprising a structural unit A1c having a carboxyl group, The aforementioned compound E is a compound having the aforementioned acid decomposable group X, The aforementioned photoacid generator D is selected from the group comprising onium salt compounds, oxime sulfonate compounds, trisulphonate compounds, nitrobenzyl sulfonate compounds, disulfide compounds and bissulfonyl diazomethane compounds More than one photoacid generator. The photosensitive composition as described in Claim 1, wherein The aforementioned acid-decomposable group X has a structure in which an acid group is protected by a protecting group decomposed by the action of an acid. The photosensitive composition as described in Claim 1 or Claim 2, wherein The aforementioned acid-decomposable group X is a tertiary ester structure or an acetal structure. The photosensitive composition as described in Claim 1 or Claim 2, wherein In said polymer A1, content of said structural unit A1a is 5-40 mass % with respect to all structural units, and content of said structural unit A1b is 10-30 mass % with respect to all structural units. The photosensitive composition as described in Claim 1 or Claim 2, wherein The acid value derived from the carboxyl group of the said polymer A1 is 150 mgKOH/g or less. The photosensitive composition as described in Claim 1 or Claim 2, wherein The total value of the acid value derived from the carboxyl group of the polymer A1 and the acid value derived from the acid group generated from the acid decomposable group X when the acid decomposable group X is completely decomposed by the action of an acid is 230 mgKOH/g or less . The photosensitive composition as described in Claim 1, wherein The above-mentioned compound E is a compound having two or more of the above-mentioned acid-decomposable groups X. The photosensitive composition as described in Claim 1 or Claim 7, wherein The aforementioned compound E is a polymer. A photosensitive composition layer formed of the photosensitive composition described in any one of claim 1 to claim 8. A transfer film comprising: a dummy support; and a photosensitive composition layer formed of the photosensitive composition described in any one of claim 1 to claim 8. The transfer film according to claim 10, further comprising an intermediate layer between the dummy support and the photosensitive composition layer. The transfer film as described in Claim 11, wherein The aforementioned intermediate layer contains a water-soluble resin. The transfer film as described in claim 12, wherein The water-soluble resin is at least one selected from the group consisting of water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyethers, phenol derivatives, and amide compounds. A method for manufacturing a laminate with a conductive pattern, which uses the transfer film described in any one of claim 10 to claim 13, the method for manufacturing a laminate with a conductive pattern has: Bonding step, bonding the transfer film and the aforementioned substrate in such a way that the surface of the aforementioned transfer film opposite to the side of the dummy support is in contact with the aforementioned conductive layer of the substrate having a conductive layer on the surface; Exposure step, performing pattern exposure on the aforementioned photosensitive composition layer; A photoresist pattern forming step, performing a development treatment on the exposed photosensitive composition layer to form a photoresist pattern; an etching treatment step or an electroplating treatment step, performing etching treatment or electroplating treatment on the aforementioned conductive layer located in the region where the aforementioned photoresist pattern is not arranged; and Photoresist pattern stripping step, stripping the aforementioned photoresist pattern, When there is the aforementioned electroplating treatment step, there is further a removal step of removing the aforementioned conductive layer exposed due to the aforementioned photoresist pattern stripping step and forming a conductive pattern on the aforementioned substrate, wherein Between the laminating step and the exposing step or between the exposing step and the developing step, there is further a dummy support peeling step for peeling off the dummy support. The method of manufacturing a laminate having a conductor pattern according to claim 14, further comprising a heating step between the step of forming the photoresist pattern and the step of stripping the photoresist pattern. The method for manufacturing a laminate having a conductor pattern according to Claim 14 or Claim 15, wherein The pH of the stripping solution used in the aforementioned photoresist pattern stripping step is above 13. The method for manufacturing a laminate having a conductor pattern according to Claim 14 or Claim 15, wherein The pH of the developer used in the aforementioned photoresist pattern forming step is less than 13. The method for manufacturing a laminate having a conductor pattern according to Claim 14 or Claim 15, wherein The value obtained by subtracting the pH of the developing solution used in the resist pattern forming step from the pH of the stripping solution used in the resist pattern stripping step is 1 or more. The method for manufacturing a laminate having a conductor pattern according to Claim 14 or Claim 15, wherein A value obtained by subtracting the temperature of the developing solution used in the resist pattern forming step from the temperature of the stripping solution used in the resist pattern stripping step is 10° C. or higher. The method for manufacturing a laminate having a conductor pattern according to Claim 14 or Claim 15, wherein The exposure method in the foregoing exposure step is any one of mask exposure, direct imaging exposure and projection exposure. The method for manufacturing a laminate having a conductor pattern according to Claim 14 or Claim 15, wherein The thickness of the aforementioned pseudo-support was less than 16 μm. The method for manufacturing a laminate having a conductor pattern according to Claim 14 or Claim 15, which includes the step of peeling off the dummy support between the bonding step and the exposing step. The method for manufacturing a laminate having a conductor pattern according to Claim 14 or Claim 15, wherein The transfer film includes an intermediate layer between the dummy support and the photosensitive composition layer, There is the aforementioned dummy support stripping step between the aforementioned laminating step and the aforementioned exposing step, The exposure step is a step of exposing the intermediate layer exposed by the dummy support stripping step to a mask.

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