TW202330641A - Photosensitive resin composition, photosensitive element, and production method of laminate - Google Patents

Abstract

A photosensitive resin composition comprising a binder polymer, a photopolymerizable compound, a photopolymerization initiator and a tetraarylbenzidine compound represented by general formula (d1). [In formula (d1): R11, R12, R13, R14, R15, R16, R17 and R18 each independently represent an alkyl group, an alkoxy group, a halogeno group, an amino group, a hydroxy group, a carboxy group or a carboxylate group; n11, n12, n13 and n14 each independently represent an integer of 0-4; and n15, n16, n17 and n18 each independently represent an integer of 0-5, provided that n15 and/or n16 represent 1 or more.].

Description

Photosensitive resin composition, photosensitive element and method for producing laminate

This disclosure relates to a photosensitive resin composition, a photosensitive element, a method for manufacturing a laminate, and the like.

When manufacturing a laminate that can be used as a printed wiring board, a resist pattern is formed in order to obtain desired wiring. A resist pattern can be formed by exposing and developing the photosensitive resin layer obtained using the photosensitive resin composition. Various compositions have been studied as photosensitive resin compositions. For example, Patent Document 1 below describes a photosensitive resin composition containing an anthracene derivative.

[Patent Document 1] International Publication No. 2007/004619

When a cured product pattern that can be used as a resist pattern is formed using a photosensitive resin composition, a linear cured product pattern having a linear line portion and a linear space portion adjacent to the line portion may be formed. Furthermore, when forming a linear cured product pattern whose space width (width of the space portion) is equal to or less than the line width (width of the line portion), resolution may be required as a characteristic of forming the line portion and the space portion well. .

An object of one aspect of the present disclosure is to provide a photosensitive resin composition which, when forming a linear cured product pattern whose space width is equal to or less than the line width, can reduce the area where the line portion and the space portion are formed satisfactorily. space width. Another object of the present disclosure is to provide a photosensitive element using the photosensitive resin composition. Another object of the present disclosure is to provide a method for producing a laminate using the above-mentioned photosensitive resin composition or the above-mentioned photosensitive element.

Several aspects of the present disclosure relate to the following [1] to [14] and the like. [1] A photosensitive resin composition containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a tetraarylbenzidine compound represented by the following general formula (d1). [chemical 1] [In formula (d1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent an alkyl group, an alkoxy group, a halo group, an amino group, a hydroxyl group, Carboxyl or carboxylate group, n11, n12, n13 and n14 each independently represent an integer of 0 to 4, n15, n16, n17 and n18 each independently represent an integer of 0 to 5, at least one of n15 and n16 is 1 or more. ] [2] The photosensitive resin composition according to [1], wherein the tetraarylbenzidine compound includes a tetraarylbenzidine compound represented by the following general formula (d2). [Chem 2] [In formula (d2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ^{16 , R 17a , R 17b , R 18a} and R ^18b each independently represent an alkyl group, an alkoxy group, a halo group , an amino group, a hydroxyl group, a carboxyl group or a carboxylate group, n11, n12, n13 and n14 each independently represent an integer of 0-4. ] [3] The photosensitive resin composition as described in [1] or [2], wherein the tetraarylbenzidine compound contains N,N'-bis[4-(2-phenylethen-1-yl) -4'-methylphenyl]-N,N'-bis(2-ethyl-6-methylphenyl)-1,1'-biphenyl-4,4'-diamine. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the content of the tetraarylbenzidine compound is relative to the total amount of the binder polymer and the photopolymerizable compound 100 parts by mass is 0.01 to 0.50 parts by mass. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the binder polymer includes a polymer having benzyl (meth)acrylate as a monomer unit. [6] The photosensitive resin composition according to [5], wherein the content of the benzyl (meth)acrylate monomer unit in the polymer is 10 to 30% by mass. [7] The photosensitive resin composition according to any one of [6] of [1], wherein the binder polymer includes a polymer having a styrene compound as a monomer unit. [8] The photosensitive resin composition according to [7], wherein the monomer unit content of the styrene compound in the polymer is 40 to 60% by mass. [9] The photosensitive resin composition according to any one of [1] to [8], wherein the weight average molecular weight of the binder polymer is 10,000 to 100,000. [10] The photosensitive resin composition according to any one of [1] to [9], wherein the photopolymerizable compound includes a bisphenol A type (meth)acrylic compound. [11] The photosensitive resin composition according to any one of [1] to [10], which is in the form of a film. [12] The photosensitive resin composition according to [11], which has a thickness of 30 μm or less. [13] A photosensitive element comprising a support and a photosensitive resin layer disposed on the support, the photosensitive resin layer comprising the photosensitive resin composition described in any one of [1] to [12] . [14] A method for producing a laminate comprising: using the photosensitive resin composition described in any one of [1] to [12] or the photosensitive element described in [13], disposing a photosensitive element on a substrate a step of forming a photosensitive resin layer; a step of photocuring a part of the photosensitive resin layer; and a step of forming a cured product pattern by removing the uncured portion of the photosensitive resin layer. [Invention effect]

According to one aspect of the present disclosure, it is possible to provide a photosensitive resin composition capable of reducing the area where the line portion and the space portion are well formed when forming a linear cured product pattern with a space width equal to or less than the line width. space width. According to another aspect of the present disclosure, a photosensitive element using the photosensitive resin composition can be provided. According to another aspect of the present disclosure, it is possible to provide a method of manufacturing a laminate using the above-mentioned photosensitive resin composition or the above-mentioned photosensitive element. According to another aspect of the present disclosure, a photosensitive resin composition or a photosensitive element for forming a resist pattern can be provided. According to another aspect of the present disclosure, a photosensitive resin composition or a photosensitive element used in the manufacture of printed wiring boards can be provided.

Embodiments of the present disclosure will be described in detail below.

In this specification, the numerical range represented by "-" means the range which includes the numerical value described before and after "-" as a minimum value and a maximum value, respectively. "More than A" in the numerical range refers to the range of A and greater than A. "Below A" in the numerical range refers to the range of A and less than A. In the numerical ranges described step by step in this specification, the upper limit or lower limit of the numerical range of a certain step can be combined arbitrarily with the upper limit or lower limit of the numerical range of another step. In the numerical range described in this specification, the upper limit or the lower limit of the numerical range can be replaced with the value shown in the Example. "A or B" only needs to include any one of A and B, and may include both. The materials exemplified in this specification can be used alone or in combination of two or more unless otherwise specified. When a plurality of substances corresponding to each component exist in the composition, unless otherwise specified, the content of each component in the composition means the total amount of the plurality of substances present in the composition. When viewed as a plan view, the term "layer" includes not only the structure formed in the shape of the entire surface but also the structure formed in a part of the shape. The term "step" is included in this term as long as the intended effect of the step can be achieved even if it cannot be clearly distinguished from other steps, except for independent steps. "(Meth)acrylic acid" means at least one of acrylic acid and its corresponding methacrylic acid, and the same applies to other similar expressions such as "(meth)acrylate". "The content of the monomer of (meth)acrylic acid" means the total amount of the monomeric unit of acrylic acid and the monomeric unit of methacrylic acid, and it is the same for other similar expressions. "Alkyl" may be linear, branched or cyclic unless otherwise specified.

In this specification, "EO modification" refers to a compound having a (poly)oxyethylene group. "PO modification" refers to a compound having a (poly)oxypropylene group. "EO·PO modification" refers to compounds having (poly)oxyethylene and (poly)oxypropylene groups. "(Poly)oxyethylene" means at least one of an oxyethylene group and a polyoxyethylene group (a group in which two or more ethylylene groups are linked via ether bonds). The same applies to other similar expressions such as "(poly)oxypropylene".

In this specification, "the solid content of the photosensitive resin composition" refers to the non-volatile content in the photosensitive resin composition after removing the volatile components (water, solvent, etc.) that can be volatilized. That is, "solid content" refers to components that do not volatilize but remain when the photosensitive resin composition is dried, and include components that are liquid, syrupy, paraffin, etc. at room temperature (25° C.).

＜Photosensitive resin composition and cured product＞ The photosensitive resin composition of this embodiment contains (A) binder polymer ((A) component), (B) photopolymerizable compound ((B) component), (C) photopolymerization initiator ((C) Component) and (D) a tetraarylbenzidine compound (component (D)) represented by the following general formula (d1). The photosensitive resin composition of this embodiment can be used as a negative photosensitive resin composition, for example. The photosensitive resin composition of this embodiment may be liquid or film-like (photosensitive film).

[Chem 3] [In formula (d1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent an alkyl group, an alkoxy group, a halo group, an amino group, a hydroxyl group, Carboxyl or carboxylate group, n11, n12, n13 and n14 each independently represent an integer of 0 to 4, n15, n16, n17 and n18 each independently represent an integer of 0 to 5, at least one of n15 and n16 is 1 or more. ]

The photosensitive resin composition of the present embodiment has photocurability, and a cured product can be obtained by photocuring the photosensitive resin composition. The cured product of this embodiment is a cured product (photocured product) of the photosensitive resin composition of this embodiment. The cured product of this embodiment may be in the form of a pattern (cured product pattern), or may be a resist pattern.

The thickness of the film-like photosensitive resin composition or the thickness of the cured product may be 1 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, 18 μm or more, or 19 μm or more. The thickness of the film-like photosensitive resin composition or cured product may be 100 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, or 19 μm or less. From these viewpoints, the thickness of the film-like photosensitive resin composition or the thickness of the cured product may be 1 to 100 μm, 5 to 50 μm, or 10 to 30 μm. The thickness of the film-like photosensitive resin composition or the thickness of the cured product may be an average thickness of 10 places.

According to the photosensitive resin composition of this embodiment, when forming a linear cured product pattern whose space width is equal to or smaller than the line width (the space width is equal to or smaller than the line width), the line portion can be formed satisfactorily. And the spatial width (minimum spatial width) of the region of the spatial part is reduced (obtaining excellent resolution). Regarding the main reason for obtaining such an effect, the present inventors speculate that the absorption efficiency of light by the component (D) is high and the reaction caused by the component (C) proceeds more effectively, thereby suppressing the development of the cured product pattern. The swelling of the liquid achieves the above effect. However, the main reason is not limited to this content. With the increase in the density of printed wiring boards in recent years, the demand for photosensitive resin compositions with excellent resolution has gradually increased. In particular, when manufacturing package substrates, it is required to be able to form a line width/space width of 10/10 (unit : μm) The photosensitive resin composition of the resist pattern below. According to the photosensitive resin composition of the present embodiment, in the evaluation described in Examples described later, for example, a resolution of 10 μm or less (preferably 8 μm or less) can be obtained.

However, when a photosensitive resin composition is used to form a linear cured pattern with a line width equal to or less than the space width (the line width is the same as the space width or smaller than the space width), as a characteristic of forming the line portion and the space portion well, , Sometimes tightness is required. According to one aspect of the photosensitive resin composition of this embodiment, when forming a linear cured product pattern whose line width is equal to or less than the space width, the line width of the region where the line portion and the space portion are formed favorably ( minimum line width) is reduced (to obtain excellent adhesion). With the increase in the density of printed wiring boards in recent years, the demand for photosensitive resin compositions with excellent adhesion has gradually increased. In particular, when making packaging substrates, it is required to be able to form a line width/space width of 10/10 ( Unit: μm) The photosensitive resin composition of the resist pattern. According to one aspect of the photosensitive resin composition of this embodiment, in the evaluation described in the Example mentioned later, the adhesiveness of 7 micrometers or less can be acquired, for example.

According to one aspect of the photosensitive resin composition of this embodiment, excellent sensitivity to activating light (a characteristic that requires a small amount of exposure to obtain a predetermined cured state) can be obtained, and the evaluation described in Examples described later Among them, for example, a sensitivity (exposure amount) of 90 mJ/cm ² or less (preferably 80 mJ/cm ² or less) can be obtained.

The photosensitive resin composition of this embodiment contains a binder polymer (excluding the compound corresponding to (D) component) as (A) component.

Examples of the component (A) include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. Acrylic resin is a resin having a compound ((meth)acrylic acid compound) having a (meth)acryl group as a monomer unit. Styrene-based resins, epoxy-based resins, and amide-based Resins, amide epoxy resins, alkyd resins, and phenolic resins are acrylic resins.

(A) Component may contain an acrylic resin from the viewpoint of being easy to obtain excellent resolution, adhesiveness, and sensitivity. From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the content of the acrylic resin may be 50% by mass or more, more than 50% by mass, 70% by mass or more, based on the total mass of the component (A). 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, or substantially 100% by mass (aspect in which the component (A) is substantially composed of an acrylic resin).

(meth)acrylic acid, (meth)acrylate, etc. are mentioned as a compound which has a (meth)acryloyl group. Examples of (meth)acrylates include alkyl (meth)acrylates (except for alkyl (meth)acrylates: compounds corresponding to cycloalkyl (meth)acrylates), (meth)acrylic acid Cycloalkyl esters (cycloalkyl (meth)acrylates), aryl (meth)acrylates (aryl (meth)acrylates), (meth)acrylamide compounds (diacetone acrylamide, etc. ), glycidyl (meth)acrylate, styrene (meth)acrylic acid, etc.

(A) Component may contain the polymer which has aryl (meth)acrylate (aryl (meth)acrylate) as a monomer unit from a viewpoint of being easy to acquire excellent resolution, adhesiveness, and sensitivity. Examples of the aryl (meth)acrylate include benzyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and the like. (A) Component may contain the polymer which has benzyl (meth)acrylate as a monomer unit from a viewpoint of being easy to acquire excellent resolution, adhesiveness, and sensitivity.

The content of monomer units of benzyl (meth)acrylate or the content of monomer units of aryl (meth)acrylate to constitute The total amount of the monomer unit of the polymer as the monomer unit may be within the following range. From the viewpoint of easily obtaining excellent resolution and adhesiveness, the content of the monomer units may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more. The content of the above-mentioned monomer units may be 23% by mass or more. From the viewpoint of easily obtaining excellent resolution and adhesiveness, the content of the monomer unit may be 50% by mass or less, less than 50% by mass, 45% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less. % or less, 25 mass % or less, 23 mass % or less, or 20 mass % or less. From these viewpoints, the content of the above monomer units may be 1 to 50% by mass, 10 to 50% by mass, 15 to 50% by mass, 1 to 30% by mass, 10 to 30% by mass, 15 to 30% by mass, 1 to 25% by mass, 10 to 25% by mass, or 15 to 25% by mass.

From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the component (A) may include a polymer having (meth)acrylic acid as a monomer unit, or a polymer having (meth)acrylic acid aryl ester and A polymer of (meth)acrylic acid as a monomer unit.

The content of the monomer unit of (meth)acrylic acid may be in the following range based on the total amount of monomer units constituting the polymer having (meth)acrylic acid as a monomer unit. From the viewpoint of easily obtaining excellent resolution and adhesion, the content of monomer units of (meth)acrylic acid may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more. % or more, 25 mass % or more, or 27 mass % or more. The content of the monomer unit of (meth)acrylic acid may be 30% by mass or more. From the viewpoint of easily obtaining excellent resolution and adhesion, the content of monomer units of (meth)acrylic acid may be 50% by mass or less, less than 50% by mass, 45% by mass or less, 40% by mass or less, 35% by mass or less. % or less, 30 mass % or less, or 27 mass % or less. From these viewpoints, the content of monomer units of (meth)acrylic acid may be 1 to 50% by mass, 10 to 50% by mass, 20 to 50% by mass, 1 to 40% by mass, 10 to 40% by mass, 20% by mass, % to 40% by mass, 1 to 30% by mass, 10 to 30% by mass, or 20 to 30% by mass.

From the viewpoint of easily obtaining excellent resolution, adhesiveness, and sensitivity, the component (A) may include a polymer having an alkyl (meth)acrylate as a monomer unit, or a polymer having an alkyl (meth)acrylate selected from the group consisting of (methyl) A polymer comprising at least one of the group consisting of aryl acrylate and (meth)acrylic acid and an alkyl (meth)acrylate as a monomer unit. Examples of the alkyl group of the alkyl (meth)acrylate include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, Dodecyl, etc., the alkyl can be various structural isomers. The number of carbon atoms in the alkyl group of the alkyl (meth)acrylate may be 1-4, 1-3, 2-3, or 1-2 from the viewpoint of easily obtaining excellent resolution, adhesiveness, and sensitivity.

The alkyl group of the alkyl (meth)acrylate may have a substituent. Examples of the substituent include hydroxyl group, amino group, epoxy group, furyl group, halogeno group (fluorine group, chlorine group, bromine group, etc.) and the like. Examples of the alkyl (meth)acrylate include hydroxyalkyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, (methyl) ) 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, α-chloro(meth)acrylic acid, α-bromo(meth)acrylic acid, etc.

The (A) component may contain a polymer having a hydroxyalkyl (meth)acrylate as a monomer unit from the viewpoint of easy acquisition of excellent resolution, adhesiveness, and sensitivity. Examples of hydroxyalkyl (meth)acrylate include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, Hydroxypentyl (meth)acrylate, hydroxyhexyl (meth)acrylate, etc.

The content of monomer units of alkyl (meth)acrylate or the content of monomer units of hydroxyalkyl (meth)acrylate to constitute a unit of a polymer having alkyl (meth)acrylate as a monomer unit The total amount of body units is used as a basis, and can be in the following ranges. The content of the above monomer units may be 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, 8% by mass or more, 10% by mass or more % or more, 15% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more. From the viewpoint of easily obtaining excellent resolution and adhesion, the content of the above-mentioned monomer units may be 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, or 30% by mass or less. % or less, 20 mass % or less, 15 mass % or less, 10 mass % or less, 8 mass % or less, 5 mass % or less, 4 mass % or less, or 3 mass % or less. From these viewpoints, the content of the above monomer units may be 0.1 to 80% by mass, 0.1 to 50% by mass, 0.1 to 20% by mass, 1 to 80% by mass, 1 to 50% by mass, 1 to 20% by mass, 5 to 80% by mass, 5 to 50% by mass, or 5 to 20% by mass.

The content of monomer units of (meth)acrylate (corresponding to the total amount of monomer units of compounds of (meth)acrylate) to constitute monomers of polymers having (meth)acrylate as monomer units The total amount of units is based on the following ranges. The monomer unit content of (meth)acrylate may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 23% by mass or more, 25% by mass or more, 28% by mass or more. Mass % or more, 30 mass % or more, 35 mass % or more, 40 mass % or more, 45 mass % or more, 50 mass % or more, more than 50 mass %, 60 mass % or more, or 70 mass % or more. From the viewpoint of easily obtaining excellent resolution and adhesion, the content of monomer units of (meth)acrylate may be 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, less than 50% by mass, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 28% by mass or less, or 25% by mass or less. From these viewpoints, the content of monomer units of (meth)acrylate may be 1 to 80% by mass, 1 to 50% by mass, 1 to 30% by mass, 10 to 80% by mass, 10 to 50% by mass, 10 to 30% by mass, 20 to 80% by mass, 20 to 50% by mass, or 20 to 30% by mass.

From the viewpoint of easily obtaining excellent resolution and adhesion, the (A) component may contain a polymer having a styrene compound as a monomer unit, or may contain a polymer having a compound selected from (meth)acrylate and (meth) A polymer comprising at least one of the group consisting of acrylic acid and a styrene compound as a monomer unit may also contain a polymer having a compound selected from the group consisting of aryl (meth)acrylate, alkyl (meth)acrylate, and (meth)acrylic acid. At least one of the group and styrene compound as a polymer of monomer units. Styrene, a styrene derivative, etc. are mentioned as a styrene compound. Examples of styrene derivatives include vinyltoluene, α-methylstyrene, and the like. The component (A) may contain a polymer having benzyl (meth)acrylate, hydroxyalkyl (meth)acrylate, and a styrene compound as monomer units from the viewpoint of easy acquisition of excellent resolution and adhesion .

The content of the monomer unit of the styrene compound may be within the following range based on the total amount of the monomer units constituting the polymer having the styrene compound as the monomer unit. From the viewpoint of easily obtaining excellent resolution and adhesion, the content of the monomer unit of the styrene compound may be 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more , 35 mass % or more, 40 mass % or more, 45 mass % or more, 48 mass % or more or 50 mass % or more. The content of the monomer unit of the styrene compound may be 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, or 55% by mass or less , 50% by mass or less, 48% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less. From these viewpoints, the content of the monomer unit of the styrene compound may be 10 to 90% by mass, 20 to 90% by mass, 30 to 90% by mass, 40 to 90% by mass, 10 to 80% by mass, or 20 to 80% by mass. % by mass, 30 to 80% by mass, 40 to 80% by mass, 10 to 60% by mass, 20 to 60% by mass, 30 to 60% by mass, or 40 to 60% by mass.

(A) The component may contain the polymer which has another monomer as a monomer unit. Examples of such monomers include vinyl alcohol ethers (vinyl-n-butyl ether, etc.), (meth)acrylonitrile, maleic acid, maleic anhydride, maleic acid Monoesters (monomethyl maleate, monoethyl maleate, monoisopropyl maleate, etc.), fumaric acid, cinnamic acid, α-cyanocinnamic acid, Conic acid, crotonic acid, propiolic acid, etc.

(A) The acid value of a component may be in the following range. (A) The acid value of the component can be 80mgKOH/g or more, 90mgKOH/g or more, 100mgKOH/g or more, more than 100mgKOH/g, 120mgKOH/g or more, 140mgKOH/g or more, 150mgKOH/g or more, 160mgKOH/g or more, 170mgKOH /g or more, 180mgKOH/g or more, or 190mgKOH/g or more. The acid value of (A) component may be 250 mgKOH/g or less, 240 mgKOH/g or less, 230 mgKOH/g or less, 210 mgKOH/g or less, 200 mgKOH/g or less, or 190 mgKOH from the viewpoint of easily obtaining excellent resolution and adhesion. /g or less or 180mgKOH/g or less. From these viewpoints, the acid value of (A) component may be 80-250 mgKOH/g, 100-200 mgKOH/g, or 120-190 mgKOH/g. (A) The acid value of a component can be adjusted by content of the monomer unit (for example, the monomer unit of (meth)acrylic acid) which comprises (A) component. (A) The acid value of a component can be measured by the method described in an Example. When the solution obtained by mixing the component (A) and volatile components such as a synthesis solvent and a dilution solvent is used as a measurement object, the acid value can be calculated by the following formula. In the case of blending component (A) with volatile components such as synthesis solvents and diluent solvents, it is also possible to pre-heat at a temperature 10°C higher than the boiling point of the volatile components for 1 to 4 hours before weighing. The acid value was then determined after removal of volatile components. Acid value=0.1×Vf×56.1/(Wp×I/100) [In the formula, Vf represents the titration amount of KOH (potassium hydroxide) aqueous solution (unit: mL), Wp represents the mass (unit: g) of the solution containing (A) component of the measurement object, and I represents the content of (A) component of the measurement object ) The proportion of non-volatile components in the solution of components (unit: mass %). ]

(A) The weight average molecular weight (Mw) of a component exists in the following range. (A) The weight average molecular weight of a component may be 10000 or more, 20000 or more, 25000 or more, 30000 or more, 35000 or more, 40000 or more, 45000 or more, or 50000 or more. The weight average molecular weight of the component (A) may be 100,000 or less, 80,000 or less, 70,000 or less, less than 70,000, 65,000 or less, 60,000 or less, 50,000 or less, 40,000 or less, or 35,000 from the viewpoint of easily obtaining excellent resolution and adhesion. the following. From these viewpoints, the weight average molecular weight of (A) component may be 10,000-100,000, 20,000-80,000, 25,000-70,000, or 30,000-60,000.

(A) The number average molecular weight (Mn) of the component may be in the following range. (A) The number average molecular weight of the component may be 5,000 or more, 10,000 or more, 12,000 or more, 15,000 or more, 16,000 or more, 18,000 or more, 20,000 or more, 21,000 or more, or 22,000 or more. The number average molecular weight of the component (A) may be 50,000 or less, 40,000 or less, 35,000 or less, 30,000 or less, 25,000 or less, 22,000 or less, 21,000 or less, 20,000 or less, or 18,000 from the viewpoint of easily obtaining excellent resolution and adhesion. Below or below 16000. From these viewpoints, the number average molecular weight of (A) component may be 5000-50000, 10000-40000, 12000-35000, or 15000-30000.

(A) The degree of dispersion (weight average molecular weight/number average molecular weight) of the component may be in the following range. (A) The degree of dispersion of the component may be 1.0 or more, 1.5 or more, 1.8 or more, 2.0 or more, 2.1 or more, 2.2 or more, or 2.3 or more. The degree of dispersion of the component (A) may be 3.0 or less, 2.8 or less, 2.5 or less, 2.3 or less, or 2.2 or less from the viewpoint of easily obtaining excellent resolution and adhesiveness. From these viewpoints, the dispersion degree of (A) component may be 1.0-3.0, 1.5-2.8, or 2.0-2.5.

The weight average molecular weight and the number average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. More specifically, it can measure under the conditions described in an Example. When it is difficult to measure a compound with a low molecular weight by the above-mentioned measuring method of weight average molecular weight and number average molecular weight, the molecular weight can be measured by another method and the average value can be calculated.

The content of the component (A) may be within the following range on the basis of the total solid content of the photosensitive resin composition. The content of component (A) may be 10% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass from the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, and the viewpoint of excellent formability of the film. % or more, 45 mass % or more, or 50 mass % or more. From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the content of the component (A) may be 90% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less or 55% by mass or less. From these viewpoints, the content of the component (A) may be 10 to 90% by mass, 10 to 80% by mass, 10 to 60% by mass, 30 to 90% by mass, 30 to 80% by mass, 30 to 60% by mass, 50 to 90% by mass, 50 to 80% by mass, or 50 to 60% by mass.

(A) Content of a component can exist in the following range with respect to 100 mass parts of total amounts of (A) component and (B) component. The content of component (A) may be 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, and 40 parts by mass from the viewpoint of easily obtaining excellent resolution, adhesion and sensitivity, and the viewpoint of excellent formability of the film. More than 45 parts by mass, more than 50 parts by mass, or more than 55 parts by mass. From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the content of component (A) may be 90 parts by mass or less, 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less. From these viewpoints, the content of the component (A) may be 10 to 90 parts by mass, 10 to 80 parts by mass, 10 to 60 parts by mass, 30 to 90 parts by mass, 30 to 80 parts by mass, 30 to 60 parts by mass, 50-90 mass parts, 50-80 mass parts, or 50-60 mass parts.

The photosensitive resin composition of this embodiment contains a photopolymerizable compound (excluding the compound corresponding to (D) component) as (B) component. The photopolymerizable compound is a compound that polymerizes with light, and may be, for example, a compound having an ethylenically unsaturated bond.

Examples of the component (B) include bisphenol A type (meth)acrylic acid compounds, EO-modified di(meth)acrylates, PO-modified di(meth)acrylates, EO/PO-modified di(meth)acrylates, base) acrylate, polyalkylene glycol di(meth)acrylate (polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc.), EO modified polyalkylene Glycol di(meth)acrylate, PO modified polyalkylene glycol di(meth)acrylate, EO·PO modified polyalkylene glycol di(meth)acrylate, trimethylol Propane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate ) acrylate, EO·PO modified trimethylolpropane tri(meth)acrylate, compounds with ditrimethylolpropane skeleton, tetramethylolmethane tri(meth)acrylate, tetramethylolpropane Methane tetra(meth)acrylate, EO modified neopentylitol tetra(meth)acrylate, PO modified neopentylitol tetra(meth)acrylate, EO·PO modified neopentylitol tetra( Meth) acrylate, EO modified dipenteoerythritol hexa(meth)acrylate, PO modified dipenteoerythritol hexa(meth)acrylate, EO·PO modified dipenteopentyl hexa(meth)acrylate Meth)acrylates, nonylphenoxypolyoxyethylene acrylates, phthalate-based compounds, alkyl (meth)acrylates, photopolymerizable cyclic ether groups capable of polymerizing at least one cation in the molecule Sexual compounds (oxetane compounds, etc.), etc.

The (B) component may contain a bisphenol A type (meth)acrylic compound from the viewpoint of being easy to obtain excellent resolution, adhesiveness, and sensitivity. Examples of bisphenol A-type (meth)acrylic compounds include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane (2,2-bis(4- ((meth)acryloxypentaethoxy)phenyl)propane, etc.), 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, 2,2 -Bis(4-((meth)acryloxypolybutoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)benzene base) propane, etc. The component (B) may contain 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane from the viewpoint of easy acquisition of excellent resolution, adhesion, and sensitivity. May also contain 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane.

The content of the bisphenol A type (meth)acrylic compound is 100% by mass or less based on the total mass of the (B) component, and may be within the following range from the viewpoint of easy acquisition of excellent resolution, adhesiveness, and sensitivity. The content of the bisphenol A type (meth)acrylic compound may be 50% by mass or more, more than 50% by mass, 60% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass. Mass% or more. The bisphenol A-type (meth)acrylic compound content is less than 100 mass %, 99 mass % or less, 98 mass % or less, 97 mass % or less, 95 mass % or less, 92 mass % or less, or 91 mass % or less. From these viewpoints, the content of the bisphenol A type (meth)acrylic compound may be 50 to 100% by mass, 70 to 99% by mass, or 80 to 95% by mass.

The content of the bisphenol A type (meth)acrylic compound may be within the following range based on the total solid content of the photosensitive resin composition from the viewpoint of easy acquisition of excellent resolution, adhesiveness, and sensitivity. The content of the bisphenol A type (meth)acrylic compound may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, or 35% by mass or more. Mass% or more. The content of the bisphenol A type (meth)acrylic compound may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less. Mass % or less or 40 mass % or less. From these viewpoints, the content of the bisphenol A type (meth)acrylic compound may be 1 to 90% by mass, 10 to 90% by mass, 20 to 90% by mass, 1 to 70% by mass, 10 to 70% by mass, 20 to 70% by mass, 1 to 50% by mass, 10 to 50% by mass, or 20 to 50% by mass.

From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the content of the bisphenol A-type (meth)acrylic compound can be as follows with respect to 100 parts by mass of the total amount of (A) component and (B) component scope. The content of the bisphenol A type (meth)acrylic compound may be 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 32 parts by mass or more. Parts by mass or more, 35 parts by mass or more, 38 parts by mass or more, or 40 parts by mass or more. The content of the bisphenol A type (meth)acrylic compound may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, or 40 parts by mass or less. From these viewpoints, the content of the bisphenol A type (meth)acrylic compound may be 1 to 90 parts by mass, 10 to 90 parts by mass, 20 to 90 parts by mass, 1 to 70 parts by mass, 10 to 70 parts by mass, 20 to 70 parts by mass, 1 to 50 parts by mass, 10 to 50 parts by mass, or 20 to 50 parts by mass.

From the viewpoint of easy acquisition of excellent resolution, adhesiveness, and sensitivity, the content of the component (B) may be within the following range on the basis of the total solid content of the photosensitive resin composition. (B) The content of the component may be 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more. The content of the component (B) may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, or 45% by mass or less. From these viewpoints, the content of the component (B) may be 10 to 90% by mass, 20 to 90% by mass, 30 to 90% by mass, 10 to 70% by mass, 20 to 70% by mass, 30 to 70% by mass, 10 to 50% by mass, 20 to 50% by mass, or 30 to 50% by mass.

The content of (B) component may be in the following range with respect to 100 parts by mass of the total amount of (A) component and (B) component from the viewpoint of easily obtaining excellent resolution, adhesiveness, and sensitivity. The content of the component (B) may be 10 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more. The content of the component (B) may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, or 45 parts by mass or less. From these viewpoints, the content of the component (B) may be 10 to 90 parts by mass, 20 to 90 parts by mass, 30 to 90 parts by mass, 10 to 70 parts by mass, 20 to 70 parts by mass, 30 to 70 parts by mass, 10 to 50 parts by mass, 20 to 50 parts by mass, or 30 to 50 parts by mass.

The photosensitive resin composition of this embodiment does not need to contain the photopolymerizable compound which has an amino group as (B) component. Examples of such photopolymerizable compounds include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, dimethylaminopropyl(methyl) ) acrylamide, diethylaminopropyl(meth)acrylamide, n-propyl(meth)acrylamide, isopropyl(meth)acrylamide, N-(meth)acrylamide Morpholine etc. The content of the photopolymerizable compound having an amine group may be 0.01 mass part or less, less than 0.01 mass part, 0.001 mass part or less, or 0.0001 mass part or less, or 0 mass % with respect to 100 mass parts of (A) component.

The photosensitive resin composition of this embodiment contains a photoinitiator (excluding the compound corresponding to (D)component) as (C)component.

Examples of the component (C) include hexaarylbisimidazole compounds; benzophenone, 2-benzyl-2-dimethylamino-1-(4-portolinophenyl)-1-butanone , 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-portoline)phenyl]-1-butanone, 4-(2 -Hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-portolinyl-acetone- Aromatic ketones such as 1; quinone compounds such as alkyl anthraquinone; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkylbenzoin; benzyl dimethyl ketal, etc. Benzyl derivatives; bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; bis(2,6-dimethylbenzoyl)-2,4,4-trimethyl Base-pentyl phosphine oxide; (2,4,6-trimethylbenzoyl) ethoxyphenyl phosphine oxide, etc.

The component (C) may contain a hexaarylbiimidazole compound from the viewpoint of easy acquisition of excellent resolution, adhesiveness, and sensitivity. The aryl group in the hexaarylbiimidazole compound may be phenyl group or the like. The hydrogen atom bonded to the aryl group in the hexaarylbiimidazole compound may be substituted by a halogen atom (chlorine atom, etc.).

The hexaarylbisimidazole compound may be a 2,4,5-triarylimidazole dimer. Examples of 2,4,5-triaryl imidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5 -Bis-(m-methoxyphenyl)imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, etc. From the viewpoint of easily obtaining excellent resolution, adhesion and sensitivity, the hexaarylbisimidazole compound may include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, and may also include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

From the viewpoint of easily obtaining excellent resolution, adhesion and sensitivity, the content of the hexaarylbiimidazole compound may be 50% by mass or more, more than 50% by mass, or 70% by mass based on the total amount of the component (C). % or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, or substantially 100% by mass (aspect in which component (C) consists essentially of a hexaarylbiimidazole compound).

From the viewpoint of easy acquisition of excellent resolution, adhesiveness, and sensitivity, the content of the component (C) may be within the following range on the basis of the total solid content of the photosensitive resin composition. The content of the component (C) may be 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, or 5.5% by mass or more. The content of the component (C) may be 20% by mass or less, 15% by mass or less, 12% by mass or less, 10% by mass or less, 8% by mass or less, 7% by mass or less, or 6% by mass or less. From these viewpoints, the content of the component (C) may be 0.1 to 20% by mass, 0.1 to 15% by mass, 0.1 to 10% by mass, 1 to 20% by mass, 1 to 15% by mass, 1 to 10% by mass, 3-20 mass %, 3-15 mass %, or 3-10 mass %.

From the viewpoint of easy acquisition of excellent resolution, adhesiveness, and sensitivity, the content of the component (C) may be in the following range with respect to 100 parts by mass of the total amount of the component (A) and the component (B). (C) The content of the component may be at least 0.1 parts by mass, at least 0.5 parts by mass, at least 1 part by mass, at least 2 parts by mass, at least 3 parts by mass, at least 4 parts by mass, at least 5 parts by mass, at least 5.5 parts by mass, or at least 6 parts by mass servings or more. The content of the component (C) may be 20 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 7 parts by mass or less, or 6 parts by mass or less. From these viewpoints, the content of the component (C) may be 0.1 to 20 parts by mass, 0.1 to 15 parts by mass, 0.1 to 10 parts by mass, 1 to 20 parts by mass, 1 to 15 parts by mass, 1 to 10 parts by mass, 3-20 mass parts, 3-15 mass parts, or 3-10 mass parts.

The photosensitive resin composition of this embodiment contains the tetraaryl benzidine compound represented by following general formula (d1) as (D) component. (D) The component can be used as a sensitizer.

[chemical 4] [In formula (d1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent an alkyl group, an alkoxy group, a halo group, an amino group, a hydroxyl group, Carboxyl or carboxylate group, n11, n12, n13 and n14 each independently represent an integer of 0 to 4, n15, n16, n17 and n18 each independently represent an integer of 0 to 5, at least one of n15 and n16 is 1 or more. ]

When a plurality of R ¹¹ exists, R ¹¹ may be the same as or different from each other. The same applies to R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ . The number of carbon atoms in the alkyl group may be 1-6, 1-4, 1-3, or 1-2 from the viewpoint of easily obtaining excellent resolution, adhesiveness, and sensitivity. The number of carbon atoms in the alkoxy group may be 1-6, 1-4, 1-3, or 1-2 from the viewpoint of easily obtaining excellent resolution, adhesiveness, and sensitivity. Examples of the halogeno group include a fluorine group, a chlorine group, a bromo group, an iodine group and the like. The amine group may be a primary or secondary amine group with substituents. Sodium salt etc. are mentioned as a carboxylate group.

The component (D) may contain a tetraarylbenzidine compound represented by the following general formula (d2) from the viewpoint of easy acquisition of excellent resolution, adhesiveness, and sensitivity. [chemical 5] [In formula (d2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ^{16 , R 17a , R 17b , R 18a} and R ^18b each independently represent an alkyl group, an alkoxy group, a halo group , an amino group, a hydroxyl group, a carboxyl group or a carboxylate group, n11, n12, n13 and n14 each independently represent an integer of 0-4. ]

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ in formula (d2) are the same as R ¹¹ , R 12 , R ¹³ , R ¹⁴ , R ¹⁵ and ^{R 16 in} formula (d1). R ^17a and R ^17b in formula (d2) are the same as R ¹⁷ in formula (d1). R ^18a and R ^18b in formula (d2) are the same as R ¹⁸ in formula (d1).

At least one selected from the group consisting of R ¹⁵ and R ¹⁶ may be an alkyl group or a methyl group from the viewpoint of easily obtaining excellent resolution, adhesiveness, and sensitivity. At least one selected from the group consisting of R ^17a and R ^18a may be an alkyl group or an ethyl group from the viewpoint of easily obtaining excellent resolution, adhesiveness, and sensitivity. At least one selected from the group consisting of R ^17b and R ^18b may be an alkyl group or a methyl group from the viewpoint of easily obtaining excellent resolution, adhesiveness, and sensitivity. From the viewpoint of easily obtaining excellent resolution, adhesiveness, and sensitivity, component (D) may contain N,N'-bis[4-(2-phenylethen-1-yl)-4'-methylbenzene base]-N,N'-bis(2-ethyl-6-methylphenyl)-1,1'-biphenyl-4,4'-diamine.

The content of the component (D) may be within the following range on the basis of the total solid content of the photosensitive resin composition. From the viewpoint of easily obtaining excellent sensitivity, the content of the component (D) may be 0.01 mass % or more, 0.03 mass % or more, 0.05 mass % or more, 0.08 mass % or more, 0.09 mass % or more, 0.10 mass % or more, or 0.13 mass % % or more, 0.15% by mass or more, 0.18% by mass or more, 0.20% by mass or more, 0.23% by mass or more, 0.25% by mass or more, or 0.27% by mass or more. The content of (D) component may be 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.80% by mass or less, 0.60% by mass or less, or 0.50% by mass from the viewpoint of easily obtaining excellent resolution and adhesion. % or less, 0.40 mass % or less, 0.30 mass % or less, 0.28 mass % or less, 0.27 mass % or less, 0.25 mass % or less, 0.23 mass % or less, 0.20 mass % or less, 0.18 mass % or less, 0.15 mass % or less, 0.13 mass % or less % or less or 0.10% by mass or less. From these viewpoints, the content of the component (D) may be 0.01 to 5% by mass, 0.01 to 1% by mass, 0.01 to 0.50% by mass, 0.01 to 0.20% by mass, 0.01 to 0.10% by mass, 0.05 to 5% by mass, 0.05-1 mass%, 0.05-0.50 mass%, 0.05-0.20 mass%, 0.05-0.10 mass%, 0.10-5 mass%, 0.10-1 mass%, 0.10-0.50 mass%, 0.10-0.20 mass%, 0.20- 5% by mass, 0.20 to 1% by mass, or 0.20 to 0.50% by mass. The absorbance of the photosensitive resin composition can be adjusted by adjusting the content of the (D)component.

(D) Content of a component can exist in the following range with respect to 100 mass parts of total amounts of (A) component and (B) component. From the viewpoint of easily obtaining excellent sensitivity, the content of component (D) may be 0.01 mass part or more, 0.03 mass part or more, 0.05 mass part or more, 0.08 mass part or more, 0.09 mass part or more, 0.10 mass part or more, 0.13 mass part or more 0.15 parts by mass or more, 0.18 parts by mass or more, 0.20 parts by mass or more, 0.23 parts by mass or more, 0.25 parts by mass or more, 0.27 parts by mass or more, 0.28 parts by mass or more, or 0.30 parts by mass or more. The content of component (D) may be 5 parts by mass or less, 3 parts by mass or less, 1 part by mass or less, 0.80 parts by mass or less, 0.60 parts by mass or less, or 0.50 parts by mass from the viewpoint of easily obtaining excellent resolution and adhesion. Parts or less, 0.40 parts by mass or less, 0.30 parts by mass or less, 0.28 parts by mass or less, 0.27 parts by mass or less, 0.25 parts by mass or less, 0.23 parts by mass or less, 0.20 parts by mass or less, 0.18 parts by mass or less, 0.15 parts by mass or less, 0.13 parts by mass part or less or 0.10 mass part or less. From these viewpoints, the content of component (D) may be 0.01 to 5 parts by mass, 0.01 to 1 part by mass, 0.01 to 0.50 parts by mass, 0.01 to 0.25 parts by mass, 0.01 to 0.15 parts by mass, 0.05 to 5 parts by mass, 0.05 ～1 mass part, 0.05～0.50 mass part, 0.05～0.25 mass part, 0.05～0.15 mass part, 0.15～5 mass part, 0.15～1 mass part, 0.15～0.50 mass part, 0.15～0.25 mass part, 0.25～5 mass part parts by mass, 0.25 to 1 part by mass, or 0.25 to 0.50 parts by mass. The absorbance of the photosensitive resin composition can be adjusted by adjusting the content of the (D)component.

The component (D) may be a compound that absorbs light in the range of 340 to 430 nm, or a compound that effectively absorbs light in the wavelength range of 365 nm and 405 nm, or a compound that absorbs light in the range of 395 to 415 nm, or may be A compound that effectively absorbs light with a wavelength of 405nm.

From the viewpoint of effectively absorbing the activating light, the molar absorption coefficient of the component (D) in the maximum absorption wavelength in the range of 395 to 415 nm (the maximum absorption wavelength closest to 405 nm) can be 10,000 to 100,000 L/(mol· cm), 20000～100000L/(mol·cm), 20000～95000L/(mol·cm), or 25000～90000L/(mol·cm). The molar absorptivity is an index of the degree of easy absorption of light.

The molar absorptivity at the maximum absorption wavelength (maximum absorption wavelength closest to 405 nm) in the range of 395 to 415 nm can be measured, for example, by the following procedure. First, using a volumetric flask and a full pipette, toluene solutions having different concentrations (mol/L) of four or more ultraviolet absorbers were prepared at room temperature (25° C.). As a diluting solvent, acetonitrile or methanol can be used as needed. The concentration "mol/L" can be calculated by dividing the mass (g) of the UV absorber added to the volumetric flask by the molecular weight (g/mol) of the UV absorber and further dividing by the capacity (L) of the volumetric flask. As a method of measuring the molecular weight (g/mol) of the ultraviolet absorber, a mass spectrometry method and the like are mentioned. Fill the toluene solution of the prepared ultraviolet absorber into a quartz cell with an optical path length of 1 cm, and use a UV-visible spectrophotometer (for example, Hitachi High-Tech Science Corporation, product name: Hitachi Spectrophotometer U-3310) to measure Absorption spectra of UV absorbers. After stabilizing the light source, the spectrophotometer was used, and then the background was measured in a 1 cm quartz cell filled with toluene, and then used for the absorption spectrum measurement of the ultraviolet absorber. As the measurement conditions, the temperature is the temperature when preparing the solution, the slit width is 2 nm, the scanning speed is 300 nm/min, the sampling interval is 0.50 nm, and the measurement range is from 600 nm to 300 nm. In each measurement, it was confirmed that the absorbance at a wavelength of 405 nm was not more than 2.0. The vertical axis takes the absorbance of the ultraviolet absorber for light with a wavelength of 405 nm, and the horizontal axis takes the product of the concentration of the ultraviolet absorber and the optical path length, and an approximate straight line is drawn by the least square method. It was confirmed that the coefficient of determination was 0.999 or more. Using the Lambert-Beer law, the slope of the obtained straight line is taken as the molar absorption coefficient (L/(mol·cm)) at the maximum absorption wavelength in the range of 395 to 415 nm (the maximum absorption wavelength closest to 405 nm) to calculate. In addition, in the above method, when the absorbance measured at the maximum absorption wavelength in the range of 395 to 415 nm (the maximum absorption wavelength closest to 405 nm) measured at a sample concentration of 1×10 ^-4 mol/L is 0.01 or less Here, the molar absorptivity is set to be 100 or less.

The photosensitive resin composition of this embodiment may contain other components (excluding the compound corresponding to (A) component, (B) component, (C) component, or (D) component). Examples of other components include hydrogen donors, polymerization inhibitors, organic solvents, dyes (excluding compounds corresponding to hydrogen donors: malachite green, etc.), tribromophenylene, photochromic agents, anti-heat agents, plasticizers, etc. Agents (p-toluamide, etc.), pigments, fillers, defoamers, flame retardants, stabilizers (light stabilizers, etc.), adhesion imparting agents, leveling agents, peel accelerators, antioxidants, fragrances , imaging agent, thermal crosslinking agent, etc.

Examples of hydrogen donors include bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, colorless compounds (for example, leuco dyes: leuco crystal violet, etc. ), N-phenylglycine, etc.

The content of the hydrogen donor or the content of the colorless compound may be within the following ranges with respect to 100 parts by mass of the total amount of (A) component and (B) component from the viewpoint of easily obtaining excellent resolution, adhesiveness, and sensitivity. The content of the hydrogen donor or the content of the colorless compound may be greater than 0 parts by mass, greater than 0.01 parts by mass, greater than 0.05 parts by mass, greater than 0.05 parts by mass, greater than 0.1 parts by mass, greater than 0.2 parts by mass, greater than 0.3 parts by mass, or 0.4 parts by mass More than or 0.5 parts by mass or more. The content of the hydrogen donor or the content of the colorless compound may be 5 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, 1.5 parts by mass or less, 1 part by mass or less, 0.8 parts by mass or less, 0.7 parts by mass or less, or 0.5 parts by mass the following. From these viewpoints, the content of the hydrogen donor or the content of the colorless compound may be more than 0 parts by mass and not more than 5 parts by mass, more than 0.05 parts by mass and not more than 5 parts by mass, or 0.1 to 5 parts by mass.

The polymerization inhibitor suppresses the polymerization in the unexposed area when forming the resist pattern, and it is easy to improve the resolution. Examples of polymerization inhibitors include tert-butylcatechol (for example, 4-tert-butylcatechol), hindered amines (for example, 2,2,6,6-tetramethyl-4-hydroxypiperol pyridine-1-oxyl), 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, etc.

The content of the polymerization inhibitor may be in the following range with respect to 100 parts by mass of the total amount of (A) component and (B) component from the viewpoint of easy improvement of resolution. The content of the polymerization inhibitor may be at least 0.001 parts by mass, at least 0.003 parts by mass, at least 0.005 parts by mass, at least 0.01 parts by mass, at least 0.015 parts by mass, at least 0.02 parts by mass, or at least 0.025 parts by mass. The content of the polymerization inhibitor may be 0.1 parts by mass or less, 0.05 parts by mass or less, 0.04 parts by mass or less, or 0.03 parts by mass or less. From these viewpoints, the content of the polymerization inhibitor may be 0.001 to 0.1 parts by mass.

Examples of the organic solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl celuso, ethyl celuso, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether, and the like.

The photosensitive resin composition of this embodiment may not contain an anthracene compound. Examples of the anthracene compound include 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene, 9,10-diethoxyanthracene, and the like. The content of the anthracene compound may be 0.5 parts by mass or less, 0.2 parts by mass or less, 0.2 parts by mass or less, 0.1 parts by mass or less, 0.1 parts by mass or less, or 0.01 It may be 0 mass % or less, or 0.001 mass part or less.

The photosensitive resin composition of this embodiment may not contain an aminobenzenesulfonamide compound. Examples of the aminobenzenesulfonamide compound include 3-amino-4-methoxy-N,N'-diethylaminobenzenesulfonamide and the like. The content of the aminobenzenesulfamide compound may be 0.5 mass parts or less, 0.3 mass parts or less, less than 0.3 mass parts, 0.1 mass parts or less, and less than 100 mass parts of the total amount of (A) component and (B) component. It may be 0.1 mass part, 0.01 mass part or less, or 0.001 mass part or less, and may be 0 mass %.

＜Photosensitive element＞ The photosensitive element of this embodiment has a support body and the photosensitive resin layer arrange|positioned on this support body, and a photosensitive resin layer contains the photosensitive resin composition of this embodiment. The photosensitive element of this embodiment may be equipped with the protective layer arrange|positioned on the photosensitive resin layer. The photosensitive element of this embodiment may include a buffer layer, an adhesive layer, a light absorbing layer, a gas barrier layer, and the like. The photosensitive element may be in the form of a sheet, or may be in the form of a photosensitive element roll wound up on a core in roll form.

Fig. 1 is a schematic cross-sectional view showing an example of a photosensitive element. As shown in FIG. 1 , a photosensitive element 1 includes a support (support film) 2 , a photosensitive resin layer 3 disposed on the support 2 , and a protective layer (protective film) 4 disposed on the photosensitive resin layer 3 . The photosensitive resin layer 3 is composed of the photosensitive resin composition of this embodiment.

The photosensitive element 1 can be obtained by the following procedure, for example. First, the photosensitive resin layer 3 is formed on the support body 2 . The photosensitive resin layer 3 can be formed by drying the coating layer formed by coating the photosensitive resin composition containing an organic solvent, for example. Next, the protective layer 4 is disposed on the photosensitive resin layer 3 .

The support and protective layer can be heat-resistant and solvent-resistant polymer film, polyester film (polyethylene terephthalate film, etc.), polyolefin film (polyethylene film, polypropylene film, etc.), hydrocarbon Polymers (except polyolefin films), etc. The type of the film constituting the protective layer and the type of film constituting the support may be the same as or different from each other.

The thickness of the support may be 1 μm or more, 5 μm or more, 10 μm or more, or 15 μm or more from the viewpoint of easily suppressing the breakage of the support body when peeling the support body from the photosensitive resin layer. The thickness of the support may be 100 μm or less, 50 μm or less, 30 μm or less, or 20 μm or less from the viewpoint of easy and preferable exposure when exposure is performed through the support. The thickness of the photosensitive resin layer (the thickness after drying; when the photosensitive resin composition contains an organic solvent, the thickness after volatilizing the organic solvent) may be the thickness of the above-mentioned film-like photosensitive resin composition.

＜Manufacturing method of laminate＞ The manufacturing method of the laminated body of this embodiment includes: using the photosensitive resin composition or photosensitive element of this embodiment to arrange the photosensitive resin layer on the substrate (for example, substrate); An exposure step of photocuring (exposure) of a part of the photosensitive resin layer; and a developing step of removing an uncured portion (unexposed portion) of the photosensitive resin layer to form a cured product pattern. The laminated body of this embodiment is obtained by the manufacturing method of the laminated body of this embodiment, and may be a printed wiring board. The laminated body of the present embodiment may have a substrate and a cured product pattern (cured product of the present embodiment) arranged on the substrate.

In the step of arranging the photosensitive resin layer, the photosensitive resin layer composed of the photosensitive resin composition of the present embodiment is arranged on the substrate. For example, the photosensitive resin layer can be formed by coating and drying the photosensitive resin composition on the substrate, or after removing the protective layer from the photosensitive element, the photosensitive resin layer of the photosensitive element can be heated while pressing connected to the base material.

In the exposing step, activating light may be irradiated with a mask placed on the photosensitive resin layer, and the area of the photosensitive resin layer other than the area where the mask is placed may be exposed to be photocured, or may not be exposed. Using a mask, activating light is irradiated in a desired pattern by a direct drawing exposure method such as an LDI exposure method or a DLP exposure method, and a part of the photosensitive resin layer is exposed and photocured. As the light source of the activating light, an ultraviolet light source or a visible light source can be used, and carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gas lasers (argon lasers, etc.), solid-state lasers (YAG lasers, etc.) can be used. lasers, etc.), semiconductor lasers, etc.

The developing method in the developing step may be, for example, wet developing or dry developing. Wet development uses a developer corresponding to the photosensitive resin composition, and can be performed by, for example, methods such as dipping, puddle, spraying, brushing, scraping, and shaking dipping. The developer is appropriately selected depending on the composition of the photosensitive resin composition, and may be an alkali developer or an organic solvent developer.

Alkaline developer can be an aqueous solution containing the following: alkali hydroxides such as hydroxides of lithium, sodium or potassium; alkali metal carbonates such as carbonates or bicarbonates of lithium, sodium, potassium or ammonium; alkalis such as potassium phosphate and sodium phosphate Metal phosphates; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; borax; sodium metasilicate; tetramethylammonium hydroxide; ethanolamine; ethylenediamine; diethylenetriamine; 2-amino- 2-Hydroxymethyl-1,3-propanediol; 1,3-diamino-2-propanol; pomaline and other bases.

Organic solvent developer can contain 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyl Organic solvents such as lactones.

The manufacturing method of the laminated body of the present embodiment may further include heating the photosensitive resin layer at 60-250° C. or exposing at 0.2-10 J/cm ² after the exposing step and/or after the developing step. The curing step of the curing part.

The method for producing a laminate according to the present embodiment may include a metal layer forming step of forming a metal layer on at least a part of a portion of the substrate where the cured product pattern is not formed after the developing step. The metal layer can be, for example, a metal copper layer. The metal layer can be formed, for example, by performing electroplating. The electroplating treatment may be one or both of electrolytic plating treatment and electroless plating treatment. The laminate of the present embodiment may have a base material, a cured product pattern disposed on the base material, and a metal layer disposed at least part of a portion of the base material where the cured product pattern is not formed.

The method of manufacturing the laminate of this embodiment may include a step of removing the pattern of the cured product after the metal layer forming step. The pattern of the cured product can be removed, for example, by developing by dipping or spraying using a strong alkaline aqueous solution.

FIG. 2 is a schematic diagram showing an example of a method of manufacturing a laminate (a method of manufacturing a printed wiring board). In one example of the method of manufacturing a laminate, first, as shown in FIG. 2( a ), a base material (for example, a circuit-forming substrate) 10 having an insulating layer 10 a and a conductive layer 10 b arranged on the insulating layer 10 a is prepared. The conductor layer 10b may be, for example, a metal copper layer.

Next, as shown in FIG. 2( b ), the photosensitive resin layer 12 is arranged on the conductive layer 10 b of the base material 10 (photosensitive resin layer arrangement step). In the step of arranging the photosensitive resin layer, the photosensitive resin layer 12 is arranged on the conductor layer 10b of the base material 10 using the photosensitive resin composition or the photosensitive element of this embodiment.

Next, as shown in FIG. 2( c ), by irradiating activating light L in the state where the mask 14 is arranged on the photosensitive resin layer 12 , and irradiating the photosensitive resin layer 12 except for the region where the mask 14 is arranged, The exposed areas are exposed to photocure.

Next, after removing the mask 14, as shown in FIG. 2(d), the region (uncured portion) in the photosensitive resin layer except for the photocured portion is removed from the substrate 10 by developing, forming a photocured portion. part (the cured product of the photosensitive resin layer) consists of a resist pattern 12a.

Next, as shown in FIG. 2( e ), a wiring layer (metal layer) 16 is formed on a portion of the conductive layer 10 b of the base material 10 where the resist pattern 12 a is not formed. The wiring layer 16 may be formed of the same kind of material as that of the conductor layer 10b, or may be formed of a different kind of material.

Next, as shown in FIG. 2( f ), the conductive layer 10 c is formed by removing the resist pattern 12 a and removing the conductive layer 10 b provided at a position corresponding to the resist pattern 12 a. Thereby, the printed wiring board 18 provided with the conductor layer 10c and the wiring layer 16 arrange|positioned on the insulating layer 10a can be obtained. The conductive layer 10b can be removed by etching. The etchant can be appropriately selected according to the type of the conductor layer 10b, for example, it can be a cupric chloride solution, a ferric chloride solution, an alkali etching solution, a hydrogen peroxide etching solution, and the like. [Example]

Hereinafter, the present disclosure will be further specifically described by means of examples, but the present disclosure is not limited to these examples.

＜Synthesis of binder polymer＞ (Binder Polymer A1) Prepared by mixing 27 parts by mass of methacrylic acid, 3 parts by mass of 2-hydroxyethyl methacrylate, 20 parts by mass of benzyl methacrylate, 50 parts by mass of styrene, and 0.9 parts by mass of azobisisobutyronitrile solution (a). A solution (b) was prepared by dissolving 0.5 parts by mass of azobisisobutyronitrile in 50 parts by mass of a liquid mixture of 30 parts by mass of methyl celuso and 20 parts by mass of toluene. In a flask equipped with a stirrer, a reflux cooler, a thermometer, a dropping funnel, and a nitrogen gas introduction tube, 500 g of a mixture of 30 parts by mass of methyl celuxo and 20 parts by mass of toluene was put into the flask, and nitrogen gas was blown into the bottle. While stirring, the temperature was raised to 80°C. After the solution (a) was dripped into the said flask over 4 hours at a constant dropping rate, the solution in the flask was stirred at 80 degreeC for 2 hours. Next, the solution (b) was dropped into the above-mentioned flask over 10 minutes at a constant dropping rate, and then the solution in the flask was stirred at 80° C. for 3 hours. Furthermore, the solution in the flask was heated to 90° C. over 30 minutes, kept at 90° C. for 2 hours, then the stirring was stopped, and the solution of the binder polymer A1 was obtained by cooling to room temperature (25° C.). The non-volatile content (solid content) of the solution of the binder polymer A1 was 49 mass %.

(Binder Polymer A2) In addition to preparing a solution by mixing 27 parts by mass of methacrylic acid, 5 parts by mass of methyl methacrylate, 23 parts by mass of benzyl methacrylate, 45 parts by mass of styrene, and 0.9 parts by mass of azobisisobutyronitrile (a ) except that the solution of binder polymer A2 was obtained in the same manner as binder polymer A1. The non-volatile content (solid content) of the solution of the binder polymer A2 was 47 mass %.

(Binder Polymer A3) In addition to preparing a solution (a) by mixing 30 parts by mass of methacrylic acid, 35 parts by mass of methyl methacrylate, 35 parts by mass of butyl methacrylate, and 0.5 parts by mass of azobisisobutyronitrile, the A solution of binder polymer A3 was obtained in the same manner as binder polymer A1. The non-volatile content (solid content) of the solution of the binder polymer A3 was 44 mass %.

(Binder Polymer A4) Except by mixing 30 parts by mass of methacrylic acid, 22 parts by mass of methyl methacrylate, 8 parts by mass of butyl methacrylate, 10 parts by mass of ethyl acrylate, 30 parts by mass of styrene and 0.5 parts by mass of azobisisobutyronitrile A solution of binder polymer A4 was obtained in the same manner as that of binder polymer A1, except that solution (a) was prepared. The non-volatile content (solid content) of the solution of the binder polymer A4 was 43 mass %.

＜Acid value of binder polymer＞ The acid value of the binder polymer A1 is 176 mgKOH/g, the acid value of the binder polymer A2 is 176 mgKOH/g, the acid value of the binder polymer A3 is 196 mgKOH/g, and the acid value of the binder polymer A4 is 196 mgKOH/g g. The acid value was measured in the following procedure. First, after accurately weighing 1 g of the binder polymer which is the measurement object of the acid value, 30 g of acetone was added to the binder polymer and dissolved uniformly to obtain a solution. Next, after appropriately adding phenolphthalein which is an indicator drug to the solution, titration was performed using a 0.1 N KOH (potassium hydroxide) aqueous solution. The acid value was found by calculating the mass (unit: mg) of KOH required to neutralize the acetone solution of the binder polymer.

＜Molecular weight of binder polymer＞ The weight average molecular weight (Mw) of the binder polymer A1 was 35,000, and the number average molecular weight (Mn) was 16,000. The weight average molecular weight (Mw) of the binder polymer A2 was 50,000, and the number average molecular weight (Mn) was 21,000. The weight average molecular weight (Mw) of the binder polymer A3 was 50,000, and the number average molecular weight (Mn) was 22,000. The weight average molecular weight (Mw) of the binder polymer A4 was 50,000, and the number average molecular weight (Mn) was 21,000. The weight average molecular weight and the number average molecular weight were measured by gel permeation chromatography (GPC) under the following conditions, and were calculated and derived using a calibration curve of standard polystyrene.

(GPC conditions) Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., product name) Column: 3 in total as follows (manufactured by SHOWA DENKO MATERIALS CO., LTD., product name) Gelpack GL-R440 Gelpack GL-R450 Gelpack GL-R400M Eluent: Tetrahydrofuran Measuring temperature: 40°C Flow rate: 2.05mL/min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., product name)

＜Preparation of photosensitive resin composition＞ (Example 1) By adding a solution of binder polymer A1 (an amount corresponding to 56 parts by mass of binder polymer (non-volatile components), 2,2-bis(4-(meth)acryloxypentaethoxy) Phenyl)propane (EO average 10mol adduct, molecular weight: 804) (manufactured by SHOWA DENKO MATERIALS CO., LTD., product name: FA-321M(70)) 35 parts by mass, 2,2-bis(4-( Methacryloxypolyethoxy)phenyl)propane (EO average 2.6mol adduct, molecular weight: 478, manufactured by KYOEISHA CHEMICAL Co., LTD., product name: BP-2EM) 5 parts by mass, (PO ) (EO) (PO) modified dimethacrylate (addition product of EO average 6 mol and PO average 12 mol (total value), molecular weight: 1114, manufactured by SHOWA DENKO MATERIALS CO., LTD., product name: FA-024M ) 4 parts by mass, photopolymerization initiator (2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, BCIM, Hampford Company Manufacturing) 6 parts by mass, sensitizer D1 (N,N'-bis[4-(2-phenylethen-1-yl)-4'-methylphenyl]-N,N'-bis(2- Ethyl-6-methylphenyl)-1,1'-biphenyl-4,4'-diamine, manufactured by TRONLY (Changzhou Qiangli), product name: PSS-402, maximum absorption wavelength: 397nm, maximum absorption Molar absorption coefficient at wavelength: 85000L/(mol·cm)) 0.10 parts by mass, hydrogen donor (colorless crystal violet, LCV, manufactured by YAMADA CHEMICAL CO., LTD.) 0.5 parts by mass, polymerization inhibitor A (4- Tertiary butylcatechol, manufactured by DIC CORPORATION, product name: DIC-TBC-5P) 0.015 parts by mass, polymerization inhibitor B (manufactured by ADEKA CORPORATION, product name: LA-7RD) 0.01 parts by mass, dye (malachite green, MKG, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 0.02 parts by mass, additive A (light stabilizer, manufactured by SHOWA DENKO MATERIALS CO., LTD., product name: FA-711MM) 1 part by mass, additive B (carboxybenzene Mixture of triazole, 5-amino-1H-tetrazole and methoxypropanol, manufactured by SUNWA CHEMICAL Co., Ltd., product name: SF-808H) 0.5 parts by mass, 8 parts by mass of methanol, 18 parts by mass of toluene part and 10 parts by mass of acetone were mixed to prepare a photosensitive resin composition.

(Example 2) Except having changed the usage-amount of the sensitizer D1 into 0.20 mass parts, it carried out similarly to Example 1, and prepared the photosensitive resin composition.

(Example 3) Except having changed the usage-amount of the sensitizer D1 into 0.30 mass parts, it carried out similarly to Example 1, and prepared the photosensitive resin composition.

(Example 4) In addition to using the solution of binder polymer A2 (56 parts by mass of binder polymer (non-volatile components)) instead of the solution of binder polymer A1 (56 parts by mass of binder polymer (non-volatile components)), with The photosensitive resin composition was prepared in the same manner as in Example 1.

(Example 5) In addition to using the solution of binder polymer A3 (56 parts by mass of binder polymer (non-volatile components)) instead of the solution of binder polymer A1 (56 parts by mass of binder polymer (non-volatile components)), with The photosensitive resin composition was prepared in the same manner as in Example 1.

(Example 6) In addition to using the solution of the binder polymer A4 (56 parts by mass of the binder polymer (non-volatile components)) instead of the solution of the binder polymer A1 (56 parts by mass of the binder polymer (non-volatile components)), with The photosensitive resin composition was prepared in the same manner as in Example 1.

(comparative example 1) Except using 0.65 parts by mass of sensitizer D2 (9,10-dibutoxyanthracene, DBA, manufactured by Kawasaki Kasei Chemicals Ltd., maximum absorption wavelength: 408 nm, molar absorption coefficient at maximum absorption wavelength: 7800 L/(mol cm)) instead of 0.10 parts by mass of the sensitizer D1, a photosensitive resin composition was prepared in the same manner as in Example 4.

(comparative example 2) In addition to using 0.10 parts by mass of sensitizer D3 (N,N'-bis[4-(2-phenylethen-1-yl)-phenyl]-N,N'-bis(2-ethyl-6- Methylphenyl)-1,1'-biphenyl-4,4'-diamine, maximum absorption wavelength: 392nm, molar absorption coefficient at maximum absorption wavelength: 68000L/(mol·cm)) instead of 0.10 mass A photosensitive resin composition was prepared in the same manner as in Example 4 except for the sensitizer D1 of 10 parts.

＜Production of photosensitive elements＞ As a support, a polyethylene terephthalate film (manufactured by TORAY INDUSTRIES, INC., product name "FS-31") with a thickness of 16 μm was prepared. After the above-mentioned photosensitive resin composition was uniformly coated on the support body, the photosensitive resin layer (photosensitive film, dried Average thickness at 10 places: 19 μm). A polyethylene film (manufactured by TAMAPOLY INC. Tochigi Factory, product name "NF-15") was bonded to the photosensitive resin layer as a protective layer to obtain a photosensitive resin layer sequentially equipped with a support, a photosensitive resin layer, and a protective layer. sex element.

＜Fabrication of laminates＞ Pickling and water washing of a copper laminate (substrate, manufactured by SHOWA DENKO MATERIALS CO., LTD., product name: MCL-E-67) with copper foil (thickness: 35 μm) arranged on both sides of a glass epoxy material Afterwards, drying was carried out with an air stream. Next, after heating the copper tension laminated board to 80° C., the photosensitive element was laminated so that the photosensitive resin layer was in contact with the copper surface while peeling off the protective layer, thereby obtaining a copper tension laminated board, A laminate of a photosensitive resin layer and a support. Lamination was performed at a pressure bonding pressure of 0.4 MPa and a roll speed of 1.0 m/min using a 110° C. hot roll.

＜Evaluation＞ (minimum developing time) The test piece was obtained by peeling off the support body after cutting the said laminated body into squares (5 cm*5 cm). Next, the unexposed photosensitive resin layer in the test piece was subjected to spray development with a pressure of 0.18 MPa using a 1% by mass sodium carbonate aqueous solution at 30° C., and the shortest time for visually confirming that the unexposed photosensitive resin layer was removed was obtained. time as the minimum development time (MD). The nozzle uses a solid cone type. The distance between the test piece and the tip of the nozzle was 6 cm, and the center of the test piece was arranged to coincide with the center of the nozzle.

(Sensitivity) After placing a 41-stage trapezoidal plate (manufactured by SHOWA DENKO MATERIALS CO., LTD.) on the support of the above-mentioned laminate, a direct-drawing exposure machine ( Manufactured by Via Mechanics, Ltd., product name: DE-1UH), the exposure amount (irradiation energy) of 15 steps after development of the remaining steps of the trapezoidal plate of 41 steps was used to expose the photosensitive resin layer through the support . The sensitivity (photosensitivity) was evaluated by the exposure amount (unit: mJ/cm ² ) at this time. The results are shown in Table 1. The lower the exposure amount, the better the sensitivity.

(analytical) After placing 41 segments of trapezoidal plates (manufactured by SHOWA DENKO MATERIALS CO., LTD.) on the support of the above-mentioned laminate, a direct-drawing exposure machine (Via Mechanics, Ltd., product name: DE-1UH), line width (L) / space width (S) (hereinafter, described as "L/S") is 3x/x (x=1～20, unit: μm , 1 μm interval) drawing patterns, the number of remaining steps after development of the 41-step trapezoidal plate became 15 steps of exposure (irradiation energy), and the photosensitive resin layer was exposed (drawn) through the support without deviation. Within 3 minutes after the exposure, post-exposure heating (PEB: Post-Exposure-Bake) was performed on conditions of 80° C. and 30 seconds using a heating oven.

After exposure, the support was peeled off from the laminate to expose the photosensitive resin layer, and the unexposed portion was removed by spraying a 1% by mass sodium carbonate aqueous solution at 30° C. for twice the above minimum developing time. After development, the minimum value (unit: μm) of the space width in the resist pattern where the space part (unexposed part) is removed without residue and the line part (exposed part) does not produce meanders and defects Instead, analytical performance was evaluated. The results are shown in Table 1. The smaller the numerical value, the better the resolution.

(tightness) After placing 41 segments of trapezoidal plates (manufactured by SHOWA DENKO MATERIALS CO., LTD.) on the support of the above-mentioned laminate, a direct-drawing exposure machine (Via Mechanics, Ltd., product name: DE-1UH), L/S is x/3x (x = 1 ~ 20, unit: μm, 1μm interval) of the drawing pattern, and the number of remaining segments after development of the 41-segment trapezoidal plate The exposure amount (irradiation energy) of 15 steps was used to expose (draw) the photosensitive resin layer through the support without shifting. Within 3 minutes after the exposure, post-exposure heating (PEB: Post-Exposure-Bake) was performed on conditions of 80° C. and 30 seconds using a heating oven.

After exposure, the support was peeled off from the laminate to expose the photosensitive resin layer, and the unexposed portion was removed by spraying a 1% by mass sodium carbonate aqueous solution at 30° C. for twice the above minimum developing time. The minimum value (unit: μm) of the line width in the resist pattern where the space portion (unexposed portion) is removed without residue after development, and the line portion (exposed portion) is formed without twists and defects Instead, the adhesiveness was evaluated. The results are shown in Table 1. The smaller this numerical value, the better the adhesion.

[Table 1] Example comparative example 1 2 3 4 5 6 1 2 binder polymer A1 A1 A1 A2 A3 A4 A2 A2 Sensitizer type D1 D1 D1 D1 D1 D1 D2 D3 Content [parts by mass] 0.10 0.20 0.30 0.10 0.10 0.10 0.65 0.10 Sensitivity [mJ/cm ² ] 80 67 33 80 80 80 92 85 Resolution [μm] 7 8 8 8 9 9 11 12 Adhesion [μm] 3 4 7 5 6 6 5 7

1: photosensitive element 2: Support body 3,12: Photosensitive resin layer 4: Protective layer 10: Substrate 10a: insulating layer 10b, 10c: conductor layer 12a: Resist pattern 14: mask 16: Wiring layer 18: Printed wiring board L: Activated light

Fig. 1 is a schematic cross-sectional view showing an example of a photosensitive element. Fig. 2 is a schematic diagram showing an example of a method for producing a laminate.

Claims (15)

A photosensitive resin composition comprising a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a tetraarylbenzidine compound represented by the following general formula (d1), [Chem. 1] In formula (d1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent an alkyl group, an alkoxy group, a halo group, an amino group, a hydroxyl group, or a carboxyl group Or carboxylate group, n11, n12, n13 and n14 each independently represent an integer of 0 to 4, n15, n16, n17 and n18 each independently represent an integer of 0 to 5, at least one of n15 and n16 is 1 above. The photosensitive resin composition according to Claim 1, wherein the aforementioned tetraaryl benzidine compound includes a tetraaryl benzidine compound represented by the following general formula (d2), [Chem. 2] In formula (d2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ^{16 , R 17a , R 17b , R 18a} and R ^18b each independently represent an alkyl group, an alkoxy group, a halo group, An amino group, a hydroxyl group, a carboxyl group, or a carboxylate group, and n11, n12, n13, and n14 each independently represent an integer of 0-4. The photosensitive resin composition as described in Claim 1, wherein The aforementioned tetraarylbenzidine compounds include N,N'-bis[4-(2-phenylethen-1-yl)-4'-methylphenyl]-N,N'-bis(2-ethyl- 6-methylphenyl)-1,1'-biphenyl-4,4'-diamine. The photosensitive resin composition as described in Claim 1, wherein Content of the said tetraaryl benzidine compound is 0.01-0.50 mass parts with respect to 100 mass parts of total amounts of the said binder polymer and the said photopolymerizable compound. The photosensitive resin composition as described in Claim 1, wherein The aforementioned binder polymer includes a polymer having benzyl (meth)acrylate as a monomer unit. The photosensitive resin composition as described in Claim 5, wherein Content of the monomer unit of the said benzyl (meth)acrylate in the said polymer is 10-30 mass %. The photosensitive resin composition as described in Claim 1, wherein The aforementioned binder polymer includes a polymer having a styrene compound as a monomer unit. The photosensitive resin composition as described in Claim 7, wherein Content of the monomer unit of the said styrene compound in the said polymer is 40-60 mass %. The photosensitive resin composition as described in Claim 1, wherein The weight average molecular weight of the said binder polymer is 10000-100000. The photosensitive resin composition as described in Claim 1, wherein The aforementioned photopolymerizable compound includes a bisphenol A type (meth)acrylic compound. The photosensitive resin composition according to Claim 1, which is in the form of a film. The photosensitive resin composition according to Claim 11, which has a thickness of 30 μm or less. A photosensitive element comprising a support and a photosensitive resin layer arranged on the support, The aforementioned photosensitive resin layer includes the photosensitive resin composition described in any one of claim 1 to claim 12. A method of manufacturing a laminate comprising: A step of disposing a photosensitive resin layer on a substrate by using the photosensitive resin composition described in any one of claim 1 to claim 12; a step of photocuring a part of the aforementioned photosensitive resin layer; and A step of forming a cured product pattern by removing the uncured portion of the aforementioned photosensitive resin layer. A method of manufacturing a laminate comprising: a step of disposing a photosensitive resin layer on a substrate by using the photosensitive element described in claim 13; a step of photocuring a part of the aforementioned photosensitive resin layer; and A step of forming a cured product pattern by removing the uncured portion of the aforementioned photosensitive resin layer.