JP2024040149A - Photosensitive resin composition, photosensitive resin film, method for producing cured product, laminate, and electronic component - Google Patents

Abstract

[Problem] To provide a photosensitive resin composition that has excellent pattern formability even when forming a thick photosensitive layer of 70 μm or more. [Solution] This photosensitive resin composition contains component (A): a compound having a photopolymerizable functional group, and component (B): a photopolymerization initiator having a molar absorption coefficient for light with a wavelength of 365 nm of less than 8.0×103 L/mol cm, and when the thickness of the photosensitive resin composition is 50 μm, the absorbance for light with a wavelength of 365 nm is less than 0.35. [Selected Figure] None

Description

The present disclosure relates to a photosensitive resin composition, a photosensitive resin film, a method for producing a cured product, a laminate, and an electronic component.

In the field of manufacturing semiconductor integrated circuits (LSI) or wiring boards, photosensitive materials are used as resists for producing conductor patterns. For example, in manufacturing wiring boards, a resist is formed using a photosensitive resin composition, and then conductive patterns, metal posts, etc. are formed by plating. More specifically, a photosensitive layer is formed on a support (substrate) using a photosensitive resin composition, etc., the photosensitive layer is exposed to light through a predetermined mask pattern, and then a conductive pattern and a metal post are formed. A resist pattern (resist) is formed by performing a development process to selectively remove (peel off) the portion where the pattern is to be formed. Next, a conductor such as copper is formed on the removed portion by plating, and then the resist pattern is removed, thereby manufacturing a wiring board including a conductor pattern, metal posts, etc.

Conventionally, thick conductor patterns and metal posts have been produced by removing a resist pattern and then growing metal plating. In order to meet such demands, for example, thick film photosensitive resists have been used in which the thickness of the photosensitive layer is approximately 30 μm, and at most, the thickness of the photosensitive layer is approximately 65 μm (see Patent Documents 1 and 2).
In addition, in recent years, in order to further improve performance, the conductor layer is made to a thickness of 150 μm by performing plating treatment while destroying the layer in the metal ion diluted layer that exists in the direction in which the plating is desired to be selectively grown using a plating solution. Attempts have been made to form it as thick as possible (see Patent Document 3).

JP2015-034926A JP 2014-074774 A Japanese Patent Application Publication No. 2014-080674

However, with conventional photosensitive resists for thick films, when a thick photosensitive layer of 70 μm or more is required to be formed, for example, it is difficult for light to pass through to the bottom, resulting in deterioration of the pattern shape. Furthermore, in the method described in Patent Document 3, plating proceeds while partially destroying the metal ion diluted layer, so it is difficult to stably form an excellent pattern. Therefore, there is a need for a photosensitive resist that has excellent pattern forming properties even when a photosensitive layer is formed with a thickness of 70 μm, or even 150 μm, which is thicker than conventional ones, or even thicker than that.

Therefore, the problem to be solved by the present disclosure was made in view of the above circumstances, and includes, for example, a photosensitive resin that has excellent pattern forming properties even when forming a thick photosensitive layer of 70 μm or more. The object of the present invention is to provide a composition, a photosensitive resin film, a method for producing a cured product, a laminate, and an electronic component (hereinafter sometimes referred to as "photosensitive resin composition, etc.").

The inventors of the present invention have conducted intensive research to solve the above problem, and have found that the problem can be solved by a photosensitive resin composition having the following structure. The present disclosure provides the following photosensitive resin composition and the like.

[1] A photosensitive resin composition comprising: (A) a component: a compound having a photopolymerizable functional group; and (B) a photopolymerization initiator having a molar absorption coefficient for light having a wavelength of 365 nm of less than 8.0 × 10 ³ L/mol cm, wherein the photosensitive resin composition has an absorbance for light having a wavelength of 365 nm of less than 0.35 when the photosensitive resin composition has a thickness of 50 μm.
[2] A photosensitive resin film having a photosensitive layer using the photosensitive resin composition according to [1] above.
[3] A step of forming a photosensitive layer on a substrate using the photosensitive resin composition described in [1] above or the photosensitive resin film described in [2] above;
A step of irradiating at least a part of the photosensitive layer with active light to form a photocured portion;
and removing at least a portion of the photosensitive layer other than the photocured portion to form a resin pattern.
[4] A laminate comprising a cured product of the photosensitive resin composition described in [1] above.
[5] An electronic component comprising a cured product of the photosensitive resin composition described in [1] above.

According to the present disclosure, it is possible to provide a photosensitive resin composition having excellent pattern forming properties even when forming a thick photosensitive layer of 70 μm or more, for example.

It is a schematic diagram which shows an example of the mask for resolution evaluation used in an Example.

The present disclosure will be described in detail below.
In this specification, a numerical range indicated using "~" indicates a range that includes the numerical values written before and after "~" as the minimum and maximum values, respectively. Furthermore, in the numerical ranges described stepwise in this specification, the upper limit or lower limit of the numerical range of one step may be replaced with the upper limit or lower limit of the numerical range of another step. In the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with the value shown in the Examples.
"(Meth)acrylic acid" means at least one of "acrylic acid" and the corresponding "methacrylic acid," and the same applies to other similar expressions such as (meth)acrylate.

[Photosensitive resin composition]
A photosensitive resin composition according to an embodiment of the present disclosure (hereinafter sometimes simply referred to as the present embodiment) includes (A) component: a compound having a photopolymerizable functional group, and (B) component: a wavelength of 365 nm. A photosensitive resin composition containing a photopolymerization initiator whose molar extinction coefficient for light is less than 8.0 × 10 ³ L/mol cm, and when the thickness of the photosensitive resin composition is 50 μm. , a photosensitive resin composition having an absorbance of less than 0.35 for light with a wavelength of 365 nm.
In this specification, "solid content" refers to the nonvolatile content excluding volatile substances such as water and solvent contained in the photosensitive resin composition, and when the resin composition is dried, it is It refers to the components that remain without being removed, and also includes those that are liquid, syrupy, and waxy at room temperature. Here, in this specification, room temperature refers to 25°C.
Hereinafter, when simply writing "molar extinction coefficient", it refers to "molar extinction coefficient for light with a wavelength of 365 nm", and when simply writing "absorbance", it means "when the thickness of the photosensitive resin composition is 50 μm". , the absorbance for light with a wavelength of 365 nm.

The photosensitive resin composition of this embodiment has an absorbance of less than 0.35 for light with a wavelength of 365 nm when the thickness of the photosensitive resin composition is 50 μm. If the absorbance of the photosensitive resin composition is less than 0.35, for example, even if a pattern is formed with a thick photosensitive layer of 70 μm or more using the photosensitive resin composition of the present embodiment, the photosensitive layer will be damaged. Since light can easily pass through to the bottom (the surface of the photosensitive layer on the substrate side), pattern formation properties can be improved. From the same viewpoint, the absorbance of the photosensitive resin composition of this embodiment can be appropriately selected from 0.30 or less, 0.25 or less, or 0.22 or less. The lower limit of absorbance can be appropriately selected from, for example, 0.001 or more, 0.005 or more, or 0.008 or more.
In addition, the absorbance of the photosensitive resin composition can be appropriately adjusted by the types and contents of the compound having a photopolymerizable functional group, the photopolymerization initiator, the inorganic filler, etc., which will be described later.
The absorbance can be measured using, for example, an ultraviolet-visible spectrophotometer (product name: "U-3310 Spectrophotometer", manufactured by Hitachi High-Technologies Corporation), using a single polyethylene terephthalate film as a reference, and measuring the absorbance for light with a wavelength of 365 nm. can be measured.
In addition, the absorbance for light with a wavelength of 365 nm when the thickness of the photosensitive resin composition is 50 μm is determined by converting the absorbance measured for a photosensitive resin composition with a thickness other than 50 μm to the absorbance at a thickness of 50 μm based on Beer-Lambert's law. You can also calculate it by converting it.

<Component (A): Compound having a photopolymerizable functional group>
Examples of the photopolymerizable functional group contained in component (A) include (meth)acryloyl groups; ethylenically unsaturated groups such as alkenyl groups such as vinyl groups and allyl groups. Among these, the component (A) may contain a compound having a (meth)acryloyl group as a photopolymerizable functional group from the viewpoint of improving pattern forming properties.
In addition, from the viewpoint of improving pattern forming properties, component (A) may contain a compound having a carbon-nitrogen bond, and may contain a compound having a urethane bond as the carbon-nitrogen bond. . In addition, from the viewpoint of improving pattern formation when a thick photosensitive layer of 70 μm or more is formed, the lower limit of the content of the compound having a photopolymerizable functional group and a urethane bond is determined by the solid content of the photosensitive resin composition. Based on the total amount, it may be appropriately selected from 70% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, or 95% by mass or more. Considering the pattern forming properties and coating properties of the resulting resin composition, and the physical properties and characteristics required for the cured product of the resin composition, there is no particular restriction on the upper limit, but it is based on the total solid content of the photosensitive resin composition. can be appropriately selected from 100% by mass or less, 99% by mass or less, 95% by mass or less, 85% by mass or less, or 80% by mass or less.
Examples of compounds having a (meth)acryloyl group include (meth)acrylates, and examples of compounds having a urethane bond as a carbon-nitrogen bond include (meth)acrylates having a urethane bond (hereinafter referred to as "urethane"). (sometimes referred to as "meth)acrylate").
The number of photopolymerizable functional groups contained in component (A) is 1 to 24 from the viewpoint of pattern formation, and 2 to 15 or 2 from the viewpoint of stabilizing the physical properties and characteristics of the obtained cured product. -12 may be selected as appropriate.
The photosensitive resin composition of the present embodiment may contain, as the component (A), a component (A1): a polymer having a photopolymerizable functional group, from the viewpoint of improving pattern formation properties. (A2) Component: A low molecular weight substance having a photopolymerizable functional group may be contained.
The component (A1) and the component (A2) will be explained in order below.

((A1) component: polymer having a photopolymerizable functional group)
Component (A1) is a polymer having a photopolymerizable functional group. "High molecular weight substance" means a compound having a weight average molecular weight (Mw) of 2,500 or more. In addition, the value of the weight average molecular weight in this specification is the value measured using tetrahydrofuran (THF) by the gel permeation chromatography (GPC) method.
The photopolymerizable functional group contained in component (A1) is as described above as the photopolymerizable functional group contained in component (A), and from the viewpoint of improving pattern formation, it is used as a photopolymerizable functional group. It may have a (meth)acryloyl group.
The number of photopolymerizable functional groups contained in component (A1) is 2 to 24 from the same viewpoint as above, and 4 to 15 or 6 from the viewpoint of stabilizing the physical properties and characteristics of the cured product obtained. -12 may be selected as appropriate.
When the number of photopolymerizable functional groups is 2 or more, it is possible to improve not only pattern formability but also heat resistance and rigidity of the cured product at high temperatures. On the other hand, if the number of photopolymerizable functional groups is 24 or less, the rigidity of the cured product will be improved and the adhesion to the substrate etc. will be improved. In addition, the resin composition can be made to have an appropriate viscosity, and the coating properties are improved, and when the resin composition after coating is irradiated with light, only the surface portion is likely to be rapidly photocured. can suppress the phenomenon that photocuring does not proceed sufficiently. As a result, excellent resolution can be obtained, so even when a thick photosensitive layer is formed, excellent pattern formability can be obtained. Furthermore, after performing at least one of photocuring and thermosetting, it is possible to further reduce the amount of unreacted photopolymerizable functional groups remaining, thereby further suppressing fluctuations in the physical properties and characteristics of the resulting cured product.
The component (A1) may include a high molecular weight substance having at least one type of skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton, and the absorbance of the photosensitive resin composition From the viewpoint of reducing , the polymer may contain a polymer having at least one type of skeleton selected from the group consisting of a chain hydrocarbon skeleton and an alicyclic skeleton.

Examples of the urethane (meth)acrylate of component (A1) include reaction products of (meth)acrylates having hydroxyl groups and isocyanate compounds having isocyanate groups.
Examples of the (meth)acrylate having a hydroxyl group include compounds having at least one hydroxyl group and at least one (meth)acryloyl group in one molecule. More specifically, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2- Hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-(o-phenylphenoxy)propyl (meth)acrylate, 2-hydroxy-3-(1-naphthoxy)propyl (meth)acrylate, 2-hydroxy- Monofunctional (meth)acrylates such as 3-(2-naphthoxy)propyl (meth)acrylate, ethoxylated products thereof, propoxylated products thereof, ethoxylated propoxylated products thereof, and caprolactone modified products thereof; trimethylol Bifunctional (meth)acrylates such as propane di(meth)acrylate, glycerin di(meth)acrylate, bis(2-(meth)acryloyloxyethyl)(2-hydroxyethyl)isocyanurate, ethoxylated products thereof, propoxylated products, ethoxylated propoxylated products thereof, and caprolactone modified products thereof; cyclohexanedimethanol type epoxy di(meth)acrylate, tricyclodecane dimethanol type epoxy di(meth)acrylate, hydrogenated bisphenol A type epoxy di(meth)acrylate. ) acrylate, hydrogenated bisphenol F type epoxy di(meth)acrylate, hydroquinone type epoxy di(meth)acrylate, resorcinol type epoxy di(meth)acrylate, catechol type epoxy di(meth)acrylate, bisphenol A type epoxy di(meth)acrylate, bisphenol type F epoxy di(meth)acrylate Bifunctional epoxy (meth)acrylates such as epoxy di(meth)acrylate, bisphenol AF type epoxy di(meth)acrylate, biphenol type epoxy di(meth)acrylate, fluorene bisphenol type epoxy di(meth)acrylate, isocyanuric acid monoallyl type epoxy di(meth)acrylate, etc. Tri- or higher functional (meth)acrylates such as ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and their ethoxylation phenol novolac type epoxy (meth)acrylate, cresol novolac type epoxy poly(meth)acrylate, isocyanuric acid type epoxy tri(meth)acrylate Tri- or more functional epoxy (meth)acrylates such as acrylate; hydroxypropylated products such as trimethylolpropane tri(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate; and the like.
These can be used alone or in combination of two or more.

Here, the ethoxylated form, propoxylated form, ethoxylated propoxylated form, and hydroxypropylated form of (meth)acrylate are each added to the alcohol compound (or phenol compound) that is the raw material for the above-mentioned (meth)acrylate, for example. It is obtained by using as a raw material one or more of an ethylene oxide group, a propylene oxide group, an ethylene oxide group, a propylene oxide group, and a hydroxypropyl group.
Further, the caprolactone modified product is obtained, for example, by using as a raw material an alcohol compound (or phenol compound), which is a raw material for the above-mentioned (meth)acrylate, modified with ε-caprolactone.

The isocyanate compound having an isocyanate group includes a compound having at least one isocyanate group in one molecule, and may be a compound having one to three isocyanate groups in one molecule. More specifically, aliphatic monoisocyanate compounds such as ethyl isocyanate, propyl isocyanate, butyl isocyanate, octadecyl isocyanate, and 2-isocyanate ethyl (meth)acrylate; alicyclic monoisocyanate compounds such as cyclohexyl isocyanate; aromatics such as phenyl isocyanate; Monoisocyanate compounds such as group monoisocyanate compounds, aliphatic diisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate; 1,3-bis(isocyanatomethyl)cyclohexane , isophorone diisocyanate, 2,5-bis(isocyanatomethyl)norbornene, bis(4-isocyanatocyclohexyl)methane, 1,2-bis(4-isocyanatocyclohexyl)ethane, 2,2-bis(4-isocyanato) Alicyclic diisocyanate compounds such as cyclohexyl)propane, 2,2-bis(4-isocyanatocyclohexyl)hexafluoropropane, and bicycloheptane triisocyanate; 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6 - Aromatic compounds such as tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, hydrogenated xylylene diisocyanate, naphthalene-1,5-diisocyanate, etc. Examples include diisocyanate compounds such as diisocyanate compounds, and multimers of these diisocyanate compounds such as uretdione dimers, isocyanurate types, and biuret trimers. These can be used alone or in combination of two or more, and the two or three isocyanate compounds constituting the multimer may be the same or different.

Among them, from the viewpoint of improving pattern forming properties, diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds, and polymers of these diisocyanate compounds may be selected as appropriate. In particular, hexamethylene diisocyanate , isophorone diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, and isocyanurate type polymers ( isocyanurate type polyisocyanate).

The reaction product of the (meth)acrylate having a hydroxyl group and an isocyanate compound has a (meth)acryloyl group as a photopolymerizable functional group and a urethane bond as a carbon-nitrogen bond, and is more Specifically, for example, an organic group derived from a (meth)acrylate having a hydroxyl group in the molecule (i.e., 1 to 5 (meth)acrylates that are residues obtained by removing the hydroxyl group from the above-mentioned (meth)acrylate having a hydroxyl group) ), urethane bonds, and organic groups derived from the above-mentioned isocyanate compounds (i.e., residues obtained by removing the isocyanate group from the above-mentioned isocyanate compounds, chain hydrocarbon skeletons, and fatty acids). It has a cyclic skeleton or an organic group having an aromatic ring skeleton. These organic groups may be the same or different.

The urethane (meth)acrylate component (A1) is, from the viewpoint of improving pattern formation, for example, a terminal isocyanate group of a polyadduct of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound. , a reaction product obtained by reacting a (meth)acrylate having a hydroxyl group.

Examples of the isocyanate compound having at least two isocyanate groups in one molecule used here include diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds among the compounds exemplified as the above-mentioned isocyanate compounds. , and multimers of these diisocyanate compounds such as uretdione-type dimers, isocyanurate-type and biuret-type trimers.
The above isocyanate compounds can be used alone or in combination of two or more.

Examples of diol compounds include diol compounds having 1 to 20 carbon atoms, and specifically, ethylene glycol, diethylene glycol, propanediol, dipropylene glycol, butanediol, pentanediol, isopentyl glycol, and hexanediol. linear or branched saturated diol compounds such as , nonanediol, decanediol, dodecanediol, dimethyldodecanediol, octadecanediol; linear or branched diol compounds such as butenediol, pentenediol, hexenediol, methylpentenediol, dimethylhexenediol, etc. Or branched unsaturated diol compounds; diol compounds having an alicyclic skeleton such as various cyclohexane diols, various cyclohexanedimethanols, various tricyclodecane dimethanols, hydrogenated bisphenol A, hydrogenated bisphenol F, and the like. Here, the above-mentioned saturated diol compounds and unsaturated diol compounds can also be collectively referred to as diol compounds having a chain hydrocarbon skeleton.
The above diol compounds can be used alone or in combination of two or more.

As the diol compound having a chain hydrocarbon skeleton, from the viewpoint of improving pattern forming properties and increasing the glass transition point (Tg) after polymerization to improve water resistance, diol compounds having a carbon number of 1 to 20 or 2 to 16 carbon atoms are used. Alternatively, it may be appropriately selected from 2 to 14 saturated diol compounds, and more specifically, it may be appropriately selected from ethylene glycol and octadecane diol.
In addition, as a diol compound having an alicyclic skeleton, from the viewpoint of improving pattern forming properties and increasing the glass transition temperature (Tg) after polymerization to improve water resistance, the diol compound has 5 to 20 carbon atoms, 5 to 20 carbon atoms, and 5 to 20 carbon atoms. Diol compounds may be appropriately selected from diol compounds having an alicyclic skeleton of 18 or 6 to 16, and more specifically, various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol; It may be appropriately selected from various cyclohexanedimethanols such as 3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol.

In addition, the (meth)acrylates having a hydroxyl group used here include those exemplified as the (meth)acrylates used in the reaction product of the above-mentioned (meth)acrylate having a hydroxyl group and an isocyanate compound having an isocyanate group. Can be mentioned.

A reaction product obtained by reacting a (meth)acrylate having a hydroxyl group with the terminal isocyanate group of a polyadduct of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound is, for example, the following general formula ( Examples include those having the structural unit represented by 3).

In general formula (3), X ₁ represents a divalent organic group having a chain hydrocarbon skeleton, alicyclic skeleton, or aromatic ring skeleton, and Y ₁ represents a chain hydrocarbon skeleton or an alicyclic skeleton. Indicates a divalent organic group having Further, when the component (A1) has a plurality of the above structural units, the plurality of X ₁ and Y ₁ may be the same or different. That is, the component (A1) includes those having at least one type of skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton.

The divalent organic group of X ₁ is an organic group derived from an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, and an aromatic diisocyanate compound exemplified as the above-mentioned compounds having an isocyanate group, that is, an organic group derived from the above-mentioned isocyanate compound. Examples include divalent organic groups having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton, which are residues excluding an isocyanate group. In addition, the divalent organic group represented by X ₁ may be these residues themselves, or residues derived from isocyanate compound derivatives such as polyadducts of the above-mentioned isocyanate compounds and diol compounds. It's okay.
From the viewpoint of improving the pattern forming property and also improving the transparency, water resistance, and moisture resistance of the resin composition in a well-balanced manner, X ₁ is a divalent organic group having an alicyclic skeleton, especially the following formula ( It may also be a divalent organic group having an alicyclic skeleton, which is a residue of isophorone diisocyanate shown in 4).

As the divalent organic group having a chain hydrocarbon skeleton or alicyclic skeleton of _Y1 , the diol compounds having a chain hydrocarbon skeleton and the diols having an alicyclic skeleton, which are exemplified as the above-mentioned diol compounds. Examples include an organic group derived from a compound, that is, a divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton, which is a residue obtained by removing a hydroxyl group from the above-mentioned diol compound.
Among these, from the viewpoint of improving pattern forming properties and increasing the glass transition temperature (Tg) after polymerization to improve water resistance, the divalent organic group having a chain hydrocarbon skeleton has 1 to 1 carbon atoms. It may be appropriately selected from the residues obtained by removing the hydroxyl group from saturated diol compounds of 20, 2 to 16, or 2 to 14. More specifically, it may be appropriately selected from the residues obtained by removing the hydroxyl group from ethylene glycol and octadecane diol. do it. In addition, from the same viewpoint, divalent organic groups having an alicyclic skeleton include diol compounds having an alicyclic skeleton having 5 to 20 carbon atoms, 5 to 18 carbon atoms, or 6 to 16 carbon atoms, excluding the hydroxyl group. More specifically, various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol can be selected as appropriate. It may be appropriately selected from residues obtained by removing the hydroxyl group from various cyclohexanedimethanols such as cyclohexanedimethanol.

Specifically, the reaction product obtained by reacting a (meth)acrylate having a hydroxyl group with the terminal isocyanate group of a polyadduct of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound includes, for example, , and compounds represented by the following general formulas (5) and (6).

In general formulas (5) and (6), n ₁ and n ₂ each independently represent an integer of 3 to 20.

In addition, when an isocyanurate trimer (isocyanurate triisocyanate), which is a trimer of diisocyanate, is used as the isocyanate compound, the reaction products include, for example, the following general formulas (7) and (8). The compounds represented are mentioned.

In general formulas (7) and (8), n ₃ and n ₄ each independently represent an integer of 2 to 20.

Commercially available products containing urethane acrylate having a structural unit represented by the above general formula (3) include UN-333 (number of functional groups: 2, Mw: 5,000), UN-1255 (number of functional groups: 2, Mw: 8,000), UN-904 (number of functional groups: 10, Mw: 4,900), UN-2600 (number of functional groups: 2, Mw: 2,500), UN-6200 (number of functional groups: 2, Mw: 6,500), UN-9000PEP (Number of functional groups: 2, Mw: 5,000), UN-9200A (Number of functional groups: 2, Mw: 15,000), UN-3320HS (Number of functional groups: 15, Mw: 4, 900), UN-6301 (Number of functional groups: 2, Mw: 33,000), UN-954: (Number of functional groups: 6, Weight average molecular weight: 4,500), UN-953: (Number of functional groups: 20, Weight average Molecular weight: 14,000-40,000), H-219 (number of functional groups: 9, weight average molecular weight: 25,000-50,000) (all above are product names, manufactured by Negami Kogyo Co., Ltd.), EBECRYL8405 (urethane Examples include an addition reaction product of acrylate/1,6-hexanediol diacrylate = 80/20, number of functional groups: 4, Mw: 2,700) (trade name, manufactured by Daicel Allnex Corporation).
In addition, as a commercially available product containing urethane methacrylate having a structural unit represented by the above general formula (3), for example, UN-6060PTM (number of functional groups: 2, Mw: 6,000, trade name, manufactured by Negami Kogyo Co., Ltd.) ) etc. In the above description, the number of functional groups in parentheses and Mw are the total number of (meth)acryloyl groups contained in the urethane (meth)acrylate and the weight average molecular weight, respectively.

Furthermore, as a commercially available product containing urethane acrylate represented by the above general formula (5), for example, UN-952 (number of functional groups: 10, Mw: 6,500 to 11,000) is represented by the general formula (8). Examples of commercially available products containing the urethane acrylate shown include UN-905 (number of functional groups: 15, Mw: 40,000 to 200,000) (all of the above are product names, manufactured by Neagami Kogyo Co., Ltd.). ).
Among these, UN-952 is particularly preferred from the viewpoints of pattern formation and photosensitivity.

The total number of (meth)acryloyl groups (the number of photopolymerizable functional groups) contained in the urethane (meth)acrylate component (A1) is 2 to 24 in one molecule, or From the viewpoint of stabilizing the physical properties and characteristics of the resulting cured product, it may be selected as appropriate from 4 to 15 or 6 to 12.

The weight average molecular weight of the component (A1) is 2,500 or more, and may be 3,000 or more from the viewpoint of improving the coating properties and resolution of the resin composition. From this point of view, it may be 3,500 or more. On the other hand, the upper limit of the weight average molecular weight may be 40,000 or less, or 30,000 or less from the viewpoint of improving the coating properties and resolution of the resin composition, and may further improve the developability and compatibility. From the viewpoint of improvement, it may be 20,000 or less.
If the weight average molecular weight is 2,500 or more, it is possible to suppress the occurrence of sagging of the applied resin composition when it is applied onto a substrate, so that excellent pattern formation properties can be obtained. Further, it is easy to form a thick photosensitive layer, and the problem of decreased reliability due to increased stress in the resin due to curing shrinkage can be suppressed.
On the other hand, if the weight average molecular weight is 40,000 or less, coating properties will be improved, it will be easier to form a thick photosensitive layer, and pattern formation properties will be improved. In addition, since the solubility in the developer becomes good, excellent resolution can be exhibited. Furthermore, the transparency of the cured product is improved, and a cured product having the excellent transmittance required for a transparent material can be obtained.

When the photosensitive resin composition of the present embodiment contains component (A1), the content of component (A1) is 10% by mass or more and 30% by mass or more based on the total solid content of the photosensitive resin composition. , or 40% by mass or more. When the content is 10% by mass or more, coating properties are improved, and even when a thick photosensitive layer is formed, excellent pattern forming properties can be obtained.
Considering the pattern forming properties and coating properties of the resulting resin composition, and the physical properties and characteristics required of the cured product of the resin composition, the upper limit of the content of component (A1) is determined by the solid content of the photosensitive resin composition. The amount may be appropriately selected from 95% by mass or less, 85% by mass or less, or 75% by mass or less based on the total amount.
In addition, the content of urethane (meth)acrylate in component (A1) is 70 to 100% by mass and 80 to 100% by mass, based on the total solid content of component (A1), from the viewpoint of improving pattern formation properties. , 90-100% by mass, 95-100% by mass, or 100% by mass (total amount).

((A2) component: low molecular weight substance having a photopolymerizable functional group)
Component (A2) is a low molecular weight substance having a photopolymerizable functional group. "Low molecular weight compound" means a compound having a weight average molecular weight of less than 2,500.
The photopolymerizable functional group contained in component (A2) is the one described above as the photopolymerizable functional group contained in component (A), and from the viewpoint of improving pattern formation, it is used as a photopolymerizable functional group. It may have a (meth)acryloyl group.
Component (A2) has at least one photopolymerizable functional group, and from the viewpoint of improving pattern formation, the number of photopolymerizable functional groups is 1 to 12, 2 to 10, or 2 to 10. 6 may be selected as appropriate.

From the point of view of pattern formation, the photosensitive resin composition of the present embodiment includes (A2-1) component: a low molecular weight substance having a photopolymerizable functional group and an isocyanuric ring, (A2-2) as the component (A2). ) component: a low molecular weight substance having a photopolymerizable functional group and a urethane bond; and (A2-3) component: at least one selected from the group consisting of a low molecular weight substance having a photopolymerizable functional group and an alicyclic skeleton. May contain seeds. When the photosensitive resin composition of the present embodiment contains at least one of these, the adhesion to the base material of an electronic component, etc. is improved, and excellent pattern formation properties tend to be obtained. In addition, in the case of a low molecular weight substance having two or more of an isocyanuric ring, a urethane bond, and an alicyclic skeleton, if it has at least an isocyanuric ring, it is classified as a component (A2-1), and a urethane bond and an alicyclic skeleton, it is classified as component (A2-2) with priority given to having a urethane bond. That is, low molecular weight substances having an alicyclic skeleton without isocyanuric rings and urethane bonds are classified as component (A2-3).

[Component (A2-1): low molecular weight substance having an isocyanuric ring]
The component (A2-1) is a low molecular weight substance having a photopolymerizable functional group and an isocyanuric ring skeleton, and may have two or more photopolymerizable functional groups from the viewpoint of improving pattern formation. , may have 2 to 5 photopolymerizable functional groups, may have 2 or 3 photopolymerizable functional groups, or may have 3 photopolymerizable functional groups.
The photopolymerizable functional group contained in component (A2-1) is the one described above as the photopolymerizable functional group contained in component (A). It may have a (meth)acryloyl group as a group.
As the component (A2-1), for example, a compound represented by the following general formula (9) can be mentioned.

（一般式（９）中、Ｒ^１３、Ｒ^１４及びＲ^１５は、各々独立に炭素数１～８のアルキレン基を示し、Ｒ^１６及びＲ^１７は、各々独立に水素原子、又はメチル基を示し、Ｒ^１８は水素原子、又は（メタ）アクリロイル基を示す。）

(In general formula (9), R ¹³ , R ¹⁴ and R ¹⁵ each independently represent an alkylene group having 1 to 8 carbon atoms, and R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group. , ^R18 represents a hydrogen atom or a (meth)acryloyl group.)

In the general formula (9), the alkylene group having 1 to 8 carbon atoms represented by R ¹³ , R ¹⁴ and R ¹⁵ may be an alkylene group having 1 to 4 carbon atoms, or may be an alkylene group having 1 to 3 carbon atoms. There may be.
Examples of the alkylene group having 1 to 8 carbon atoms include methylene group, ethylene group, propylene group, butylene group, isopropylene group, isobutylene group, t-butylene group, pentylene group, hexylene group, etc. , an ethylene group may be used from the viewpoint of improving pattern formability.
In general formula (9), R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group, and may be a hydrogen atom from the viewpoint of improving sensitivity.
In general formula (9), R ¹⁸ represents a hydrogen atom or a (meth)acryloyl group, and may be a (meth)acryloyl group from the viewpoint of improving pattern forming properties.

The compound represented by the general formula (9) may be one or more selected from the group consisting of the compound represented by the following formula (9-1) and the compound represented by the following formula (9-2). From the viewpoint of improving pattern forming properties, a compound represented by the following formula (9-1) may be used.

The weight average molecular weight of the component (A2-1) is less than 2,500, and from the viewpoint of improving pattern forming properties, it is appropriately selected from 200 to 1,500, 300 to 1,000, or 350 to 600. It's okay.

As the component (A2-1), a commercially available product may be used. Commercially available products include, for example, "A-9300" (a compound represented by the above formula (9-1)) manufactured by Shin Nakamura Chemical Co., Ltd., and "M-215" (a compound represented by the above formula (9-1)) manufactured by Toagosei Co., Ltd. 9-2) and the like.
Component (A2-1) can be used alone or in combination of two or more.

[(A2-2) component: low molecular weight substance having urethane bond]
The component (A2-2) is a low molecular weight substance having a photopolymerizable functional group and a urethane bond, and may have two or more photopolymerizable functional groups from the viewpoint of improving pattern formation. It may have 2 to 6 photopolymerizable functional groups, or it may have 2 photopolymerizable functional groups.
The photopolymerizable functional group contained in component (A2-2) is the same as the photopolymerizable functional group contained in component (A) above. It may have a (meth)acryloyl group as a group.

As the component (A2-2), for example, a reaction product of a (meth)acrylate having a hydroxyl group and an isocyanate compound having an isocyanate group can be mentioned. Here, examples of the (meth)acrylate and isocyanate compound having a hydroxyl group include the (meth)acrylate and isocyanate compounds having a hydroxyl group which are respectively exemplified as those used for producing the component (A1). Here, examples of the materials appropriately selected from the viewpoint of improving pattern formability include the same materials as those appropriately selected from the same viewpoint as those used for producing component (A1).

In addition, as the component (A2-2), a reaction is performed in which the terminal isocyanate group of a polyadduct of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound is reacted with a (meth)acrylate having a hydroxyl group. products. Here, as the isocyanate compound having at least two isocyanate groups in one molecule, the diol compound, and the (meth)acrylate having a hydroxyl group, each of the isocyanate compounds in one molecule exemplified as those used for producing the component (A1) Examples include isocyanate compounds having at least two groups, diol compounds, and (meth)acrylates having hydroxyl groups. Here, examples of the material to be appropriately selected from the viewpoint of improving pattern formability and the like include those which are appropriately selected from the same viewpoint as those used for generating the component (A1).
Examples of this reaction product include urethane (meth)acrylate having a structural unit represented by the following general formula (10).

In the general formula ( _{10 )} , Indicates a divalent organic group having That is, the component (A2-2) includes those having at least one type of skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton. Examples of X ₂ and Y ₂ are the same as X ₁ and Y ₁ in general formula (3), respectively.
From the viewpoint of improving the pattern forming property and also improving the transparency, water resistance, and moisture resistance of the resin composition in a well-balanced manner, X ₂ is a divalent organic group having a chain hydrocarbon skeleton, a branched chain The divalent organic group having a hydrocarbon skeleton, a branched alkylene group having 2 to 12 carbon atoms, and, for example, the residue of the aliphatic diisocyanate compound mentioned above may be selected as appropriate. Further, from the same viewpoint, Y ₂ may be appropriately selected from a divalent organic group having an alicyclic skeleton, for example, the residue of a diol compound having an alicyclic skeleton as described above.

Specific examples of the component (A2-2) include urethane acrylate represented by the following general formula (11).

In the above general formula (11), n ₅ represents an integer of 1 to 4. R ¹⁹ and R ²⁰ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least three of each of the plurality of R ¹⁹ and R ²⁰ are alkyl groups having 1 to 4 carbon atoms. .
Among the urethane acrylates represented by the above general formula (11), X ₂ in the above general formula (10) is a residue of trimethylhexamethylene diisocyanate, which is a divalent organic group having a chain hydrocarbon skeleton, and Y Commercially available products containing urethane acrylate having a structural unit in which ₂ is a residue of cyclohexanedimethanol, a divalent organic group having an alicyclic skeleton, include TMCH-5R (trade name, number of functional groups: 2, Mw: 950, manufactured by Hitachi Chemical Co., Ltd.), etc.
In addition, commercially available products containing urethane (meth)acrylate having a structural unit represented by the above general formula (10) include KRM8452 (number of functional groups: 10, Mw: 1,200, manufactured by Daicel Allnex Corporation), UN -3320HA (number of functional groups: 6, Mw: 1,500, manufactured by Neagami Kogyo Co., Ltd.), UN-3320HC (number of functional groups: 6, Mw: 1,500, manufactured by Negami Kogyo Co., Ltd.), and the like. In the above description, the number of functional groups in parentheses and Mw are the total number of (meth)acryloyl groups contained in the urethane (meth)acrylate and the weight average molecular weight, respectively.

The weight average molecular weight of the component (A2-2) is less than 2,500, and may be 1,500 or less from the viewpoint of improving adhesion, and may be 1,000 or less from the viewpoint of improving resolution. There may be. On the other hand, the lower limit of the weight average molecular weight may be 500 or more from the viewpoint of film forming properties, although it can be used as appropriate depending on the desired purpose.

[Component (A2-3): low molecular weight substance having an alicyclic skeleton]
The component (A2-3) is a low molecular weight substance having a photopolymerizable functional group and an alicyclic skeleton, and from the viewpoint of improving pattern formation, it may have two or more photopolymerizable functional groups. It may have 2 to 4 photopolymerizable functional groups, or it may have 2 photopolymerizable functional groups.
The photopolymerizable functional group contained in component (A2-3) is the same as the photopolymerizable functional group contained in component (A) above. It may have a (meth)acryloyl group as a group.
The alicyclic skeleton possessed by the component (A2-3) is not particularly limited, but includes, for example, an alicyclic hydrocarbon skeleton having 5 to 20 carbon atoms. The alicyclic hydrocarbon skeleton is at least one selected from the group consisting of a cyclopentane skeleton, a cyclohexane skeleton, a cyclooctane skeleton, a cyclodecane skeleton, a norbornane skeleton, a dicyclopentane skeleton, and a tricyclodecane skeleton. Good too. Among these, a tricyclodecane skeleton may be used from the viewpoint of improving pattern formability.

The weight average molecular weight of the component (A2-3) is less than 2,500, and may be 1,500 or less from the viewpoint of improving adhesion, and further may be 1,000 or less from the viewpoint of improving resolution. The number may be 500 or less. On the other hand, the lower limit of the weight average molecular weight may be 150 or more, or 200 or more from the viewpoint of film forming properties, although it can be used as appropriate depending on the desired purpose.
From the viewpoint of film-forming properties, the component (A2-3) may be tricyclodecane dimethanol diacrylate.

When the photosensitive resin composition of the present embodiment contains component (A2), the content of component (A2) is 3% by mass or more and 5% by mass or more based on the total solid content of the photosensitive resin composition. , 10% by mass or more, or 20% by mass or more. When the content of component (A2) is 3% by mass or more, excellent pattern formability can be obtained even when a thick photosensitive layer is formed, and excellent rigidity of the cured product can also be obtained. From the same point of view, the upper limit of the content of component (A2) is set as appropriate from 70% by mass or less, 60% by mass or less, or 50% by mass or less based on the total solid content of the photosensitive resin composition. Just choose.

When the photosensitive resin composition of the present embodiment contains component (A1) and component (A2), the content of component (A2) based on 100 parts by mass of the total solid content of component (A1) is From the viewpoint of improving formability and rigidity of the cured product, the amount may be appropriately selected from 20 to 120 parts by mass, 25 to 110 parts by mass, or 30 to 100 parts by mass.

When component (A2) contains component (A2-1), the content of component (A2-1) in the total solid content of component (A2) is 15% by mass or more, 40% by mass or more, 70% by mass % or more, 90% by mass or more, or 95% by mass or more. When the content of the component (A2-1) is 15% by mass or more, excellent pattern forming properties can be obtained even when a thick photosensitive layer is formed, and excellent rigidity of the cured product can also be obtained. From the same viewpoint, the upper limit of the component (A2-1) is 100% by mass or less, and 100% by mass, that is, all of the component (A2) may be the component (A2-1).
When component (A2) contains component (A2-2), the content of component (A2-2) in the total solid content of component (A2) is 20 to 100% by mass, 40 to 95% by mass, Alternatively, it may be appropriately selected from 50 to 90% by mass.
When component (A2) contains component (A2-3), the content of component (A2-3) in the total solid content of component (A2) is 10 to 50% by mass, 15 to 40% by mass, Alternatively, it may be appropriately selected from 20 to 30% by mass.

<(B) component: photopolymerization initiator>
The photosensitive resin composition of the present embodiment contains, as component (B), a photopolymerization initiator whose molar absorption coefficient for light with a wavelength of 365 nm is less than 8.0×10 ³ L/mol·cm.
By containing the component (B) as a photopolymerization initiator, the photosensitive resin composition of the present embodiment can suppress the absorbance of the photosensitive resin composition to a low level. Since light can easily pass through to the surface (the surface of the surface), pattern formation properties can be improved. Further, by setting the molar absorption coefficient of the photopolymerization initiator within the above range, it is possible to suppress the progress of the photopolymerization reaction in areas other than the exposed areas, thereby providing excellent pattern formation properties.
The molar extinction coefficient of component (B) is 5.0×10 ³ L/mol・cm or less, 3.0×10 ³ L/mol・cm or less, 1.0×10 Appropriately from ³ L/mol・cm or less, 0.5×10 ³ L/mol・cm or less, 0.2×10 ³ L/mol・cm or less, or 0.1×10 ³ L/mol・cm or less Just choose. The lower limit of the molar absorption coefficient of component (B) is not particularly limited, but may be appropriately selected from, for example, 1 L/mol·cm or more, 5 L/mol·cm or more, or 10 L/mol·cm or more.
The molar extinction coefficient of component (B) can be measured, for example, using a UV-visible spectrophotometer by the method described in the Examples.

Component (B) is not particularly limited as long as it has a molar extinction coefficient of less than 8.0×10 ³ L/mol·cm and can polymerize the photosensitive resin, and can be used with commonly used light. It can be appropriately selected from polymerization initiators. From the viewpoint of improving pattern forming properties, those that generate free radicals when exposed to actinic rays, such as acylphosphine oxides, oxime esters, aromatic ketones, quinones, alkylphenones, imidazole, acridine, and phenylglycine. Examples include photopolymerization initiators such as coumarin-based and coumarin-based photopolymerization initiators. Among these, the component (B) may contain at least one selected from the group consisting of an alkylphenone photopolymerization initiator and an acylphosphine oxide photopolymerization initiator.

The acylphosphine oxide photopolymerization initiator has an acylphosphine oxide group (>P(=O)-C(=O)- group), for example, (2,6-dimethoxybenzoyl)-2,4 , 6-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("IRGACURE-TPO" (manufactured by BASF)), ethyl-2 , 4,6-trimethylbenzoylphenylphosphinate, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("IRGACURE-819" (manufactured by BASF)), (2,5-dihydroxyphenyl)diphenylphosphine oxide, (p-hydroxyphenyl)diphenylphosphine oxide, bis(p-hydroxyphenyl)phenylphosphine oxide, tris(p-hydroxyphenyl)phosphine oxide, and the like.

The oxime ester photopolymerization initiator is a photopolymerization initiator having an oxime ester bond, for example, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) ( Product name: OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) (Product name: OXE -02, manufactured by BASF), 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime] (trade name: Quantacure-PDO, manufactured by Nippon Kayaku Co., Ltd.), and the like.

Examples of the aromatic ketone photopolymerization initiator include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4 -Methoxy-4'-dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one ("IRGACURE-651" (manufactured by BASF)), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)-butan-1-one ("IRGACURE-369" (manufactured by BASF)), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one (“IRGACURE-907” (manufactured by BASF)), etc.

Examples of the quinone photopolymerization initiator include 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, , 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, etc. It will be done.

Examples of the alkylphenone photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin phenyl ether, and 2,2-dimethoxy-1,2-diphenylethane-1- ("IRGACURE-651" (manufactured by BASF)), 1-hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE-184" (manufactured by BASF)), 2-hydroxy-2-methyl-1-phenyl-propane- 1-one ("IRGACURE-1173" (manufactured by BASF)), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one ("IRGACURE-1173" (manufactured by BASF)), 2959" (manufactured by BASF)), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one ("IRGACURE -127'' (manufactured by BASF).

Examples of imidazole-based photopolymerization initiators include 2,4,5-triarylimidazole dimers such as 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenyl 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer such as -1,3-diazol-2-yl]-4,5-diphenylimidazole, 2-(o-chlorophenyl)-4,5- Di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2- Examples include (p-methoxyphenyl)-4,5-diphenylimidazole dimer.

Examples of the acridine-based photopolymerization initiator include 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane.

Examples of the phenylglycine-based photopolymerization initiator include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

Examples of coumarin-based photopolymerization initiators include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, and 7-methylamino-4-methylcoumarin. , 7-ethylamino-4-methylcoumarin, 7-methylaminocyclopenta[c]coumarin, 7-aminocyclopenta[c]coumarin, 7-diethylaminocyclopenta[c]coumarin, 4,6-dimethyl-7- Ethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin , 4,6-diethyl-7-dimethylaminocoumarin, 2,3,6,7,10,11-hexanehydro-1H,5H-cyclopenta[3,4][1]benzopyrano-[6,7,8- ij] Quinolidin 12(9H)-one, 7-diethylamino-5',7'-dimethoxy-3,3'-carbonylbiscoumarin, 3,3'-carbonylbis[7-(diethylamino)coumarin], 7-diethylamino Examples include -3-thienoxysilkmarine and the like.

Among these, from the viewpoint of improving pattern forming properties, component (B) is at least one selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). It may contain one kind.

（一般式（１）中、Ｒ^１、Ｒ^２及びＲ^３は、各々独立に、水素原子、炭素数１～８のアルキル基、又は炭素数１～８のアルコキシ基を示し、Ｒ^４及びＲ^５は、各々独立に、水素原子、炭素数１～８のアルキル基、炭素数１～８のアルコキシ基、又は炭素数６～１２のアリール基を示す。水素原子以外のＲ^１～Ｒ^５は、各々置換基を有していてもよい。）

(In general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, and R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. R ¹ to R ⁵ other than hydrogen atoms are , each may have a substituent.)

（一般式（２）中、Ｒ^６は、水酸基、炭素数１～８のアルコキシ基、又はアミノ基を示し、Ｒ^７及びＲ^８は、各々独立に、水素原子、炭素数１～８のアルキル基、炭素数１～８のアルコキシ基、又は炭素数６～１２のアリール基を示す。Ｒ^７とＲ^８は、互いに結合して、炭素数３～１６の環状構造を形成していてもよい。水酸基及び水素原子以外のＲ^６～Ｒ^８は、各々置換基を有していてもよく、置換基を有するアミノ基は、置換基同士が互いに結合して、炭素数３～１２の環状構造を形成していてもよい。Ｒ^９は、各々独立に、水素原子、ハロゲン原子、水酸基、アミノ基、メルカプト基、又は酸素原子、窒素原子及び硫黄原子から選ばれる１種以上の原子を含んでいてもよい炭素数１～１０の有機基を示す。）

(In general formula (2), R ⁶ represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an amino group, and R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, group, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms.R ⁷ and R ⁸ may be bonded to each other to form a cyclic structure having 3 to 16 carbon atoms. R ⁶ to R ⁸ other than the hydroxyl group and the hydrogen atom may each have a substituent, and in the amino group having a substituent, the substituents bond to each other to form a cyclic structure having 3 to 12 carbon atoms. ^R9 may each independently contain a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom. (Indicates an optional organic group with 1 to 10 carbon atoms.)

In general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.
The alkyl group having 1 to 8 carbon atoms represented by R ¹ , R ² and R ³ may be an alkyl group having 1 to 4 carbon atoms, or may be an alkyl group having 1 or 2 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-heptyl group, n-hexyl group, n-octyl group, and the like.
The alkoxy group having 1 to 8 carbon atoms represented by R ¹ , R ² and R ³ may be an alkoxy group having 1 to 4 carbon atoms, or may be an alkoxy group having 1 or 2 carbon atoms. Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, n-heptyloxy group, n-hexyloxy group, n-octyloxy group, etc. Can be mentioned.
Among these groups, R ¹ , R ² and R ³ may be methyl groups from the viewpoint of improving resolution.

In general formula (1), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. .
The alkyl group having 1 to 8 carbon atoms and the alkoxy group having 1 to 8 carbon atoms represented by R ⁴ and R ⁵ are explained in the same manner as in the case of R ¹ , R ² and R ³ .
The aryl group having 6 to 12 carbon atoms represented by R ⁴ and R ⁵ may be an aryl group having 6 to 10 carbon atoms, or may be an aryl group having 6 to 8 carbon atoms. Examples of the aryl group include phenyl group and naphthyl group.

Examples of substituents that R ¹ to R ⁵ may have include a halogen atom, a carboxy group, a hydroxy group, an amino group, a mercapto group, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms. and an aryl group having 6 to 12 carbon atoms. Examples of the alkyl group, alkoxy group and aryl group which are substituents that R ¹ to R ⁵ may have include those similar to the alkyl group, alkoxy group and aryl group explained as R ¹ to R ⁵ . .

In the general formula (2), R ⁶ represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an amino group.
The alkoxy group represented by R ⁶ is explained in the same manner as R ¹ , R ² and R ³ in general formula (1).
Among these groups, R ⁶ may be a hydroxyl group or a methoxy group from the viewpoint of improving pattern forming properties.

In general formula (2), R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. .
The alkyl group, alkoxy group and aryl group represented by R ⁷ and R ⁸ are explained in the same manner as in the case of R ¹ to R ⁵ in general formula (1).
R ⁷ and R ⁸ may be bonded to each other to form a cyclic structure having 3 to 16 carbon atoms.
The cyclic structure may be a cyclic structure having 4 to 10 carbon atoms, or may be a cyclic structure having 5 to 8 carbon atoms.
The cyclic structure may be an alicyclic structure from the viewpoint of improving pattern formability, and examples of the alicyclic structure include a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, a cyclooctane structure, and the like. These alicyclic structures may also include a carbon atom to which R ⁷ and R ⁸ are directly bonded together.

The substituents that R ⁶ to R ⁸ may have are explained in the same manner as the substituents that R ¹ to R ⁵ may have in the general formula (1).
However, in the amino group having a substituent, the substituents may be bonded to each other to form a cyclic structure having 3 to 12 carbon atoms.
The cyclic structure formed by the substituent of the amino group may be a cyclic structure having 3 to 10 carbon atoms, or may be a cyclic structure having 3 to 5 carbon atoms.
The cyclic structure may be a 5- to 10-membered ring containing the nitrogen atom of the amino group, a 5- to 7-membered ring containing the nitrogen atom of the amino group, or a 6-membered ring containing the nitrogen atom of the amino group. It may be a ring. Furthermore, these cyclic structures may contain heteroatoms other than nitrogen atoms, such as oxygen atoms. A specific example of a cyclic structure formed by a substituent of an amino group includes a structure represented by the following formula (2-1).

In general formula (2), R ⁹ each independently contains a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom. Indicates an organic group having 1 to 10 carbon atoms.
The organic group having 1 to 10 carbon atoms represented by R ⁹ may be an organic group having 1 to 6 carbon atoms, or may be an organic group having 1 to 4 carbon atoms.
The organic group having 1 to 10 carbon atoms represented by R ⁹ may be a hydrocarbon group such as an alkyl group, an alkenyl group, or an aryl group. These alkyl groups, alkenyl groups and aryl groups are explained in the same manner as the alkyl groups, alkenyl groups and aryl groups represented by R ¹ to R ⁵ in the general formula (1).
Examples of the organic group having 1 to 10 carbon atoms and containing an oxygen atom represented by R ⁹ include an alkoxy group.
Examples of the organic group having 1 to 10 carbon atoms and containing a nitrogen atom represented by R ⁹ include a group represented by the above formula (2-1).
The organic group having 1 to 10 carbon atoms and containing a sulfur atom represented by R ⁹ includes, for example, an alkylthio group such as a methylthio group.

The content of component (B) is such that when the thickness of the photosensitive resin composition of this embodiment is 50 μm, the absorbance for light with a wavelength of 365 nm is less than 0.35, the amount that is 0.34 or less, 0 What is necessary is just to select suitably from the amount which becomes 0.30 or less, the amount which becomes 0.26 or less, or the amount which becomes 0.22 or less. By setting the content of component (B) as above, for example, even when a pattern is formed with a thick photosensitive layer of 70 μm or more using the photosensitive resin composition of this embodiment, the bottom part of the photosensitive layer (photosensitive Since light can easily pass through to the surface of the layer (on the substrate side), pattern formability can be improved.

The content of component (B) is usually from 0.05 to 30% by mass, 0.2 to 20% by mass, or 0.5 to 15% by mass based on the total solid content of the photosensitive resin composition. You can select it as appropriate. By setting it as the said content, the sensitivity of a photosensitive resin composition can be improved, deterioration of a resist shape can be suppressed, and pattern formability can be improved.

Further, the content of component (B) may be determined according to the molar extinction coefficient, molecular weight, etc. of component (B), and can be determined by the following formula from the molar extinction coefficient, molecular weight, and content of the photopolymerization initiator. The value P expressed by may be appropriately selected from the amount such that it is 0.1 or more, 0.2 or more, or 0.3 or more, and is 3 or less, 2 or less, or 1.2 or less. The amount may be selected as appropriate. When P represented by formula (i) is within the above range, excellent pattern formability can be obtained.
P=A×B/C (i)
A: Molar extinction coefficient of photopolymerization initiator for light with a wavelength of 365 nm (L/mol・cm)
B: Content (% by mass) of photopolymerization initiator relative to the total amount of the photosensitive resin composition (however, if the photosensitive resin composition contains a filler, the mass of the filler is excluded)
C: Molecular weight of photopolymerization initiator

In addition to the above component (B), three types of esters such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. (B') photopolymerization initiation aids such as class amines can be used alone or in combination of two or more.

<(C) component: silane compound>
Moreover, the photosensitive resin composition of this embodiment can further contain (C) a silane compound.
As component (C), a known silane coupling agent can be used. Component (C) can improve the adhesion of electronic components to substrates, especially when the substrates contain silicon (e.g., glass substrates, silicon wafers, epoxy resin-impregnated glass cloth substrates, etc.). is valid. Examples of silane coupling agents include alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; (meth)acryloxypropyltrimethoxysilane, (meth)acryloxypropylmethyldimethoxysilane (meth)acryloyl group-containing alkoxysilanes such as; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1, Amine-based alkoxysilanes such as 3-dimethylbutylidene) propylamine; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidoxypropylmethyldi Glycidoxy group-containing alkoxysilanes such as isopropenoxysilane; alicyclic epoxy group-containing alkoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; ureido group-containing alkoxysilanes such as 3-ureidopropyltriethoxysilane Silane; Mercapto group-containing alkoxysilane such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane; Carbamate group-containing alkoxysilane such as triethoxysilylpropylethyl carbamate; 3-(triethoxysilyl)propyl succinic anhydride Polybasic acid anhydride group-containing alkoxysilanes such as silanes and the like can be mentioned. These can be used alone or in combination of two or more.
From the viewpoint of further improving adhesiveness, (meth)acryloyl group-containing alkoxysilanes such as (meth)acryloxypropyltrimethoxysilane and (meth)acryloxypropylmethyldimethoxysilane, glycidoxypropyltrimethoxysilane, and glycidoxy A silane coupling agent having an ethylenically unsaturated group in the molecule may be used, such as a glycidoxy group-containing alkoxysilane such as propylmethyldiethoxysilane and glycidoxypropylmethyldiisopropenoxysilane.

When the photosensitive resin composition contains component (C), the content of component (C) is 0.05 to 15% by mass, 0.1 to 10% by mass based on the total solid content of the photosensitive resin composition. The amount may be appropriately selected from mass%, 0.1 to 7% by mass, 1 to 7% by mass, or 1 to 5% by mass. By setting the content as above, deterioration of resist shape can be suppressed and pattern formability can be improved.

<(D) component: high Tg polymer>
The photosensitive resin composition of the present embodiment may contain, as component (D), a polymer having a glass transition temperature of 70 to 150° C. and having no carbon-nitrogen bond. "High molecular weight material" is the same as the definition for component (A1) above. By containing component (D), it has the effect of suppressing tackiness of the photosensitive resin composition.
Component (D) may contain an ethylenically unsaturated group from the viewpoint of pattern formation and reduction of tackiness. Examples of the ethylenically unsaturated group include a (meth)acryloyl group and a vinyl group, and from the viewpoint of pattern formation, a (meth)acryloyl group may be used.
Component (D) may contain a high molecular weight substance having at least one type of skeleton selected from the group consisting of an alicyclic skeleton and an aromatic ring skeleton, from the viewpoint of pattern formation and reducing tackiness. From this point of view, it may contain a polymer having an alicyclic skeleton.

The polymer having an alicyclic skeleton is, for example, a part of the acid group derived from the acid group-containing acrylic resin (d1) having no carbon-nitrogen bond and an alicyclic skeleton having no carbon-nitrogen bond. It can be produced by reacting the epoxy group derived from the epoxy group-containing unsaturated compound (d2) with the formula epoxy group-containing unsaturated compound (d2).
The acid group-containing acrylic resin (d1) that does not have a carbon-nitrogen bond can be made from monomers such as an acid having an ethylenically unsaturated group, an ester of (meth)acrylic acid, a vinyl aromatic compound, or a polyolefin compound. A copolymer obtained by copolymerizing one or more selected types can be used. Specifically, acids with ethylenically unsaturated groups such as (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, and (anhydrous)maleic acid are essential components. , methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl ( Esters of (meth)acrylic acid such as meth)acrylate; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene; monomers of polyolefin compounds such as butadiene, isoprene, chloroprene, and methyl; Examples include copolymers obtained by copolymerizing one or more monomers selected from other monomers such as isopropenyl ketone, vinyl acetate, and vinyl propionate.
The acid value of component (d1) may be 15 mgKOH/g or more, and may be 40 to 500 mgKOH/g. Because component (d1) has such an acid value, a sufficient amount of acid groups will remain in component (D) even after the component (d1) and component (d2) described below are reacted. Become.

The alicyclic epoxy group-containing unsaturated compound (d2) having no carbon-nitrogen bond is preferably a compound having one ethylenically unsaturated group and one alicyclic epoxy group in one molecule. Specific examples include compounds represented by any of the following formulas (I) to (X).

Here, R ^D1 is each independently a hydrogen atom or a methyl group. Each R ^D2 is independently an aliphatic saturated hydrocarbon group.
The aliphatic saturated hydrocarbon group represented by R ^D2 includes a linear or branched alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, an arylene group having 6 to 14 carbon atoms, and Examples include divalent organic groups consisting of combinations of these. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, and a hexamethylene group. Examples of the cycloalkylene group include a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group. Examples of the arylene group include a phenylene group and a naphthylene group. Examples of the divalent organic group consisting of a combination of these include -CH ₂ -phenylene group -CH ₂ -, -CH ₂ -cyclohexylene group -CH ₂ -, and the like.
R ^D2 includes methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group, and cyclohexylene group from the viewpoint of pattern forming property and reduction of tackiness. The group may be a -CH ₂ -phenylene group -CH ₂ -, a methylene group, an ethylene group, a propylene group, or a methylene group.

The alicyclic epoxy group-containing unsaturated compound (d2) having no carbon-nitrogen bond may be a compound represented by the above formula (III) from the viewpoint of pattern forming properties.
As the component (D), commercially available products may be used, such as (ACA) Z250 of the Cyclomer P series (manufactured by Daicel Allnex Corporation, acid value: 101.7 mgKOH/g). (ACA) Z250 is a resin composed of three structural units represented by the following formula, produced by the reaction of an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound.

（式中、Ｒ^Ｄ１は水素原子又はメチル基を表す。Ｒ^Ｄ３は炭素数１～６のアルキル基、又は炭素数１～６のヒドロキシアルキル基を表す。）

(In the formula, R ^D1 represents a hydrogen atom or a methyl group. ^{R D3} represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms.)

The glass transition temperature of component (D) is 70 to 150°C, but may be 100 to 150°C, 115 to 150°C, or 125 to 150°C. Here, the glass transition temperature of component (D) is a value measured by the following method.
(Method for measuring glass transition temperature of component (D))
As a pretreatment for measurement, component (D) is heated at 120° C. for 3 hours and then cooled to prepare a sample.
Using 10 mg of the sample, the temperature was raised in a temperature range of 25 to 200°C at a heating rate of 20°C/min under a nitrogen stream using a differential scanning calorimeter (manufactured by Shimadzu Corporation, product name: DSC-50). and eliminate the influence of solvents, etc. After cooling to 25° C., the temperature is raised again under the same conditions, and the temperature at which the baseline deviation starts is defined as the glass transition temperature.

The weight average molecular weight of component (D) may be 3,000 to 50,000, 4,000 to 40,000, or 5,000 to 30,000. If it is 3,000 or more, the tack suppression effect tends to be greater, and if it is 50,000 or less, the resolution tends to be improved.

When the photosensitive resin composition of the present embodiment contains component (D), the content of component (D) is determined from the viewpoint of pattern formation and reduction of tackiness between component (A1) and component (D). The amount may be 5 to 60 parts by weight, 10 to 40 parts by weight, or 10 to 30 parts by weight based on a total of 100 parts by weight of the components.

<(E) component: thermal radical polymerization initiator>
Moreover, the photosensitive resin composition of this embodiment can further contain (E) a thermal radical polymerization initiator. Component (E) is not particularly limited and includes, for example, α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, etc. dialkyl peroxides; ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methyl cyclohexanone peroxide; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)- 2-Methylcyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-hexyl) peroxyketals such as (peroxy)-3,3,5-trimethylcyclohexane; hydroperoxides such as p-menthane hydroperoxide; diacylperoxides such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide, benzoyl peroxide, etc. Oxide; Peroxy such as bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutyl peroxycarbonate Carbonate; t-butyl peroxypivalate, t-hexyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-Ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxy Oxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurylate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate , t-butylperoxybenzoate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, and other peroxyesters. Polymerization initiator, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile) Examples include azo polymerization initiators such as.

Component (E) includes peroxide polymerization initiators, dialkyl peroxide polymerization initiators, and the like, from the viewpoint of improving pattern formation properties, among which dicumyl peroxide can be selected. Moreover, (E) component can be used individually or in combination of 2 or more types.

When component (E) is included, its content is 0.1 to 10% by mass, 0.2 to 5% by mass, or 0.3 to 1% by mass, based on the total solid content of the photosensitive resin composition. It may be appropriately selected from 5% by mass. By setting it as the said content, the heat resistance of a photosensitive resin composition will be improved, and the reliability at the time of using it as a permanent film will be improved.

<(F) component: inorganic filler>
The photosensitive resin composition of this embodiment contains (F) an inorganic filler for the purpose of further improving various properties such as adhesion between the photosensitive resin composition and the substrate, heat resistance, and rigidity of the cured product. I can do it.
As the component (F), for example, silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), silicon nitride (Si ₃ N ₄ ), barium titanate (BaO・TiO ₂ ), barium carbonate (BaCO ₃ ), magnesium carbonate (MgCO ₃ ), aluminum hydroxide (Al(OH) ₃ ), magnesium hydroxide (Mg(OH) ₂ ), titanium Lead acid (PbO・TiO ₂ ), lead zirconate titanate (PZT), lanthanum lead zirconate titanate (PLZT), gallium oxide (Ga ₂ O ₃ ), spinel (MgO・Al ₂ O ₃ ), mullite (3Al Contains _2O3.2SiO2 ), cordierite ( _{2MgO.2Al2O3.5SiO2 )} , talc ( _{3MgO.4SiO2.H2O ) , aluminum} titanate ( _TiO2.Al2O3 ), _{and yttria .} Zirconia ( _{Y2O3 ・ ZrO2} ), barium silicate (BaO・_8SiO2 ), boron nitride (BN), calcium carbonate (CaCO3), barium sulfate ( _{BaSO4 )} , calcium sulfate ( _CaSO4 ), zinc oxide (ZnO), magnesium titanate (MgO.TiO ₂ ), hydrotalcite, mica, calcined kaolin, carbon (C), etc. can be used. These inorganic fillers can be used alone or in combination of two or more.

The average particle size of the component (F) should be appropriately selected from 0.01 to 3 μm, 0.01 to 2 μm, or 0.02 to 1 μm from the viewpoint of improving adhesiveness, heat resistance, and rigidity of the cured product. Bye. Here, the average particle size of component (F) is the average particle size of the inorganic filler in a state dispersed in the photosensitive resin composition, and is a value obtained by measuring as follows. First, after diluting (or dissolving) the photosensitive resin composition 1,000 times with methyl ethyl ketone, it was measured using a submicron particle analyzer (manufactured by Beckman Coulter, Inc., trade name: N5) according to the international standard ISO13321. Accordingly, particles dispersed in a solvent with a refractive index of 1.38 are measured, and the particle diameter at an integrated value of 50% (volume basis) in the particle size distribution is defined as the average particle diameter. In addition, component (F) contained in the photosensitive layer provided on the carrier film or the cured film of the photosensitive resin composition is also diluted (or dissolved) 1,000 times (by volume) using a solvent as described above. ), it can be measured using the above-mentioned submicron particle analyzer.

The content of component (F) may be appropriately selected from the following, with an upper limit of 10% by mass or less, 5% by mass or less, or 1% by mass or less, based on the total solid content of the photosensitive resin composition, and a lower limit of 0% by mass or less. It may be appropriately selected from more than 0% by mass, or may be 0% by mass (excluding). As described above, by substantially not containing component (F), the transmittance of the photosensitive resin composition is improved, and even when a pattern is formed with a thick photosensitive layer of 70 μm or more, for example, the photosensitive layer Since light can easily pass through to the bottom of the photosensitive layer (the surface of the photosensitive layer on the substrate side), pattern formation properties are improved.

<Other additives>
The photosensitive resin composition of this embodiment may further contain additives such as a sensitizer, a heat-resistant polymer, a thermal crosslinking agent, and an adhesion aid other than the component (C), if necessary. I can do it.

Examples of sensitizers include pyrazolines, anthracenes, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbenes, triazines, thiophenes, and naphthalimides. Examples include agents. These can be used alone or in combination of two or more.

Examples of heat-resistant polymers include polyoxazole and their precursors, novolac resins such as phenol novolak and cresol novolac, and polyamides, which have high heat resistance and are used as engineering plastics from the viewpoint of improving processability. Examples include imide and polyamide. These can be used alone or in combination of two or more.

From the viewpoint of improving the rigidity of the cured product, thermal crosslinking agents include, for example, epoxy resins, phenol resins substituted with a methylol group or alkoxymethyl group at the α position, and a group consisting of a methylol group or an alkoxymethyl group at the N position. Examples include melamine resins and urea resins substituted with at least one selected member. These can be used alone or in combination of two or more.

The content of these other additives is not particularly limited as long as it does not inhibit the effects of the photosensitive resin composition of the present embodiment. For example, the content of these other additives is 0. It may be appropriately selected from .1 to 10% by mass, 0.3 to 5% by mass, or 0.5 to 5% by mass.

The contents of component (A), component (B), components (C) to (F) used as desired, and other additives in the photosensitive resin composition of this embodiment are as follows. When the thickness of the photosensitive resin composition is 50 μm, the absorbance for light with a wavelength of 365 nm is appropriately determined within a range of less than 0.35.

<Diluent>
A diluent can be used in the photosensitive resin composition of this embodiment, if necessary. Examples of diluents include alcohols having 1 to 6 carbon atoms such as isopropanol, isobutanol, and t-butanol; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; dimethyl Sulfur atom-containing compounds such as sulfoxide and sulfolane; esters such as γ-butyrolactone and dimethyl carbonate; cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate , esters such as propylene glycol monoethyl ether acetate, and other polar solvents. These can be used alone or in combination of two or more.

The amount of the diluent used may be appropriately selected from the amount such that the total solid content in the photosensitive resin composition is 50 to 90% by mass, 60 to 80% by mass, or 65 to 75% by mass. That is, when a diluent is used, the content of the diluent in the photosensitive resin composition may be appropriately selected from 10 to 50% by mass, 20 to 40% by mass, or 25 to 35% by mass. By controlling the amount of the diluent used within the above range, the coatability of the photosensitive resin composition improves, and it becomes possible to form a pattern with higher definition.
For example, when it is intended to form a photosensitive layer with a thickness of 70 μm or more, the viscosity of the photosensitive resin composition at 25° C. should be 0.5 to 20 Pa·s, or , 1 to 10 Pa·s.

The photosensitive resin composition of the present embodiment is prepared by mixing the above-mentioned (A) component, (B) component, components (C) to (F) used as desired, other additives, and a diluent using a roll mill or a bead mill. It can be obtained by uniformly kneading and mixing.

The photosensitive resin composition of this embodiment may be used in liquid form or in film form.
When used in liquid form, there are no particular limitations on the method of applying the photosensitive resin composition of this embodiment, but examples include printing methods, spin coating methods, spray coating methods, jet dispensing methods, inkjet methods, dip coating methods, etc. Various coating methods can be mentioned. Among these, from the viewpoint of forming a thick photosensitive layer more easily, a printing method or a spin coating method may be selected as appropriate.
When used in the form of a film, it can be used, for example, in the form of a photosensitive resin film, which will be described later. In this case, a photosensitive layer of a desired thickness can be formed by laminating using a laminator or the like.

[Photosensitive resin film]
The photosensitive resin film of this embodiment has a photosensitive layer using the photosensitive resin composition of this embodiment. The photosensitive resin film of this embodiment may have a carrier film.
In this specification, the term "layer" includes not only a structure formed on the entire surface but also a structure formed on a part of the layer when observed in a plan view.

The photosensitive resin film of this embodiment can be produced by, for example, applying the photosensitive resin composition of this embodiment onto a carrier film using the various coating methods described above to form a coating film, and drying the coating film. , a photosensitive layer can be formed and manufactured. Moreover, when the photosensitive resin composition of this embodiment contains a diluent, at least a portion of the diluent may be removed during drying.

For drying the coating film, hot air drying, a dryer using far infrared rays, or near infrared rays can be used, and the drying temperature ranges from 60 to 120°C, 70 to 110°C, or 90 to 110°C. You can select it as appropriate. Further, the drying time may be appropriately selected from 1 to 60 minutes, 2 to 30 minutes, or 5 to 20 minutes. If the photosensitive resin composition of this embodiment contains a diluent, at least a portion of the diluent can be removed by drying under the above conditions.

Examples of the carrier film include resin films such as polyester resin films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), and polyolefin resin films such as polypropylene and polyethylene. A polyester resin film may be selected from the viewpoint of improving the mechanical strength and heat resistance of the photosensitive resin film.
The thickness of the carrier film may be appropriately selected from 10 μm to 3 mm or 10 to 200 μm, taking into consideration handleability and the like.

The thickness of the photosensitive layer may be appropriately selected from 1 to 500 μm, 10 to 300 μm, or 30 to 100 μm. By setting it to 30 μm or more, for example, when forming a photosensitive layer with a thickness of 150 μm or more, the number of lamination operations can be further reduced, and by setting it to 100 μm or less, the photosensitive resin film can be wound around the core. When the core is wound, deformation of the photosensitive layer due to stress difference between the inside and outside of the winding core can be further reduced. Considering the effect that the photosensitive resin composition of the present embodiment has, that excellent pattern formation properties can be obtained even when a thick photosensitive layer is formed, the thickness may be 70 μm or more, and the thickness may be more than 100 μm. There may be. Note that a photosensitive layer having a thickness of 70 μm or more can be obtained, for example, by bonding together a carrier film with a photosensitive layer formed thereon and a protective layer described below with a photosensitive layer formed thereon. A photosensitive resin film including a thick photosensitive layer and a protective layer in this order can be obtained.

Moreover, in the photosensitive resin film of this embodiment, a protective layer can also be laminated on the surface of the photosensitive layer opposite to the surface in contact with the carrier film. As the protective layer, for example, a resin film such as polyethylene or polypropylene may be used. Further, the same resin film as the carrier film described above may be used, or a different resin film may be used.

[Method for producing cured product]
The method for producing a cured product of the present embodiment includes a step of providing a photosensitive layer on a substrate using the photosensitive resin composition of the present embodiment or a photosensitive resin film (photosensitive layer forming step), and at least one of the photosensitive layers. a step of irradiating the photosensitive layer with actinic rays to form a photocured portion (exposure step), and a step of removing at least a portion of the photosensitive layer other than the photocured portion to form a resin pattern (removal step). have in order. Further, if desired, the method further includes a step of heat-treating the resin pattern (heating step). The method for producing a cured product of this embodiment enables desired pattern formation, and the photosensitive material of this embodiment has excellent pattern forming properties even when a thick photosensitive layer of, for example, 70 μm or more is formed. Taking advantage of the characteristics of the resin composition, it is possible to form a desired pattern with a cured product having a thickness of, for example, 70 μm or more. In this specification, the term "process" refers not only to an independent process, but also to a "process" if the intended effect of the process is achieved, even if the process cannot be clearly distinguished from other processes. include.

(Photosensitive layer forming process)
In forming the photosensitive layer, the photosensitive resin composition or the photosensitive resin film of this embodiment is applied or laminated onto a substrate, respectively, to form the photosensitive layer.
Examples of the substrate include glass substrates, silicon wafers, metal oxide insulators such as TiO ₂ and SiO ₂ , silicon nitride, ceramic piezoelectric substrates, and epoxy resin-impregnated glass cloth substrates.

When forming a photosensitive layer by coating a photosensitive resin composition on a substrate, it is sufficient to apply the photosensitive resin composition dissolved in the above-mentioned diluent in the form of a solution to the substrate. The resulting coating film may be dried. Coating and drying may be performed by the various coating methods and coating film drying methods described above for producing the photosensitive resin film.
Furthermore, when using a photosensitive resin film, the photosensitive layer can be formed by a lamination method using a laminator or the like.

The thickness of the photosensitive layer provided on the substrate varies depending on the formation method (coating method or lamination method), solid content concentration and viscosity of the photosensitive resin composition, etc., but as a lower limit of the thickness of the photosensitive layer after drying, The thickness may be appropriately selected from 10 μm or more, 30 μm or more, 50 μm or more, 70 μm or more, 100 μm or more, more than 100 μm, or 150 μm or more. Further, the upper limit is not particularly limited as long as a resin pattern can be formed, but may be appropriately selected from, for example, 500 μm or less, 300 μm or less, or 250 μm or less. The thickness of the photosensitive layer may be appropriately selected from the above range depending on the application, and when used for electronic components etc., the thickness may be appropriately selected from 70 μm or more, more than 100 μm, or 150 μm or more as a lower limit, and 500 μm as an upper limit. Hereinafter, the thickness may be appropriately selected from 300 μm or less or 250 μm or less.
In the method for producing a cured product of the present embodiment, since the photosensitive layer is formed using the photosensitive resin composition of the present embodiment, it is possible to form a thick photosensitive layer. For example, when forming a photosensitive layer with a thickness of 150 μm or more, it is not formed by one-time coating (and drying if necessary) or by lamination, but by applying it multiple times until the desired thickness is achieved (and drying if necessary). (drying) or lamination may be repeated.

(Exposure process)
In the exposure step, if necessary, at least a portion of the photosensitive layer provided on the substrate in the photosensitive layer forming step is irradiated with actinic rays to photocure the exposed portion to form a cured portion. When irradiating the actinic rays, the photosensitive layer may be irradiated with the actinic rays through a mask having a desired pattern. Alternatively, an LDI (Laser Direct Imaging) exposure method, a DLP (Digital Light Processing) exposure method, etc. may be used. Actinic light may be irradiated by direct writing exposure method.
Further, from the viewpoint of improving pattern formability, post-exposure bake (PEB) may be performed using a hot plate, dryer, etc. after exposure. Drying conditions are not particularly limited, but drying may be carried out at a temperature of 60 to 120°C or 70 to 110°C for 15 seconds to 5 minutes or 30 seconds to 3 minutes.

The exposure amount of actinic rays may be appropriately selected from 10 to 2,000 mJ/cm ² , 100 to 1,500 mJ/cm ² , or 300 to 1,000 mJ/cm ² . Examples of the actinic rays used include ultraviolet rays, visible rays, electron beams, and X-rays. Further, as a light source, a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, etc. can be used.

(Removal process)
In the removal step, at least a portion of the photosensitive layer formed in the exposure step other than the hardened portion (unexposed portion) is removed to form a resin pattern. The unexposed areas may be removed using, for example, a developer such as an organic solvent.
Examples of the organic solvent include ethanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, and N-methylpyrrolidone. Among them, cyclopentanone can be used from the viewpoint of development speed. These can be used alone or in combination of two or more.
Furthermore, various commonly used additives may be added to the organic solvent used as the developer.

After removing the unexposed areas with a developer, if necessary, wash (rinse) with water, alcohol such as methanol, ethanol, isopropyl alcohol, n-butyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether acetate, etc. You may.

(Heating process)
The heating process is a process that is adopted as necessary, and is a process of heat-treating the resin pattern formed in the removal process to form a cured product. The heat treatment is preferably carried out for 1 to 2 hours while selecting a heating temperature and increasing the temperature in stages. The heating temperature may be appropriately selected from 120 to 240°C, 140 to 230°C, or 150 to 220°C. In addition, when increasing the temperature in stages, for example, after heating at least one of around 120°C and around 160°C for 10 to 50 minutes, or for 20 to 40 minutes, heat treatment is performed at around 220°C for 30 to 100 minutes. The heat treatment may be performed for 50 to 70 minutes.

The thickness of the obtained resin pattern is the same as the thickness of the photosensitive layer after drying, and the lower limit is 10 μm or more, 30 μm or more, 50 μm or more, 70 μm or more, 100 μm or more, more than 100 μm, or 150 μm or more as appropriate. The upper limit may be appropriately selected from 500 μm or less, 300 μm or less, or 250 μm or less. The thickness of the resin pattern may be appropriately selected from the above range depending on the application, and when used for electronic components etc., the thickness may be appropriately selected from the lower limit of 70 μm or more, more than 100 μm, or 150 μm or more, and the upper limit of 500 μm. Hereinafter, the thickness may be appropriately selected from 300 μm or less or 250 μm or less.

[Laminated body]
The laminate of this embodiment includes a cured product of the photosensitive resin composition of this embodiment, and includes various types of substrates used in the method for producing the cured product, carrier films for photosensitive resin films, etc. Examples include those in which the cured product is provided on a support. The cured product of the photosensitive resin composition of this embodiment can be formed, for example, by the method for producing a cured product of this embodiment described above.

The thickness of the cured product in the laminate of this embodiment may be appropriately selected from 10 μm or more, 30 μm or more, 50 μm or more, 70 μm or more, 100 μm or more, 100 μm or more, or 150 μm or more as a lower limit, and 500 μm or less and 300 μm as an upper limit. The thickness may be appropriately selected from 250 μm or less. The thickness of the cured product may be appropriately selected from the above range depending on the application, and when used for electronic components etc., the thickness may be appropriately selected from 70 μm or more, more than 100 μm, or 150 μm or more as a lower limit, and 500 μm as an upper limit. Hereinafter, the thickness may be appropriately selected from 300 μm or less or 250 μm or less.

The cured product provided on the substrate obtained by the above-mentioned method for producing a cured product uses the photosensitive resin composition of this embodiment, and excellent pattern formation properties can be obtained even with a thick photosensitive layer of, for example, 70 μm or more. Therefore, for example, with the trend toward smaller size and higher performance of electronic devices, it is possible to respond to the demand for electronic circuit boards that require thicker cured material to be provided on the board in a more precise pattern. . Further, for example, by using the cured product formed from the photosensitive resin composition of this embodiment as an insulating film in the plating process in the manufacture of electronic circuit boards, it is possible to suppress a decrease in yield due to short circuits between wirings. can.
Therefore, the laminate of this embodiment is used, for example, as an electronic component such as an electronic circuit board in a mobile terminal such as a mobile phone.

Hereinafter, the objects and advantages of this embodiment will be explained in more detail based on Examples and Comparative Examples, but this embodiment is not limited to the following Examples.

(Method for measuring weight average molecular weight)
The weight average molecular weight is a value determined by GPC standard polystyrene conversion using the following apparatus, and was measured using a solution in which 0.5 mg of the polymer was dissolved in 1 mL of tetrahydrofuran (THF).
Equipment name: Tosoh Corporation HLC-8320GPC
Column: Gelpack R-420, R-430, and R-440 (3-piece connection)
Detector: RI detector Column temperature: 40°C
Eluent: THF
Flow rate: 1ml/min Standard material: polystyrene

(Measurement method of molar extinction coefficient)
The absorbance of the photopolymerization initiator was measured using an ultraviolet-visible spectrophotometer (trade name: U-3010, manufactured by Hitachi High-Technologies Corporation) and a 1 cm thick quartz cell. Specifically, 0.001 g of photopolymerization initiator was dissolved in 0.01 L of methanol to obtain a 0.1% by mass sample solution. Furthermore, the obtained 0.1% by mass sample solution was diluted 10 times and 100 times, respectively, to prepare sample solutions of 0.01% by mass and 0.001% by mass, respectively. The absorbance at a wavelength of 365 nm of the sample solution at each concentration was measured, and the molar extinction coefficient was calculated from the slope when the horizontal axis is the molar concentration and the vertical axis is the absorbance.

(Examples 1 to 21, Comparative Examples 1 to 3)
The compositions were blended according to the formulations shown in Tables 1 and 2 (the units of numerical values in the tables are parts by mass, and in the case of solutions, they are equivalent to solid content), and kneaded in a three-roll mill to form a photosensitive resin. I prepared something. N,N-dimethylacetamide was added so that the solid content concentration was 60% by mass to obtain a photosensitive resin composition.

Next, the photosensitive resin composition obtained above was used to carry out various evaluations under the conditions shown below.

[Preparation of photosensitive resin film]
A polyethylene terephthalate film (trade name: A-4100, manufactured by Teijin Ltd.) with a thickness of 50 μm was used as a carrier film, and the resin compositions of Examples and Comparative Examples were applied onto the carrier film so that the thickness after drying would be 50 μm. was applied evenly. Next, a photosensitive layer was formed by heating and drying at 100° C. for 15 minutes using a hot air convection dryer, thereby producing a photosensitive resin film having a carrier film and a photosensitive layer.

[Measurement of absorbance]
Regarding the photosensitive resin film obtained in the above [Preparation of photosensitive resin film], the absorbance of the photosensitive layer to light having a wavelength of 365 nm was measured at a thickness of 50 μm (thickness after drying). Specifically, the absorbance (Abs) at a wavelength of 365 nm was measured using a UV-visible spectrophotometer (product name: "U-3310 Spectrophotometer", manufactured by Hitachi High-Technologies Corporation). A single polyethylene terephthalate (PET) film was used as a reference. The measurement results are shown in Tables 1 and 2.

[Evaluation of pattern formation]
A photosensitive resin film is placed on a glass epoxy substrate (obtained by etching copper of MCL-E-679F (manufactured by Hitachi Chemical Co., Ltd., trade name)) with the photosensitive layer facing the glass epoxy substrate side. After lamination, the carrier film was removed. Lamination was performed at 60° C. using a laminator. Next, a photosensitive resin film is laminated again on the photosensitive layer using the method described above, the carrier film is removed, and this process is repeated three times to form a 200 μm thick photosensitive layer and carrier film on the glass epoxy substrate. A laminate was obtained.
A resolution evaluation mask (6 types of line widths (5 μm, 8 μm, 10 μm, 15 μm, 20 μm, 25 μm) and 5 types of line spaces (5 μm, 8 μm, 10 μm, 25 μm) and 5 types of line spaces ( 50 μm, 80 μm, 100 μm, 150 μm, 200 μm), and then placed an i-ray filter (HB-0365, manufactured by Asahi Spectroscopy Co., Ltd.), and a high-precision parallel exposure machine (Mikasa Co., Ltd.). The sample was exposed to light with a wavelength of 365 nm (i-line) at an exposure dose of 300 mJ/cm ² using a 365 nm wavelength (i-line). The exposed sample was heated for 1 minute on a 90° C. hot plate.
Thereafter, the carrier film was removed, and the film was developed by immersing it in a developer (cyclopentanone) for 20 minutes. Pattern formability was evaluated by drying the developed pattern at room temperature for 30 minutes and observing it using a metallurgical microscope. Evaluation was performed based on the following criteria. Here, "formable" means that the unexposed portions are removed cleanly and there are no defects such as collapse in the line portions (exposed portions). The evaluation results are shown in Tables 1 and 2. In addition, "line (μm) / space (μm)" described in the table has the narrowest line space among the patterns that could be formed, and among the patterns that have the narrowest line space, It means line width value (μm)/line space value (μm) of a pattern having the narrowest line width that could be formed.
A: It was possible to form a pattern having a line width of 15 μm or less and a line space of 100 μm or less (hereinafter, these patterns are referred to as "pattern A").
B: Pattern A could not be formed, but it was possible to form a pattern with a line width of 15 μm or less and a line space of 150 to 200 μm, or a pattern with a line width of 20 to 25 μm and a line space of 50 to 100 μm. (Hereinafter, these patterns will be referred to as "pattern B").
C: Patterns A and B could not be formed, but a pattern having a line width of 20 to 25 μm and a line space of 150 to 200 μm could be formed.
D: Not all patterns could be formed.

[Evaluation of insulation reliability]
Insulation reliability was evaluated using a high temperature and high humidity bias test. The thicknesses obtained in Examples 1 to 21 were placed on a comb-shaped copper electrode of TEG (Test Element Group) (product name: WALTS-KIT EM0101JY, manufactured by WALTS, L/S = 40 μm/15 μm), which is an evaluation device. A 50 μm photosensitive resin film was attached using a laminator at 60° C. with the photosensitive layer facing the interdigitated copper electrode side. Next, after exposure to i-line at an exposure dose of 1,000 mJ/cm ² , the carrier film was removed after heating on a 90° C. hot plate for 1 minute. Furthermore, after heating in an oven at 200° C. for 1 hour, the sample was cooled to room temperature to obtain a measurement sample.
A lead wire was attached to the TEG electrode part of the obtained measurement sample with solder, and a high temperature, high humidity bias test was conducted (voltage: 5 V (DC), test time: 100 hours, 85°C, 85% RH (high temperature, high humidity). machine (manufactured by ESPEC)). As a result, all of the measurement samples obtained using the photosensitive resin films of Examples 1 to 21 maintained a resistance value of 1.0×10 ⁷ Ω or more during the test period (100 hours), which was sufficient. It was confirmed that the insulation reliability was excellent.

（式中、Ｒ^Ｄ１は水素原子又はメチル基を表す。Ｒ^Ｄ３は炭素数１～６のアルキル基、又は炭素数１～６のヒドロキシアルキル基を表す。） Details of each material in Tables 1 and 2 are as follows.
[(A1) Component]
・UN-952: Urethane acrylate (manufactured by Negami Kogyo Co., Ltd., product name, number of functional groups: 10, weight average molecular weight: 9,000, is a reaction product of an acrylate having a hydroxyl group and a diisocyanate compound, and contains an acryloyl group in the molecule) (Photopolymerizable functional group), urethane bond (carbon-nitrogen bond), chain hydrocarbon skeleton, and alicyclic hydrocarbon skeleton.)
・UN-954: Urethane acrylate (manufactured by Negami Kogyo Co., Ltd., product name, number of functional groups: 6, weight average molecular weight: 4,500)
[(A2) component]
・TMCH-5R: Urethane acrylate (manufactured by Hitachi Chemical Co., Ltd., product name, number of functional groups: 2, weight average molecular weight: 950, acryloyl group (photopolymerizable functional group) in the molecule, urethane bond (carbon-nitrogen bond), It is a compound having a chain hydrocarbon skeleton and an alicyclic hydrocarbon skeleton, and falls under component (A2-2).)
・A-9300: Isocyanuric acid ethylene oxide modified triacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., trade name, molecular weight: 423, is a compound represented by the above formula (9-1) and corresponds to the component (A2-1) do.)
・UN-3320HA: Urethane (meth)acrylate (manufactured by Negami Kogyo Co., Ltd., product name, number of functional groups: 6, weight average molecular weight: 1,500, urethane (meth)acrylate having a structural unit represented by the above general formula (10) ) Acrylate and falls under component (A2-2).)
・A-DCP: Tricyclodecane dimethanol diacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., trade name, corresponds to component (A2-3))
[(B) Component]
・TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide "IRGACURE-TPO" (manufactured by BASF, trade name)
・I-651: "IRGACURE-651" which is 2,2-dimethoxy-1,2-diphenylethan-1-one (manufactured by BASF, trade name)
・I-184: "IRGACURE-184" which is 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, trade name)
・I-819: "IRGACURE-819" which is bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by BASF, trade name)
・OXE-01: 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) "IRGACURE-OXE-01" (manufactured by BASF, product name)
[(C) Component]
・KBM-803: 3-Mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name)
[(D) Component]
・Z250: Cyclomer P (ACA) Z250 (manufactured by Daicel Allnex Corporation, trade name, 3 expressed by the following formula produced by the reaction of an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound) (weight average molecular weight: 19,000 to 25,000)).

(In the formula, R ^D1 represents a hydrogen atom or a methyl group. ^{R D3} represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms.)

From Tables 1 and 2, it was confirmed that the photosensitive resin compositions of the present embodiments of Examples 1 to 21 had excellent pattern forming properties. On the other hand, in the photosensitive resin compositions of Comparative Examples 1 and 3, which have an absorbance of 0.35 or more, the pattern is filled, and the photosensitive resin composition of Comparative Example 2 turns into a gel, and both have poor pattern forming properties. It was bad.

Claims (20)

(A) component: a compound having a photopolymerizable functional group, and (B) component: light with a molar absorption coefficient of 1 L/mol・cm or more and less than 8.0×10 ³ L/mol・cm for light with a wavelength of 365 nm. A photosensitive resin composition for a resist containing a polymerization initiator and a component (C): a silane compound,
The component (B) contains at least one selected from the group consisting of an aromatic ketone photopolymerization initiator and an alkylphenone photopolymerization initiator, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. death,
The content of the component (C) is 1 to 15% by mass based on the total solid content of the photosensitive resin composition,
When the thickness of the photosensitive resin composition is 50 μm, the photosensitive resin composition has an absorbance of 0.001 or more and less than 0.35 for light with a wavelength of 365 nm (provided that the absorbance for light having at least one ethylenically unsaturated group A photosensitive resin composition comprising a polymerizable compound (a1), a photopolymerization initiator (b1), and a compound (c1) having a hindered phenol structure, wherein the component (a1) contains a (meth)acrylate compound. A photosensitive resin composition comprising: a carboxyl group-containing resin, a photopolymerization initiator, a photosensitive acrylate compound, and a filler, the filler having a refractive index of 1.5 to 1.6; and the dry coating film exhibits an absorbance of at least one of 0.01 to 0.2 at a wavelength of 365 nm or 0.01 to 0.2 at a wavelength of 405 nm per 25 μm thickness. composition; in the resin composition, 15-70% by weight of a (meth)acrylate monomer (a2) having an ethylene oxide chain in the molecule, 5-50% by weight of urethane (meth)acrylate (b2), 2- An ultraviolet curable resin composition for optical discs containing 50% by weight of epoxy (meth)acrylate (c2) and 1 to 10% by weight of a photopolymerization initiator (d2), the glass transition temperature of the cured film thereof is 10 to 65°C, and the maximum value of the mechanical loss coefficient tan δ of the cured film is in the range of 0.35 to 0.75; and a curable component. (excluding active energy ray-curable coating compositions containing the following components (a3) to (d3) in the proportions shown below).
(a3) Urethane (meth)acrylate with a weight average molecular weight of 1,000 to 60,000: 5 to 50% by weight in the total amount of curable components
(b3) Compound having a hydrophilic group and one ethylenically unsaturated group: 5 to 45% by weight in the total amount of curable components
(c3) A compound having a cyclic hydrocarbon group and one ethylenically unsaturated group, other than component (b3): 5 to 65% by weight in the total amount of curable components
(d3) Compounds having ethylenically unsaturated groups other than components (a3) to (c3): 0 to 40% by weight in the total amount of curable components (A) component: a compound having a photopolymerizable functional group, and (B) component: light with a molar extinction coefficient of 1 L/mol・cm or more and 0.5×10 ³ L/mol・cm or less for light with a wavelength of 365 nm. A photosensitive resin composition for a resist containing a polymerization initiator and a component (C): a silane compound,
The component (B) contains at least one selected from the group consisting of an aromatic ketone photopolymerization initiator and an alkylphenone photopolymerization initiator, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. death,
When the thickness of the photosensitive resin composition is 50 μm, the photosensitive resin composition has an absorbance of 0.001 or more and less than 0.35 for light with a wavelength of 365 nm (provided that the absorbance for light having at least one ethylenically unsaturated group A photosensitive resin composition comprising a polymerizable compound (a1), a photopolymerization initiator (b1), and a compound (c1) having a hindered phenol structure, wherein the component (a1) contains a (meth)acrylate compound. A photosensitive resin composition comprising: a carboxyl group-containing resin, a photopolymerization initiator, a photosensitive acrylate compound, and a filler, the filler having a refractive index of 1.5 to 1.6; and the dry coating film exhibits an absorbance of at least one of 0.01 to 0.2 at a wavelength of 365 nm or 0.01 to 0.2 at a wavelength of 405 nm per 25 μm thickness. composition; in the resin composition, 15-70% by weight of a (meth)acrylate monomer (a2) having an ethylene oxide chain in the molecule, 5-50% by weight of urethane (meth)acrylate (b2), 2- An ultraviolet curable resin composition for optical discs containing 50% by weight of epoxy (meth)acrylate (c2) and 1 to 10% by weight of a photopolymerization initiator (d2), the glass transition temperature of the cured film thereof is 10 to 65°C, and the maximum value of the mechanical loss coefficient tan δ of the cured film is in the range of 0.35 to 0.75; and a curable component. (excluding active energy ray-curable coating compositions containing the following components (a3) to (d3) in the proportions shown below).
(a3) Urethane (meth)acrylate with a weight average molecular weight of 1,000 to 60,000: 5 to 50% by weight in the total amount of curable components
(b3) Compound having a hydrophilic group and one ethylenically unsaturated group: 5 to 45% by weight in the total amount of curable components
(c3) A compound having a cyclic hydrocarbon group and one ethylenically unsaturated group, other than component (b3): 5 to 65% by weight in the total amount of curable components
(d3) Compounds having ethylenically unsaturated groups other than components (a3) to (c3): 0 to 40% by weight in the total amount of curable components The photosensitive resin composition according to claim 2, wherein the content of the component (C) is 0.05 to 15% by mass based on the total solid content of the photosensitive resin composition. The aromatic ketone photopolymerization initiator is benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4' -dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and 2- The photosensitive resin according to any one of claims 1 to 3, comprising at least one member selected from the group consisting of methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one. Composition. The alkylphenone photopolymerization initiator is benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl. -Phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane- At least one selected from the group consisting of 1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one. The photosensitive resin composition according to any one of claims 1 to 4, comprising one type. Claims 1 to 5, wherein the component (B) contains a photopolymerization initiator whose molar extinction coefficient for light with a wavelength of 365 nm is 1 L/mol·cm or more and 0.1×10 ³ L/mol·cm or less. The photosensitive resin composition according to any one of the items. The photosensitive resin according to any one of claims 1 to 6, wherein the content of the component (B) is 0.05 to 30% by mass based on the total solid content in the photosensitive resin composition. Composition. Photosensitivity according to any one of claims 1 to 7, wherein the content of the component (B) is such that the value P expressed by the following formula (i) is 0.1 or more and 3 or less. Resin composition.
P=A×B/C (i)
A: Molar extinction coefficient of photopolymerization initiator for light with a wavelength of 365 nm (L/mol・cm)
B: Content (% by mass) of component (B) relative to the total amount of the photosensitive resin composition (however, if the photosensitive resin composition contains a filler, the mass of the filler is excluded)
C: Molecular weight of photopolymerization initiator As the (A) component, (A1) component: a polymer with a weight average molecular weight of 2,500 or more having a photopolymerizable functional group, and (A2) component: a weight average molecular weight of 2,500 having a photopolymerizable functional group. The photosensitive resin composition according to any one of claims 1 to 8, which contains a low molecular weight substance of less than 10%. The photosensitive resin composition according to claim 9, wherein the component (A2) contains a low molecular weight substance having a photopolymerizable functional group and a urethane bond. The content of the component (A1), the component (A2), and the component (B) is 10 to 95% by mass, 3 to 70% by mass, and 0% by mass, respectively, based on the total solid content in the photosensitive resin composition. The photosensitive resin composition according to claim 9 or 10, which has a content of .05 to 30% by mass. The photosensitive resin composition according to any one of claims 1 to 11, wherein the component (C) contains a (meth)acryloyl group-containing alkoxysilane. The photosensitive resin composition according to any one of claims 1 to 12, wherein the component (C) contains (meth)acryloxypropyltrimethoxysilane. A photosensitive resin film having a photosensitive layer using the photosensitive resin composition according to any one of claims 1 to 13. Forming a photosensitive layer on the substrate using the photosensitive resin composition according to any one of claims 1 to 13 or the photosensitive resin film according to claim 14,
irradiating at least a portion of the photosensitive layer with actinic rays to form a photocured portion;
A method for producing a cured product, comprising the steps of: removing at least a portion of the photosensitive layer other than the photocured portion to form a resin pattern. The method for producing a cured product according to claim 15, further comprising the step of heat-treating the resin pattern. The method for producing a cured product according to claim 15 or 16, wherein the resin pattern has a thickness of 70 to 300 μm. A laminate comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 13. The laminate according to claim 18, wherein the thickness of the cured product is 70 to 300 μm. An electronic component comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 13.

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