Photosensitive resin composition, photosensitive resin film, method for producing cured product, laminate, and electronic component

Abstract

This photosensitive resin composition comprises: component (A) which is a high molecular weight body having a photopolymerizable functional group and a carbon-nitrogen bond; component (B) which is a low molecular weight body having a photopolymerizable functional group; component (C) which is a photopolymerization initiator; and component (D) which is a triazole-based compound.

Description

[Technical Field]

[0001] 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. [Background technology]

[0002] In the manufacturing fields of semiconductor integrated circuits (LSIs) or wiring boards, photosensitive materials are used as resists for producing conductor patterns. For example, in the manufacture of wiring boards, a resist is formed using a photosensitive resin composition, and then a conductor pattern, metal posts, etc. are formed by plating. More specifically, a photosensitive layer is formed on a support (substrate) using a photosensitive resin composition or the like, and the photosensitive layer is exposed to light through a predetermined mask pattern. A development process is then performed so that the portions where the conductor pattern, metal posts, etc. will be formed can be selectively removed (peeled off), thereby forming a resist pattern (resist). Next, a conductor such as copper is formed on the removed portions by plating, and the resist pattern is then removed, thereby producing a wiring board equipped with a conductor pattern, metal posts, etc.

[0003] Conventionally, thick conductor patterns and metal posts have been fabricated by growing metal plating after removing the resist pattern. To meet such demands, for example, thick-film photosensitive resists with a photosensitive layer thickness of about 30 μm, or at most about 65 μm, have been used (see Patent Documents 1 and 2).

[0004] In recent years, in order to further improve performance, attempts have been made to form a conductor layer as thick as approximately 150 μm by performing a plating process while destroying the layer of the metal ion dilute layer that exists in the direction of the desired plating growth using a plating solution (see Patent Document 3). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-034926 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-074774 [Patent Document 3] Japanese Patent Application Laid-Open No. 2014-080674 Summary of the Invention [Problem to be solved by the invention]

[0006] However, with conventional thick-film photosensitive resists, when a thick photosensitive layer of, for example, 70 μm or more is required, light has difficulty passing through to the bottom, which can result in poor pattern shape. Furthermore, with the method described in Patent Document 3, plating proceeds while partially destroying the metal ion dilute layer, making it difficult to stably form an excellent pattern. Therefore, there is a demand for photosensitive resists that have excellent pattern-forming properties, even when a photosensitive layer of 70 μm, or even 150 μm or more thick (thickness perpendicular to the substrate), which is thicker than conventional ones, is formed.

[0007] Furthermore, copper wiring is mounted on the substrate of an electronic component such as an inductor. When a resist pattern is formed on a substrate having such copper wiring, there is a problem that development residues are likely to be generated on the copper surface after development. In particular, when the photosensitive layer is made thick, the problem of development residues tends to become more pronounced. Therefore, there is a demand for a photosensitive layer that can suppress the generation of development residues on the copper surface.

[0008] Furthermore, when forming a resist pattern on a substrate having copper wiring, the photosensitive layer is required to achieve excellent pattern formability on both the surface where the copper wiring is formed and the surface where the copper wiring is not formed. Furthermore, when forming a photosensitive layer on a substrate having copper wiring and exposing it, it is necessary to expose under the same exposure conditions regardless of whether the copper wiring is formed or not. If the exposure conditions for forming a high-resolution resist pattern differ (there is a mismatch) between the copper wiring and the surface where the copper wiring is not formed, a problem occurs in that a uniform resist pattern cannot be formed. Therefore, the photosensitive layer is further required to achieve excellent pattern formability under the same exposure conditions on both the surface where the copper wiring is formed and the surface where the copper wiring is not formed.

[0009] The present disclosure has been made in view of the above circumstances, and aims to provide a photosensitive resin composition that can suppress the generation of development residues on copper surfaces and that can achieve excellent pattern formability under the same exposure conditions on both copper surface-containing and non-copper surface-containing surfaces of a substrate, as well as a photosensitive resin film, a method for producing a cured product, a laminate, and an electronic component (hereinafter, these may be referred to as "photosensitive resin composition, etc."). [Means for solving the problem]

[0010] As a result of extensive research to solve the above problems, the present inventors have found that the problems can be solved by a photosensitive resin composition etc. having the following configuration. The present disclosure provides the following photosensitive resin composition etc.

[0011] [1] A photosensitive resin composition comprising: (A) component: a high molecular weight compound having a photopolymerizable functional group and a carbon-nitrogen bond; (B) component: a low molecular weight compound having a photopolymerizable functional group; (C) component: a photopolymerization initiator; and (D) component: a triazole-based compound. [2] The photosensitive resin composition according to [1] above, wherein the component (D) contains a benzotriazole-based compound. [3] The photosensitive resin composition according to [1] or [2] above, wherein the content of the component (D) is 0.1 to 10 mass % based on the total solid content of the photosensitive resin composition. [4] The photosensitive resin composition according to any one of the above [1] to [3], wherein the component (A) contains a polymer having a (meth)acryloyl group as a photopolymerizable functional group. [5] The photosensitive resin composition according to any one of the above [1] to [4], wherein the component (A) contains a polymer having a urethane bond as a carbon-nitrogen bond. [6] The photosensitive resin composition according to any one of [1] to [5] above, wherein the component (A) contains a high molecular weight compound having six or more ethylenically unsaturated groups as photopolymerizable functional groups and having a weight-average molecular weight of 2,500 or more. [7] The photosensitive resin composition according to any one of the above [1] to [6], wherein the component (A) contains a polymer having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton. [8] The photosensitive resin composition according to any one of the above [1] to [7], wherein the component (B) comprises at least one member selected from the group consisting of a low-molecular-weight compound having a urethane bond, a low-molecular-weight compound having an isocyanuric ring, and a low-molecular-weight compound having an alicyclic skeleton. [9] The photosensitive resin composition according to any one of the above [1] to [7], wherein the component (B) contains a low-molecular weight compound having at least one (meth)acryloyl group and a urethane bond.

[10] The photosensitive resin composition according to any one of [1] to [9] above, wherein the component (C) comprises a compound represented by the following general formula (C1) or a compound represented by the following general formula (C2): [ka] [R C1 , R C2 and R C3 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; R C4 and R C5each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. C1 ~R C5 may each have a substituent.] [ka] [R C6 represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an amino group, and R C7 and R C8 R each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. C7 and R C8 may be bonded to each other to form a ring structure having 3 to 16 carbon atoms. R other than a hydroxyl group and a hydrogen atom C6 ~R C8 may each have a substituent, and in the case of amino groups having a substituent, the substituents may be bonded to each other to form a ring structure having 3 to 12 carbon atoms. C9 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an organic group having 1 to 10 carbon atoms which may contain one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom.

[11] The photosensitive resin composition according to any one of the above [1] to

[10] , further comprising: (E) component: a polymer having a glass transition temperature of 70 to 150°C and no carbon-nitrogen bond.

[12] The photosensitive resin composition according to any one of the above [1] to

[11] , further comprising a component (F): a silane compound.

[13] A photosensitive resin film having a photosensitive layer using the photosensitive resin composition according to any one of [1] to

[12] above.

[14] A method for producing a cured product, comprising the steps of: providing a photosensitive layer on a substrate using the photosensitive resin composition according to any one of [1] to

[12] above or the photosensitive resin film according to

[13] above; irradiating at least a portion of the photosensitive layer with actinic rays 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.

[15] The method for producing a cured product according to

[14] above, further comprising a step of heat-treating the resin pattern.

[16] The method for producing a cured product according to

[14] or

[15] above, wherein the thickness of the resin pattern is 70 μm or more and 300 μm or less.

[17] The method for producing a cured product according to any one of the above

[14] to

[16] , further comprising the step of heat-treating the photosensitive layer after providing the photosensitive layer on the substrate.

[18] A laminate comprising a cured product of the photosensitive resin composition according to any one of [1] to

[12] above.

[19] The laminate according to

[18] above, wherein the thickness of the cured product is 70 μm or more and 300 μm or less.

[20] An electronic part comprising a cured product of the photosensitive resin composition according to any one of [1] to

[12] above. [Effects of the Invention]

[0012] According to the present disclosure, it is possible to provide a photosensitive resin composition and the like that can suppress the generation of development residues on copper surfaces and can achieve excellent pattern formability under the same exposure conditions on both surfaces of a substrate, in areas having a copper surface and areas not having a copper surface. [Brief explanation of the drawings]

[0013] [Figure 1] 10A and 10B are diagrams showing the pattern shape of the writing data used when exposing by the direct writing exposure machine in the embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0014] The present disclosure will be described in detail below. In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. Furthermore, in numerical ranges described in stages in this specification, the upper or lower limit of a numerical range in one stage may be replaced with the upper or lower limit of a numerical range in another stage. In numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples.

[0015] In this specification, "(meth)acrylic acid" means at least one of "acrylic acid" and its corresponding "methacrylic acid," and the same applies to other similar expressions such as (meth)acrylate.

[0016] In this specification, the term "solid content" refers to the non-volatile content excluding volatile substances such as water and solvent contained in the photosensitive resin composition, and refers to components that remain without volatilization when the resin composition is dried, and also includes liquid, starch syrup-like, and wax-like components at room temperature around 25°C.

[0017] [Photosensitive resin composition] The photosensitive resin composition according to an embodiment of the present disclosure (hereinafter, may be simply referred to as the present embodiment) contains component (A): a high molecular weight compound having a photopolymerizable functional group and a carbon-nitrogen bond, component (B): a low molecular weight compound having a photopolymerizable functional group, component (C): a photopolymerization initiator, and component (D): a triazole-based compound.

[0018] The photosensitive resin composition of this embodiment contains a high-molecular-weight compound (A) having the specific structure, a low-molecular-weight compound (B) having the specific structure, a photopolymerization initiator (C), and a triazole-based compound (D). This composition can suppress the generation of development residues on copper surfaces, and can achieve excellent pattern formation under the same exposure conditions on both copper and non-copper surfaces of a substrate. The inventors speculate that the reason for this effect is as follows: The triazole-based compound (D) has the property that the nitrogen atom in the triazole skeleton easily coordinates to the copper surface of the substrate. Due to this high coordination ability with the copper surface, the triazole-based compound tends to be localized near the copper surface. As a result, a triazole-based compound layer containing a high concentration of the triazole-based compound is formed on the surface of a photosensitive layer formed using the photosensitive resin composition that contacts the copper surface. The presence of this triazole-based compound layer is believed to reduce the opportunity for other organic substances constituting the photosensitive resin composition to come into contact with the copper surface, thereby significantly suppressing the adhesion of other organic substances to the copper surface and the generation of development residues. Furthermore, the triazole-based compound has excellent adhesion to the copper surface, is easily removable by development, and does not impair the curability of the photosensitive resin composition. Therefore, even when a thick photosensitive layer is formed on the copper surface to form a resist pattern with a narrow line width and narrow line space, excellent pattern formability can be achieved. Furthermore, when the radical concentration in the reaction system is high, such as under conditions of high exposure dose, hydrogen from the triazole-based compound is believed to be abstracted, thereby functioning as a polymerization inhibitor. This widens the process margin, allowing excellent pattern formability to be achieved under the same exposure conditions on both substrates with and without a copper surface. From the above, according to the photosensitive resin composition of the present embodiment, even when a thick photosensitive layer (for example, a thickness of 70 μm or more) is formed, excellent pattern formability can be achieved under the same exposure conditions on both the copper surface and non-copper surface of the substrate, and the generation of development residues on the copper surface can be suppressed.

[0019] Hereinafter, each component constituting the photosensitive resin composition of the present embodiment will be described.

[0020] <(A) Component: High molecular weight substance> The photosensitive resin composition of this embodiment contains, as component (A), a polymer having a photopolymerizable functional group and a carbon-nitrogen bond. The term "polymer" refers to a compound having a weight-average molecular weight (Mw) of 2,500 or more. In this specification, the weight-average molecular weight (Mw) is determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) and converted into standard polystyrene.

[0021] Examples of photopolymerizable functional groups contained in component (A) include ethylenically unsaturated groups such as (meth)acryloyl groups; and alkenyl groups such as vinyl groups and allyl groups. From the viewpoint of improving pattern formability, component (A) may contain a polymer having a (meth)acryloyl group as the photopolymerizable functional group, and may further contain a polymer having a urethane bond as the carbon-nitrogen bond. Examples of polymers having a (meth)acryloyl group include (meth)acrylates, and examples of polymers having a urethane bond as the carbon-nitrogen bond include (meth)acrylates having a urethane bond (hereinafter, sometimes referred to as "urethane(meth)acrylates").

[0022] Component (A) has at least one of these photopolymerizable functional groups and at least one carbon-nitrogen bond. The total number of photopolymerizable functional groups (number of functional groups) contained in the polymer of component (A) can be appropriately selected from 2 to 30, 2 to 24, 2 to 20, or 2 to 15 per molecule from the viewpoints of improving pattern formability and heat resistance, and can also be appropriately selected from 6 to 12, 6 to 10, or 6 to 8 from the viewpoints of stabilizing the physical properties and characteristics of the resulting cured product and reducing tackiness.

[0023] In this specification, "tackiness" refers to the surface tackiness of a photosensitive layer formed using a photosensitive resin composition (when a liquid photosensitive resin composition is directly applied to a substrate, the surface tackiness of the coating film after application and drying). If the tackiness is high, the manufacturing equipment is likely to be contaminated, which may require interruption of the manufacturing process to clean the equipment or may cause defects in the photosensitive layer. Therefore, there is a demand for reducing the tackiness.

[0024] Furthermore, the component (A) may contain a polymer having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton.

[0025] Examples of high molecular weight urethane (meth)acrylates include reaction products obtained by reacting a terminal isocyanate group of a polyaddition product of an isocyanate compound having at least two isocyanate groups per molecule with a diol compound, with a (meth)acrylate having a hydroxyl group.

[0026] Specific examples of isocyanate compounds having at least two isocyanate groups in one molecule include aliphatic diisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, and 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-isocyanatocyclohexyl)propane, and 2,2-bis(4-isocyanatocyclohexyl)propane. Examples of suitable diisocyanate compounds include alicyclic diisocyanate compounds such as 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, hydrogenated xylylene diisocyanate, and aromatic diisocyanate compounds such as naphthalene-1,5-diisocyanate, as well as multimers of these diisocyanate compounds, such as uretdione dimers, isocyanurate dimers, and biuret trimers. These compounds may 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 these, from the viewpoint of improving pattern formability, it is possible to appropriately select from alicyclic diisocyanate compounds and multimers of such diisocyanate compounds, and in particular, it is possible to appropriately select from isophorone diisocyanate and isocyanurate multimers (isocyanurate polyisocyanates). The above isocyanate compounds can be used alone or in combination of two or more kinds.

[0027] Examples of diol compounds include diol compounds having 1 to 20 carbon atoms, and specific examples include linear or branched saturated diol compounds such as ethylene glycol, diethylene glycol, propanediol, dipropylene glycol, butanediol, pentanediol, isopentyl glycol, hexanediol, nonanediol, decanediol, dodecanediol, dimethyldodecanediol, and octadecanediol; linear or branched unsaturated diol compounds such as butenediol, pentenediol, hexenediol, methylpentenediol, and dimethylhexenediol; and diol compounds having an alicyclic skeleton such as various cyclohexanediols, various cyclohexanedimethanols, various tricyclodecanedimethanols, hydrogenated bisphenol A, and hydrogenated bisphenol F. Here, the saturated diol compounds and unsaturated diol compounds can 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.

[0028] The diol compound having a chain hydrocarbon skeleton may be appropriately selected from saturated diol compounds having 1 to 20, 2 to 16, or 2 to 14 carbon atoms, from the viewpoint of improving pattern formability and increasing the glass transition temperature (Tg) after polymerization to improve water resistance, and more specifically, may be appropriately selected from ethylene glycol and octadecanediol.

[0029] Furthermore, the diol compound having an alicyclic skeleton may be appropriately selected from diol compounds having an alicyclic skeleton having 5 to 20, 5 to 18, or 6 to 16 carbon atoms, from the viewpoint of improving pattern formability and increasing the glass transition temperature (Tg) after polymerization to improve water resistance. More specifically, the diol compound may be appropriately selected from various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol, and various cyclohexanedimethanols such as 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol.

[0030] 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, monofunctional (meth)acrylates such as 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-3-(2-naphthoxy)propyl (meth)acrylate, ethoxylated products thereof, propoxylated products thereof, ethoxylated propoxylated products thereof, and caprolactone-modified products thereof; bifunctional (meth)acrylates such as trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, bis(2-(meth)acryloyloxyethyl)(2-hydroxyethyl)isocyanurate, and the like; Ethoxylated products, propoxylated products thereof, ethoxylated propoxylated products thereof, and caprolactone-modified products thereof; bifunctional epoxy (meth)acrylates such as cyclohexanedimethanol-type epoxy di(meth)acrylate, tricyclodecanedimethanol-type epoxy di(meth)acrylate, hydrogenated bisphenol A-type epoxy di(meth)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 F-type epoxy di(meth)acrylate, bisphenol AF-type epoxy di(meth)acrylate, biphenol-type epoxy di(meth)acrylate, fluorene bisphenol-type epoxy di(meth)acrylate, and monoallyl isocyanurate-type epoxy di(meth)acrylate;Examples of the epoxy (meth)acrylate include trifunctional or higher functional (meth)acrylates such as ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate, as well as their ethoxylated, propoxylated, and ethoxylated propoxylated derivatives, and caprolactone-modified derivatives; trifunctional or higher functional epoxy (meth)acrylates such as phenol novolac epoxy (meth)acrylate, cresol novolac epoxy poly(meth)acrylate, and isocyanuric acid epoxy tri(meth)acrylate; and hydroxypropylated derivatives such as trimethylolpropane tri(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate. These may be used alone or in combination of two or more.

[0031] Here, the ethoxylated, propoxylated, ethoxylated propoxylated, and hydroxypropylated (meth)acrylates can be obtained, for example, by using as raw materials an alcohol compound (or a phenol compound) that is a raw material for the (meth)acrylate, to which one or more ethylene oxide groups, propylene oxide groups, ethylene oxide and propylene oxide groups, and hydroxypropyl groups have been added. The caprolactone modified product can be obtained by, for example, using an alcohol compound (or a phenol compound) that is a raw material for the (meth)acrylate, modified with ε-caprolactone as a raw material.

[0032] Examples of reaction products obtained by reacting a terminal isocyanate group of a polyaddition product of an isocyanate compound having at least two isocyanate groups per molecule with a diol compound with a (meth)acrylate having a hydroxyl group include those having a structural unit represented by the following general formula (1):

[0033] [ka]

[0034] In general formula (1), X 1 represents a divalent organic group having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton, and Y 1 represents a divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton. When component (A) has a plurality of the above structural units, a plurality of X 1 , Y 1 and may be the same or different. That is, the component (A) may be one having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton.

[0035] X 1 Examples of the divalent organic group include organic groups derived from the aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds exemplified above as compounds having an isocyanate group, i.e., divalent organic groups having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton, which are residues obtained by removing the isocyanate group from the above isocyanate compounds. 1 The divalent organic group represented by the formula (I) may be these residues themselves, or may be residues derived from isocyanate compound derivatives such as the polyaddition products of the above-mentioned isocyanate compounds and diol compounds.

[0036] From the viewpoint of improving pattern formability and improving transparency, water resistance, and moisture resistance of the resin composition in a balanced manner, X 1 may be a divalent organic group having an alicyclic skeleton, particularly a divalent organic group having an alicyclic skeleton which is a residue of isophorone diisocyanate represented by the following formula (2).

[0037] [ka]

[0038] Y 1Examples of the divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton include organic groups derived from the diol compounds having a chain hydrocarbon skeleton and the diol compounds having an alicyclic skeleton exemplified above as the diol compounds, i.e., divalent organic groups having a chain hydrocarbon skeleton or an alicyclic skeleton which are residues obtained by removing hydroxyl groups from the above diol compounds.

[0039] In particular, from the viewpoints of improving pattern formability and increasing the glass transition temperature (Tg) after polymerization to improve water resistance, the divalent organic group having a chain hydrocarbon skeleton may be appropriately selected from residues obtained by removing hydroxyl groups from saturated diol compounds having 1 to 20, 2 to 16, or 2 to 14 carbon atoms, more specifically, from residues obtained by removing hydroxyl groups from ethylene glycol or octadecanediol. From the same viewpoint, the divalent organic group having an alicyclic skeleton may be appropriately selected from residues obtained by removing hydroxyl groups from diol compounds having an alicyclic skeleton having 5 to 20, 5 to 18, or 6 to 16 carbon atoms, more specifically, from residues obtained by removing hydroxyl groups from various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol, and various cyclohexanedimethanols such as 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol.

[0040] Specific examples of reaction products obtained by reacting a terminal isocyanate group of a polyaddition product of an isocyanate compound having at least two isocyanate groups per molecule with a diol compound with a (meth)acrylate having a hydroxyl group include compounds represented by the following general formulas (3) and (4).

[0041] [ka]

[0042] In the general formulae (3) and (4), n1 and n2 each independently represent an integer of 3 to 20.

[0043] Furthermore, when an isocyanurate trimer (isocyanurate triisocyanate), which is a trimer of diisocyanate, is used as the isocyanate compound, examples of the reaction product include compounds represented by the following general formulas (5) and (6).

[0044] [ka]

[0045] In the general formulae (5) and (6), n3 and n4 each independently represent an integer of 2 to 20.

[0046] Commercially available products containing urethane acrylates represented by general formula (1) or (3) include UN-952 (functional groups: 10, Mw: 6,500-11,000), UN-953 (functional groups: 20, Mw: 14,000-40,000), UN-954 (functional groups: 6, Mw: 4,500), and H-219 (functional groups: 9, Mw: 25,000-50,000) (all trade names, manufactured by Negami Chemical Industrial Co., Ltd.). Commercially available products containing urethane acrylates represented by general formula (6) include UN-905 (functional groups: 15, Mw: 40,000-200,000) (trade name, manufactured by Negami Chemical Industrial Co., Ltd.). Among these, UN-952 and UN-954 are preferred, and UN-954 is more preferred, from the viewpoints of pattern formability and photosensitivity. 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.

[0047] The total number of (meth)acryloyl groups (number of photopolymerizable functional groups) contained in the high molecular weight urethane (meth)acrylate may be appropriately selected from 2 to 30, 2 to 24, 2 to 20, or 2 to 15 per molecule from the viewpoint of improving pattern formability and heat resistance, and may be appropriately selected from 6 to 12, 6 to 10, or 6 to 8 from the viewpoint of stabilizing the physical properties and characteristics of the resulting cured product and reducing tackiness. If the number of photopolymerizable functional groups is 6 or more, pattern formability as well as heat resistance and rigidity of the cured product at high temperatures can be improved. On the other hand, if the number of photopolymerizable functional groups is 30 or less, the rigidity of the cured product is improved and adhesion to a substrate or the like is improved. In addition, a resin composition with appropriate viscosity can be obtained, improving coatability. When the applied resin composition is irradiated with light, the phenomenon in which only the surface portion tends to photocure rapidly while the interior portion is not photocured sufficiently can be suppressed, resulting in excellent resolution, and excellent pattern formability can be obtained even when a thick photosensitive layer is formed. Furthermore, after at least one of photocuring and thermal curing is performed, the amount of unreacted (meth)acryloyl groups remaining can be reduced, thereby further suppressing fluctuations in the physical properties and characteristics of the resulting cured product.

[0048] The weight-average molecular weight of component (A) is 2,500 or more, and may be 3,000 or more from the viewpoint of improving the coatability and resolution of the resin composition, and may be 3,500 or more from the viewpoint of improving the developability and compatibility. On the other hand, the upper limit of the weight-average molecular weight may be 100,000 or less or 50,000 or less from the viewpoint of improving the coatability and resolution of the resin composition, and may be 40,000 or less or 20,000 or less from the viewpoint of improving the developability and compatibility. A weight-average molecular weight of 2,500 or more can suppress the occurrence of sagging of the composition when applied to a substrate, resulting in excellent film-forming properties. It also makes it easier to form a thick photosensitive layer, which can prevent problems such as increased stress in the resin due to cure shrinkage and reduced reliability. On the other hand, if the weight-average molecular weight is 100,000 or less, the coating property is improved, it becomes easy to form a thick photosensitive layer, and the pattern formability is improved. In addition, the solubility in the developer is also good, so that excellent resolution can be achieved. Furthermore, the transparency of the cured product is improved, and it is possible to obtain a cured product with the excellent transmittance required for a transparent material.

[0049] As described above, one aspect of this embodiment may be a photosensitive resin composition in which component (A) contains a high molecular weight polymer having 6 to 30 ethylenically unsaturated groups as photopolymerizable functional groups and a weight-average molecular weight of 2,500 to 100,000. Alternatively, component (A) may be a photosensitive resin composition in which component (A) contains a high molecular weight polymer having 6 to 8 ethylenically unsaturated groups as photopolymerizable functional groups and a weight-average molecular weight of 2,500 to 50,000.

[0050] The content of component (A) may be appropriately selected from 10% by mass or more, 20% by mass or more, or 30% by mass or more based on the total solid content of the photosensitive resin composition. When the content is 10% by mass or more, the coating property is improved, and excellent pattern formability can be obtained even when a thick photosensitive layer is formed. Taking into consideration the pattern formability and coatability of the resulting resin composition, and the physical properties and characteristics required of a cured product of the resin composition, the upper limit of the content of component (A) may be appropriately selected from 95 mass % or less, 85 mass % or less, or 75 mass % or less, based on the total solid content of the photosensitive resin composition.

[0051] Furthermore, from the viewpoint of improving pattern formability, the content of the high molecular weight urethane (meth)acrylate in component (A) may be appropriately selected from 70 to 100 mass%, 80 to 100 mass%, 90 to 100 mass%, 95 to 100 mass%, or 100 mass% (total amount) based on the total solid content of component (A).

[0052] <(B) Component: Low molecular weight substance> The photosensitive resin composition of this embodiment contains a low-molecular-weight compound having a photopolymerizable functional group as component (B). The term "low-molecular-weight compound" refers to a compound having a weight-average molecular weight of less than 2,500. Even if the low-molecular-weight compound having a photopolymerizable functional group contains a silicon atom, it is classified as component (B) because it is a low-molecular-weight compound having a photopolymerizable functional group, rather than a silane compound of component (F), which will be described later.

[0053] Examples of photopolymerizable functional groups contained in component (B) include ethylenically unsaturated groups such as (meth)acryloyl groups, and alkenyl groups such as vinyl groups and allyl groups. Component (B) may be a low-molecular-weight compound having at least one photopolymerizable functional group, and from the viewpoint of improving pattern formability, component (B) may have a (meth)acryloyl group as the photopolymerizable functional group. From the viewpoint of improving pattern formability, component (B) may have two or more photopolymerizable functional groups, or may have 2 to 5 photopolymerizable functional groups.

[0054] The photosensitive resin composition of this embodiment preferably contains, as component (B), at least one selected from the group consisting of component (B1): a low-molecular-weight compound having an isocyanuric ring, component (B2): a low-molecular-weight compound having a urethane bond, and component (B3): a low-molecular-weight compound having an alicyclic skeleton. By including at least one of these compounds in the photosensitive resin composition of this embodiment, adhesion to the substrate of an electronic component tends to be improved, resulting in excellent pattern formability. Note that, in the case of a low-molecular-weight compound 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 component (B1). Furthermore, if it has both a urethane bond and an alicyclic skeleton, it is classified as component (B2) based on the presence of the urethane bond. In other words, a low-molecular-weight compound having an alicyclic skeleton but no isocyanuric ring or urethane bond is classified as component (B3).

[0055] (Component (B1): Low molecular weight substance having an isocyanuric ring) From the viewpoint of improving pattern formability, the component (B1) may have two or more photopolymerizable functional groups, 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 the component (B1) is the same as the photopolymerizable functional group contained in the component (B) described above, and from the viewpoint of improving pattern formability, the photopolymerizable functional group may contain a (meth)acryloyl group.

[0056] An example of the component (B1) is a compound represented by the following general formula (7). [ka] (In general formula (7), R 4 , R 5 and R 6 each independently represents an alkylene group having 1 to 6 carbon atoms; R 7 and R 8 each independently represents a hydrogen atom or a methyl group, and R 9 represents a hydrogen atom or a (meth)acryloyl group.

[0057] In general formula (7), R 4 , R 5 and R 6 The alkylene group having 1 to 6 carbon atoms represented by may be an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, an isopropylene group, an isobutylene group, a t-butylene group, a pentylene group, and a hexylene group. Among these, an ethylene group may be used from the viewpoint of improving pattern formability.

[0058] In general formula (7), R 7 and R 8 each independently represents a hydrogen atom or a methyl group, and may be a hydrogen atom from the viewpoint of improving pattern formability.

[0059] In general formula (7), R 9 represents a hydrogen atom or a (meth)acryloyl group, and may be a (meth)acryloyl group from the viewpoint of improving pattern formability.

[0060] The compound represented by general formula (7) may be one or more selected from the group consisting of compounds represented by the following formula (7-1) and compounds represented by the following formula (7-2), and from the viewpoint of improving pattern formability, may be a compound represented by the following formula (7-1).

[0061] [ka]

[0062] The weight-average molecular weight of the component (B1) is less than 2,500, and may be appropriately selected from the range of 200 to 1,500, 300 to 1,000, or 350 to 600 from the viewpoint of improving pattern formability.

[0063] The component (B1) may be a commercially available product, such as "A-9300" (a compound represented by the above formula (7-1)) manufactured by Shin-Nakamura Chemical Co., Ltd., or "M-215" (a compound represented by the above formula (7-2)) manufactured by Toagosei Co., Ltd. The component (B1) can be used alone or in combination of two or more types.

[0064] (Component (B2): low molecular weight substance having a urethane bond) From the viewpoint of improving pattern formability, the component (B2) may have two or more photopolymerizable functional groups, may have 2 to 6 photopolymerizable functional groups, may have 2 to 4 photopolymerizable functional groups, or may have two photopolymerizable functional groups.

[0065] The photopolymerizable functional group contained in the component (B2) is the same as the photopolymerizable functional group contained in the component (B) described above, and from the viewpoint of improving pattern formability, the photopolymerizable functional group may contain a (meth)acryloyl group. In this specification, the component (B2) having a (meth)acryloyl group as a photopolymerizable functional group may be simply referred to as a "low molecular weight urethane (meth)acrylate."

[0066] Examples of low-molecular-weight urethane (meth)acrylates include reaction products of (meth)acrylates having a hydroxyl group and isocyanate compounds having an isocyanate group. Examples of the (meth)acrylates having a hydroxyl group and the isocyanate compounds include the acrylates having a hydroxyl group and the isocyanate compounds exemplified as raw materials used to produce the polymers described in the description of component (A) above. In addition to the isocyanate compounds listed above, monoisocyanate compounds can also be used. Examples of monoisocyanate compounds include aliphatic monoisocyanate compounds such as ethyl isocyanate, propyl isocyanate, butyl isocyanate, octadecyl isocyanate, and 2-isocyanatoethyl (meth)acrylate; alicyclic monoisocyanate compounds such as cyclohexyl isocyanate; and aromatic monoisocyanate compounds such as phenyl isocyanate. Examples of materials that can be appropriately selected from the viewpoint of improving pattern formability include the same materials that can be appropriately selected from the viewpoint of producing polymers.

[0067] Further, examples of low-molecular-weight urethane (meth)acrylates include reaction products in which a terminal isocyanate group of a polyaddition product of an isocyanate compound having at least two isocyanate groups per molecule and a diol compound is reacted with a (meth)acrylate having a hydroxyl group. Examples of the isocyanate compound having at least two isocyanate groups per molecule, the diol compound, and the (meth)acrylate having a hydroxyl group include the isocyanate compound having at least two isocyanate groups per molecule, the diol compound, and the (meth)acrylate having a hydroxyl group, respectively, exemplified as those used to produce high-molecular-weight polymers. Examples of materials appropriately selected from the viewpoint of improving pattern formability include the same materials appropriately selected from the same viewpoint as those used to produce high-molecular-weight polymers. Examples of this reaction product include those having a structural unit represented by the following general formula (8).

[0068] [ka]

[0069] In general formula (8), X 2 represents a divalent organic group having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton, and Y 2 represents a divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton. That is, the component (B2) may be a group having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton. X 2 and Y 2 As for X in general formula (1), 1 and Y 1 The same is exemplified.

[0070] From the viewpoint of improving pattern formability and improving transparency, water resistance, and moisture resistance of the resin composition in a balanced manner, X 2 may be appropriately selected from divalent organic groups having a chain hydrocarbon skeleton, divalent organic groups having a branched chain hydrocarbon skeleton, and branched alkylene groups having 2 to 12 carbon atoms, such as residues of the above-mentioned aliphatic diisocyanate compounds. 2 may be appropriately selected from divalent organic groups having an alicyclic skeleton, for example, residues of the above-mentioned diol compounds having an alicyclic skeleton.

[0071] Specific examples of low molecular weight urethane (meth)acrylates include urethane acrylates represented by the following general formula (9).

[0072] [ka]

[0073] In the above general formula (9), n5 represents an integer of 1 to 4. 10 and R 11 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and multiple R10 and R 11 At least three of the groups are alkyl groups having 1 to 4 carbon atoms.

[0074] Among the urethane acrylates represented by the general formula (9), X in the general formula (8) 2 is a residue of trimethylhexamethylene diisocyanate, which is a divalent organic group having a chain hydrocarbon skeleton, and Y 2 is a residue of cyclohexanedimethanol, which is a divalent organic group having an alicyclic skeleton. Examples of commercially available products containing urethane acrylate include TMCH-5R (trade name, number of functional groups: 2, Mw: 950, manufactured by Hitachi Chemical Co., Ltd.).

[0075] Commercially available products containing a urethane (meth)acrylate having a structural unit represented by the general formula (8) 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 Negami Chemical Industrial Co., Ltd.), and UN-3320HC (number of functional groups: 6, Mw: 1,500, manufactured by Negami Chemical Industrial Co., Ltd.) In the above description, the number of functional groups and Mw in parentheses represent the total number of (meth)acryloyl groups contained in the urethane (meth)acrylate and the weight-average molecular weight, respectively.

[0076] The weight-average molecular weight of component (B2) is less than 2,500, and may be 2,000 or less from the viewpoint of improving adhesion, and may be 1,500 or less or 1,000 or less from the viewpoint of improving resolution. On the other hand, the lower limit of the weight-average molecular weight can be appropriately set depending on the desired purpose, but may be 500 or more, or 700 or more from the viewpoint of film formability. By including the component (B2) as the component (B), the effect of improving pattern formability is enhanced.

[0077] (Component (B3): low molecular weight compound having an alicyclic skeleton) From the viewpoint of improving pattern formability, the component (B3) may have two or more photopolymerizable functional groups, may have two to four photopolymerizable functional groups, or may have two photopolymerizable functional groups. The photopolymerizable functional group contained in the component (B3) is the same as the photopolymerizable functional group contained in the component (B) described above, and from the viewpoint of improving pattern formability, the photopolymerizable functional group may contain a (meth)acryloyl group. The alicyclic skeleton contained in component (B3) is not particularly limited, and examples thereof include alicyclic hydrocarbon skeletons having 5 to 20 carbon atoms. The alicyclic hydrocarbon skeleton may be 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. Among these, a tricyclodecane skeleton may be used from the viewpoint of improving pattern formability.

[0078] The weight-average molecular weight of component (B3) is less than 2,500, and may be 2,000 or less from the viewpoint of improving adhesion, and may be 1,500 or less, 1,000 or less, or 500 or less from the viewpoint of improving resolution. On the other hand, the lower limit of the weight-average molecular weight can be appropriately set depending on the desired purpose, but may be 150 or more, or 200 or more from the viewpoint of film formability.

[0079] From the viewpoint of pattern forming properties, the component (B3) may be tricyclodecane dimethanol diacrylate.

[0080] The component (B3) may be a commercially available product, such as A-DCP (tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0081] The content (total content) of the (B) component may be appropriately selected from 5% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more, based on the total solid content of the photosensitive resin composition. If the content of the (B) component is 5% 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 viewpoint, the upper limit of the content of the (B) component may be appropriately selected 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.

[0082] The content of the component (B) relative to 100 parts by mass of the total solid content of the components (A) and (E) (however, if the component (E) is not contained, only the component (A)) may be appropriately selected from 20 to 120 parts by mass, 25 to 100 parts by mass, 30 to 80 parts by mass, or 40 to 80 parts by mass, from the viewpoint of improving pattern formability and rigidity of the cured product.

[0083] The total content of components (B1) to (B3) in component (B) can be appropriately selected from 50% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, or substantially 100% by mass. When at least two of the above components (B1) to (B3) are used, the content of component (B2) relative to the total solid content of component (B) may be appropriately selected from 10% by mass or more, 15% by mass or more, or 20% by mass or more. A content of component (B2) of 10% by mass or more provides excellent pattern formability even when a thick photosensitive layer is formed, and also provides excellent rigidity of the cured product. From the same viewpoint, the upper limit of component (B2) may be appropriately selected from 90% by mass or less, 80% by mass or less, or 70% by mass or less.

[0084] <Component (C): Photopolymerization initiator> The photosensitive resin composition of this embodiment contains a photopolymerization initiator as component (C). Component (C) is not particularly limited as long as it can polymerize at least one of components (A) and (B), and can be appropriately selected from commonly used photopolymerization initiators. From the viewpoint of improving pattern formability, examples of photopolymerization initiators that generate free radicals when exposed to actinic rays include acylphosphine oxides, oxime esters, aromatic ketones, quinones, alkylphenones, imidazoles, acridines, phenylglycines, and coumarins.

[0085] The acylphosphine oxide photopolymerization initiator has an acylphosphine oxide group [>P(=O)-C(=O)-R], and examples thereof include (2,6-dimethoxybenzoyl)-2,4,6-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("IRGACURE-TPO" (BASF)), ethyl-2,4,6-trimethylbenzoylphenylphosphinate, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("IRGACURE-819" (BASF)), (2,5-dihydroxyphenyl)diphenylphosphine oxide, (p-hydroxyphenyl)diphenylphosphine oxide, bis(p-hydroxyphenyl)phenylphosphine oxide, and tris(p-hydroxyphenyl)phosphine oxide.

[0086] The oxime ester photopolymerization initiator is a photopolymerization initiator having an oxime ester bond, and examples thereof include 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) (trade name: OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: OXE-02, manufactured by BASF), and 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime] (trade name: Quantacure-PDO, manufactured by Nippon Kayaku Co., Ltd.).

[0087] Examples of aromatic ketone photopolymerization initiators include benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one ("IRGACURE-651" (BASF)), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one ("IRGACURE-369" (BASF)), and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one ("IRGACURE-907" (BASF)).

[0088] Examples of quinone photopolymerization initiators include 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone.

[0089] Examples of alkylphenone-based photopolymerization initiators include benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin phenyl ether; 2,2-dimethoxy-1,2-diphenylethan-1-one ("IRGACURE-651" (BASF)); 1-hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE-184" (BASF)); 2-hydroxy-2-methyl-1- Examples include phenyl-propan-1-one ("IRGACURE-1173" (BASF)), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one ("IRGACURE-2959" (BASF)), and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one ("IRGACURE-127" (BASF)).

[0090] Examples of the imidazole-based photopolymerization initiator include 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimers such as 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenyl-1,3-diazol-2-yl]-4,5-diphenylimidazole, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimers, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimers, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimers, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimers.

[0091] Examples of the acridine-based photopolymerization initiator include 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane.

[0092] Examples of the phenylglycine-based photopolymerization initiator include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0093] Furthermore, examples of the coumarin-based photopolymerization initiator include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, 7-ethylamino-4-methylcoumarin, 7-dimethylaminocyclopenta[c]coumarin, 7-aminocyclopenta[c]coumarin, 7-diethylaminocyclopenta[c]coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, and 4,6-dimethyl-7-diethylaminocoumarin. coumarin, 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]quinolizine 12(9H)-one, 7-diethylamino-5',7'-dimethoxy-3,3'-carbonylbiscoumarin, 3,3'-carbonylbis[7-(diethylamino)coumarin], 7-(diethylamino)-3-(2-thienyl)coumarin, and the like.

[0094] Among these (C) photopolymerization initiators, a compound represented by the following general formula (C1) or a compound represented by the following general formula (C2) may be used from the viewpoint of improving pattern formability.

[0095] [ka] (R C1 , R C2 and R C3 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; R C4 and R C5 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. C1 ~R C5 may each have a substituent.

[0096] [ka]

[0097] (R C6 represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an amino group, and R C7 and R C8 R each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. C7 and R C8 may be bonded to each other to form a ring structure having 3 to 16 carbon atoms. R other than a hydroxyl group and a hydrogen atom C6 ~R C8 may each have a substituent, and in the case of amino groups having a substituent, the substituents may be bonded to each other to form a ring structure having 3 to 12 carbon atoms. C9 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an organic group having 1 to 10 carbon atoms which may contain one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom.

[0098] In general formula (C1), R C1 , R C2 and R C3 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R C1 , R C2 and R C3 The alkyl group having 1 to 6 carbon atoms represented by may be an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 or 2 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-heptyl group, and an n-hexyl group. R C1 , R C2 and R C3The alkoxy group having 1 to 6 carbon atoms represented by may be an alkoxy group having 1 to 3 carbon atoms, or an alkoxy group having 1 or 2 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, an n-butoxy group, and a tert-butoxy group. Among these groups, R C1 , R C2 and R C3 may be a methyl group from the viewpoint of improving pattern formability.

[0099] In general formula (C1), R C4 and R C5 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. R C4 and R C5 The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms represented by R C1 , R C2 and R C3 This is explained in the same way as in the case of R C4 and R C5 The aryl group having 6 to 12 carbon atoms represented by may be an aryl group having 6 to 10 carbon atoms, or an aryl group having 6 to 8 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.

[0100] R C1 ~R C5 Examples of the substituent that R may have include a halogen atom, a carboxy group, a hydroxy group, an amino group, a mercapto group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms. C1 ~R C5 The alkyl group, alkoxy group and aryl group which may be substituted by R C1 ~R C5 Examples of the alkyl group, alkoxy group, and aryl group are the same as those described above.

[0101] In general formula (C2), RC6 represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an amino group. R C6 The alkoxy group represented by is R C1 , R C2 and R C3 This is explained in the same way as in the case of Among these groups, R C6 may be a hydroxyl group from the viewpoint of improving pattern formability.

[0102] In general formula (C2), R C7 and R C8 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 C7 and R C8 The alkyl group, alkoxy group and aryl group represented by R in general formula (C1) C1 ~R C5 Examples of the alkyl group, alkoxy group and aryl group are the same as those represented by the formula (I). R C7 and R C8 may be bonded to each other to form a ring 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, and a cyclooctane structure. C7 and R C8 may contain carbon atoms that are directly bonded together.

[0103] R C6 ~R C8 The substituents that may be possessed by R in the above general formula (C1) are C1 ~R C5 The substituents that may be possessed by the group are explained in the same manner as those of the group. However, in the amino group having a substituent, the substituents may be bonded to each other to form a ring 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. Furthermore, these cyclic structures may contain a heteroatom other than the nitrogen atom, such as an oxygen atom. A specific example of a cyclic structure formed by a substituent of an amino group is a structure represented by the following formula (C3) (morpholino group). [ka]

[0104] In general formula (C2), R C9 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an organic group having 1 to 10 carbon atoms which may contain one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom. R C9 The organic group having 1 to 10 carbon atoms represented by may be an organic group having 1 to 6 carbon atoms, or an organic group having 1 to 4 carbon atoms. R C9 The organic group having 1 to 10 carbon atoms represented by 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 include those represented by R C1 ~R C5 Examples of the alkyl group, alkenyl group and aryl group include the same as those represented by the formula (I). R C9 Examples of the organic group having 1 to 10 carbon atoms and containing an oxygen atom represented by the formula (I) include an alkoxy group having 1 to 10 carbon atoms. R C9 Examples of the organic group having 1 to 10 carbon atoms and containing a nitrogen atom represented by the formula include groups represented by the above general formula (C3). R C9Examples of the organic group having 1 to 10 carbon atoms and containing a sulfur atom represented by include alkylthio groups such as methylthio groups.

[0105] The content of component (C) may be appropriately selected from the following: an amount that results in an absorbance of 0.35 or less, 0.3 or less, 0.2 or less, or 0.1 or less for light with a wavelength of 365 nm when the photosensitive layer formed from the photosensitive resin composition has a thickness (after drying) of 50 μm. By adjusting the content to the above range, even when a pattern is formed using a thick photosensitive layer, for example, 70 μm or more, light can easily pass through to the bottom of the photosensitive layer (the surface of the photosensitive layer facing the substrate), thereby improving pattern formability. The absorbance can be measured for light with a wavelength of 365 nm using, for example, a UV-visible spectrophotometer (product name: "U-3310 Spectrophotometer," manufactured by Hitachi High-Technologies Corporation) using polyethylene terephthalate film alone as a reference.

[0106] The content of component (C) may be appropriately determined based on the absorbance of the photosensitive layer at a thickness of 50 μm, and may usually be appropriately selected from 0.05 to 20 mass%, 0.05 to 12 mass%, 0.1 to 8 mass%, 0.1 to 5 mass%, or 0.1 to 3 mass%, based on the total solid content of the photosensitive resin composition. By setting the content within the above range, the sensitivity of the photosensitive resin composition can be improved, deterioration of the resist shape can be suppressed, and pattern formability can be improved.

[0107] In addition to the component (C) described above, (C') photopolymerization initiation aids such as tertiary amines such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine can also be used alone or in combination of two or more.

[0108] <Component (D): Triazole-based compound> The photosensitive resin composition of this embodiment contains a triazole-based compound as component (D). The triazole-based compound is a compound having a triazole skeleton. Triazole-based compounds have excellent adhesion to copper surfaces, are easily removable by development, and do not impair the curability of the photosensitive resin composition. Therefore, even when forming a thick photosensitive layer on a copper surface and forming a resist pattern with a narrow line width and narrow line space, excellent pattern formation can be achieved. Furthermore, under conditions of high exposure dose and other high radical concentrations in the reaction system, hydrogen from the triazole-based compound is believed to be abstracted, acting as a polymerization inhibitor. This widens the process margin and enables excellent pattern formation under the same exposure conditions for both substrates with and without a copper surface. Furthermore, triazole-based compounds are more soluble in solvents and easier to handle than tetrazole, a heterocyclic compound. In the case of tetrazole-based compounds, there is a possibility that tetrazole-based compounds may precipitate during storage stability tests of photosensitive resin films under refrigeration. Among triazole-based compounds, benzotriazole is more preferred.

[0109] Examples of triazole compounds include 1,2,3-triazole, 1,2,4-triazole, benzotriazole, and derivatives thereof. Specific examples of triazole compounds include 1-methyl-1,2,3-triazole, 1-phenyl-1,2,3-triazole, 4-methyl-2-phenyl-1,2,3-triazole, 1-methyl-1,2,4-triazole, 1,3-diphenyl-1,2,4-triazole, benzotriazole, 1-methylbenzotriazole, 5,6-dimethylbenzotriazole, and 2-phenylbenzotriazole. These compounds can be used alone or in combination of two or more.

[0110] The component (D) preferably contains a benzotriazole-based compound having a benzotriazole skeleton. The use of a benzotriazole-based compound provides excellent adhesion to copper surfaces, is easily removable by development, and does not impair the curability of the photosensitive resin composition. Therefore, even when a thick photosensitive layer is formed on the copper surface to form a resist pattern with a narrow line width and a narrow line space, an excellent pattern tends to be formed. Furthermore, from the viewpoint of more fully obtaining the above-mentioned effects, benzotriazole is preferred among benzotriazole-based compounds.

[0111] The molecular weight of the triazole-based compound is preferably 100 or more, more preferably 150 or more. The molecular weight of the triazole-based compound is preferably 5000 or less, more preferably 2000 or less. When the molecular weight is 100 or more, the compound tends to be less likely to volatilize during application. On the other hand, when the molecular weight is 5000 or less, the triazole-based compound tends to be more mobile during the first heating step described below, facilitating coordination with the substrate, providing excellent adhesion to the copper surface, and further improving the effect of reducing development residues.

[0112] The content of component (D) in the photosensitive resin composition may be 0.1 to 10 mass%, 1.0 to 8.0 mass%, or 3.0 to 6.0 mass%, based on the total solid content of the photosensitive resin composition. When the content of component (D) is 0.1 mass% or more, there is a tendency for further reduction in development residue to be more effective, and when it is 10 mass% or less, there is a tendency for both reduction in development residue and pattern formability at the same exposure dose to be more easily achieved.

[0113] <(E) component: high Tg polymer> The photosensitive resin composition of this embodiment may contain, as component (E), a polymer having a glass transition temperature of 70 to 150°C and no carbon-nitrogen bond. The "polymer" is defined the same as in the above-mentioned component (A). The inclusion of component (E) has the effect of suppressing tackiness of the photosensitive resin composition.

[0114] From the viewpoint of pattern formability and reduced tackiness, component (E) may contain an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a (meth)acryloyl group and a vinyl group, and from the viewpoint of pattern formability, the ethylenically unsaturated group may be a (meth)acryloyl group.

[0115] The component (E) may contain a polymer having at least one skeleton selected from the group consisting of an alicyclic skeleton and an aromatic ring skeleton, and from the viewpoints of pattern formability and reduced tackiness, may contain a polymer having an alicyclic skeleton.

[0116] The polymer having an alicyclic skeleton can be produced, for example, by reacting a portion of the acid groups derived from an acid group-containing acrylic resin (e1) having no carbon-nitrogen bond with epoxy groups derived from an alicyclic epoxy group-containing unsaturated compound (e2) having no carbon-nitrogen bond.

[0117] The acid group-containing acrylic resin (e1) having no carbon-nitrogen bond can be a copolymer obtained by copolymerizing an acid having an ethylenically unsaturated group with one or more monomers selected from the group consisting of esters of (meth)acrylic acid, vinyl aromatic compounds, polyolefin compounds, and the like. Specific examples include copolymers obtained by copolymerizing an acid having an ethylenically unsaturated group, such as (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, or (anhydrous) maleic acid, as an essential component, with one or more monomers selected from (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, and p-chlorostyrene; polyolefin compound monomers such as butadiene, isoprene, and chloroprene; and other monomers such as methyl isopropenyl ketone, vinyl acetate, and vinyl propionate.

[0118] The acid value of component (e1) may be 15 mgKOH / g or more, or may be 40 to 500 mgKOH / g. When component (e1) has such an acid value, a sufficient amount of acid groups remains in component (E) even after component (e1) is reacted with component (e2), which will be described later.

[0119] The alicyclic epoxy group-containing unsaturated compound (e2) having no carbon-nitrogen bond is preferably a compound having one ethylenically unsaturated group and an alicyclic epoxy group in one molecule. Specific examples thereof include compounds represented by any of the following formulae (I) to (X):

[0120] [ka]

[0121] [ka]

[0122] where R E1 are each independently a hydrogen atom or a methyl group. E2 are each independently a saturated aliphatic hydrocarbon group. R E2 Examples of the aliphatic saturated hydrocarbon group represented by the formula (I) include 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 divalent organic groups formed by a combination thereof. 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 formed by a combination thereof include a -CH2-phenylene group -CH2- and a -CH2-cyclohexylene group -CH2-. R E2 From the viewpoint of pattern formability and reducing tackiness, the alkyl group may be a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, or a -CH-phenylene group -CH-, or may be a methylene group, an ethylene group, a propylene group, or may be a methylene group.

[0123] The alicyclic epoxy group-containing unsaturated compound (e2) having no carbon-nitrogen bond may be a compound represented by the above formula (III) from the viewpoint of pattern formability.

[0124] Component (E) may be a commercially available product, such as (ACA)Z250 from 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 (XI), which are produced by reacting an acid group-containing acrylic resin with an alicyclic epoxy group-containing unsaturated compound.

[0125] [ka] (In the formula, R E1 represents a hydrogen atom or a methyl group. E3 represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms.

[0126] The glass transition temperature of component (E) is 70 to 150° C., but may alternatively be 100 to 150° C., 115 to 150° C., or 125 to 150° C. Here, the glass transition temperature of component (E) is a value measured by the following method.

[0127] (Method for measuring the glass transition temperature of component (E)) As a pretreatment for the measurement, component (E) is heated at 120°C for 3 hours and then cooled to prepare a sample. Using 10 mg of the sample, a differential scanning calorimeter (Shimadzu Corporation, product name: DSC-50) is used to heat the sample in a nitrogen stream over a temperature range of 25 to 200°C at a heating rate of 20°C / min to eliminate the influence of the solvent, etc. After cooling to 25°C, the sample is again heated under the same conditions, and the temperature at which the baseline begins to deviate is taken as the glass transition temperature.

[0128] The weight average molecular weight of component (E) 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.

[0129] When the photosensitive resin composition of the present embodiment contains the component (E), the content of the component (E) may be 5 to 60 parts by mass, 10 to 40 parts by mass, or 10 to 30 parts by mass relative to 100 parts by mass of the total of the components (A) and (E), from the viewpoints of pattern formability and reducing tackiness.

[0130] <Component (F): Silane compound> The photosensitive resin composition of this embodiment may further contain (F) a silane compound. A known silane coupling agent can be used as the component (F). The component (F) can improve adhesion to the substrate of an electronic component, and is particularly effective when the substrate contains silicon (e.g., a glass substrate, a silicon wafer, an epoxy resin-impregnated glass cloth substrate, etc.). Examples of silane coupling agents include alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; (meth)acryloxypropyltrimethoxysilane, (meth)acryloxypropylmethyldimethoxysilane, and other (meth)acryloyl group-containing alkoxysilanes; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, and other amine-based alkoxysilanes; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and glycidoxypropyltriethoxysilane; Examples of suitable alkoxysilanes include glycidoxy group-containing alkoxysilanes such as glycidoxypropylmethyldiethoxysilane and glycidoxypropylmethyldiisopropenoxysilane; alicyclic epoxy group-containing alkoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; ureido group-containing alkoxysilanes such as 3-ureidopropyltriethoxysilane; mercapto group-containing alkoxysilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane; carbamate group-containing alkoxysilanes such as triethoxysilylpropylethylcarbamate; and polybasic acid anhydride group-containing alkoxysilanes such as 3-(triethoxysilyl)propylsuccinic anhydride. These may be used alone or in combination of two or more. From the viewpoint of further improving adhesion, a silane coupling agent having an ethylenically unsaturated group in the molecule may be used, such as a (meth)acryloyl group-containing alkoxysilane such as (meth)acryloxypropyltrimethoxysilane or (meth)acryloxypropylmethyldimethoxysilane, or a glycidoxy group-containing alkoxysilane such as glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldiethoxysilane or glycidoxypropylmethyldiisopropenoxysilane.

[0131] When the photosensitive resin composition of this embodiment contains component (F), the content of component (F) may be appropriately selected from 0.05 to 15 mass%, 0.1 to 10 mass%, 0.1 to 7 mass%, 1 to 7 mass%, or 1 to 5 mass%, based on the total solid content of the photosensitive resin composition. By setting the content within the above range, deterioration of the resist shape can be suppressed and pattern formability can be improved.

[0132] <Component (G): Thermal radical polymerization initiator> The photosensitive resin composition of this embodiment may further contain (G) a thermal radical polymerization initiator. The component (G) is not particularly limited, and examples thereof include dialkyl peroxides such as α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, and 1,1-bis(t-butylperoxy)-2-methylcyclohexane. Peroxyketals such as 1,1-bis(t-hexylperoxy)cyclohexane and 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane; hydroperoxides such as p-menthane hydroperoxide; diacyl peroxides such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide, and benzoyl peroxide; peroxycarbonates such as bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and di-3-methoxybutyl peroxycarbonate;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-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurylate, t-butyl Examples of the initiator include peroxide-based polymerization initiators such as peroxyesters such as peroxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, and t-butyl peroxyacetate, and azo-based polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile);

[0133] From the viewpoint of improving pattern formability, the component (G) can be selected from peroxide polymerization initiators and dialkyl peroxide polymerization initiators, among which dicumyl peroxide can be selected. The component (G) can be used alone or in combination of two or more types.

[0134] When the photosensitive resin composition of this embodiment contains component (G), the content thereof may be appropriately selected from 0.1 to 10 mass%, 0.2 to 5 mass%, or 0.3 to 1.5 mass%, based on the total solid content of the photosensitive resin composition. By setting the content within the above range, the heat resistance of the photosensitive resin composition is improved, and the reliability when used as a permanent film is improved.

[0135] <Component (H): Inorganic filler> The photosensitive resin composition of the present embodiment may contain component (H) 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.

[0136] Examples of the (H) component include silica (SiO2), alumina (Al2O3), titania (TiO2), tantalum oxide (Ta2O5), zirconia (ZrO2), silicon nitride (Si3N4), barium titanate (BaO·TiO2), barium carbonate (BaCO3), magnesium carbonate (MgCO3), aluminum hydroxide (Al(OH)3), magnesium hydroxide (Mg(OH)2), lead titanate (PbO·TiO2), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga2O3), spinel (MgO·Al2O3), magnesium hydroxide (Mg(OH)2), lead zirconate ... zirconate titanate (PLZT), gallium oxide (Ga2O3), spinel (MgO·Al2O3), magnesium hydroxide (Mg(OH)2), lead zirconate titanate (PbO·TiO2), lead zirconate titanate (PZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zir Examples of inorganic fillers that can be used include zirconia (Y2O3·ZrO2), zirconia silicate (BaO·8SiO2), boron nitride (BN), calcium carbonate (CaCO3), barium sulfate (BaSO4), calcium sulfate (CaSO4), zinc oxide (ZnO), magnesium titanate (MgO·TiO2), hydrotalcite, mica, calcined kaolin, and carbon (C). These inorganic fillers can be used alone or in combination.

[0137] The average particle size of component (H) may 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. Here, the average particle size of component (H) refers to the average particle size of the inorganic filler dispersed in the photosensitive resin composition, and is a value obtained by measuring as follows. First, the photosensitive resin composition is diluted (or dissolved) 1000 times with methyl ethyl ketone, and then particles dispersed in the solvent are measured using a submicron particle analyzer (manufactured by Beckman Coulter, Inc., product name: N5) in accordance with the international standard ISO 13321 at a refractive index of 1.38. The particle size at 50% cumulative (volume basis) in the particle size distribution is defined as the average particle size. Furthermore, component (H) contained in the photosensitive layer provided on the carrier film or the cured film of the photosensitive resin composition can also be measured using the submicron particle analyzer after diluting (or dissolving) the composition 1000 times (volume ratio) with a solvent as described above.

[0138] When the photosensitive resin composition of this embodiment contains component (H), the content of component (H) may be appropriately selected from the following: 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; a lower limit of more than 0% by mass, or even 0% by mass (i.e., it may not be contained). By substantially not containing component (H), the transmittance of the photosensitive resin composition is improved. For example, even when a pattern is formed using a thick photosensitive layer of 70 μm or more, light can easily pass through to the bottom of the photosensitive layer (the surface of the photosensitive layer facing the substrate), improving pattern formability.

[0139] <Secondary thiol compounds> The photosensitive resin composition of this embodiment may contain a secondary thiol compound. When a secondary thiol compound is added to the photosensitive resin composition, the content thereof may be 0.02 to 1.0 mass%, 0.02 to 0.4 mass%, or 0.02 to 0.2 mass% based on the total solid content of the photosensitive resin composition. When the content of the secondary thiol compound is 0.02 mass% or more, the resolution on the copper surface tends to be further improved, and when it is 1.0 mass% or less, high resolution tends to be possible with reduced residue.

[0140] <Other additives> The photosensitive resin composition of the present 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 (F) as needed.

[0141] Examples of sensitizers include pyrazolines, anthracenes, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbenes, triazines, thiophenes, naphthalimides, etc. These can be used alone or in combination of two or more.

[0142] Examples of heat-resistant polymers that can be used as engineering plastics from the viewpoint of improving processability include polyoxazoles and their precursors, novolak resins such as phenol novolak and cresol novolak, polyamideimides, polyamides, etc. These may be used alone or in combination of two or more thereof.

[0143] Examples of the thermal crosslinking agent, from the viewpoint of improving the rigidity of the cured product, include epoxy resins, phenolic resins substituted at the α-position with a methylol group or an alkoxymethyl group, melamine resins substituted at the N-position with at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, and urea resins. These may be used alone or in combination of two or more.

[0144] The content of these other additives is not particularly limited as long as it is within a range that does not impair the effects of the photosensitive resin composition of the present embodiment, and may be appropriately selected from, for example, 0.1 to 10 mass %, 0.3 to 5 mass %, or 0.5 to 5 mass % based on the total solid content of the photosensitive resin composition.

[0145] <Diluent> A diluent can be used in the photosensitive resin composition of this embodiment, if necessary. Examples of diluents include polar solvents such as 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; sulfur-containing solvents, such as dimethyl sulfoxide and sulfolane; esters, such as γ-butyrolactone and dimethyl carbonate; and esters, such as cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These diluents can be used alone or in combination of two or more.

[0146] The amount of diluent used may be appropriately selected from amounts such that the total solid content in the photosensitive resin composition is 50 to 90 mass%, 60 to 80 mass%, or 65 to 75 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 mass%, 20 to 40 mass%, or 25 to 35 mass%. By setting the amount of diluent used within the above range, the coatability of the photosensitive resin composition is improved, and it becomes possible to form a more precise pattern.

[0147] Furthermore, for example, when a photosensitive layer having a thickness of 70 μm or more is to be formed, the amount of diluent used can be set to an amount such that the viscosity of the photosensitive resin composition at 25°C is 0.5 to 20 Pa·s or 1 to 10 Pa·s, taking into consideration the ease of forming the photosensitive layer.

[0148] The photosensitive resin composition of the present embodiment can be obtained by uniformly kneading and mixing the above-mentioned components (A) to (D), as well as the optional components (E) to (H), other additives, and a diluent, using a roll mill, a bead mill, or the like.

[0149] The photosensitive resin composition of the present embodiment may be used in the form of a liquid or a film.

[0150] When used in a liquid form, the method for applying the photosensitive resin composition of the present embodiment is not particularly limited, and examples thereof include various application methods such as printing, spin coating, spray coating, jet dispensing, inkjet coating, dip coating, etc. Among these, from the viewpoint of more easily forming a thick photosensitive layer, the printing method or spin coating method may be appropriately selected.

[0151] When used in the form of a film, it can be used, for example, in the form of a photosensitive resin film described below. In this case, a photosensitive layer of the desired thickness can be formed by laminating layers using a laminator or the like.

[0152] The absorbance of a 50 μm thick (thickness after drying) photosensitive layer formed from the photosensitive resin composition of this embodiment for light with a wavelength of 365 nm can be appropriately selected from 0.35 or less, 0.3 or less, 0.2 or less, or 0.1 or less. When the absorbance of the 50 μm thick photosensitive layer is 0.35 or less, even when a pattern is formed using a thick photosensitive layer, for example, 70 μm or more, light can easily pass through to the bottom of the photosensitive layer (the surface of the photosensitive layer facing the substrate), thereby improving pattern formability. The absorbance of a 50 μm thick photosensitive layer for light with a wavelength of 365 nm can also be determined by converting the absorbance measured for a photosensitive layer with a thickness other than 50 μm to the absorbance for a 50 μm thick layer based on the Beer-Lambert law.

[0153] [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 with a shape formed over the entire surface when observed in a plan view, but also a structure with a shape formed only in a portion thereof.

[0154] The photosensitive resin film of the present embodiment can be produced, for example, by applying the photosensitive resin composition of the present embodiment to a carrier film by any of the above-mentioned coating methods to form a coating film, and then drying the coating film to form a photosensitive layer. When the photosensitive resin composition of the present embodiment contains a diluent, at least a part of the diluent may be removed during drying.

[0155] The coating film can be dried using hot air drying or a dryer using far-infrared or near-infrared rays, and the drying temperature can be appropriately selected from 60 to 120°C, 70 to 110°C, or 90 to 110°C. The drying time can 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, drying under the above conditions can also remove at least a portion of the diluent.

[0156] 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.

[0157] The thickness of the carrier film may be appropriately selected from 10 μm to 3 mm or 10 to 200 μm, taking into consideration ease of handling and the like.

[0158] 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 the thickness to 30 μm or more, for example, when forming a photosensitive layer having a thickness of 150 μm or more, the number of operations such as lamination can be further reduced. Furthermore, by setting the thickness to 100 μm or less, deformation of the photosensitive layer due to the stress difference between the inside and outside of the core can be further reduced when the photosensitive resin film is wound around the core. Considering the effect of the photosensitive resin composition of this embodiment, which is capable of obtaining excellent pattern formability even when a thick photosensitive layer is formed, the thickness of the photosensitive layer may be 70 μm or more, or even more than 100 μm. A photosensitive layer having a thickness of 70 μm or more may be formed, for example, by laminating a photosensitive layer formed on a carrier film with a photosensitive layer formed on a protective layer described below. This makes it possible to obtain a photosensitive resin film having a carrier film, a thick photosensitive layer, and a protective layer in this order.

[0159] In addition, the photosensitive resin film of this embodiment may have a protective layer laminated on the surface of the photosensitive layer opposite to the surface in contact with the carrier film. For example, a resin film such as polyethylene or polypropylene may be used as the protective layer. The resin film may be the same as or different from the above-described carrier film.

[0160] [Method of manufacturing the cured product] The method for producing a cured product of this embodiment sequentially includes the steps of providing a photosensitive layer on a substrate using the photosensitive resin composition or photosensitive resin film of this embodiment (photosensitive layer formation step), irradiating at least a portion of the photosensitive layer with actinic radiation to form a photocured portion (exposure step), and removing at least a portion of the photosensitive layer other than the photocured portion to form a resin pattern (removal step). Optionally, the method further includes a step of heat-treating the photosensitive layer provided on the substrate in the photosensitive layer formation step (first heating step). Also, optional, the method further includes a step of heat-treating the resin pattern (second heating step). The method for producing a cured product of this embodiment enables the formation of a desired pattern. Furthermore, by taking advantage of the characteristic of the photosensitive resin composition of this embodiment, which exhibits excellent pattern-forming properties even when a thick photosensitive layer of, for example, 70 μm or more is formed, the desired pattern can be formed using a thick cured product of, for example, 70 μm or more. In this specification, the term "step" refers not only to an independent step, but also to a step that cannot be clearly distinguished from other steps, as long as the intended effect of the step is achieved.

[0161] (Photosensitive layer formation process) In forming the photosensitive layer, the photosensitive resin composition or the photosensitive resin film of this embodiment can be applied or laminated on a substrate, respectively, to form the photosensitive layer.

[0162] Examples of the substrate include a glass substrate, a silicon wafer, a metal oxide insulator such as TiO2 or SiO2, silicon nitride, a ceramic piezoelectric substrate, and an epoxy resin-impregnated glass cloth substrate. The substrate may also have a copper surface, such as copper wiring, on a portion of its surface. When a resist pattern is formed on such a substrate, part of which is a copper surface, the photosensitive resin composition of this embodiment can achieve excellent pattern formation under the same exposure conditions on both the copper surface and the non-copper surface of the substrate, and can also suppress the generation of development residues on the copper surface.

[0163] When forming a photosensitive layer by coating a substrate with a photosensitive resin composition, the photosensitive resin composition may be dissolved in the diluent to form a solution, and then coated onto the substrate. If necessary, the coating film obtained by coating 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.

[0164] When a photosensitive resin film is used, the photosensitive layer can be formed by a lamination method using a laminator or the like.

[0165] The thickness of the photosensitive layer provided on the substrate varies depending on the formation method (coating method or lamination method), the solids concentration and viscosity of the photosensitive resin composition, etc., but the lower limit of the dried photosensitive layer 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. 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. When used for electronic components, etc., the lower limit may be appropriately selected from 70 μm or more, more than 100 μm, or 150 μm or more, and the upper limit may be appropriately selected from 500 μm or less, 300 μm or less, or 250 μm or less.

[0166] In the method for producing a cured product of this embodiment, a photosensitive layer is formed using the photosensitive resin composition of this embodiment, so that a thick photosensitive layer can be formed. For example, when forming a photosensitive layer having a thickness of 150 μm or more, the layer may not be formed by a single coating (and drying, if necessary) or lamination, but may be formed by repeating multiple coatings (and drying, if necessary) or laminations until the desired thickness is achieved.

[0167] (1st heating step) The first heating step is an optional step in which the photosensitive layer formed on the substrate in the photosensitive layer forming step is heat-treated. The heating temperature may be appropriately selected from 50 to 120°C, 70 to 110°C, or 90 to 100°C. The heating time may be appropriately selected from 30 seconds to 30 minutes, 1 to 15 minutes, or 5 to 10 minutes. By performing the first heating step, the triazole-based compound is more likely to be coordinated to the copper surface, facilitating the formation of a triazole-based compound layer at the interface between the photosensitive layer and the copper surface. As a result, contact between organic substances in the photosensitive layer other than the triazole-based compound and the copper surface is more effectively inhibited, thereby further preventing the organic substances from adhering to the copper surface and becoming development residues.

[0168] (Exposure process) In the exposure step, the photosensitive layer formed on the substrate in the photosensitive layer forming step is at least partially irradiated with actinic rays as needed, and the exposed portion is photocured to form a cured portion. When irradiating with actinic rays, the photosensitive layer may be irradiated with actinic rays through a mask having a desired pattern, or may be irradiated with actinic rays by a direct writing exposure method such as LDI (Laser Direct Imaging) exposure method or DLP (Digital Light Processing) exposure method.

[0169] Furthermore, from the viewpoint of improving pattern formability, post-exposure baking (PEB) may be performed after exposure using a hot plate, dryer, etc. The drying conditions are not particularly limited, but may be performed 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.

[0170] The exposure dose of actinic rays is 10 to 2,000 mJ / cm 2 , 100-1,500mJ / cm 2 , or 300 to 1,000 mJ / cm 2 Examples of actinic rays that can be used include ultraviolet rays, visible light, electron beams, and X-rays. Examples of light sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and halogen lamps.

[0171] (Removal process) In the removal step, at least a portion of the photosensitive layer formed in the exposure step other than the cured portion (unexposed portion) is removed to form a resin pattern. The unexposed portion may be removed using, for example, a developer such as an organic solvent.

[0172] Examples of organic solvents 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. In addition, various commonly used additives may be added to the organic solvent used as the developer.

[0173] After removing the unexposed areas with the developer, the film may be washed (rinsed) with water, alcohol such as methanol, ethanol or isopropyl alcohol, n-butyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether acetate, or the like, if necessary.

[0174] (Second heating step) The second heating step is an optional step in which the resin pattern formed in the removing step is heat-treated to form a cured product. The heat treatment is preferably carried out for 1 to 2 hours while the temperature is increased stepwise at a selected heating temperature. The heating temperature may be appropriately selected from 120 to 240°C, 140 to 230°C, or 150 to 220°C. When the temperature is increased stepwise, for example, heat treatment may be carried out at at least one of approximately 120°C and approximately 160°C for 10 to 50 minutes or 20 to 40 minutes, followed by heat treatment at approximately 220°C for 30 to 100 minutes or 50 to 70 minutes.

[0175] The thickness of the resulting resin pattern is the same as the thickness of the photosensitive layer after drying, and may be appropriately selected from a lower limit of 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, and an upper limit of 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 in electronic components, etc., the lower limit may be appropriately selected from a lower limit of 70 μm or more, more than 100 μm, or 150 μm or more, and an upper limit may be appropriately selected from a lower limit of 500 μm or less, 300 μm or less, or 250 μm or less.

[0176] [Laminate] The laminate of this embodiment includes a cured product of the photosensitive resin composition of this embodiment, and examples thereof include a laminate including the cured product on various supports such as a substrate used in the above-described method for producing a cured product, a carrier film for a photosensitive resin film, etc. The cured product of the photosensitive resin composition of this embodiment can be formed, for example, by the above-described method for producing a cured product of this embodiment.

[0177] The thickness of the cured product in the laminate of this embodiment may be appropriately selected from a lower limit of 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, and an upper limit of 500 μm or less, 300 μm or less, or 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 in electronic components, etc., the lower limit may be appropriately selected from a lower limit of 70 μm or more, more than 100 μm, or 150 μm or more, and an upper limit may be appropriately selected from a lower limit of 500 μm or less, 300 μm or less, or 250 μm or less.

[0178] The cured product provided on a substrate obtained by the above-described method for producing a cured product uses the photosensitive resin composition of this embodiment, and excellent pattern formability can be obtained even with a thick photosensitive layer, for example, 70 μm or more. Therefore, it is possible to meet the demand for electronic circuit boards that require thick cured products to be provided on substrates in finer patterns, in line with the trend toward miniaturization and higher performance of electronic devices. Furthermore, for example, by using a cured product formed from the photosensitive resin composition of this embodiment as an insulating film in a plating process in the production of electronic circuit boards, it is possible to suppress a decrease in yield due to short circuits between wiring. Therefore, the laminate of this embodiment can be used as an electronic component such as an electronic circuit board in a mobile terminal such as a mobile phone.

[0179] Furthermore, according to the above-described method for producing a cured product, by using the photosensitive resin composition of the present embodiment, when a resist pattern is formed on a substrate having a copper surface, such as copper wiring, on part of its surface, excellent pattern formability can be achieved under the same exposure conditions on both the surface of the substrate, that is, the portion having the copper surface, and the portion not having the copper surface, and the occurrence of development residues on the copper surface can be suppressed. Therefore, the laminate of this embodiment can be used as an electronic component such as an electronic circuit board, for example, an inductor. [Example]

[0180] The objects and advantages of this embodiment will be explained in more detail below based on examples and comparative examples, but this embodiment is not limited to the following examples. The methods for measuring the weight average molecular weight of each component and the glass transition temperature of component (E) are as follows.

[0181] (Measurement of weight average molecular weight) The weight average molecular weight was determined by the GPC method using the following equipment in terms of standard polystyrene, and was measured using a solution in which 0.5 mg of polymer was dissolved in 1 mL of tetrahydrofuran (THF). Device name: Tosoh Corporation HLC-8320GPC Columns: Gelpack R-420, R-430, and R-440 (3 columns connected) Detector: RI detector Column temperature: 40℃ Eluent:THF Flow rate: 1ml / min Standard material: polystyrene

[0182] (Measurement of glass transition temperature of component (E)) As a pretreatment for the measurement, component (E) was heated at 120°C for 3 hours and then cooled to prepare a sample. Using 10 mg of the sample, a differential scanning calorimeter (Shimadzu Corporation, product name: DSC-50) was used to heat the sample in a nitrogen stream in a temperature range of 25 to 200°C at a heating rate of 20°C / min, then cooled to 25°C, and then heated again under the same conditions. The temperature at which the baseline began to deviate was taken as the glass transition temperature.

[0183] (Examples 1 to 7 and Comparative Examples 1 to 2) The components were mixed according to the formulation shown in Table 1 (the units of values ​​in the table are parts by mass, and in the case of a solution, the amounts are converted to solids), and kneaded using a three-roll mill to prepare a photosensitive resin composition. N,N-dimethylacetamide was added so that the solids concentration became 60% by mass, and a photosensitive resin composition was obtained.

[0184] Next, the photosensitive resin composition obtained above was evaluated by the following methods. The evaluation results are shown in Table 1.

[0185] [Preparation of photosensitive resin film] A 50 μm-thick polyethylene terephthalate film (manufactured by Teijin Limited, product name: A-4100) was used as a carrier film, and the photosensitive resin compositions of the Examples and Comparative Examples were uniformly coated onto the carrier film so that the thickness after drying would be 50 μm. Next, a photosensitive layer was formed by heating and drying at 100° C. for 15 minutes using a hot air convection dryer, and a photosensitive resin film having a carrier film and a photosensitive layer was produced.

[0186] [Evaluation of pattern formation (resolution)] The substrates used were a glass epoxy substrate with a copper surface (product name: MCL-E-679FGB, manufactured by Hitachi Chemical Co., Ltd.; hereinafter, also referred to as the "Cu-containing substrate") and a substrate obtained by etching the copper from the glass epoxy substrate (hereinafter, also referred to as the "Cu-free substrate"). A photosensitive resin film was laminated onto the substrate with the photosensitive layer facing the glass epoxy substrate, and the carrier film was removed. The lamination was performed at 60°C using a laminator. Next, a photosensitive resin film was laminated again onto the photosensitive layer using the method described above, and the carrier film was removed. This process was repeated three times to obtain a laminate comprising a 200 μm-thick photosensitive layer and a carrier film on a glass epoxy substrate. In Examples 2, 6, and 7, the laminate prepared by the method described above was further subjected to a heat treatment (first heating step) in which it was heated at 90°C for 5 minutes.

[0187] From the carrier film side of the laminate, writing data having the pattern shape shown in Figure 1 (line space: three types: 70 μm, 50 μm, and 30 μm, all line widths 12 μm) was exposed as the exposed area using a direct writing exposure machine (manufactured by Orbotech Japan Co., Ltd., product name: Paragon 9000) with a semiconductor laser as the light source and a dominant wavelength of 355 nm. At this time, the laminate was divided into three regions, and the three regions were exposed to different exposure doses (120 mJ / cm 2 , 150 mJ / cm 2 , 180mJ / cm 2 ) The exposed sample was then post-exposure baked for 1 minute on a hot plate at 90°C. The patterning data shown in Figure 1 has an exposed area 10 and a non-exposed area 20, with the width W of the exposed area 10 corresponding to the line width and the width S of the non-exposed area 20 corresponding to the line space.

[0188] The carrier film was then removed, and the substrate was developed by immersion in a developer (cyclopentanone) for 20 minutes. The developed pattern was dried at room temperature for 30 minutes and observed using a metallurgical microscope to evaluate pattern formability. Evaluation was performed according to the following criteria. Here, "formable" means that the unexposed areas were completely removed and there were no defects such as distortion of the line areas (exposed areas) or filling in of the space areas. The evaluation results are shown in Table 1. A: It was possible to form a line space of 30 μm. B: It was not possible to form a line with a line space of 30 μm, but it was possible to form a line with a line space of 50 μm. C: It was not possible to form a line space of 50 μm or less, but it was possible to form a line space of 70 μm. D: No line space was formed.

[0189] The resolution mismatch elimination ability was evaluated according to the following criteria. An evaluation result of A or B was deemed acceptable. An evaluation result of A can be considered to have achieved excellent pattern formability under the same exposure conditions on both the copper surface and non-copper surface of the substrate. A: There is an exposure dose at which the pattern formability is rated A for both the substrate with Cu and the substrate without Cu at the same exposure dose. B: For both the substrate with Cu and the substrate without Cu, there is an exposure dose at which the pattern formability is rated A or B at the same exposure dose. C: There is no exposure dose at which the pattern formability is rated A or B for both the substrate with Cu and the substrate without Cu.

[0190] [Evaluation of development residues on glass epoxy substrates with copper surfaces] For the developed Cu-containing substrates prepared for the evaluation of pattern formability, the copper surface of the area where the photosensitive layer had been removed by development was observed using a metallurgical microscope to evaluate development residues. The evaluation was performed by observing the copper surface when the line space was 70 μm and the exposure dose that gave the best pattern formability was used for exposure and development, and was performed according to the following criteria. An evaluation result of A was considered to be acceptable. The evaluation results are shown in Table 1. A: The color of the copper surface itself is shown. This indicates that there is almost no residue. B: Interference fringes (rainbow colors) are observed, indicating the presence of a small amount of residue. C: Residual organic matter (white) is observed, indicating a large amount of residue.

[0191] [Table 1]

[0192] Details of each material in Table 1 are as follows: [Component (A)] UN-954: Urethane acrylate (manufactured by Negami Chemical Industrial Co., Ltd., product name, number of functional groups: 6, weight average molecular weight (Mw): 4,500)

[0193] [(B) Component] A-9300: isocyanuric acid ethylene oxide-modified triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 423, a compound represented by the above formula (7-1), which corresponds to component (B1)). TMCH-5R: Urethane acrylate (manufactured by Hitachi Chemical Co., Ltd., product name, number of functional groups: 2, weight-average molecular weight (Mw): 950, a compound having an acryloyl group (photopolymerizable functional group), a urethane bond (carbon-nitrogen bond), a chain hydrocarbon skeleton, and an alicyclic hydrocarbon skeleton within the molecule; corresponds to component (B2)).

[0194] [(C) component] I-184: 1-hydroxycyclohexylphenyl ketone "IRGACURE-184" (BASF, trade name)

[0195] [(D) component] BT: Benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: 1,2,3-benzotriazole)

[0196] [(E) component] Z250: Cyclomer P (ACA) Z250 (manufactured by Daicel-Allnex Corporation, a resin consisting of three structural units represented by the above formula (XI) produced by reacting an acid group-containing acrylic resin with an alicyclic epoxy group-containing unsaturated compound (weight average molecular weight: 19,000 to 25,000)).

[0197] [Component (F)] KBM-503: 3-methacryloxypropyltrimethoxysilane (product name, manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-803: 3-mercaptopropyltrimethoxysilane (product name, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0198] From Table 1, it was confirmed that the photosensitive resin compositions of Examples 1 to 7 have excellent pattern formability even on the copper surface of a Cu-containing substrate by adjusting the exposure dose, and can eliminate the mismatch in pattern formability between a Cu-free substrate and a Cu-containing substrate, and can reduce development residues on the Cu surface after development.

Claims

1. The composition comprises: component (A): a high molecular weight material having a photopolymerizable functional group and a carbon-nitrogen bond and a weight average molecular weight of 2,500 or more; component (B): a low molecular weight material having a photopolymerizable functional group; component (C): a photopolymerization initiator; component (D): a triazole-based compound; and component (E): a high molecular weight material having a glass transition temperature of 70 to 150°C, not having a carbon-nitrogen bond, and a weight average molecular weight of 2,500 or more; the content of the component (B) is 20 to 80 parts by mass based on 100 parts by mass of the total solid content of the component (A) and the component (E), The component (A) contains a urethane (meth)acrylate having a total number of (meth)acryloyl groups of 6 to 30, The component (B) comprises at least one member selected from the group consisting of a low-molecular-weight compound having a urethane bond, a low-molecular-weight compound having an isocyanuric ring, and a low-molecular-weight compound having an alicyclic skeleton.

2. The composition comprises: (A) component: a high molecular weight material having a photopolymerizable functional group and a carbon-nitrogen bond and a weight average molecular weight of 2,500 or more; (B) component: a low molecular weight material having a photopolymerizable functional group; (C) component: a photopolymerization initiator; and (D) component: a triazole-based compound; the content of the component (B) is 20 to 80 parts by mass based on 100 parts by mass of the total solid content of the component (A), The component (A) contains a urethane (meth)acrylate having a total number of (meth)acryloyl groups of 6 to 30, the component (B) contains at least one selected from the group consisting of a low-molecular-weight compound having a urethane bond, a low-molecular-weight compound having an isocyanuric ring, and a low-molecular-weight compound having an alicyclic skeleton, The component (D) is a photosensitive resin composition containing a benzotriazole-based compound (provided that the photosensitive resin composition has a glass transition temperature of 70 to 150°C, does not contain a high-molecular-weight compound having no carbon-nitrogen bond and a weight-average molecular weight of 2,500 or more).

3. The photosensitive resin composition according to claim 1 , wherein the component (D) comprises a benzotriazole-based compound.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the content of the component (D) is 0.1 to 10 mass% based on the total solid content of the photosensitive resin composition.

5. 5. The photosensitive resin composition according to claim 1, wherein the component (A) contains a high molecular weight compound having six or more ethylenically unsaturated groups as photopolymerizable functional groups and having a weight average molecular weight of 2,500 or more.

6. 6. The photosensitive resin composition according to claim 1, wherein the component (A) comprises a polymer having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton.

7. 7. The photosensitive resin composition according to claim 1, wherein the component (B) comprises a low-molecular-weight compound having at least one (meth)acryloyl group and a urethane bond.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the component (C) comprises a compound represented by the following general formula (C1) or a compound represented by the following general formula (C2): 【Chemistry 1】 [R Ｃ１ , R Ｃ２ and R Ｃ３ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; R Ｃ４ and R Ｃ５ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Ｃ１ ~R Ｃ５ may each have a substituent. 【Chemistry 2】 [R Ｃ６ represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an amino group; R Ｃ７ and R Ｃ８ R each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. Ｃ７ and R Ｃ８ may be bonded to each other to form a ring structure having 3 to 16 carbon atoms. Ｃ６ ~R Ｃ８ may each have a substituent, and the substituents of the amino groups having a substituent may be bonded to each other to form a ring structure having 3 to 12 carbon atoms. Ｃ９ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an organic group having 1 to 10 carbon atoms which may contain one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom.]

9. The photosensitive resin composition according to any one of claims 1 to 8, further comprising a component (F): a silane compound.

10. A photosensitive resin film having a photosensitive layer using the photosensitive resin composition according to any one of claims 1 to 9.

11. A method for producing a cured product, the method comprising the steps of: providing a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 9 or the photosensitive resin film according to claim 10; irradiating at least a portion of the photosensitive layer with actinic rays 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.

12. The method for producing a cured product according to claim 11 , further comprising a step of heat treating the resin pattern.

13. The method for producing a cured product according to claim 11 or 12, wherein the resin pattern has a thickness of 70 μm or more and 300 μm or less.

14. The method for producing a cured product according to any one of claims 11 to 13, further comprising a step of heat-treating the photosensitive layer after providing the photosensitive layer on the substrate.

15. A laminate comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 9.

16. The laminate according to claim 15, wherein the thickness of the cured product is 70 μm or more and 300 μm or less.

17. An electronic component comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 9.

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