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

Abstract

To provide a photosensitive resin composition that has excellent patterning properties even when forming a photosensitive layer having a large thickness, for example, of 70 μm or more, and a photosensitive resin film, a method for producing a cured product, a laminate, and an electronic component.SOLUTION: A photosensitive resin composition includes (A) component: a high-molecular-weight body having a photopolymerizable functional group and a carbon-nitrogen bond, (B) component: a low-molecular-weight body having a photopolymerizable functional group and a carbon-nitrogen bond, and (C) component: a photopolymerization initiator. The (B) component includes a low-molecular-weight body having an acryloyl group as a photopolymerizable functional group. There are also provided a photosensitive resin film including the same, a method for producing a cured product, a laminate, and an electronic component.SELECTED DRAWING: None

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 field of manufacturing semiconductor integrated circuits (LSI) 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, the photosensitive layer is exposed through a predetermined mask pattern, and then a development process is performed so that the parts where the conductor pattern, metal posts, etc. are to 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 parts by plating, and then the resist pattern is removed, thereby manufacturing a wiring board equipped with a conductor pattern, metal posts, etc.

[0003] Conventionally, thick conductor patterns and metal posts have been produced by growing metal plating after removing the resist pattern. In order 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). In recent years, in order to achieve even higher performance, attempts have been made to form a conductor layer as thick as about 150 μm by performing a plating process while destroying, with a plating solution, the layer of the dilute metal ion layer that exists in the direction of the desired selective plating growth (see Patent Document 3). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2015-034926 A [Patent Document 2] JP 2014-074774 A [Patent Document 3] JP 2014-080674 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, in the case of conventional thick-film photosensitive resists, when a thick photosensitive layer of, for example, 70 μm or more is required to be formed, light does not easily pass through to the bottom, and the pattern shape may deteriorate. In addition, in the method described in Patent Document 3, plating is carried out while partially destroying the metal ion dilute layer, so it is difficult to stably form an excellent pattern. Therefore, a photosensitive resist having excellent pattern forming properties is required even when a photosensitive layer of 70 μm or even 150 μm or more thicker than the conventional one is formed.

[0006] Therefore, the problem that the present disclosure aims to solve has been made in consideration of the above circumstances, and is to provide a photosensitive resin composition, a photosensitive resin film, a method for producing a cured product, a laminate, and an electronic component (hereinafter sometimes referred to as a "photosensitive resin composition, etc.") that have excellent pattern formability even when a thick photosensitive layer of, for example, 70 μm or more is formed. [Means for solving the problem]

[0007] As a result of intensive research into solving the above problems, the present inventors have found that the problems can be solved by a photosensitive resin composition having the following configuration. The present disclosure provides the following photosensitive resin composition.

[0008] [1] A photosensitive resin composition comprising: (A) component: a high molecular weight material having a photopolymerizable functional group and a carbon-nitrogen bond; (B) component: a low molecular weight material having a photopolymerizable functional group and a carbon-nitrogen bond; and (C) component: a photopolymerization initiator, wherein the (B) component contains a low molecular weight material having an acryloyl group as the photopolymerizable functional group. [2] A photosensitive resin film having a photosensitive layer using the photosensitive resin composition described in [1] above. [3] A method for producing a cured product, comprising the steps of: providing a photosensitive layer on a substrate using the photosensitive resin composition described in [1] above or the photosensitive resin film described in [2] 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. [4] A laminate comprising a cured product of the photosensitive resin composition described in [1] above. [5] An electronic component comprising a cured product of the photosensitive resin composition described in [1] above. Effect of the Invention

[0009] According to the present disclosure, it is possible to provide a photosensitive resin composition or the like that has excellent pattern formability even when a thick photosensitive layer of, for example, 70 μm or more is formed. [Brief description of the drawings]

[0010] [Figure 1] FIG. 2 is a schematic diagram showing an example of a resolution evaluation mask used in the examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present disclosure will be described in detail below. In this specification, a numerical range indicated using "~" indicates a range including the numerical values ​​described before and after "~" as the minimum and maximum values, respectively, and the minimum and maximum values ​​described in stages may be arbitrarily combined. Furthermore, in a numerical range described in stages in this specification, the upper limit or lower limit of a numerical range in a certain stage may be arbitrarily combined with the upper limit or lower limit of a numerical range in another stage. Furthermore, in a numerical range described in this specification, the upper limit or lower limit of the numerical range may be replaced with a value shown in the examples. The term "(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.

[0012] [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) is a photosensitive resin composition that contains component (A): a high molecular weight material having a photopolymerizable functional group and a carbon-nitrogen bond, component (B): a low molecular weight material having a photopolymerizable functional group and a carbon-nitrogen bond, and component (C): a photopolymerization initiator, wherein component (B) contains a low molecular weight material having an acryloyl group as a photopolymerizable functional group. 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 the components that remain without volatilization when the resin composition is dried, and also includes those that are liquid, syrup-like, or wax-like at room temperature (25°C). Each component will be explained below.

[0013] <(A) Component: High molecular weight substance> The photosensitive resin composition of the present embodiment contains a polymer having a photopolymerizable functional group and a carbon-nitrogen bond as component (A). The term "polymer" refers to a compound having a weight-average molecular weight of 2,000 or more. In this specification, the weight-average molecular weight (Mw) is a value determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) and converted into standard polystyrene. Examples of the photopolymerizable functional group possessed by the polymer of component (A) include (meth)acryloyl group; ethylenically unsaturated groups such as alkenyl groups such as allyl group and vinyl group. From the viewpoint of improving pattern formability, component (A) may contain a polymer having a (meth)acryloyl group as a photopolymerizable functional group, and may further contain a polymer having a urethane bond as a carbon-nitrogen bond. Examples of the polymer having a (meth)acryloyl group as a photopolymerizable functional group include (meth)acrylate, and examples of the polymer having a urethane bond as a carbon-nitrogen bond include urethane (meth)acrylate. 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.

[0014] The 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 the component (A) may be appropriately selected from 2 to 15 in one molecule from the viewpoint of improving pattern formability and heat resistance, and from 2 to 12 or 2 to 10 from the viewpoint of stabilizing the physical properties and characteristics of the obtained cured product.

[0015] An example of the urethane (meth)acrylate of the component (A) is a reaction product of a (meth)acrylate having a hydroxyl group and an isocyanate compound having an isocyanate group. 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 cyclohexane dimethanol type epoxy di(meth)acrylate, tricyclodecane dimethanol 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 (meth)acrylates having three or more functional groups, such as ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate, include their ethoxylated products, their propoxylated products, their ethoxylated propoxylated products, and their caprolactone-modified products; their trifunctional or higher epoxy (meth)acrylates, such as phenol novolac epoxy (meth)acrylate, cresol novolac epoxy poly(meth)acrylate, and isocyanuric acid epoxy tri(meth)acrylate; and their hydroxypropylated products, such as trimethylolpropane tri(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate. These may be used alone or in combination of two or more.

[0016] Here, the ethoxylated, propoxylated, ethoxylated propoxylated, and hydroxypropylated (meth)acrylates are obtained, for example, by using as a raw material an alcohol compound (or a phenol compound) serving as the raw material for the (meth)acrylate, to which one or more ethylene oxide groups, propylene oxide groups, ethylene oxide groups 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.

[0017] The isocyanate compound having an isocyanate group includes a compound having at least one isocyanate group in one molecule, and may be a compound having 1 to 3 isocyanate groups in one molecule. More specifically, the 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; aromatic monoisocyanate compounds such as phenyl isocyanate; 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)methane, and the like. alicyclic diisocyanate compounds such as 2,2-bis(4-isocyanatocyclohexyl)ethane, 2,2-bis(4-isocyanatocyclohexyl)propane, 2,2-bis(4-isocyanatocyclohexyl)hexafluoropropane, and bicycloheptane triisocyanate; 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 naphthalene-1,5-diisocyanate; and polymers such as uretdione dimers, isocyanurate types, and biuret trimers of these diisocyanate compounds. These may be used alone or in combination of two or more kinds, and the two or three isocyanate compounds constituting the polymer may be the same or different.

[0018] Among these, from the viewpoint of improving pattern formability, the diisocyanate compound may be appropriately selected from diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds, and polymers of these diisocyanate compounds, and in particular, may be appropriately selected from hexamethylene diisocyanate, isophorone diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, and isocyanurate-type polymers (isocyanurate-type polyisocyanates).

[0019] The reaction product of the (meth)acrylate having a hydroxyl group and the isocyanate compound has a (meth)acryloyl group as a photopolymerizable functional group and a urethane bond as a carbon-nitrogen bond, and more specifically, for example, has an organic group derived from the (meth)acrylate having a hydroxyl group in the molecule (i.e., an organic group having 1 to 5 (meth)acryloyl groups, which is a residue obtained by removing a hydroxyl group from the (meth)acrylate having a hydroxyl group), a urethane bond, and an organic group derived from the isocyanate compound (i.e., an organic group having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton, which is a residue obtained by removing an isocyanate group from the isocyanate compound). These organic groups may be the same or different.

[0020] From the viewpoint of improving pattern formability, the urethane (meth)acrylate of the component (A) may include, for example, a reaction product obtained by reacting a terminal isocyanate group of a polyaddition product of an isocyanate compound having at least two isocyanate groups in one molecule with a diol compound, with a (meth)acrylate having a hydroxyl group.

[0021] Examples of the isocyanate compound having at least two isocyanate groups in one molecule used here include diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds among the compounds exemplified above as the isocyanate compound, as well as multimers of these diisocyanate compounds such as uretdione dimers, isocyanurate dimers, and biuret trimers. The above isocyanate compounds can be used alone or in combination of two or more kinds.

[0022] Examples of the diol compound include diol compounds having 1 to 20 carbon atoms, and specific examples thereof 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 above-mentioned 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 kinds.

[0023] 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 viewpoints of improving pattern formability and increasing the glass transition point (Tg) after polymerization to improve water resistance, and more specifically, may be appropriately selected from ethylene glycol and octadecanediol. In addition, 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 point (Tg) after polymerization to improve water resistance. More specifically, the diol compound may be appropriately selected from various cyclohexane diols such as 1,3-cyclohexane diol and 1,4-cyclohexane diol, and various cyclohexane dimethanols such as 1,3-cyclohexane dimethanol and 1,4-cyclohexane dimethanol.

[0024] In addition, the (meth)acrylate having a hydroxyl group used here may be any of the (meth)acrylates exemplified above as the (meth)acrylate used in the reaction product of the (meth)acrylate having a hydroxyl group and an isocyanate compound having an isocyanate group.

[0025] 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 in one 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).

[0026] [ka]

[0027] In the general formula (1), X1 represents a divalent organic group having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton, and Y1 represents a divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton. When the component (A) has a plurality of the above structural units, the plurality of X1s and Y1s may be the same or different. That is, the component (A) may have at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton.

[0028] The divalent organic group of X1 may be an organic group derived from an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, or an aromatic diisocyanate compound, which are given as examples of the compound having an isocyanate group, i.e., a divalent organic group having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton, which is a residue obtained by removing an isocyanate group from the isocyanate compound. The divalent organic group represented by X1 may be these residues themselves, or may be a residue derived from an isocyanate compound derivative, such as a polyaddition product of the isocyanate compound and a diol compound. From the viewpoints of improving pattern formability and improving the transparency, water resistance, and moisture resistance of the resin composition in a well-balanced manner, X1 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).

[0029] [ka]

[0030] Examples of the divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton for Y1 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. Among them, from the viewpoint of improving the pattern formability and increasing the glass transition point (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.

[0031] 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 in one molecule with a diol compound with a (meth)acrylate having a hydroxyl group include compounds represented by the following general formulas (3) and (4).

[0032] [ka]

[0033] In formulae (3) and (4), n1 and n2 each independently represent an integer of 3 to 20.

[0034] Furthermore, examples of reaction products obtained when an isocyanurate trimer (isocyanurate triisocyanate), which is a trimer of a diisocyanate, is used as the isocyanate compound include compounds represented by the following general formulas (5) and (6).

[0035] [ka]

[0036] In formulae (5) and (6), n3 and n4 each independently represent an integer of 2 to 20.

[0037] Commercially available products containing a urethane acrylate having a structural unit represented by the above general formula (1) include, for example, UN-333 (functional group number: 2, Mw: 5,000), UN-1255 (functional group number: 2, Mw: 8,000), UN-904 (functional group number: 10, Mw: 4,900), UN-2600 (functional group number: 2, Mw: 2,500), UN-6200 (functional group number: 2, Mw: 6,500), UN-9000PEP (functional group number: 2, Mw: 5,000), U Examples of such copolymers include N-9200A (functional groups: 2, Mw: 15,000), UN-3320HS (functional groups: 15, Mw: 4,900), UN-6301 (functional groups: 2, Mw: 33,000) (all trade names, manufactured by Negami Chemical Industries, Ltd.), and EBECRYL8405 (addition product of urethane acrylate / 1,6-hexanediol diacrylate = 80 / 20, functional groups: 4, Mw: 2,700) (trade name, manufactured by Daicel-Allnex Corporation). In addition, examples of commercially available products containing urethane methacrylate having a structural unit represented by the above general formula (1) include UN-6060PTM (functional group number: 2, Mw: 6,000, product name, manufactured by Negami Chemical Industries, Ltd.) etc. In the above description, the functional group number and Mw in parentheses are the total number of (meth)acryloyl groups contained in the urethane (meth)acrylate and the weight average molecular weight, respectively.

[0038] In addition, a commercially available product containing the urethane (meth)acrylate represented by the above general formula (3) is, for example, UN-952 (number of functional groups: 10, Mw: 6,500 to 11,000), and a commercially available product containing the urethane (meth)acrylate represented by the general formula (6) is, for example, UN-905 (number of functional groups: 15, Mw: 40,000 to 200,000) (all of the above are trade names, manufactured by Negami Chemical Industries, Ltd.). Among these, UN-952 is particularly preferred from the viewpoints of pattern formability and photosensitivity.

[0039] The total number of (meth)acryloyl groups (number of functional groups) contained in the urethane (meth)acrylate of component (A) may be appropriately selected from 2 to 15 in one molecule from the viewpoint of improving pattern formability and heat resistance, and from 2 to 12 or 2 to 10 from the viewpoint of stabilizing the physical properties and characteristics of the obtained cured product. If the number of functional groups is 2 or more, the pattern formability, heat resistance, and rigidity of the cured product at high temperatures can be improved. On the other hand, if the number of functional groups is 15 or less, the rigidity of the cured product is improved, and the adhesion to the substrate or the like is improved. In addition, a resin composition having a suitable viscosity can be obtained, and the coatability can be improved. When the resin composition after coating is irradiated with light, the phenomenon that only the surface part is easily photocured rapidly and the inside is not photocured sufficiently can be suppressed, and excellent resolution can be obtained, so that even when a thick photosensitive layer is formed, excellent pattern formability can be obtained. Furthermore, after at least one of photocuring and heat curing is performed, the remaining unreacted (meth)acryloyl group can be reduced, and the fluctuation of the physical properties and characteristics of the obtained cured product can be further suppressed.

[0040] The weight average molecular weight of the polymer of component (A) is 2,000 or more, and from the viewpoint of improving the coatability and resolution of the resin composition, it may be 2,500 or more, and from the viewpoint of improving the developability and compatibility, it may be 3,000 or more. On the other hand, the upper limit of the weight average molecular weight may be 40,000 or less, or 30,000 or less, from the viewpoint of improving the coatability and resolution of the resin composition, and may be 20,000 or less, from the viewpoint of improving the developability and compatibility. If the weight average molecular weight is 2,000 or more, the occurrence of dripping of the composition when applied onto a substrate can be suppressed, resulting in excellent pattern forming properties. In addition, it is easy to form a thick photosensitive layer, and the problem of increased stress on the resin due to cure shrinkage and reduced reliability can be suppressed. On the other hand, if the weight average molecular weight is 40,000 or less, the coating property is improved, a thick photosensitive layer is easily formed, and the pattern forming property is improved. In addition, the solubility in the developer is also good, so that excellent resolution can be expressed. Furthermore, the transparency of the cured product is improved, and a cured product having excellent transmittance required for a transparent material can be obtained.

[0041] The content of the component (A) may be appropriately selected from 10% by mass or more, 30% by mass or more, or 50% by mass or more based on the total solid content of the photosensitive resin composition. If the content is 10% by mass or more, the coating property is improved, and even when a thick photosensitive layer is formed, excellent pattern formability can be obtained. 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. Furthermore, from the viewpoint of improving pattern formability, the content of the urethane (meth)acrylate in the 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 the component (A).

[0042] <(B) Component: Low molecular weight substance> The photosensitive resin composition of the present embodiment contains a low molecular weight compound having a photopolymerizable functional group and a carbon-nitrogen bond as component (B), and the component (B) contains a low molecular weight compound having an acryloyl group as the photopolymerizable functional group. The "low molecular weight compound" refers to a compound having a weight average molecular weight of less than 2,000. The (B) component contains a low molecular weight material having an acryloyl group as a photopolymerizable functional group. When the (B) component contains at least a low molecular weight material having an acryloyl group, sufficiently excellent pattern formability can be obtained. For example, when a compound containing a methacryloyl group but not containing an acryloyl group is used alone, it is difficult to obtain sufficient pattern formability. The (B) component may contain a urethane acrylate having a urethane bond as a carbon-nitrogen bond from the viewpoint of improving pattern formability. In general, a low molecular weight material having an acryloyl group requires a higher activation energy during photopolymerization than a low molecular weight material having a methacryloyl group, and the sensitivity is improved. In addition, when the low molecular weight material further has a carbon-nitrogen bond, it can act as a chain transfer agent for radical polymerization, and excellent pattern formability can be obtained.

[0043] The component (B) has at least one acryloyl group and at least one carbon-nitrogen bond. The total number of acryloyl groups (functional groups) contained in the low molecular weight component (B) may be appropriately selected from 2 to 15 in one molecule from the viewpoint of improving pattern formability and heat resistance, and from 2 to 12 or 2 to 10 from the viewpoint of stabilizing the physical properties and characteristics of the resulting cured product.

[0044] The urethane acrylate of the component (B) may be a reaction product of an acrylate having a hydroxyl group and an isocyanate compound having an isocyanate group. Here, the acrylate having a hydroxyl group and the isocyanate compound may be the acrylate having a hydroxyl group and the isocyanate compound exemplified as those used for producing a polymer. Here, examples of those appropriately selected from the viewpoint of improving pattern formability and the like include the same ones as those appropriately selected from the viewpoint of producing a polymer.

[0045] In addition, the low molecular weight urethane acrylate may be a reaction product in which an acrylate having a hydroxyl group is reacted with a terminal isocyanate group of a polyaddition product of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound. Here, the isocyanate compound having at least two isocyanate groups in one molecule, the diol compound, and the acrylate having a hydroxyl group may be the isocyanate compound having at least two isocyanate groups in one molecule, the diol compound, and the acrylate having a hydroxyl group, which are exemplified as those used to generate a high molecular weight substance. Here, examples of those appropriately selected from the viewpoint of improving pattern formability, etc., include the same ones as those appropriately selected from the same viewpoint as those used to generate a high molecular weight substance. An example of this reaction product is one having a structural unit represented by the following general formula (7).

[0046] [ka]

[0047] In the general formula (7), X2 represents a divalent organic group having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton, and Y2 represents a divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton. That is, the (B) component may have at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton. Examples of X2 and Y2 are the same as X1 and Y1 in the general formula (1), respectively. From the viewpoint of improving the pattern formability and improving the transparency, water resistance, and moisture resistance of the resin composition in a well-balanced manner, X2 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. From the same viewpoint, Y2 may be appropriately selected from divalent organic groups having an alicyclic skeleton, such as residues of the above-mentioned diol compounds having an alicyclic skeleton.

[0048] Specific examples of urethane acrylates that can be used as the component (B) include compounds represented by the following general formula (8).

[0049] [ka]

[0050] In the above general formula (8), n5 represents an integer of 1 to 4. 4 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and 4 and R 5 and at least three of them are alkyl groups having 1 to 4 carbon atoms. Among the urethane acrylates represented by the above general formula (8), examples of commercially available products containing a urethane acrylate having a structural unit in which X2 in the above general formula (7) is a residue of trimethylhexamethylene diisocyanate, which is a divalent organic group having a chain hydrocarbon skeleton, and Y2 is a residue of cyclohexanedimethanol, which is a divalent organic group having an alicyclic skeleton, include TMCH-5R (trade name, number of functional groups: 2, Mw: 950, manufactured by Hitachi Chemical Co., Ltd.). In addition, examples of commercially available products containing a urethane acrylate having a structural unit represented by the above general formula (7) include KRM8452 (functional group number: 10, Mw: 1,200, manufactured by Daicel-Allnex Co., Ltd.), UN-3320HA (functional group number: 6, Mw: 1,500), UN-3320HC (functional group number: 6, Mw: 1,500, manufactured by Negami Chemical Industries Co., Ltd.), etc. In the above description, the functional group number and Mw in parentheses are the functional group number and weight average molecular weight of the urethane acrylate, respectively.

[0051] The weight-average molecular weight of the low molecular weight component (B) is less than 2,000, and may be 1,800 or less from the viewpoint of improving adhesion, and may be 1,500 or less from the viewpoint of improving resolution. On the other hand, the lower limit of the weight-average molecular weight may be 500 or more from the viewpoint of film formability, although it may be appropriately set depending on the desired purpose.

[0052] The content of the (B) component may be appropriately selected from 3% by mass or more, 5% by mass or more, 10% by mass or more, or 20% by mass or more based on the total solid content of the photosensitive resin composition. If the content is 3% by mass or more, excellent pattern formability can be obtained even when a thick photosensitive layer is formed, and excellent rigidity of the cured product can also be obtained. From the same 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. The content of the (B) component based on the total solid content of the (A) component may be appropriately selected from 25 to 90 mass %, 30 to 80 mass %, or 35 to 65 mass % from the viewpoint of improving pattern formability and rigidity of the cured product. In this embodiment, a low molecular weight material having a photopolymerizable functional group other than an acryloyl group may be included depending on the desired purpose. The content of the low molecular weight material having an acryloyl group as a photopolymerizable functional group based on the total solid content of the (B) component may be appropriately selected from 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more. If the content is 70% 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 low molecular weight material having an acryloyl group as a photopolymerizable functional group is 100% by mass or less, and 100% by mass, i.e., the entire amount of the (B) component may have an acryloyl group as a photopolymerizable functional group.

[0053] <Component (C): Photopolymerization initiator> The photosensitive resin composition of the present embodiment contains a photopolymerization initiator as component (C). The component (C) is not particularly limited as long as it can polymerize at least one of the components (A) and (B), and can be appropriately selected from photopolymerization initiators that are commonly used. From the viewpoint of improving pattern formability, examples of photopolymerization initiators that generate free radicals when exposed to active light include acylphosphine oxide-based, oxime ester-based, aromatic ketone-based, quinone-based, alkylphenone-based, imidazole-based, acridine-based, phenylglycine-based, and coumarin-based photopolymerization initiators.

[0054] The acylphosphine oxide photopolymerization initiator has an acylphosphine oxide group (>P(=O)-C(=O)- group), and examples thereof include (2,6-dimethoxybenzoyl)-2,4,6-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name: IRGACURE-TPO, manufactured by BASF), ethyl-2,4,6-trimethylbenzoylphenylphosphinate, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (trade name: IRGACURE-819, manufactured by BASF), (2,5-dihydroxyphenyl)diphenylphosphine oxide, (p-hydroxyphenyl)diphenylphosphine oxide, bis(p-hydroxyphenyl)phenylphosphine oxide, and tris(p-hydroxyphenyl)phosphine oxide.

[0055] 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.).

[0056] Examples of aromatic ketone-based photopolymerization initiators include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: IRGACURE-651, manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one (trade name: IRGACURE-369, manufactured by BASF), and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one (trade name: IRGACURE-907, manufactured by BASF).

[0057] Examples of quinone-based 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.

[0058] Examples of the alkylphenone-based photopolymerization initiator 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 (trade name: IRGACURE-651, manufactured by BASF), 1-hydroxy-cyclohexyl-phenyl ketone (trade name: IRGACURE-184, manufactured by BASF), 2-hydroxy-2-methyl-1 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (trade name: IRGACURE-1173, manufactured by BASF), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (trade name: IRGACURE-2959, manufactured by BASF), and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropan-1-one (trade name: IRGACURE-127, manufactured by BASF).

[0059] 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.

[0060] Examples of the acridine-based photopolymerization initiator include 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane.

[0061] Examples of the phenylglycine-based photopolymerization initiator include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0062] 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-diethylaminocyclopenta[c]coumarin. 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-thienylbiscoumarin, and the like.

[0063] From the viewpoint of improving photocurability and sensitivity and improving pattern formability, it can be appropriately selected from acylphosphine oxide photopolymerization initiators. The above-mentioned (C) component can be used alone or in combination of two or more kinds. In addition, the (C) component may be synthesized by a conventional method or may be a commercially available product.

[0064] The content of the (C) component may be appropriately selected from the amount at which the absorbance of light having a wavelength of 365 nm is 0.35 or less, 0.3 or less, 0.2 or less, or 0.1 or less when the photosensitive layer formed from the photosensitive resin composition has a thickness (thickness after drying) of 50 μm. By setting the content as above, even when a pattern is formed with a thick photosensitive layer of, for example, 70 μm or more, light can easily pass through to the bottom of the photosensitive layer (the surface of the photosensitive layer on the substrate side), thereby improving pattern formability. Here, the absorbance can be measured, for example, by using a UV-visible spectrophotometer (product name: U-3310 Spectrophotometer, manufactured by Hitachi High-Technologies Corporation) and a polyethylene terephthalate film alone as a reference, to measure the absorbance of light having a wavelength of 365 nm. In addition, the absorbance of light with a wavelength of 365 nm when the photosensitive layer has a thickness of 50 μm can also be determined by converting the absorbance of a photosensitive layer with a thickness other than 50 μm into the absorbance for a thickness of 50 μm based on Lambert-Beer's law.

[0065] In addition to the above-mentioned component (C), a photopolymerization initiator assistant such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, or other tertiary amines can be used as component (C'). These components (C') can be used alone or in combination of two or more.

[0066] The content of the (C) component may be appropriately determined according to the absorbance at a thickness of 50 μm of the photosensitive layer as described above, and may be appropriately selected from 0.05 to 20 mass%, 0.1 to 10 mass%, or 0.15 to 5 mass% based on the total solid content of the photosensitive resin composition. By setting the content to 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.

[0067] <Component (D): Thermal radical polymerization initiator> The photosensitive resin composition of the present embodiment may further contain (D) a thermal radical polymerization initiator. The component (D) 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, 1,1-bis(t- 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 polymerization initiator include peroxide-based polymerization initiators such as peroxy esters such as peroxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxybenzoate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, and t-butylperoxyacetate, and azo-based polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile);

[0068] From the viewpoint of improving pattern formability, the component (D) may be a peroxide-based polymerization initiator or a dialkyl peroxide-based polymerization initiator, among which dicumyl peroxide may be selected. The component (D) may be used alone or in combination of two or more kinds.

[0069] When the component (D) is contained, its content 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.

[0070] <(E) Component: Inorganic filler> The photosensitive resin composition of the present embodiment may contain component (E) 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. Examples of the (E) 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), and magnesium hydroxide (Mg(OH)2). Examples of inorganic fillers that can be used include zirconia containing yttria (Y2O3·ZrO2), barium 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 of two or more.

[0071] The average particle size of the component (E) 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 the adhesiveness, heat resistance, and rigidity of the cured product. Here, the average particle size of the component (E) is the average particle size of the inorganic filler in a state dispersed in the photosensitive resin composition, and is a value obtained by measuring as follows. First, the photosensitive resin composition is diluted (or dissolved) 1,000 times with methyl ethyl ketone, and then the particles dispersed in the solvent are measured at a refractive index of 1.38 using a submicron particle analyzer (trade name: N5, manufactured by Beckman Coulter, Inc.) in accordance with the international standard ISO13321, and the particle size at an integrated value of 50% (volume basis) in the particle size distribution is taken as the average particle size. Furthermore, the component (E) 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 component (E) 1,000 times (volume ratio) using a solvent as described above.

[0072] The content of the (E) component may be appropriately selected from the upper limit of 10% by mass or less, 5% by mass or less, or 1% by mass or less, and the lower limit may be appropriately selected from more than 0% by mass, or may be 0% by mass (not included), based on the total solid content of the photosensitive resin composition. In this way, by substantially not including the (E) component, the transmittance of the photosensitive resin composition is improved, and even when a pattern is formed with a thick photosensitive layer of, for example, 70 μm or more, light easily passes through to the bottom of the photosensitive layer (the surface of the photosensitive layer on the substrate side), improving pattern formability.

[0073] <Other additives> The photosensitive resin composition of the present embodiment may further contain additives such as a silane coupling agent, a sensitizer, a heat-resistant polymer, a thermal crosslinking agent, and an adhesive aid, as necessary.

[0074] Silane coupling agents can improve the adhesion of electronic components to substrates, and are particularly effective when the substrate contains silicon (e.g., glass substrates, silicon wafers, epoxy resin-impregnated glass cloth substrates, etc.). Examples of silane coupling agents include alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; (meth)acryloyl group-containing alkoxysilanes such as (meth)acryloxypropyltrimethoxysilane and (meth)acryloxypropylmethyldimethoxysilane; amine-based alkoxysilanes such as aminopropyltrimethoxysilane and aminopropyltriethoxysilane; glycidoxy group-containing alkoxysilanes such as glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldiethoxysilane, and glycidoxypropylmethyldiisopropenoxysilane. These can 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, 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, may be used.

[0075] Examples of the sensitizer 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.

[0076] Examples of the heat-resistant polymers include polyoxazoles and their precursors, which have high heat resistance and are used as engineering plastics from the viewpoint of improving processability, novolak resins such as phenol novolak and cresol novolak, polyamideimides, polyamides, etc. These may be used alone or in combination of two or more.

[0077] 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 selected from the group consisting of a methylol group and an alkoxymethyl group, urea resins, etc. These can be used alone or in combination of two or more.

[0078] The adhesion aid can be used as desired to improve the adhesion between the photosensitive resin composition and the substrate, and examples thereof include organic silane compounds such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, triethoxysilylpropylethyl carbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. These can be used alone or in combination of two or more.

[0079] 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.

[0080] <Diluent> A diluent can be used in the photosensitive resin composition of the present embodiment as necessary. Examples of diluents include alcohols having 1 to 6 carbon atoms, such as isopropanol, isobutanol, and t-butanol; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; sulfur-containing compounds, 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 can be used alone or in combination of two or more.

[0081] The amount of the diluent used may be appropriately selected from an amount that results in a total solid content in the photosensitive resin composition of 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 the diluent used within the above range, the coatability of the photosensitive resin composition is improved, and a more precise pattern can be formed. Furthermore, for example, when forming a photosensitive layer having a thickness of 70 μm or more, the amount can be set so 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.

[0082] The photosensitive resin composition of the present embodiment can be obtained by uniformly kneading and mixing the above-mentioned components (A) to (C), as well as the optional components (D) and (E), other additives, and a diluent, using a roll mill, a bead mill, or the like.

[0083] The photosensitive resin composition of the present embodiment may be used in the form of a liquid or a film. 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, 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. 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 using a laminator or the like.

[0084] The photosensitive layer formed from the photosensitive resin composition of this embodiment has 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 has a thickness of 50 μm (thickness after drying). If the absorbance of the photosensitive layer when the photosensitive layer has a thickness of 50 μm is 0.35 or less, even when a pattern is formed using a thick photosensitive layer of, for example, 70 μm or more, light can easily pass through the bottom of the photosensitive layer (the surface of the photosensitive layer facing the substrate), thereby improving pattern formability.

[0085] [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 also have a carrier film. In this specification, the term "layer" includes a structure having a shape formed on the entire surface when observed in a plan view, as well as a structure having a shape formed on a part of the surface.

[0086] The photosensitive resin film of the present embodiment can be produced, for example, by applying the photosensitive resin composition of the present embodiment onto a carrier film by the above-mentioned various coating methods to form a coating film, and 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.

[0087] The coating film can be dried using a hot air dryer, a dryer using far infrared rays, or a near infrared ray, and the drying temperature may be appropriately selected from 60 to 120° C., 70 to 110° C., or 90 to 110° C. The drying time may be appropriately selected from 1 to 60 minutes, 2 to 30 minutes, or 5 to 20 minutes. If the photosensitive resin composition of the present embodiment contains a diluent, drying under the above conditions can also remove at least a portion of the diluent.

[0088] Examples of the carrier film include polyester resin films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), and polyolefin resin films such as polypropylene and polyethylene. From the viewpoint of improving the mechanical strength and heat resistance of the photosensitive resin film, a polyester resin film may be selected. 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.

[0089] 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, and 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 winding core when the photosensitive resin film is wound around the winding core can be further reduced. Considering the effect of obtaining excellent pattern formability even when a thick photosensitive layer is formed, which is possessed by the photosensitive resin composition of this embodiment, the thickness may be 70 μm or more, or may be a thickness exceeding 100 μm. Note that, for example, a photosensitive layer having a thickness of 70 μm or more can be obtained by laminating a photosensitive layer formed on a carrier film and a photosensitive layer formed on a protective layer described later, to obtain a photosensitive resin film having a carrier film, a thick photosensitive layer, and a protective layer in this order.

[0090] In addition, the photosensitive resin film of this embodiment can also have a protective layer laminated on the surface opposite to the surface of the photosensitive layer that contacts the carrier film. For example, a resin film such as polyethylene or polypropylene may be used as the protective layer. In addition, the same resin film as the carrier film described above may be used, or a different resin film may be used.

[0091] [Method of manufacturing the cured product] The method for producing a cured product of this embodiment 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 forming step), irradiating at least a part of the photosensitive layer with active light to form a photocured portion (exposure step), and removing at least a part of the photosensitive layer other than the photocured portion to form a resin pattern (removal step). In addition, if desired, the method further includes a step of heat treating the resin pattern (heating step). The method for producing a cured product of this embodiment enables the formation of a desired pattern, and by taking advantage of the characteristics of the photosensitive resin composition of this embodiment that has 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 by 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.

[0092] (Photosensitive layer formation process) In forming the photosensitive layer, the photosensitive resin composition or the photosensitive resin film of the present embodiment can be applied or laminated on a substrate to form the photosensitive layer. Examples of the substrate include glass substrates, silicon wafers, metal oxide insulators such as TiO2 and SiO2, silicon nitride, ceramic piezoelectric substrates, and epoxy resin-impregnated glass cloth substrates.

[0093] When forming a photosensitive layer by applying a photosensitive resin composition to a substrate, the photosensitive resin composition may be dissolved in the diluent to form a solution, and then applied to the substrate, and the coating film obtained by application may be dried as necessary. The application and drying may be performed by the various application methods and coating film drying methods described above for the preparation of the photosensitive resin film. When a photosensitive resin film is used, the photosensitive layer can be formed by a lamination method using a laminator or the like.

[0094] The thickness of the photosensitive layer provided on the substrate varies depending on the forming method (coating method or lamination method), the solid content concentration and viscosity of the photosensitive resin composition, etc., but the lower limit of the thickness of the photosensitive layer after drying 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, and when used for electronic parts, 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. In the method for producing a cured product of the present embodiment, a photosensitive layer is formed using the photosensitive resin composition of the present 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, it is possible to repeat coating (and drying, if necessary) or lamination several times until a desired thickness is obtained, instead of forming the layer by one coating (and drying, if necessary) or lamination.

[0095] (Exposure process) In the exposure step, the photosensitive layer provided on the substrate in the photosensitive layer forming step is at least partially irradiated with active light as necessary, and the exposed portion is photocured to form a cured portion. When irradiating with active light, the photosensitive layer may be irradiated with active light through a mask having a desired pattern, or may be irradiated with active light by a direct writing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method. In order to improve pattern formability, post-exposure baking (PEB) may be performed after exposure using a hot plate, a 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.

[0096] The exposure dose of actinic radiation is 10 to 2,000 mJ / cm 2 , 100~1,500mJ / cm 2 , or 300 to 1,000 mJ / cm 2 Examples of the actinic rays used include ultraviolet rays, visible rays, electron beams, X-rays, etc. Examples of the light source that can be used include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, halogen lamps, etc.

[0097] (Removal process) In the removal step, at least a part of the portion (unexposed portion) other than the cured portion of the photosensitive layer formed in the exposure step is removed to form a resin pattern. The removal of the unexposed portion may be performed, for example, using a developer such as an organic solvent. 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 kinds. In addition, various additives that are usually used may be added to the organic solvent used as the developer.

[0098] 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.

[0099] (Heating process) The heating step is a step that is adopted as necessary, and is a step in which the resin pattern formed in the removing step is heat-treated to form a cured product. The heating step is preferably carried out for 1 to 2 hours while the heating temperature is selected and gradually increased. The heating temperature may be appropriately selected from 120 to 240°C, 140 to 230°C, or 150 to 220°C. In addition, when the temperature is gradually increased, for example, the heating step may be performed at least at about 120°C or about 160°C for 10 to 50 minutes or 20 to 40 minutes, and then at about 220°C for 30 to 100 minutes or 50 to 70 minutes.

[0100] The thickness of the obtained resin pattern is the same as the thickness of the photosensitive layer after drying, and 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 as a lower limit, and may be appropriately selected from 500 μm or less, 300 μm or less, or 250 μm or less as an upper limit. The thickness of the resin pattern may be appropriately selected from the above range depending on the application, and when used for electronic parts, etc., the lower limit may be appropriately selected from 70 μm or more, more than 100 μm, or 150 μm or more as a lower limit, and may be appropriately selected from 500 μm or less, 300 μm or less, or 250 μm or less as an upper limit.

[0101] [Laminates and electronic components] The laminate of the present embodiment includes a cured product of the photosensitive resin composition of the present embodiment, and examples of the laminate include a cured product on various supports such as a substrate used in the above-mentioned method for producing a cured product, a carrier film of a photosensitive resin film, etc. The cured product of the photosensitive resin composition of the present embodiment can be formed, for example, by the above-mentioned method for producing a cured product of the present embodiment.

[0102] The thickness of the cured product in the laminate of this embodiment may be appropriately selected from 10 μm or more, 30 μm or more, 50 μm or more, 70 μm or more, 100 μm or more, more than 100 μm, or 150 μm or more as a lower limit, and 500 μm or less, 300 μm or less, or 250 μm or less as an upper limit. The thickness of the cured product may be appropriately selected from the above range depending on the application, and when used for electronic parts, etc., the lower limit may be appropriately selected from 70 μm or more, more than 100 μm, or 150 μm or more as a lower limit, and 500 μm or less, 300 μm or less, or 250 μm or less as an upper limit.

[0103] The cured product provided on the substrate obtained by the above-mentioned method for producing a cured product uses the photosensitive resin composition of this embodiment, and since excellent pattern formability can be obtained even with a thick photosensitive layer of, for example, 70 μm or more, it is possible to meet the demand for electronic circuit boards that require a thick cured product to be provided on the substrate in a finer pattern in accordance with the trend toward miniaturization and high performance of electronic devices. In addition, for example, in the plating process in the production of electronic circuit boards, a reduction in yield due to short circuits between wirings can be suppressed by using the cured product formed by the photosensitive resin composition of this embodiment as an insulating film. Therefore, the laminate of this embodiment is used as an electronic component such as an electronic circuit board in a mobile terminal such as a mobile phone. EXAMPLES

[0104] Hereinafter, the objects and advantages of the present embodiment will be described more specifically based on examples and comparative examples, but the present embodiment is not limited to the following examples.

[0105] (Synthesis Example 1: Synthesis of Resin P-1) 635 g of methyl methacrylate, 30 g of butyl acrylate, 245 g of butyl methacrylate, and 75 g of 2-hydroxyethyl methacrylate were mixed to obtain a monomer mixture. 0.9 g of 2,2'-azodiisobutyronitrile was dissolved in the obtained monomer mixture to obtain a mixed liquid. 1030 g of propylene glycol monomethyl ether acetate was added as a solvent to a 1 L autoclave equipped with a stirrer and a condenser, and the above mixed liquid was added while stirring. Next, the stirring speed was 100 min. -1 The mixture was then polymerized at 90°C for 6 hours under a nitrogen atmosphere to obtain an acrylic resin solution (Resin P-1). The weight-average molecular weight of the obtained acrylic resin was 43,370. Here, 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 the 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) Detector: RI detector Column temperature: 40℃ Eluent:THF Flow rate: 1ml / min Standard material: polystyrene

[0106] (Examples 1 to 5, Comparative Examples 1 to 8) The compositions were mixed according to the formulation shown in Table 1 (the values ​​in the table indicate the parts by mass of each material, and in the case of a solution, the values ​​indicate the parts by mass converted into solid content), and kneaded using a three-roll mill to prepare a photosensitive resin composition. N,N-Dimethylacetamide was added so that the solid content concentration became 60% by mass, and a photosensitive resin composition was obtained.

[0107] [Table 1]

[0108] Details of each material in Table 1 are as follows: ·UN-952: Urethane acrylate (manufactured by Negami Chemical Industries, Ltd., product name, number of functional groups: 10, weight average molecular weight: 9,000, a reaction product of an acrylate having a hydroxyl group and a diisocyanate compound, and has an acryloyl group (photopolymerizable functional group), a urethane bond (carbon-nitrogen bond), a chain hydrocarbon skeleton, and an alicyclic hydrocarbon skeleton in the molecule.) Resin P-1: Acrylic resin prepared in Synthesis Example 1 (weight average molecular weight: 43,370) Z250: Cyclomer P (ACA) Z250 (trade name, manufactured by Daicel Allnex Co., Ltd., has an acryloyl group (photopolymerizable functional group) in the molecule but does not have a carbon-nitrogen bond.) TMCH-5R: Urethane acrylate (manufactured by Hitachi Chemical Co., Ltd., product name, number of functional groups: 2, weight average molecular weight: 950, contains an acryloyl group (photopolymerizable functional group), a urethane bond (carbon-nitrogen bond), a chain hydrocarbon skeleton, and an alicyclic hydrocarbon skeleton in the molecule.) FA-324A: EO modified bisphenol A diacrylate (Hitachi Chemical Co., Ltd., product name, number of functional groups: 2, weight average molecular weight: 512) FA-7220M: Amide bond-containing methacrylate (Hitachi Chemical Co., Ltd., product name) I-819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (BASF, trade name) Percumyl D: Dicumyl peroxide (trade name, manufactured by NOF Corp.) KBM-503: Methacryloxypropyltrimethoxysilane (product name, manufactured by Shin-Etsu Chemical Co., Ltd.) AY43-031: Silane coupling agent (product name, manufactured by Dow Corning Toray Co., Ltd.)

[0109] Next, the photosensitive resin composition obtained above was used to carry out various evaluations under the conditions shown below. The evaluation results are shown in Table 2.

[0110] [Preparation of photosensitive resin film] A 50 μm-thick polyethylene terephthalate film (product name: A-4100, manufactured by Teijin Limited) was used as a carrier film, and the resin compositions of the Examples and Comparative Examples were uniformly applied onto the carrier film so that the thickness after drying would be 50 μm. Next, the resin compositions were dried by heating at 100° C. for 15 minutes using a hot air convection dryer to form a photosensitive layer, and a photosensitive resin film having the carrier film and the photosensitive layer was produced.

[0111] [Evaluation of pattern formability] A photosensitive resin film was laminated on a glass epoxy substrate (obtained by etching copper from MCL-E-679F (trade name, manufactured by Hitachi Chemical Co., Ltd.)) with the photosensitive layer of the film facing the glass epoxy substrate, and the carrier film was removed. The lamination was performed at 60°C using a laminator. Next, the photosensitive resin film was laminated again on the photosensitive layer by the above-mentioned method, 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. A resolution evaluation mask (details will be described later) was placed on the carrier film of the laminate, and an i-line filter (product name: HB-0365, manufactured by Asahi Spectroscopy Co., Ltd.) was then placed on top, followed by exposure using a high-precision parallel exposure machine (manufactured by Mikasa Co., Ltd.). At this time, the laminate was divided into three regions, and the three regions were exposed to different exposure doses (600, 1,000, and 1,400 mJ / cm2). 2 The sample was exposed to light with a wavelength of 365 nm (i-line) at a wavelength of 100 nm. After exposure, the sample was post-exposure baked on a hot plate at 90° C. for 1 minute. Thereafter, the carrier film was removed, and the pattern was developed by immersing in a developer (cyclopentanone) for 20 minutes. The developed pattern was dried at room temperature for 30 minutes, and observed using a metal microscope to evaluate pattern formability. The evaluation was performed according to the following criteria. Here, "formable" means that the unexposed portion was completely removed, and there were no defects such as collapse in the line portion (exposed portion). Table 2 shows the evaluation results using the photosensitive resin compositions of Examples 1 to 5, and Table 3 shows the evaluation results using the resin compositions of Comparative Examples 1 to 7. A: 6-1 to 6-8, 7-1 to 7-6, and 8-1 to 8-5 were possible to form. B: 7-7 to 7-8 and 8-6 to 8-8 could be formed. C: A pattern with a line width of 30 μm or less could not be formed, or the photosensitive layer peeled off after development.

[0112] Here, the resolution evaluation mask is a mask having a predetermined line pitch and line width, and has an L-shaped and linear pattern shown in FIG. 1 (the unit of values ​​in FIG. 1 is μm). FIG. 1 is a schematic diagram showing a resolution evaluation mask having a line pitch of 200 μm and a line width of 30 μm among the resolution evaluation masks. In this embodiment, a mask having several combinations of line pitch and line width is used, and is represented by AB (A is a value corresponding to the line pitch, and B is a value corresponding to the line width) according to the line pitch and line width, and A is 6, 7, and 8 for line pitches of 100, 150, and 200 μm, respectively, and B is 1 to 8 for line widths of 5, 8, 10, 12, 15, 20, 25, and 30 μm, respectively (see Table 4). For example, a pattern having a line pitch of 100 μm and a line width of 5 μm is called 6-1, and a pattern having a line pitch of 200 μm and a line width of 30 μm as shown in Fig. 1 is called 8-8. It can be said that the smaller the values ​​of A and B, the more difficult it is to form a pattern. In other words, a photosensitive resin composition that can form a pattern even using a mask having small values ​​of A and B can be said to have better pattern formability.

[0113] [Table 2]

[0114] [Table 3]

[0115] [Table 4]

[0116] From Table 2, it was confirmed that the photosensitive resin compositions of this embodiment of Examples 1 to 5 had excellent pattern formability. In contrast, when the resin compositions of Comparative Examples 1 and 2, which did not contain the component (B), were used, the exposure dose of 600 (mJ / cm 2 ), even a pattern could not be formed, and when the resin compositions of Comparative Examples 3 and 4 not containing the components (A) and (B) were used, the exposure dose was 1400 (mJ / cm 2 When the resin compositions of Comparative Examples 5 to 7, which contained the component (B) but not the component (A), were used, the resin composition of Comparative Example 6 was used, and the exposure dose was 1400 (mJ / cm 2 ) a pattern could be formed, but no pattern could be formed in the other cases. Furthermore, when the resin composition of Comparative Example 8, which contained the component (A) but did not contain a low molecular weight compound having an acryloyl group as a photopolymerizable functional group, was used, no pattern could be formed at all.

[0117] [Measurement of absorbance] For the photosensitive resin film obtained in the above [Preparation of photosensitive resin film], the absorbance of light with a wavelength of 365 nm was measured when the photosensitive layer had a thickness (thickness after drying) of 50 μm. Specifically, the absorbance (Abs) at a wavelength of 365 nm was measured using an ultraviolet-visible spectrophotometer (product name: U-3310 Spectrophotometer, manufactured by Hitachi High-Technologies Corporation). A polyethylene terephthalate (PET) film alone was used as a reference. The measurement results are shown in Table 5.

[0118] [Table 5]

[0119] From the results in Table 5, it was confirmed that the photosensitive resin compositions of this embodiment in Examples 1 to 5 had small absorbances of 0.35 or less, 0.3 or less, or 0.2 or less for light with a wavelength of 365 nm when the photosensitive layer had a thickness (thickness after drying) of 50 μm, and light passed through to the bottom of the photosensitive layer (the surface of the photosensitive layer facing the substrate), thereby exhibiting excellent pattern formability. On the other hand, the resin compositions of Comparative Examples 3 to 7 had absorbances greater than 0.36.

[0120] [Evaluation of insulation reliability] The photosensitive resin films having a thickness of 50 μm obtained in Examples 1 to 5 were laminated on the interdigital copper electrodes of a TEG (Test Element Group) (WALTZ-KIT EM0101JY (product name, manufactured by WALTZ, L / S=40 μm / 15 μm)) which was an evaluation device, with the photosensitive layer facing the interdigital copper electrodes. The lamination was performed at 60° C. using a laminator. Next, 1000 mJ / cm 2 was applied with i-line. 2 After the exposure, the sample was heated on a hot plate at 90°C for 1 minute, and then the carrier film was removed. The sample was then heated in an oven at 200°C for 1 hour, and then cooled to room temperature to obtain a measurement sample. Lead wires were attached to the TEG electrodes of the obtained measurement samples with solder, and a high-temperature, high-humidity bias test was performed (voltage: 5 V (DC), test time: 100 hours, 85° C., 85% RH (using a high-temperature, high-humidity chamber (manufactured by ESPEC))). As a result, the measurement samples obtained using the photosensitive resin films of Examples 1 to 5 all had a resistance value of 1.0×10 7 The above was maintained, and it was confirmed that the insulation reliability was excellent.

[0121] According to the present disclosure, the following embodiments are provided. [1] A photosensitive resin composition comprising: (A) component: a high molecular weight material having a photopolymerizable functional group and a carbon-nitrogen bond; (B) component: a low molecular weight material having a photopolymerizable functional group and a carbon-nitrogen bond; and (C) component: a photopolymerization initiator, wherein the (B) component contains a low molecular weight material having an acryloyl group as the photopolymerizable functional group. [2] The photosensitive resin composition according to [1], wherein the component (A) contains a polymer having a (meth)acryloyl group as a photopolymerizable functional group. [3] The photosensitive resin composition according to [1] or [2], wherein the component (A) contains a polymer having a urethane bond as a carbon-nitrogen bond. [4] The photosensitive resin composition according to any one of [1] to [3], 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. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the component (B) contains a low molecular weight compound having a urethane bond as a carbon-nitrogen bond. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the component (C) contains an acylphosphine oxide-based photopolymerization initiator. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the contents of the component (A), the component (B), and the component (C) are 10 to 95 mass%, 3 to 70 mass%, and 0.05 to 20 mass%, respectively, based on the total solid content in the photosensitive resin composition. [8] The photosensitive resin composition according to any one of [1] to [7], further comprising a component (D): a thermal radical polymerization initiator. [9] The photosensitive resin composition according to any one of [1] to [8], which has an absorbance of 0.35 or less for light having a wavelength of 365 nm at a thickness of 50 μm.

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

[11] 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 [9] or the photosensitive resin film according to

[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

[11] , further comprising a step of heat treating the resin pattern.

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

[12] , wherein the resin pattern has a thickness of 70 μm or more and 300 μm or less.

[14] A laminate comprising a cured product of the photosensitive resin composition according to any one of [1] to [9].

[15] The laminate according to

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

[16] An electronic part comprising a cured product of the photosensitive resin composition according to any one of [1] to [9].

Claims

1. Component (A): a high molecular weight compound having a photopolymerizable functional group and a carbon-nitrogen bond and a weight average molecular weight of 3,000 to 30,000; Component (B): a low molecular weight substance having a photopolymerizable functional group and a carbon-nitrogen bond and a weight average molecular weight of less than 2,000; (C) component: a photopolymerization initiator; the component (A) contains a polymer having a (meth)acryloyl group as a photopolymerizable functional group, the total number of photopolymerizable functional groups contained in the polymer is 4 to 15, the component (B) contains a low-molecular-weight compound having an acryloyl group as a photopolymerizable functional group and a urethane bond as a carbon-nitrogen bond, the content of the component (B) is 25 to 90 mass% based on the total solid content of the component (A), a photosensitive resin composition in which the content of the component (C) is 0.05 to 20 mass % based on the total amount of solids in the photosensitive resin composition (provided that: an alkali-soluble transparent resin composition comprising (A) a carboxyl group-containing photosensitive resin, (B) an α-hydroxyketone-based photopolymerization initiator, (C) a diluent, and (D) an epoxy compound; a photosensitive resin composition comprising (A) a carboxyl group-containing resin, (B) a urethane (meth)acrylate having 6 or more functional groups, (C) a photopolymerization initiator, and (D) titanium oxide; a photosensitive resin composition in which at least (A) a radical polymerizable group is present in the molecule; (B) a urethane bond- and carboxyl group-containing resin that is substantially free of a radically polymerizable group, (C) a radically polymerizable compound, (D) a reactive group-containing compound that is reactive with a carboxyl group and substantially free of an aromatic ring in the molecule, (E) a photopolymerization initiator, (F) rutile-type titanium oxide, and (G) a phosphinate, and is substantially free of a silicon-containing organic compound; and a curable composition containing silica particles having an ethylenically unsaturated group.

2. Component (A): a high molecular weight substance having a photopolymerizable functional group and a carbon-nitrogen bond and a weight average molecular weight of 2,000 to 30,000; Component (B): a low molecular weight substance having a photopolymerizable functional group and a carbon-nitrogen bond and a weight average molecular weight of less than 2,000; (C) component: a photopolymerization initiator; the component (A) contains a polymer having a (meth)acryloyl group as a photopolymerizable functional group, the total number of photopolymerizable functional groups contained in the polymer is 4 to 15, the content of the component (A) is 10% by mass or more based on the total amount of solids in the photosensitive resin composition, the component (B) contains a low-molecular-weight compound having an acryloyl group as a photopolymerizable functional group and a urethane bond as a carbon-nitrogen bond, the content of the component (B) is 25 to 90 mass% based on the total solid content of the component (A), A photosensitive resin composition in which the content of the component (C) is 0.05 to 20 mass% based on the total solid content in the photosensitive resin composition (however, this excludes: a photosensitive resin composition comprising (A) a carboxyl group-containing resin, (B) a urethane (meth)acrylate having 6 or more functional groups, (C) a photopolymerization initiator, and (D) titanium oxide; a white photosensitive resin composition comprising at least (A) a urethane bond- and carboxyl group-containing resin that is substantially free of radically polymerizable groups in the molecule, (B) a urethane bond- and carboxyl group-containing resin that contains radically polymerizable groups in the molecule, (C) a radically polymerizable compound, (D) a reactive group-containing compound that is reactive with carboxyl groups and substantially does not contain an aromatic ring in the molecule, (E) a photopolymerization initiator, (F) rutile titanium oxide, and (G) a phosphinate, and that is substantially free of silicon-containing organic compounds; and a curable composition containing silica particles having ethylenically unsaturated groups).

3. A photosensitive resin composition according to claim 1 or 2, wherein the component (A) contains a polymer having a urethane bond as a carbon-nitrogen bond.

4. A photosensitive resin composition described in any one of claims 1 to 3, 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.

5. A photosensitive resin composition described in any one of claims 1 to 4, wherein the component (C) contains an acylphosphine oxide-based photopolymerization initiator.

6. A photosensitive resin composition described in any one of claims 1 to 5, wherein the contents of the (A) component and the (B) component are 10 to 95 mass% and 3 to 70 mass%, respectively, based on the total solid content in the photosensitive resin composition.

7. A photosensitive resin composition described in any one of claims 1 to 6, further containing component (D): a thermal radical polymerization initiator.

8. A photosensitive resin composition described in any one of claims 1 to 7, which has an absorbance of 0.35 or less for light with a wavelength of 365 nm at a thickness of 50 μm.

9. A photosensitive resin film having a photosensitive layer using the photosensitive resin composition described in any one of claims 1 to 8.

10. A method for producing a cured product, comprising the steps of providing a photosensitive layer on a substrate using the photosensitive resin composition described in any one of claims 1 to 8, or the photosensitive resin film described in claim 9, irradiating at least a portion of the photosensitive layer with active light to form a photocured portion, and removing at least a portion of the photosensitive layer other than the photocured portion to form a resin pattern.

11. A method for producing a cured product as described in claim 10, further comprising a step of heat-treating the resin pattern.

12. A method for producing a cured product as described in Claim 11, wherein the thickness of the resin pattern is 70 μm or more and 300 μm or less.

13. A laminate comprising a cured product of the photosensitive resin composition described in any one of claims 1 to 8.

14. A laminate as described in claim 13, wherein the thickness of the cured product is 70 μm or more and 300 μm or less.

15. An electronic component comprising a cured product of the photosensitive resin composition described in any one of claims 1 to 8.

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