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

Abstract

The invention relates to a photosensitive resin composition, a photosensitive resin film, a method for producing a cured product, a laminate, and an electronic device. A photosensitive resin composition according to the present invention contains: component (A): a high molecular weight body having a photopolymerizable functional group and a carbon-nitrogen bond; component (B): a low molecular weight body having a photopolymerizable functional group; component (C): a photopolymerization initiator; and component (D): a triazole compound.

Description

[0001] This application is a divisional application of Chinese application No. 201980097779.4, whose application date is July 10, 2019 and whose invention name is “Photosensitive resin composition, photosensitive resin film, method for producing cured product, laminate and electronic device”. Technical Field

[0002] The present invention relates to a photosensitive resin composition, a photosensitive resin film, a method for producing a cured product, a laminate and an electronic device. Background Art

[0003] In the field of manufacturing semiconductor integrated circuits (LSI) or wiring boards, photosensitive materials are used as photoresists for making conductor patterns. For example, in the manufacture of wiring boards, a photoresist is formed using a photosensitive resin composition, and then a conductor pattern, a metal column, etc. are formed by plating. More specifically, a photosensitive layer is formed on a support (substrate) using a photosensitive resin composition, etc., and the photosensitive layer is exposed through a prescribed mask pattern, and then a development process is performed to selectively remove (peel off) the portion where the conductor pattern, metal column, etc. are formed, thereby forming a photoresist pattern (photoresist). Then, in the removed portion, a conductor such as copper is formed by plating, and then the photoresist pattern is removed, thereby being able to manufacture a wiring board having a conductor pattern, a metal column, etc.

[0004] In the past, thick conductor patterns and metal pillars were produced by growing a metal plating layer after removing the photoresist pattern. In order to meet such requirements, for example, as a thick film photosensitive photoresist, a photoresist with a photosensitive layer thickness of about 30 μm (even if thick, it is about 65 μm) is used (see Patent Documents 1 and 2).

[0005] In recent years, attempts have been made to further improve performance by performing plating while selectively destroying the layer in the direction of plating growth in a metal ion-diluted layer, thereby forming a thick conductor layer of about 150 μm in thickness (see Patent Document 3).

[0006] Previous technical literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2015-034926

[0009] Patent Document 2: Japanese Patent Application Publication No. 2014-074774

[0010] Patent Document 3: Japanese Patent Application Publication No. 2014-080674 Summary of the invention

[0011] Technical issues to be solved by the invention

[0012] The existing thick film photosensitive photoresist has the following situation: for example, when it is required to form a thick photosensitive layer of more than 70 μm, it is difficult for light to reach the bottom and the pattern shape is deteriorated. In addition, in the method described in Patent Document 3, it is difficult to form a stable and excellent pattern because the metal ion thin layer is locally destroyed while plating. Therefore, a photosensitive photoresist is required that has excellent pattern formation even when a photosensitive layer of 70 μm or 150 μm or more (thickness in the direction perpendicular to the substrate) thicker than the existing thickness is formed.

[0013] In addition, copper wiring is mounted on the substrate of electronic devices such as inductors. When a photoresist pattern is formed on a substrate having such copper wiring, there is a problem that development residues are easily generated on the copper surface after development. In particular, when the photosensitive layer is thickened, there is a tendency for the above-mentioned development residue problem to become more obvious. Therefore, there is a need for such a photosensitive layer that suppresses the generation of development residues on the copper surface.

[0014] Furthermore, when a photoresist pattern is formed on a substrate having copper wiring, the photosensitive layer is required to achieve excellent pattern formation on both surfaces of the portion where the copper wiring is formed and the portion where the copper wiring is not formed. Furthermore, when a photosensitive layer is formed on a substrate having copper wiring and is exposed, it is necessary to expose under the same exposure conditions without distinguishing between the portion where the copper wiring is formed and the portion where the copper wiring is not formed. If the exposure conditions that can form a high-resolution photoresist pattern are different (there is a mismatch) at the portion where the copper wiring is formed and the portion where the copper wiring is not formed, the problem of not being able to form a uniform photoresist pattern will arise. Therefore, it is further required that the photosensitive layer achieve excellent pattern formation under the same exposure conditions on both surfaces of the portion where the copper wiring is formed and the portion where the copper wiring is not formed.

[0015] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive resin composition, a photosensitive resin film using the photosensitive resin composition, a method for producing a cured product, a laminate, and an electronic device (hereinafter sometimes referred to as "photosensitive resin composition, etc."). The photosensitive resin composition can suppress the generation of development residues on a copper surface and can achieve excellent pattern forming properties under the same exposure conditions on both surfaces of a portion having a copper surface and a portion not having a copper surface of a substrate.

[0016] Means for solving technical problems

[0017] The present inventors have conducted intensive studies to solve the above-mentioned problems, and have found that the problems can be solved by a photosensitive resin composition having the following structure. The present invention provides the following photosensitive resin composition.

[0018] [1] A photosensitive resin composition comprising:

[0019] (A) component: a high molecular weight body having a photopolymerizable functional group and a carbon-nitrogen bond;

[0020] (B) component: a low molecular weight body having a photopolymerizable functional group;

[0021] (C) component: a photopolymerization initiator; and

[0022] Component (D): triazole compound.

[0023] [2] The photosensitive resin composition according to [1] above, wherein

[0024] The component (D) includes a benzotriazole compound.

[0025] [3] The photosensitive resin composition according to [1] or [2] above, wherein

[0026] The content of the component (D) is 0.1 to 10% by mass based on the total solid content of the photosensitive resin composition.

[0027] [4] The photosensitive resin composition according to any one of [1] to [3] above, wherein

[0028] The component (A) contains a high molecular weight body having a (meth)acryloyl group as a photopolymerizable functional group.

[0029] [5] The photosensitive resin composition according to any one of [1] to [4] above

[0030] The component (A) includes a high molecular weight body having a urethane bond as a carbon-nitrogen bond.

[0031] [6] The photosensitive resin composition according to any one of [1] to [5] above, wherein

[0032] The component (A) includes a high molecular weight body having 6 or more ethylenically unsaturated groups as photopolymerizable functional groups and having a weight average molecular weight of 2,500 or more.

[0033] [7] The photosensitive resin composition according to any one of [1] to [6] above, wherein

[0034] The component (A) comprises a high molecular weight body having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton.

[0035] [8] The photosensitive resin composition according to any one of [1] to [7] above, wherein

[0036] The component (B) includes at least one selected from the group consisting of a low molecular weight body having a urethane bond, a low molecular weight body having an isocyanurate ring, and a low molecular weight body having an alicyclic skeleton.

[0037] [9] The photosensitive resin composition according to any one of [1] to [7] above, wherein

[0038] The component (B) includes a low molecular weight body having at least one (meth)acryloyl group and a urethane bond.

[0039]

[10] The photosensitive resin composition according to any one of [1] to [9] above, wherein

[0040] The component (C) includes a compound represented by the following general formula (C1) or a compound represented by the following general formula (C2).

[0041]

[0042] [R C1 , R C2 and R C3 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R C4 and R C5 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. C1 ~R C5 Each may have a substituent.]

[0043]

[0044] [R C6 represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an amino group, and R C7 and R C8 R each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. C7 With R C8 They may be bonded to each other to form a ring structure having 3 to 16 carbon atoms. C6 ~R C8 Each of them may have a substituent, and the substituents of the amino group having a substituent may be bonded to each other to form a cyclic structure having 3 to 12 carbon atoms. C9 Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an organic group having 1 to 10 carbon atoms which may contain one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom.]

[0045]

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

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

[0046]

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

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

[0047]

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

[12] .

[0048]

[14] A method for producing a solidified product, comprising:

[0049] A step of providing a photosensitive layer on a substrate using the photosensitive resin composition described in any one of [1] to

[12] or the photosensitive resin film described in

[13] ;

[0050] A step of irradiating at least a portion of the photosensitive layer with active light to form a photocured portion; and

[0051] A step of removing at least a portion of the photosensitive layer except for the photocured portion to form a resin pattern.

[0052]

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

[14] , further comprising the step of heating the resin pattern.

[0053]

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

[14] or

[15] , wherein:

[0054] The resin pattern has a thickness of 70 μm or more and 300 μm or less.

[0055]

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

[14] to

[16] , further comprising:

[0056] A step of providing a photosensitive layer on a substrate and then heating the photosensitive layer.

[0057]

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

[12] above.

[0058]

[19] The laminate according to

[18] above, wherein

[0059] The thickness of the cured product is 70 μm or more and 300 μm or less.

[0060]

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

[12] above.

[0061] Effects of the Invention

[0062] According to the present invention, a photosensitive resin composition can be provided, which can suppress the generation of development residues on a copper surface and can achieve excellent patterning properties under the same exposure conditions on both surfaces of a portion having a copper surface and a portion not having a copper surface of a substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] Figure 1 This is a diagram showing the pattern shape of imaging data used when exposure is performed by a direct imaging exposure device in the example. DETAILED DESCRIPTION

[0064] Hereinafter, the present invention will be described in detail.

[0065] In this specification, the numerical range represented by "to" refers to a range that includes the numerical values ​​recorded before and after "to" as the minimum value and the maximum value, respectively. In addition, in the numerical range recorded in stages in this specification, the upper limit or lower limit of the numerical range of a certain stage can be replaced by the upper limit or lower limit of the numerical range of another stage. In the numerical range recorded in this specification, the upper limit or lower limit of the numerical range can be replaced by the value shown in the examples.

[0066] In the present specification, "(meth)acrylic acid" means at least one of "acrylic acid" and its corresponding "methacrylic acid", and the same applies to other similar expressions such as (meth)acrylate.

[0067] In this specification, "solid content" refers to the non-volatile components contained in the photosensitive resin composition except for volatile substances such as water and solvents, and means the components that do not volatilize and remain when the resin composition is dried, and includes components that are liquid, syrupy and waxy at room temperature of about 25°C.

[0068] [Photosensitive resin composition]

[0069] The photosensitive resin composition involved in an embodiment of the present invention (hereinafter sometimes referred to as the present embodiment) contains (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, (C) component: a photopolymerization initiator, and (D) component: a triazole compound.

[0070] According to the photosensitive resin composition of the present embodiment, by containing the (A) component having the above-mentioned specific structure: a high molecular weight body, the (B) component having the above-mentioned specific structure: a low molecular weight body, the (C) component: a photopolymerization initiator, and the (D) component: a triazole compound, it is possible to suppress the generation of development residues on the copper surface and to achieve excellent pattern formation under the same exposure conditions on both surfaces of the substrate having a copper surface and a portion without a copper surface. The present inventors speculate that the reason for obtaining such a result is as follows. That is, the triazole compound as the (D) component has the property that the nitrogen atom in the triazole skeleton is easily coordinated with the copper surface of the substrate. Due to this high coordination ability to the copper surface, the triazole compound is easily biased near the copper surface. As a result, a triazole compound layer in which the triazole compound exists in a high concentration is formed on the surface of the side in contact with the copper surface of the photosensitive layer formed using the photosensitive resin composition. Moreover, it is believed that due to the presence of the triazole compound layer, the chance of other organic substances constituting the photosensitive resin composition contacting the copper surface is reduced, thereby greatly suppressing the situation where other organic substances adhere to the copper surface and generate development residues. Moreover, since the triazole compound has excellent adhesion to the copper surface and can be easily removed by development, and does not damage the curability of the photosensitive resin composition, even when a thick film photosensitive layer is formed on the copper surface and a photoresist pattern with a fine line width and a narrow line spacing is formed, excellent pattern formation can be achieved. In addition, it is believed that under conditions such as high exposure, when the concentration of free radicals in the reaction system is high, the hydrogen of the triazole compound is removed and acts as an inhibitor, and the process margin is increased, and pattern formation can be achieved under the same exposure conditions on both substrates with copper surfaces and substrates without copper surfaces. From the above content, it can be seen that according to the photosensitive resin composition of this embodiment, even when a thick film (for example, a thickness of 70 μm or more) of the photosensitive layer is formed, excellent pattern formation can be achieved on both surfaces of the substrate with a copper surface and a substrate without a copper surface under the same exposure conditions, and the generation of development residues on the copper surface can be suppressed.

[0071] Hereinafter, each component constituting the photosensitive resin composition according to the present embodiment will be described.

[0072] <(A) Component: High molecular weight body>

[0073] The photosensitive resin composition of the present embodiment contains a high molecular weight having a photopolymerizable functional group and a carbon-nitrogen bond as component (A). "High molecular weight" refers to a compound having a weight average molecular weight (Mw) of 2,500 or more. In addition, in this specification, the value of the weight average molecular weight (Mw) is a value obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) and converted according to standard polystyrene.

[0074] As the photopolymerizable functional group contained in the component (A), for example, there can be mentioned a (meth)acryloyl group; alkenyl groups such as vinyl and allyl groups; and other ethylenically unsaturated groups. From the viewpoint of improving pattern formation, the component (A) may contain a high molecular weight body having a (meth)acryloyl group as a photopolymerizable functional group, and may further contain a high molecular weight body having a carbamate bond as a carbon-nitrogen bond. As the high molecular weight body having a (meth)acryloyl group, for example, there can be mentioned a (meth)acrylate, and as the high molecular weight body having a carbamate bond as a carbon-nitrogen bond, for example, there can be mentioned a (meth)acrylate having a carbamate bond (hereinafter, sometimes referred to as "carbamate (meth)acrylate").

[0075] The component (A) has at least one such photopolymerizable functional group and at least one carbon-nitrogen bond. The total number of photopolymerizable functional groups (functional group number) contained in the high molecular weight body of the component (A) in one molecule can be appropriately selected from 2 to 30, 2 to 24, 2 to 20 or 2 to 15 from the viewpoint of improving pattern formation and heat resistance, and can be appropriately selected from 6 to 12, 6 to 10 or 6 to 8 from the viewpoint of stabilizing the physical properties and characteristics of the obtained cured product and reducing the viscosity.

[0076] In addition, in this specification, "stickiness" refers to the surface adhesiveness of the photosensitive layer formed by the photosensitive resin composition (when the liquid photosensitive resin composition is directly applied to the substrate, it refers to the surface adhesiveness of the coating film after application and drying). If the viscosity is high, there is a possibility that the manufacturing equipment is easily contaminated, the manufacturing is interrupted for cleaning the equipment, or defects occur in the photosensitive layer. Therefore, it is necessary to reduce the viscosity.

[0077] Furthermore, the component (A) may contain a high molecular weight body having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton.

[0078] Examples of high molecular weight urethane (meth)acrylates include reaction products obtained by reacting a terminal isocyanate group of an addition polymer of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound with a (meth)acrylate having a hydroxyl group.

[0079] Specific examples of the isocyanate compound having at least two isocyanate groups in one molecule include aliphatic diisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, and dodecamethylene diisocyanate; 1,3-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, 2,5-bis(isocyanatomethyl)norbornene, bis(4-isocyanatocyclohexyl)methane, 1,2-bis(4-isocyanatocyclohexyl)ethane, 2,2-bis(4-isocyanatocyclohexyl)propane, 2,2-bis(4-isocyanatocyclohexyl)propane, alicyclic diisocyanate compounds such as cyclohexyl (acid ato) hexafluoropropane, bicycloheptane triisocyanate, etc.; aromatic diisocyanate compounds such as 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, hydrogenated xylene diisocyanate, naphthalene-1,5-diisocyanate, etc.; diisocyanate compounds, and polymers such as uretdione dimers, isocyanurate types, and biuret trimers of these diisocyanate compounds, etc. These can be used alone or in combination of two or more, and the two or three isocyanate compounds constituting the polymer may be the same or different.

[0080] Among them, from the viewpoint of improving pattern forming properties, it is only necessary to appropriately select from alicyclic diisocyanate compounds and polymers of the diisocyanate compounds, and in particular, appropriately select from isophorone diisocyanate and isocyanurate type polymers (isocyanurate type polyisocyanates).

[0081] The above isocyanate compounds can be used alone or in combination of two or more.

[0082] Furthermore, as the diol compound, for example, there can be mentioned diol compounds having 1 to 20 carbon atoms, specifically, there can be mentioned straight-chain or branched saturated diol compounds such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, isopentanediol, hexanediol, nonanediol, decanediol, dodecanediol, dimethyldodecanediol, octadecanediol, etc.; straight-chain or branched unsaturated diol compounds such as butene diol, pentene diol, hexene diol, methylpentene diol, dimethylhexene diol, etc.; and diol compounds having an alicyclic skeleton such as various cyclohexane diols, various cyclohexanedimethanes, various tricyclodecanedimethylethanes, hydrogenated bisphenol A, hydrogenated bisphenol F, etc. Here, the above-mentioned saturated diol compounds and unsaturated diol compounds are also collectively referred to as diol compounds having a chain hydrocarbon skeleton.

[0083] The above diol compounds can be used alone or in combination of two or more.

[0084] 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, and more specifically, may be appropriately selected from ethylene glycol and octadecanediol, from the viewpoint of improving pattern formation and increasing the glass transition temperature (Tg) after polymerization to improve water resistance.

[0085] Furthermore, as the diol compound having an alicyclic skeleton, from the viewpoint of improving pattern forming properties and increasing the glass transition temperature (Tg) after polymerization to improve water resistance, it can be appropriately selected from diol compounds having an alicyclic skeleton having 5 to 20, 5 to 18, or 6 to 16 carbon atoms. More specifically, it can be appropriately selected from various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol, and various cyclohexanedimethanes such as 1,3-cyclohexanedimethane and 1,4-cyclohexanedimethane.

[0086] Examples of (meth)acrylates having a hydroxyl group include compounds having at least one hydroxyl group and at least one (meth)acryloyl group in one molecule. More specifically, examples include 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-naphthyloxy)propyl (meth)acrylate, and 2-hydroxy-3-(2-naphthyloxy)propyl (meth)acrylate, and ethoxylated and propoxylated versions thereof. , ethoxylated propoxylated products thereof and their caprolactone modified products; trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, di(2-(meth)acryloyloxyethyl)(2-hydroxyethyl)isocyanurate and other bifunctional (meth)acrylates, their ethoxylated products, their propoxylated products, their ethoxylated propoxylated products and their caprolactone modified products; cyclohexanedimethane type epoxy di(meth)acrylate, tricyclodecanedimethane type epoxy di(meth)acrylate, hydrogenated bisphenol A type epoxy di(meth)acrylate, hydrogenated bisphenol F type epoxy di(meth)acrylate ) 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, biphenyl type epoxy di(meth)acrylate, fluorene bisphenol type epoxy di(meth)acrylate, isocyanuric acid monoallyl type epoxy di(meth)acrylate and other bifunctional epoxy (meth)acrylates; ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, (Meth)acrylates having three or more functions, such as acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, their ethoxylates, their propoxylates, their ethoxylated propoxylates and their caprolactone modified bodies; epoxy (meth)acrylates having three or more functions, such as phenol novolac type epoxy (meth)acrylate, cresol novolac type epoxy poly(meth)acrylate, isocyanuric acid type epoxy tri(meth)acrylate; hydroxypropylated products such as trimethylolpropane tri(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate, etc.

[0087] These can be used alone or in combination of two or more.

[0088] Here, the ethoxylates, propoxylates, ethoxylated propoxylates and hydroxypropylated products of (meth)acrylates are obtained, for example, by using as raw materials a substance obtained by adding one or more ethylene oxide groups, propylene oxide groups, ethylene oxide groups and propylene oxide groups, and hydroxypropyl groups to an alcohol compound (or phenol compound) serving as a raw material for the above-mentioned (meth)acrylate.

[0089] The caprolactone-modified product can be obtained, for example, by using as a raw material an alcohol compound (or a phenol compound) used as a raw material of the (meth)acrylic acid ester modified with ε-caprolactone.

[0090] Examples of the reaction product obtained by reacting a terminal isocyanate group of an addition polymer of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound with a (meth)acrylate having a hydroxyl group include a reaction product having a structural unit represented by the following general formula (1).

[0091]

[0092] In the general formula (1), X 1 represents a divalent organic group having a chain hydrocarbon skeleton, an alicyclic skeleton or an aromatic ring skeleton, and Y 1 represents a divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton. 1 , Y 1 That is, as the (A) component, there can be mentioned a component having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton.

[0093] As X 1 The divalent organic group may be an organic group derived from an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, or an aromatic diisocyanate compound, which is exemplified as 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. 1 The divalent organic group represented by may be these residues themselves or may be a residue derived from an isocyanate compound derivative such as an addition polymer of the above-mentioned isocyanate compound and a diol compound.

[0094] From the viewpoint of improving pattern formation and improving the transparency, water resistance and moisture resistance of the resin composition in a balanced manner, X 1 It may be a divalent organic group having an alicyclic skeleton, and particularly, it may be a divalent organic group having an alicyclic skeleton which is a residue of isophorone diisocyanate represented by the following formula (2).

[0095]

[0096] As a 1 The divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton can be an organic group derived from a diol compound having a chain hydrocarbon skeleton and a diol compound having an alicyclic skeleton as exemplified by the above-mentioned diol compound, that is, a divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton which is a residue obtained by removing a hydroxyl group from the above-mentioned diol compound.

[0097] Among them, from the viewpoint of improving pattern formation and raising the glass transition temperature (Tg) after polymerization to improve water resistance, as the divalent organic group having a chain hydrocarbon skeleton, it is appropriate to select a residue obtained by removing a hydroxyl group from a saturated diol compound having 1 to 20, 2 to 16 or 2 to 14 carbon atoms, more specifically, it is appropriate to select a residue obtained by removing a hydroxyl group from ethylene glycol and octadecanediol. And from the same viewpoint, as the divalent organic group having an alicyclic skeleton, it is appropriate to select a residue obtained by removing a hydroxyl group from a diol compound having 5 to 20, 5 to 18 or 6 to 16 carbon atoms, more specifically, it is appropriate to select a residue obtained by removing a hydroxyl group from various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol, and various cyclohexanedimethanes such as 1,3-cyclohexanedimethane and 1,4-cyclohexanedimethane.

[0098] Specific examples of the reaction product obtained by reacting a terminal isocyanate group of an addition polymer of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound with a (meth)acrylate having a hydroxyl group include compounds represented by the following general formulas (3) and (4).

[0099]

[0100] In the general formulae (3) and (4), n1 and n2 each independently represent an integer of 3 to 20.

[0101] Examples of the reaction product when an isocyanurate trimer (isocyanurate triisocyanate), which is a trimer of diisocyanate, is used as the isocyanate compound include compounds represented by the following general formulae (5) and (6).

[0102]

[0103] In the general formulae (5) and (6), n3 and n4 each independently represent an integer of 2 to 20.

[0104] Examples of commercially available products containing urethane acrylates represented by the general formula (1) or (3) include UN-952 (number of functional groups: 10, Mw: 6,500 to 11,000), UN-953 (number of functional groups: 20, Mw: 14,000 to 40,000), UN-954 (number of functional groups: 6, Mw: 4,500), and H-219 (number of functional groups: 9, Mw: 25,000 to 50,000) (all trade names, manufactured by Negami Chemical Industrial Co., Ltd.). Examples of commercially available products containing urethane acrylates represented by the general formula (6) include UN-905 (number of functional groups: 1 to 5, Mw: 40,000 to 200,000) (trade name, manufactured by Negami Chemical Industrial Co., Ltd.).

[0105] Among these, UN-952 and UN-954 are preferred, and UN-954 is more preferred, from the viewpoint of pattern formability and photosensitivity.

[0106] In the above description, the number of functional groups and Mw in parentheses are the total number and weight average molecular weight of (meth)acryloyl groups contained in the urethane (meth)acrylate, respectively.

[0107] The total number of (meth)acryloyl groups contained in one molecule of the high molecular weight urethane (meth)acrylate (the number of photopolymerizable functional groups) may be appropriately selected from 2 to 30, 2 to 24, 2 to 20 or 2 to 15 from the viewpoint of improving pattern formation and heat resistance, and may be appropriately selected from 6 to 12, 6 to 10 or 6 to 8 from the viewpoint of stabilizing the physical properties and characteristics of the obtained cured product and reducing the viscosity.

[0108] If the number of photopolymerizable functional groups is 6 or more, the heat resistance and the rigidity of the cured product at high temperature can be improved together with the pattern forming property. On the other hand, if the number of photopolymerizable functional groups is 30 or less, the rigidity of the cured product is improved and the adhesion with the substrate, etc. is improved. In addition, a resin composition with an appropriate viscosity can be made, and the coating property is improved. When the coated resin composition is irradiated with light, the phenomenon that only the surface part is easy to be quickly photocured while the inside is not fully photocured can be suppressed, and excellent resolution can be obtained. Therefore, even in the case of forming a thick photosensitive layer, excellent pattern forming property can be obtained. In addition, after curing by performing at least one of photocuring and thermal curing, the residue of unreacted (meth) acryloyl groups can be further reduced, and the changes in the physical properties and characteristics of the obtained cured product can be further suppressed.

[0109] The weight average molecular weight of component (A) is 2,500 or more, and may be 3,000 or more from the viewpoint of improving the coating property and resolution of the resin composition, and may be 3,500 or more from the viewpoint of further improving the developability and compatibility. On the other hand, the upper limit of the weight average molecular weight may be 100,000 or less or 50,000 or less from the viewpoint of improving the coating property and resolution of the resin composition, and may be 40,000 or less or 20,000 or less from the viewpoint of further improving the developability and compatibility.

[0110] If the weight average molecular weight is 2,500 or more, the composition applied can be prevented from dripping when applied on a substrate, thereby obtaining excellent film forming properties. In addition, a thick photosensitive layer can be easily formed, and the problem of increased stress of the resin due to shrinkage during curing and decreased reliability can be prevented.

[0111] On the other hand, if the weight average molecular weight is 100,000 or less, the coating property is improved, a thick photosensitive layer is easily formed, and the pattern forming property is improved. In addition, since the solubility in the developer is also improved, it is possible to show excellent resolution. In addition, it is possible to obtain a cured product with improved transparency and excellent transmittance required as a transparent material.

[0112] According to the above, as one mode of the present embodiment, it can be a photosensitive resin composition, wherein the component (A) contains a high molecular weight having 6 to 30 ethylenically unsaturated groups as photopolymerizable functional groups and a weight average molecular weight of 2,500 to 100,000. In addition, it can also be a photosensitive resin composition as follows, wherein the component (A) contains a high molecular weight having 6 to 8 ethylenically unsaturated groups as photopolymerizable functional groups and a weight average molecular weight of 2,500 to 50,000.

[0113] The content of component (A) is appropriately selected from 10% by mass or more, 20% by mass or more, or 30% by mass or more based on the total solid content of the photosensitive resin composition. 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 formation can be obtained.

[0114] Taking into account the pattern forming properties and coating properties of the obtained resin composition and the physical properties and characteristics required for the cured product of the resin composition, the upper limit of the content of component (A) can be appropriately selected from 95% by mass or less, 85% by mass or less, or 75% by mass or less, based on the total solid content of the photosensitive resin composition.

[0115] Furthermore, from the viewpoint of improving pattern formation properties, the content of the high molecular weight urethane (meth) acrylate in the component (A) may be appropriately selected from 70 to 100% by mass, 80 to 100% by mass, 90 to 100% by mass, 95 to 100% by mass or 100% by mass (total amount) based on the total solid content of the component (A).

[0116] <Component (B): Low molecular weight body>

[0117] The photosensitive resin composition of the present embodiment contains a low molecular weight body having a photopolymerizable functional group as the (B) component. "Low molecular weight body" refers to a compound having a weight average molecular weight of less than 2,500. Here, even if the low molecular weight body having a photopolymerizable functional group has a silicon atom, it is classified as the (B) component with priority being the low molecular weight body having a photopolymerizable functional group rather than the silane compound of the (F) component described later.

[0118] As the photopolymerizable functional group contained in the component (B), for example, there can be mentioned (meth)acryloyl group; alkenyl groups such as vinyl and allyl groups; and other ethylenically unsaturated groups. The component (B) only needs to be a low molecular weight body having at least one photopolymerizable functional group. From the viewpoint of improving pattern formation, the component (B) may have a (meth)acryloyl group as a photopolymerizable functional group. From the viewpoint of improving pattern formation, the component (B) may have two or more photopolymerizable functional groups, and may have 2 to 5 photopolymerizable functional groups.

[0119] The photosensitive resin composition of the present embodiment preferably contains at least one selected from the group consisting of (B1) component: a low molecular weight body having an isocyanurate ring, (B2) component: a low molecular weight body having a carbamate bond, and (B3) component: a low molecular weight body having an alicyclic skeleton as the (B) component. The photosensitive resin composition of the present embodiment has a tendency to improve the adhesion with the substrate of the electronic device, etc., and to obtain excellent pattern formation by containing at least one of these. In addition, in the case of a low molecular weight body having two or more of an isocyanurate ring, a carbamate bond, and an alicyclic skeleton, as long as at least an isocyanurate ring is present, it is classified as the (B1) component, and when having a carbamate bond and an alicyclic skeleton, the case having a carbamate bond is prioritized and classified as the (B2) component. That is, a low molecular weight body having an alicyclic skeleton without an isocyanurate ring and a carbamate bond is classified as the (B3) component.

[0120] (Component (B1): low molecular weight substance having an isocyanurate ring)

[0121] From the viewpoint of improving pattern forming properties, the component (B1) may have two or more photopolymerizable functional groups, may have 2 to 5 photopolymerizable functional groups, may have 2 or 3 photopolymerizable functional groups, or may have 3 photopolymerizable functional groups.

[0122] The photopolymerizable functional group contained in the component (B1) is described as the photopolymerizable functional group contained in the component (B), but the photopolymerizable functional group may have a (meth)acryloyl group from the viewpoint of improving pattern forming properties.

[0123] Examples of the component (B1) include compounds represented by the following general formula (7).

[0124]

[0125] (In general formula (7), R 4 , R 5 and R 6 Each independently represents an alkylene group having 1 to 6 carbon atoms, and R 7 and R 8 Each independently represents a hydrogen atom or a methyl group, R 9 represents a hydrogen atom or a (meth)acryloyl group.)

[0126] In the general formula (7), R 4 , R 5 and R 6 The alkylene group having 1 to 6 carbon atoms represented may be an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 3 carbon atoms.

[0127] Examples of the alkylene group having 1 to 6 carbon atoms include methylene, vinyl, propenyl, butenyl, isopropenyl, isobutenyl, tert-butenyl, pentenyl, and hexenyl. Among these, vinyl groups may be used from the viewpoint of improving pattern forming properties.

[0128] In the general formula (7), R 7 and R 8 Each independently represents a hydrogen atom or a methyl group, and may be a hydrogen atom from the viewpoint of improving pattern forming properties.

[0129] In the general formula (7), R 9 It represents a hydrogen atom or a (meth)acryloyl group, and may be a (meth)acryloyl group from the viewpoint of improving pattern forming properties.

[0130] The compound represented by the general formula (7) may be one or more selected from the group consisting of compounds represented by the following formula (7-1) and compounds represented by the following formula (7-2). From the viewpoint of improving pattern forming properties, the compound may also be represented by the following formula (7-1).

[0131]

[0132] The weight average molecular weight of the component (B1) is less than 2,500, and can be appropriately selected from 200 to 1,500, 300 to 1,000, or 350 to 600 from the viewpoint of improving pattern forming properties.

[0133] The component (B1) may be a commercially available product, such as "A-9300" manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd. (a compound represented by the above formula (7-1)), and "M-215" manufactured by TOAGOSEI CO., LTD. (a compound represented by the above formula (7-2)).

[0134] The component (B1) can be used alone or in combination of two or more.

[0135] (Component (B2): low molecular weight substance having a urethane bond)

[0136] From the viewpoint of improving pattern forming properties, the component (B2) may have two or more photopolymerizable functional groups, may have 2 to 6 photopolymerizable functional groups, may have 2 to 4 photopolymerizable functional groups, or may have 2 photopolymerizable functional groups.

[0137] The photopolymerizable functional group contained in the component (B2) will be described as the photopolymerizable functional group contained in the component (B). From the viewpoint of improving pattern forming properties, the photopolymerizable functional group may include a (meth)acryloyl group.

[0138] In this specification, the (B2) component having a (meth)acryloyl group as a photopolymerizable functional group may be simply referred to as "urethane (meth)acrylate of a low molecular weight body".

[0139] As a low molecular weight urethane (meth) acrylate, for example, a reaction product of a (meth) acrylate having a hydroxyl group and an isocyanate compound having an isocyanate group can be cited. Here, as a (meth) acrylate and an isocyanate compound having a hydroxyl group, an acrylate and an isocyanate compound having a hydroxyl group, which are raw materials used in the generation of a high molecular weight body described in the description of the above-mentioned (A) component, can be cited. In addition, regarding the isocyanate compound, in addition to the above, a monoisocyanate compound can also be used. As a monoisocyanate compound, for example, aliphatic monoisocyanate compounds such as ethyl isocyanate, propyl isocyanate, butyl isocyanate, octadecyl isocyanate, methacrylate-2-isocyanatoethyl can be cited; alicyclic monoisocyanate compounds such as cyclohexyl isocyanate; aromatic monoisocyanate compounds such as phenyl isocyanate, etc.

[0140] Here, as a compound appropriately selected from the viewpoint of improving pattern forming properties, etc., a compound appropriately selected as a compound for generating a high molecular weight body from the same viewpoint is exemplified.

[0141] In addition, as a low molecular weight urethane (meth) acrylate, a reaction product obtained by reacting the terminal isocyanate group of an addition polymer of an isocyanate compound having at least 2 isocyanate groups in one molecule and a diol compound with a (meth) acrylate having a hydroxyl group can be cited. Here, as an isocyanate compound having at least 2 isocyanate groups in one molecule, a diol compound, and a (meth) acrylate having a hydroxyl group, exemplified as a raw material used in the generation of a high molecular weight body, respectively, an isocyanate compound having at least 2 isocyanate groups in one molecule, a diol compound, and a (meth) acrylate having a hydroxyl group can be cited. Here, as a compound appropriately selected from the viewpoint of improving pattern formation, etc., from the same viewpoint, an example is given of a compound appropriately selected as a compound for generating a high molecular weight body.

[0142] Examples of the reaction product include a reaction product having a structural unit represented by the following general formula (8).

[0143]

[0144] In the general formula (8), X 2 represents a divalent organic group having a chain hydrocarbon skeleton, an alicyclic skeleton or an aromatic ring skeleton, and Y 2 represents a divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton. That is, as the (B2) component, there can be cited a component having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton and an aromatic ring skeleton. 2 and Y 2 , respectively with X of the general formula (1) 1 and Y 1 Same example.

[0145] From the viewpoint of improving pattern formation and improving the transparency, water resistance and moisture resistance of the resin composition in a balanced manner, X 2 It can be appropriately selected from a divalent organic group having a chain hydrocarbon skeleton, a branched divalent organic group having a chain hydrocarbon skeleton, a branched alkylene group having 2 to 12 carbon atoms, for example, a residue appropriately selected from the above-mentioned aliphatic diisocyanate compound. 2 It may be appropriately selected from divalent organic groups having an alicyclic skeleton, for example, a residue of a diol compound having an alicyclic skeleton as described above.

[0146] Specific examples of the low molecular weight urethane (meth)acrylate include urethane acrylates represented by the following general formula (9).

[0147]

[0148] In the above general formula (9), n5 represents an integer of 1 to 4. 10 and R 11 Each of the R 10 and R 11 At least three of them are alkyl groups having 1 to 4 carbon atoms.

[0149] Among the urethane acrylates represented by the general formula (9), commercially available products containing urethane acrylates having the following structural units include, for example, TMCH-5R (trade name, number of functional groups: 2, Mw: 950, manufactured by Hitachi Chemical Co., Ltd.), wherein X in the general formula (8) is 2 is a residue of trimethylhexamethylene diisocyanate, a divalent organic group having a chain hydrocarbon skeleton, 2 It is a residue of cyclohexanedimethane which is a divalent organic group having an alicyclic skeleton.

[0150] In addition, commercially available products of urethane (meth) acrylates containing a structural unit represented by the above general formula (8) include KRM8452 (number of functional groups: 10, Mw: 1,200, manufactured by DAICEL-ALLNEX LTD.), UN-3320HA (number of functional groups: 6, Mw: 1,500, manufactured by Negami Chemical Industrial Co., Ltd.), and UN-3320HC (number of functional groups: 6, Mw: 1,500, manufactured by Negami Chemical Industrial Co., Ltd.) In the above description, the number of functional groups and Mw in parentheses are the total number and weight average molecular weight of (meth)acryloyl groups contained in the urethane (meth) acrylate, respectively.

[0151] The weight average molecular weight of component (B2) is less than 2,500, but may be 2,000 or less from the viewpoint of improving adhesion, and may be 1,500 or less or 1,000 or less from the viewpoint of further improving resolvability. On the other hand, the lower limit of the weight average molecular weight can be appropriately used according to the desired purpose, but may be 500 or more or 700 or more from the viewpoint of film formability.

[0152] By containing the component (B2) as the component (B), the effect of improving pattern forming properties increases.

[0153] (Component (B3): low molecular weight product having an alicyclic skeleton)

[0154] From the viewpoint of improving pattern forming properties, the component (B3) may have two or more photopolymerizable functional groups, may have 2 to 4 photopolymerizable functional groups, or may have two photopolymerizable functional groups.

[0155] The photopolymerizable functional group contained in the component (B3) will be described as the photopolymerizable functional group contained in the component (B). From the viewpoint of improving pattern forming properties, the photopolymerizable functional group may include a (meth)acryloyl group.

[0156] The alicyclic skeleton possessed by the component (B3) is not particularly limited, and for example, an alicyclic hydrocarbon skeleton having 5 to 20 carbon atoms can be cited. The alicyclic hydrocarbon skeleton can be at least one selected from the group consisting of a cyclopentane skeleton, a cyclohexane skeleton, a cyclooctane skeleton, a cyclodecane skeleton, a norbornane skeleton, a dicyclopentane skeleton, and a tricyclodecane skeleton. Among these, from the viewpoint of improving pattern formation, a tricyclodecane skeleton can be used.

[0157] The weight average molecular weight of the component (B3) is less than 2,500, but may be 2,000 or less from the viewpoint of improving adhesion, and may be 1,500 or less, 1,000 or less, or 500 or less from the viewpoint of further improving resolvability. On the other hand, the lower limit of the weight average molecular weight can be appropriately used depending on the desired purpose, but may be 150 or more, or 200 or more from the viewpoint of film formability.

[0158] As the component (B3), tricyclodecane dimethanol diacrylate may be used from the viewpoint of pattern forming properties.

[0159] As the component (B3), a commercially available product may be used. Examples of the commercially available product include A-DCP (tricyclodecane dimethanol diacrylate, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.).

[0160] Based on the total solid content of the photosensitive resin composition, the content (total content) of component (B) can be appropriately selected from 5% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more. If the content of component (B) is 5% by mass or more, even when a thick photosensitive layer is formed, excellent pattern formation can be obtained, and excellent rigidity of the cured product can also be obtained. From the same point of view, based on the total solid content of the photosensitive resin composition, the upper limit of the content of component (B) can be appropriately selected from 70% by mass or less, 60% by mass or less, or 50% by mass or less.

[0161] From the viewpoint of improving pattern forming properties and rigidity of the cured product, the content of component (B) is appropriately selected from 20 to 120 parts by mass, 25 to 100 parts by mass, 30 to 80 parts by mass, or 40 to 80 parts by mass based on 100 parts by mass of the total solid content of components (A) and (E) (but only component (A) when component (E) is not contained).

[0162] The total content of the components (B1) to (B3) in the component (B) can be appropriately selected from 50% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, or substantially 100% by mass.

[0163] When at least two of the above-mentioned (B1) to (B3) components are used, the content of the (B2) component in the total solid content of the (B) component can be appropriately selected from 10% by mass or more, 15% by mass or more, or 20% by mass or more. If the content of the (B2) component is 10% by mass or more, even when a thick photosensitive layer is formed, excellent pattern formation can be obtained, and excellent rigidity of the cured product can also be obtained. From the same viewpoint, the upper limit of the (B2) component can be appropriately selected from 90% by mass or less, 80% by mass or less, or 70% by mass or less.

[0164] <Component (C): Photopolymerization initiator>

[0165] The photosensitive resin composition of the present embodiment includes a photopolymerization initiator as component (C). As component (C), as long as at least one of component (A) and component (B) can be polymerized, there is no particular limitation, and it can be appropriately selected from commonly used photopolymerization initiators. From the viewpoint of improving pattern formation, photopolymerization initiators that generate free radicals by active light can be cited, for example, acylphosphine oxide-based, oxime ester-based, aromatic ketone-based, quinone-based, alkylphenone-based, imidazole-based, acridine-based, phenylglycine-based, coumarin-based and other photopolymerization initiators.

[0166] The acylphosphine oxide-based photopolymerization initiator has an acylphosphine oxide group [>P(=O)-C(=O)-R], and examples thereof include (2,6-dimethoxybenzoyl)-2,4,6-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("IRGACURE-TPO" (manufactured by BASF)), 2,4,6-trimethylbenzoylphenylethyl hypophosphite, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("IRGACURE-819" (manufactured by BASF)), (2,5-dihydroxyphenyl)diphenylphosphine oxide, (p-hydroxyphenyl)diphenylphosphine oxide, bis(p-hydroxyphenyl)phenylphosphine oxide, tris(p-hydroxyphenyl)phosphine oxide, and the like.

[0167] Oxime ester photopolymerization initiators are photopolymerization initiators 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.).

[0168] Examples of the aromatic ketone-based photopolymerization initiator include benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one ("IRGACURE-651" (manufactured by BASF)), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one ("IRGACURE-369" (manufactured by BASF)), and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one ("IRGACURE-907" (manufactured by BASF)).

[0169] As quinone-based photopolymerization initiators, for example, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, etc. can be mentioned.

[0170] Examples of the alkylphenone-based photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether and other benzoin-based compounds, 2,2-dimethoxy-1,2-diphenylethane-1-one ("IRGACURE-651" (manufactured by BASF)), 1-hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE-184" (manufactured by BASF)), 2-hydroxy-2-methyl-1-phenyl-propane-1-one. ("IRGACURE-1173" (manufactured by BASF)), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one ("IRGACURE-2959" (manufactured by BASF)), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one ("IRGACURE-127" (manufactured by BASF)), etc.

[0171] Examples of the 2,4,5-triarylimidazole dimer used as the imidazole-based photopolymerization initiator include 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenyl-1,3-oxadiazol-2-yl]-4,5-diphenylimidazole and the like, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0172] Examples of the acridine-based photopolymerization initiator include 9-phenylacridine and 1,7-bis(9,9′-acridinyl)heptane.

[0173] Examples of the phenylglycine-based photopolymerization initiator include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0174] In addition, 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, 4,6-dimethyl-7-di ... coumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, 4,6-diethyl-7-dimethylaminocoumarin, 2,3,6,7,10,11-hexanehydro-1H,5H-cyclopenta[3,4][1]benzopyrano[6,7,8-ij]quinolizine-12(9H)-one, 7-diethylamino-5',7'-dimethoxy-3,3'-carbonylbiscoumarin, 3,3'-carbonylbis[7-(diethylamino)coumarin], 7-(diethylamino)-3-(2-thienyl)coumarin, and the like.

[0175] Among these (C) photopolymerization initiators, from the viewpoint of improving pattern forming properties, a compound represented by the following general formula (C1) or a compound represented by the following general formula (C2) can be used.

[0176]

[0177] (R C1 , R C2 and R C3 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R C4 and R C5 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. C1 ~R C5 Each of them may have a substituent.)

[0178]

[0179] (R C6 represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an amino group, and R C7 and R C8 R each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. C7 With R C8 They may be bonded to each other to form a ring structure having 3 to 16 carbon atoms. C6 ~RC8 Each of them may have a substituent, and the substituents of the amino group having a substituent may be bonded to each other to form a cyclic structure having 3 to 12 carbon atoms. C9 Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an organic group having 1 to 10 carbon atoms which may contain one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom.

[0180] In the general formula (C1), R C1 , R C2 and R C3 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

[0181] R C1 , R C2 and R C3 The alkyl group having 1 to 6 carbon atoms may be an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 or 2 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, n-heptyl, and n-hexyl.

[0182] R C1 , R C2 and R C3 The alkoxy group having 1 to 6 carbon atoms may be an alkoxy group having 1 to 3 carbon atoms or an alkoxy group having 1 or 2 carbon atoms. Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, and tert-butoxy.

[0183] Among these groups, R C1 , R C2 and R C3 It may be methyl.

[0184] In the general formula (C1), R C4 and R C5 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0185] With R C1 , R C2 and R C3 The same explanation is given for R C4 and R C5 The represented alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms.

[0186] R C4 and R C5The aryl group having 6 to 12 carbon atoms represented may be an aryl group having 6 to 10 carbon atoms or an aryl group having 6 to 8 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.

[0187] As R C1 ~R C5 The substituent that may be present includes, for example, a halogen atom, a carboxyl group, a hydroxyl group, an amino group, a mercapto group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and the like. C1 ~R C5 The alkyl group, alkoxy group and aryl group which may be substituted include the following as R C1 ~R C5 The alkyl group, alkoxy group and aryl group described above are the same groups.

[0188] In the general formula (C2), R C6 It represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an amino group.

[0189] R of the general formula (C1) C1 , R C2 and R C3 The same explanation is given for R C6 The alkoxy group represented by

[0190] Among these groups, R C6 It may be a hydroxyl group.

[0191] In the general formula (C2), R C7 and R C8 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0192] R C7 and R C8 The alkyl, alkoxy and aryl groups represented by the formula (C1) include C1 ~R C5 The alkyl group, alkoxy group and aryl group represented are the same groups.

[0193] R C7 With R C8 They may be bonded to each other to form a ring structure having 3 to 16 carbon atoms.

[0194] The cyclic structure may be a cyclic structure having 4 to 10 carbon atoms, or a cyclic structure having 5 to 8 carbon atoms.

[0195] From the viewpoint of improving pattern formation, the cyclic structure may be an alicyclic structure, and examples of the alicyclic structure include a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. Furthermore, these alicyclic structures may contain R C7 and R C8 Carbon atoms that are directly bonded together.

[0196] R of the above general formula (C1) C1 ~R C5 The substituents which may be present are explained in the same manner as for R C6 ~R C8 The substituted groups may be present.

[0197] The substituents of the substituted amino group may be bonded to each other to form a cyclic structure having 3 to 12 carbon atoms.

[0198] The cyclic structure formed by the substituent of the amino group may be a cyclic structure having 3 to 10 carbon atoms, or may be a cyclic structure having 3 to 5 carbon atoms.

[0199] The above-mentioned cyclic structure may be a 5-10-membered ring containing the nitrogen atom of the amino group, may be a 5-7-membered ring containing the nitrogen atom of the amino group, or may be a 6-membered ring containing the nitrogen atom of the amino group. Moreover, these cyclic structures may contain heteroatoms other than nitrogen atoms such as oxygen atoms. As a specific example of the cyclic structure formed by the substituent of the amino group, a structure (morpholinyl) represented by the following formula (C3) can be cited.

[0200]

[0201] In the general formula (C2), R C9 Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an organic group having 1 to 10 carbon atoms which may contain one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom.

[0202] R C9 The organic group having 1 to 10 carbon atoms represented may be an organic group having 1 to 6 carbon atoms or an organic group having 1 to 4 carbon atoms.

[0203] As R C9 The organic group having 1 to 10 carbon atoms represented by may be a hydrocarbon group such as an alkyl group, an alkenyl group, or an aryl group. Examples of such alkyl groups, alkenyl groups, and aryl groups include those corresponding to R of the general formula (C1) C1 ~R C5 The alkyl, alkenyl and aryl groups represented are the same groups.

[0204] As R C9Examples of the organic group having 1 to 10 carbon atoms and containing an oxygen atom include an alkoxy group having 1 to 10 carbon atoms.

[0205] As R C9 Examples of the organic group having 1 to 10 carbon atoms and containing a nitrogen atom include groups represented by the above-mentioned general formula (C3).

[0206] As including R C9 Examples of the organic group having 1 to 10 carbon atoms of the sulfur atom represented by include alkylthio groups such as methylthio group and the like.

[0207] As the content of component (C), the amount selected appropriately is an amount that makes the absorbance of the photosensitive layer formed by the photosensitive resin composition at a thickness (thickness after drying) of 50 μm to light of a wavelength of 365 nm less than 0.35, less than 0.3, less than 0.2, or less than 0.1. By setting it to the above content, for example, even when a pattern is formed on a photosensitive layer thicker than 70 μm, light can easily and appropriately pass to the bottom of the photosensitive layer (the surface on the substrate side of the photosensitive layer), thereby improving the pattern forming property. Here, regarding the absorbance, for example, an ultraviolet visible spectrophotometer (product name: "U-3310 Spectrophotometer", manufactured by Hitachi High-Tech Corporation) can be used, and the absorbance to light of a wavelength of 365 nm can be measured using a polyethylene terephthalate film monomer as a reference.

[0208] The content of component (C) can be determined based on the absorbance of the photosensitive layer at a thickness of 50 μm, and is usually appropriately selected from 0.05 to 20 mass %, 0.05 to 12 mass %, 0.1 to 8 mass %, 0.1 to 5 mass % or 0.1 to 3 mass % based on the total solid content of the photosensitive resin composition. By setting the above content, the sensitivity of the photosensitive resin composition can be improved, the degradation of the photoresist shape can be suppressed, and the pattern forming property can be improved.

[0209] In addition to the above-mentioned component (C), a photopolymerization initiation aid (C') such as ethyl N,N-dimethylaminobenzoate, isopentyl N,N-dimethylaminobenzoate, pentyl 4-dimethylaminobenzoate, triethylamine, triethanolamine or other tertiary amines may be used alone or in combination of two or more.

[0210] <Component (D): Triazole Compound>

[0211] The photosensitive resin composition of the present embodiment contains a triazole compound as a (D) component. The triazole compound is a compound having a triazole skeleton. Since the triazole compound has excellent adhesion to the copper surface and can be easily removed by development, and does not damage the curability of the photosensitive resin composition, even when a thick film of photosensitive layer is formed on the copper surface and a photoresist pattern with a thin line width and a narrow line spacing is formed, excellent pattern formation can be achieved. In addition, it is believed that in the case of a high concentration of free radicals in the reaction system under conditions such as high exposure, the hydrogen of the triazole compound is removed and acts as an inhibitor, and the process margin increases, and pattern formation can be achieved under the same exposure conditions on substrates with copper surfaces and substrates without copper surfaces. Moreover, the triazole compound has a high solubility in a solvent and is easy to handle compared to tetrazole, one of the heterocyclic compounds. In the case of a tetrazole compound, it is possible to precipitate a tetrazole compound in a storage stability test of the photosensitive resin film under refrigeration. Among the triazole compounds, benzotriazole is more preferred.

[0212] As triazole compounds, for example, 1,2,3-triazole, 1,2,4-triazole, benzotriazole and their derivatives can be cited. As triazole compounds, more specifically, for example, 1-methyl-1,2,3-triazole, 1-phenyl-1,2,3-triazole, 4-methyl-2-phenyl-1,2,3-triazole, 1-methyl-1,2,4-triazole, 1,3-diphenyl-1,2,4-triazole, benzotriazole, 1-methylbenzotriazole, 5,6-dimethylbenzotriazole, 2-phenylbenzotriazole, etc. can be cited. These can be used alone or in combination of two or more.

[0213] The component (D) preferably includes a benzotriazole compound having a benzotriazole skeleton. By using a benzotriazole compound, since it has excellent adhesion to the copper surface and can be easily removed by development, and does not impair the curability of the photosensitive resin composition, there is a tendency that even when a thick photosensitive layer is formed on the copper surface and a photoresist pattern with a thin line width and a narrow line spacing is formed, an excellent pattern can be formed. In addition, from the viewpoint of more fully obtaining the above-mentioned effects, benzotriazole is preferred among the benzotriazole compounds.

[0214] The molecular weight of the triazole compound is preferably 100 or more, more preferably 150 or more. In addition, the molecular weight of the triazole compound is preferably 5000 or less, more preferably 2000 or less. If the molecular weight is 100 or more, there is a tendency that it is not easy to volatilize during coating. On the other hand, if the molecular weight is 5000 or less, the triazole compound is easy to move during the first heating step described later and becomes easy to coordinate with the substrate, and there is a tendency that the adhesion with the copper surface is excellent and the development residue reduction effect is further improved.

[0215] The content of component (D) in the photosensitive resin composition may be 0.1 to 10% by mass, 1.0 to 8.0% by mass, or 3.0 to 6.0% by mass, based on the total solid content of the photosensitive resin composition. If the content of component (D) is 0.1% by mass or more, there is a tendency to further effectively reduce the development residue, and if it is 10% by mass or less, there is a tendency to more easily balance the reduction of development residue and pattern formation under the same exposure amount.

[0216] <Component (E): High Tg High Molecular Weight Body>

[0217] The photosensitive resin composition of this embodiment may contain a high molecular weight body having a glass transition temperature of 70 to 150° C. and having no carbon-nitrogen bond as the component (E). The definition of “high molecular weight body” is the same as that of the above-mentioned component (A). By containing the component (E), the viscosity of the photosensitive resin composition is suppressed.

[0218] From the viewpoint of pattern formation and viscosity reduction, the component (E) may contain an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a (meth)acryloyl group and a vinyl group. From the viewpoint of pattern formation, the component (E) may be a (meth)acryloyl group.

[0219] The component (E) may contain a high molecular weight body having at least one skeleton selected from the group consisting of an alicyclic skeleton and an aromatic ring skeleton, and may contain a high molecular weight body having an alicyclic skeleton from the viewpoint of pattern formation and the viewpoint of reducing viscosity.

[0220] For example, the high molecular weight product having an alicyclic skeleton can be produced by reacting a part of the acid groups derived from the acid group-containing acrylic resin (e1) having no carbon-nitrogen bond with the epoxy groups derived from the alicyclic epoxy group-containing unsaturated compound (e2) having no carbon-nitrogen bond.

[0221] As the acid group-containing acrylic resin (e1) having no carbon-nitrogen bond, a copolymer obtained by copolymerizing one or more monomers selected from the group consisting of acids having ethylenically unsaturated groups, (meth)acrylic acid esters, vinyl aromatic compounds, polyolefin compounds and the like can be used. Specifically, there can be mentioned copolymers obtained by copolymerizing an acid having an ethylenically unsaturated group such as (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, maleic anhydride, etc. as an essential component with an ester of (meth)acrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc.; a vinyl aromatic compound such as styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, etc.; a monomer of a polyolefin compound such as butadiene, isoprene, chloroprene, etc.; and other monomers such as methyl isopropenyl ketone, vinyl acetate, vinyl propionate, etc., at least one monomer.

[0222] The acid value of component (e1) may be 15 mgKOH / g or more, or 40 to 500 mgKOH / g. When component (e1) has such an acid value, a sufficient amount of acid groups will remain in component (E) even after component (e1) reacts with component (e2) described later.

[0223] The alicyclic epoxy group-containing unsaturated compound (e2) having no carbon-nitrogen bond is preferably a compound having one ethylenically unsaturated group and an alicyclic epoxy group in one molecule. Specifically, for example, there can be mentioned compounds represented by any of the following formulae (I) to (X).

[0224]

[0225]

[0226] Here, RE1 is independently a hydrogen atom or a methyl group. 2 Each is independently an aliphatic saturated hydrocarbon group.

[0227] As RE 2The aliphatic saturated hydrocarbon groups represented include linear or branched alkylene groups having 1 to 6 carbon atoms, cycloalkylene groups having 3 to 8 carbon atoms, arylene groups having 6 to 14 carbon atoms, and divalent organic groups composed of combinations thereof. Examples of alkylene groups include methylene, vinyl, propenyl, tetramethylene, ethylvinyl, pentamethylene, and hexamethylene. Examples of cycloalkane groups include cyclopentenyl, cyclohexenyl, and cyclooctenyl. Examples of arylene groups include phenylene and naphthyl. Examples of divalent organic groups composed of combinations thereof include -CH2-phenylene-CH2-, -CH2-cyclohexenyl-CH2-, and the like.

[0228] As RE 2 From the viewpoint of pattern formation and reduction of viscosity, it can be methylene, vinyl, propenyl, tetramethylene, ethylvinyl, pentamethylene, hexamethylene, phenylene, cyclohexylene or -CH2-phenylene-CH2-, it can be methylene, vinyl or propenyl, or it can be methylene.

[0229] As the alicyclic epoxy group-containing unsaturated compound (e2) having no carbon-nitrogen bond, a compound represented by the above formula (III) may be used from the viewpoint of pattern forming properties.

[0230] As the component (E), commercial products can be used, for example, CYCLOMER P series (ACA) Z250 (manufactured by DAICEL-ALLNEX LTD., acid value 101.7 mgKOH / g) etc. (ACA) Z250 is a resin composed of three structural units represented by the following formula (XI) produced by the reaction of an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound.

[0231]

[0232] (Where R E1 represents a hydrogen atom or a methyl group. E3 represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms. )

[0233] The glass transition temperature of the component (E) is 70 to 150° C., but may be 100 to 150° C., 115 to 150° C., or 125 to 150° C. Here, the glass transition temperature of the component (E) is a value measured by the following method.

[0234] (Method for measuring glass transition temperature of component (E))

[0235] As a pretreatment for measurement, the component (E) was heated at 120° C. for 3 hours and then cooled to prepare a sample.

[0236] Using 10 mg of this sample, a differential scanning calorimeter (manufactured by SHIMADZU CORPORATION, trade name: DSC-50) was used to increase the temperature at a rate of 20°C / min in a temperature range of 25 to 200°C under a nitrogen stream to exclude the influence of solvents, etc. After cooling to 25°C, the temperature was increased again under the same conditions, and the temperature at which the baseline began to deviate was taken as the glass transition temperature.

[0237] The weight average molecular weight of the component (E) may be 3,000 to 50,000, 4,000 to 40,000, or 5,000 to 30,000. If it is 3,000 or more, the viscosity suppressing effect tends to be greater, and if it is 50,000 or less, the resolving power tends to be improved.

[0238] When the photosensitive resin composition of the present embodiment contains component (E), from the viewpoint of pattern formation and the viewpoint of reducing viscosity, the content of component (E) may be 5 to 60 parts by mass, 10 to 40 parts by mass, or 10 to 30 parts by mass relative to 100 parts by mass of the total of components (A) and (E).

[0239] <Component (F): Silane compound>

[0240] In addition, the photosensitive resin composition of the present embodiment may further contain (F) a silane compound. As the (F) component, a known silane coupling agent may be used. The (F) component may improve adhesion to the substrate of the electronic device, and is particularly effective when the substrate is a silicon-containing substrate (e.g., a glass substrate, a silicon wafer, an epoxy resin-impregnated glass cloth substrate, etc.). Examples of the silane coupling agent include alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; alkoxysilanes containing (meth)acryloyl groups such as (meth)acryloxypropyltrimethoxysilane and (meth)acryloxypropylmethyldimethoxysilane; amine alkoxysilanes such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and 3-triethoxysilyl-N-(1,3-dimethylbutenyl)propylamine; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and amine alkoxysilanes such as N-(1,3-dimethylbutenyl)propylamine; Alkoxysilanes containing glycidoxy groups such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; Alkoxysilanes containing alicyclic epoxy groups such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; Alkoxysilanes containing urea groups such as 3-ureidopropyltriethoxysilane; Alkoxysilanes containing mercapto groups such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane; Alkoxysilanes containing carbamate groups such as triethoxysilylpropylethylcarbamate; Alkoxysilanes containing polyacid anhydride groups such as 3-(triethoxysilyl)propylsuccinic anhydride, etc. These can be used alone or in combination of two or more.

[0241] From the viewpoint of further improving the adhesion, a silane coupling agent having an ethylenically unsaturated group in the molecule, such as (meth)acryloxypropyltrimethoxysilane, (meth)acryloxypropylmethyldimethoxysilane and other (meth)acryloxypropylalkoxysilane, or (meth)acryloxypropylmethylalkoxysilane, or (meth)acryloxypropyltrimethoxysilane, (meth)acryloxypropylmethyldiethoxysilane, or (meth)acryloxypropylmethyldiisopropoxysilane and other (meth)acryloxypropylalkoxysilane.

[0242] When the photosensitive resin composition of the present embodiment contains component (F), the content of component (F) is appropriately selected from 0.05 to 15 mass %, 0.1 to 10 mass %, 0.1 to 7 mass %, 1 to 7 mass % or 1 to 5 mass % based on the total solid content of the photosensitive resin composition. By setting the above content, the degradation of the photoresist shape can be suppressed and the pattern forming property can be improved.

[0243] <Component (G): Thermal Radical Polymerization Initiator>

[0244] In addition, the photosensitive resin composition of the present embodiment may further contain (G) a thermal free radical polymerization initiator. The (G) component is not particularly limited, and examples thereof include dialkyl peroxides such as α,α'-bis(tert-butylperoxy)diisopropylbenzene, diisopropylbenzene peroxide, tert-butylisopropylbenzene peroxide, and di-tert-butyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-2-methylcyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-tetramethylbenzene peroxide; Peroxyacetals such as 1,1-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane; hydroperoxides such as p-menthane hydroperoxide; diacyl peroxides such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide, and benzoyl peroxide; bis(4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutyl Peroxy carbonates such as tert-butyl peroxy tert-butyl ... Peroxide polymerization initiators such as peroxyesters such as tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-butyl peroxybenzoate, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, and tert-butyl peroxyacetate; and azo polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile).

[0245] As the component (G), from the viewpoint of improving pattern forming properties, a peroxide-based polymerization initiator or a dialkyl peroxide-based polymerization initiator can be selected, and among them, dicumyl peroxide can be selected. Furthermore, the component (G) can be used alone or in combination of two or more.

[0246] When the photosensitive resin composition of the present embodiment contains component (G), its content is 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 it to the above content, the heat resistance of the photosensitive resin composition is improved, and the reliability when used as a permanent film is improved.

[0247] <(H) Component: Inorganic filler>

[0248] The photosensitive resin composition of the present embodiment may contain the component (H) for the purpose of further improving various properties such as the adhesion between the photosensitive resin composition and the substrate, heat resistance, and rigidity of the cured product.

[0249] As the (H) component, for example, silicon dioxide (SiO2), aluminum oxide (Al2O3), titanium dioxide (TiO2), tantalum oxide (Ta2O5), zirconium oxide (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·A l2O3), mullite (3A12O3·2SiO2), cordierite (2MgO·2Al2O3·5SiO2), talc (3MgO·4SiO2·H2O), aluminum titanate (TiO2·Al2O3), zirconium oxide 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, carbon (C), etc. These inorganic fillers can be used alone or in combination of two or more.

[0250] From the viewpoint of improving adhesion, heat resistance and rigidity of the cured product, the average particle size of the component (H) is appropriately selected from 0.01 to 3 μm, 0.01 to 2 μm or 0.02 to 1 μm. Here, the average particle size of the component (H) is the average particle size of the inorganic filler in a state dispersed in the photosensitive resin composition, and is set to the value obtained by the following measurement. First, after the photosensitive resin composition is diluted (or dissolved) 1000 times with methyl ethyl ketone, a submicron particle analyzer (manufactured by Beckman Coulter, Inc., trade name: N5) is used to measure the particles dispersed in the solvent with a refractive index of 1.38 in accordance with the international standard ISO13321, and the particle size at the cumulative value of 50% (volume basis) in the particle size distribution is taken as the average particle size. Furthermore, the component (H) contained in the photosensitive layer or the cured film of the photosensitive resin composition provided on the carrier film was also diluted (or dissolved) to 1000 times (volume ratio) using a solvent in the same manner as above and then measured using the submicron particle analyzer.

[0251] When the photosensitive resin composition of the present embodiment contains the component (H), the upper limit of the content thereof may be appropriately selected from 10% by mass or less, 5% by mass or less, or 1% by mass or less, based on the total solid content of the photosensitive resin composition, and the lower limit may be selected from a range exceeding 0% by mass, and may also be 0% by mass (i.e., it may not be included). Thus, by substantially not containing the component (H), the transmittance of the photosensitive resin composition is improved, for example, even when a pattern is formed on a photosensitive layer having a thickness of 70 μm or more, light can easily pass through the bottom of the photosensitive layer (the surface on the substrate side of the photosensitive layer), thereby improving pattern formation.

[0252] <Secondary thiol compound>

[0253] The photosensitive resin composition of the present embodiment may contain a secondary thiol compound. When a secondary thiol compound is added to the photosensitive resin composition, the content thereof may be 0.02 to 1.0 mass %, 0.02 to 0.4 mass % or 0.02 to 0.2 mass % based on the total solid content of the photosensitive resin composition. If the content of the secondary thiol compound is 0.02 mass % or more, there is a tendency to further improve the resolution on the copper surface, and if it is 1.0 mass % or less, there is a tendency to achieve high resolution with reduced residue.

[0254] <Other additives>

[0255] The photosensitive resin composition of the present embodiment may further contain additives such as a sensitizer, a heat-resistant high molecular weight body, a thermal crosslinking agent, and an adhesion aid other than the above-mentioned (F) component, as necessary.

[0256] 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.

[0257] As heat-resistant high molecular weight bodies, for example, from the viewpoint of improving processability, polyoxazoles and their precursors, phenol novolacs, cresol novolacs and other novolac resins, polyamide-imides, polyamides, etc., which are heat-resistant and used as engineering plastics, can be cited. These can be used alone or in combination of two or more.

[0258] As the heat crosslinking agent, from the viewpoint of improving the rigidity of the cured product, for example, epoxy resin, phenol resin substituted with methylol or alkoxymethyl at the α-position, melamine resin substituted with at least one selected from the group consisting of methylol and alkoxymethyl at the N-position, urea-formaldehyde resin, etc. can be cited. These can be used alone or in combination of two or more.

[0259] 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 this embodiment, and can be, for example, appropriately selected from 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.

[0260] <Thinner>

[0261] In the photosensitive resin composition of this embodiment, a diluent can be used as needed. As the diluent, for example, alcohols having 1 to 6 carbon atoms such as isopropyl alcohol, isobutyl alcohol, and tert-butyl alcohol; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; sulfur-containing compounds such as dimethyl sulfoxide and cyclopentane; esters such as v-butyrolactone and dimethyl carbonate; esters such as cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, diethylene glycol acetate, ethyl diethylene glycol acetate, butyl diethylene glycol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate, and the like polar solvents can be used alone or in combination of two or more.

[0262] The amount of the diluent used is appropriately selected from an amount in which the total solid content in the photosensitive resin composition is 50 to 90% by mass, 60 to 80% by mass, or 65 to 75% by mass. That is, the content of the diluent in the photosensitive resin composition when the diluent is used is appropriately selected from 10 to 50% by mass, 20 to 40% by mass, or 25 to 35% by mass. By setting the amount of the diluent used within the above range, the coating properties of the photosensitive resin composition are improved, and a pattern with higher fineness can be formed.

[0263] For example, when a photosensitive layer having a thickness of 70 μm or more is to be formed, the amount of the diluent used can be such that the viscosity of the photosensitive resin composition at 25° C. becomes 0.5 to 20 Pa·s or 1 to 10 Pa·s in consideration of the ease of forming the photosensitive layer.

[0264] The photosensitive resin composition of the present embodiment can be obtained by uniformly kneading and mixing the above-mentioned components (A) to (D), components (E) to (H) used as needed, other additives, and a diluent by a roll mill, a bead mill, or the like.

[0265] The photosensitive resin composition of the present embodiment may be used in a liquid state or in a film state.

[0266] When used as a liquid, the coating method of the photosensitive resin composition of the present embodiment is not particularly limited, and various coating methods such as printing, spin coating, spray coating, inkjet, and dip coating can be cited. Among these, from the viewpoint of more easily forming a thick photosensitive layer, printing or spin coating can be appropriately selected.

[0267] When used in a film form, for example, it can be used in the form of a photosensitive resin film described later. In this case, a photosensitive layer having a desired thickness can be formed by laminating using a laminator or the like.

[0268] The absorbance of the photosensitive layer formed by the photosensitive resin composition of the present embodiment to light of wavelength 365nm at a thickness (thickness after drying) of 50μm can be appropriately selected from 0.35 or less, 0.3 or less, 0.2 or less, or 0.1 or less. If the absorbance of the photosensitive layer at a thickness of 50μm of the photosensitive layer is less than 0.35, for example, even when a pattern is formed on a thick photosensitive layer of more than 70μm, light can easily pass to the bottom of the photosensitive layer (the surface on the substrate side of the photosensitive layer), thereby improving the pattern forming property. In addition, the absorbance of the photosensitive layer to light of wavelength 365nm when the thickness is 50μm can also be calculated as follows: the absorbance measured for a photosensitive layer other than 50μm in thickness is converted into the absorbance of a thickness of 50μm according to the Beer-Lambert law.

[0269] [Photosensitive resin film]

[0270] The photosensitive resin film of the present embodiment has a photosensitive layer using the photosensitive resin composition of the present embodiment. The photosensitive resin film of the present embodiment may have a carrier film. In this specification, the term "layer" includes not only a structure of a shape formed on the entire surface when observed as a plan view, but also a structure of a shape formed locally.

[0271] The photosensitive resin film of the present embodiment can be manufactured, for example, as follows: the photosensitive resin composition of the present embodiment is coated on a carrier film by the above-mentioned various coating methods to form a coating film and the coating film is dried to form a photosensitive layer. In addition, when the photosensitive resin composition of the present embodiment contains a diluent, at least a portion of the diluent can be removed during drying.

[0272] The coating film can be dried using a dryer using hot air drying, far infrared or near infrared rays, etc., and the drying temperature can be appropriately selected from 60 to 120° C., 70 to 110° C., or 90 to 110° C. In addition, the drying time can be appropriately selected from 1 to 60 minutes, 2 to 30 minutes, or 5 to 20 minutes. If drying is performed under the above conditions, when the photosensitive resin composition of the present embodiment contains a diluent, at least a portion of the diluent can also be removed.

[0273] As the carrier film, there can be mentioned resin films such as polyester resin films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), 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 can also be selected.

[0274] The thickness of the carrier film may be appropriately selected from 10 μm to 3 mm or 10 to 200 μm in consideration of the handling properties and the like.

[0275] The thickness of the photosensitive layer is 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 a photosensitive layer having a thickness of 150 μm or more is formed, the number of operations performed by lamination and the like can be further reduced. In addition, by setting the thickness to 100 μm or less, when the photosensitive resin film is wound on a core, the deformation of the photosensitive layer caused by the stress difference between the inside and outside of the core can be further reduced. Considering the effect of the photosensitive resin composition of the present embodiment that excellent pattern formation can be obtained in the case of forming a thick photosensitive layer, the thickness of the photosensitive layer can be 70 μm or more, or a thickness exceeding 100 μm. In addition, for example, a photosensitive layer having a thickness of 70 μm or more can be formed by laminating a portion of the photosensitive layer formed on a carrier film with a portion of the photosensitive layer formed on a protective layer described later. Thus, a photosensitive resin film having a carrier film, a thick photosensitive layer, and a protective layer in sequence can be obtained.

[0276] Furthermore, the photosensitive resin film of this embodiment can also be laminated with a protective layer on the surface of the photosensitive layer opposite to the surface in contact with the carrier film. As the protective layer, for example, a resin film such as polyethylene or polypropylene can be used. Furthermore, the same resin film as the above-mentioned carrier film can be used, or a different resin film can be used.

[0277] [Method for producing cured product]

[0278] The method for manufacturing a cured product of the present embodiment includes, in sequence, a process of providing a photosensitive layer on a substrate using the photosensitive resin composition or photosensitive resin film of the present embodiment (photosensitive layer forming process), a process of irradiating at least a portion of the photosensitive layer with active light to form a photocured portion (exposure process), and a process of removing at least a portion of the photosensitive layer other than the photocured portion to form a resin pattern (removal process). As required, there is further a process of heating the photosensitive layer provided on the substrate in the photosensitive layer forming process (first heating process). And, as required, there is further a process of heating the above-mentioned resin pattern (second heating process). By the method for manufacturing a cured product of the present embodiment, a desired pattern can be formed, and, for example, by utilizing the characteristics of the photosensitive resin composition of the present embodiment having excellent pattern forming properties even when a thick photosensitive layer of more than 70 μm is formed, for example, a desired pattern can be formed by a thick cured product of more than 70 μm. In this specification, the term "process" refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended effect of the process can be achieved, it is also included in the "process".

[0279] (Photosensitive layer forming step)

[0280] When forming the photosensitive layer, the photosensitive layer can be formed by applying or laminating the photosensitive resin composition or the photosensitive resin film of the present embodiment on each substrate.

[0281] As the substrate, for example, a glass substrate, a silicon wafer, a metal oxide insulator such as TiO2, SiO2, silicon nitride, a ceramic piezoelectric substrate, an epoxy resin impregnated glass cloth substrate, etc. can be cited. In addition, the substrate can be a substrate having a copper surface such as copper wiring on a part of the surface. According to the photosensitive resin composition of this embodiment, when a photoresist pattern is formed on such a substrate having a copper surface as a part of the surface, excellent pattern formation can be achieved on both surfaces of the portion having a copper surface and the portion not having a copper surface of the substrate under the same exposure conditions, and the generation of development residue on the copper surface can be suppressed.

[0282] When the photosensitive resin composition is applied to the substrate to form a photosensitive layer, the photosensitive resin composition dissolved in the above diluent to form a solution can be applied to the substrate, and the coating obtained by the application can be dried as needed. The application and drying can be carried out by various coating methods and coating drying methods described in the preparation of the above photosensitive resin film.

[0283] Furthermore, when a photosensitive resin film is used, the photosensitive layer can be formed by a lamination method using a laminator or the like.

[0284] The thickness of the photosensitive layer provided on the substrate varies according to the formation method (coating method or lamination method), the solid content concentration and viscosity of the photosensitive resin composition, etc., but as the lower limit of the thickness of the photosensitive layer after drying, it is 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. And, as an upper limit, as long as a resin pattern can be formed, there is no particular restriction, for example, it is appropriately selected from 500 μm or less, 300 μm or less or 250 μm or less. The thickness of the photosensitive layer can be appropriately selected from the above range according to the purpose. When used in electronic devices, etc., as a lower limit, it can be appropriately selected from 70 μm or more, more than 100 μm or more than 150 μm, and as an upper limit, it can be appropriately selected from 500 μm or less, 300 μm or less or 250 μm or less.

[0285] In the method for producing a cured product of the present embodiment, the photosensitive resin composition of the present embodiment is used to form a photosensitive layer, so a thick photosensitive layer can be formed. For example, when forming a photosensitive layer with a thickness of 150 μm or more, multiple repeated coatings (and drying as needed) or laminations can be performed until the desired thickness is reached, rather than forming it by a single coating (and drying as needed) or lamination.

[0286] (First Heating Step)

[0287] The first heating process is a process adopted as needed, and is a process for the photosensitive layer provided on the substrate in the photosensitive layer forming process. The heating temperature can be appropriately selected from 50 to 120°C, 70 to 110°C or 90 to 100°C. In addition, the heating time can be appropriately selected from 30 seconds to 30 minutes, 1 minute to 15 minutes or 5 minutes to 10 minutes. By performing the first heating process, the triazole compound is easily coordinated with the copper surface, and a triazole compound layer is easily formed at the interface between the photosensitive layer and the copper surface. As a result, the contact between the organic matter in the photosensitive layer other than the triazole compound and the copper surface is effectively suppressed, thereby further suppressing the organic matter from adhering to the copper surface and becoming a development residue.

[0288] (Exposure process)

[0289] In the exposure step, at least a portion of the photosensitive layer provided on the substrate in the photosensitive layer forming step is irradiated with active light as needed, and the exposed portion is photocured to form a cured portion. When irradiating the 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 imaging exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method.

[0290] In addition, from the viewpoint of improving pattern formation, after exposure, post-exposure baking (PEB) may be performed using a hot plate, a dryer, etc. The drying conditions are not particularly limited, as long as the drying is 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.

[0291] The exposure amount of active light is appropriately selected from 10 to 2,000 mJ / cm 2 100~1,500mJ / cm 2 or 300~1,000mJ / cm 2 As the active light used, ultraviolet rays, visible rays, electron beams, X-rays, etc. can be cited. In addition, as the light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a halogen lamp, etc. can be used.

[0292] (Removal process)

[0293] In the removal step, at least a portion of the photosensitive layer formed in the exposure step except the cured portion (unexposed portion) is removed to form a resin pattern. For example, the unexposed portion may be removed using a developer such as an organic solvent.

[0294] Examples of the organic solvent include ethanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, and N-methylpyrrolidone. Among them, cyclopentanone can be used from the viewpoint of development speed. These can be used alone or in combination of two or more.

[0295] Furthermore, various additives that are generally used may be added to the organic solvent used as the developer.

[0296] After the unexposed area is removed by the developer, it may be washed (rinsed) with water, alcohol such as methane, ethane, isopropyl alcohol, n-butyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether acetate, or the like as necessary.

[0297] (Second Heating Step)

[0298] The second heating process is a process adopted as needed, which is a process of heating the resin pattern formed in the removal process to form a cured product. The heating process is preferably carried out for 1 to 2 hours while selecting a heating temperature and heating it in stages. The heating temperature is appropriately selected from 120 to 240°C, 140 to 230°C or 150 to 220°C. In addition, when heating in stages, for example, after heating at at least one temperature of about 120°C or about 160°C for 10 to 50 minutes or 20 to 40 minutes, it is possible to heat at about 220°C for 30 to 100 minutes or 50 to 70 minutes.

[0299] The thickness of the obtained resin pattern is the same as the thickness of the above-mentioned photosensitive layer after drying. As the lower limit, it can 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 more than 150 μm, and as the upper limit, it can be appropriately selected from 500 μm or less, 300 μm or less, or 250 μm or less. The thickness of the resin pattern can be appropriately selected from the above range according to the purpose. When used in electronic devices, etc., as the lower limit, it can be appropriately selected from 70 μm or more, more than 100 μm or more than 150 μm, and as the upper limit, it can be appropriately selected from 500 μm or less, 300 μm or less, or 250 μm or less.

[0300] [Laminated body]

[0301] The laminated body of the present embodiment includes a cured product of the photosensitive resin composition of the present embodiment, and for example, a laminated body including the cured product on various supports such as a substrate used in the method for producing the cured product, a carrier film of a photosensitive resin film, etc. For example, the cured product of the photosensitive resin composition of the present embodiment can be formed by the method for producing the cured product of the present embodiment described above.

[0302] Regarding the thickness of the cured product in the laminate of the present embodiment, as the lower limit, it is 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 more than 150 μm, and as the upper limit, it is appropriately selected from 500 μm or less, 300 μm or less, or 250 μm or less. The thickness of the cured product can be appropriately selected from the above range according to the purpose. When used in electronic devices, etc., as the lower limit, it is appropriately selected from 70 μm or more, more than 100 μm or more than 150 μm, and as the upper limit, it is appropriately selected from 500 μm or less, 300 μm or less, or 250 μm or less.

[0303] For example, the cured product provided on the substrate obtained by the method for manufacturing the cured product described above can obtain excellent pattern forming properties even on a thick photosensitive layer of 70 μm or more by using the photosensitive resin composition of the present embodiment, and thus can meet the demand for electronic circuit substrates as follows: with the trend of miniaturization and high performance of electronic equipment, it is necessary to provide a thick cured product on the substrate with a finer pattern. In addition, in the plating process when manufacturing the electronic circuit substrate, for example, by using the cured product formed from the photosensitive resin composition of the present embodiment as an insulating film, it is possible to suppress the reduction in yield caused by short circuits between wirings.

[0304] Therefore, for example, the laminated body of the present embodiment can be used as an electronic device such as an electronic circuit board of a mobile terminal such as a mobile phone.

[0305] Furthermore, according to the method for producing the cured product, by using the photosensitive resin composition of the present embodiment, when a photoresist pattern is formed on a substrate having a copper surface locally on the surface of a copper wiring or the like, excellent pattern forming properties can be achieved on both surfaces of the substrate, i.e., a portion having a copper surface and a portion not having a copper surface, under the same exposure conditions, and generation of development residues on the copper surface can be suppressed.

[0306] Therefore, for example, the laminated body of the present embodiment can be used as an electronic device such as an electronic circuit substrate such as an inductor.

[0307] Example

[0308] The purpose and advantages of the present embodiment are further described in detail below based on examples and comparative examples, but the present embodiment is not limited to the following examples. In addition, the method for measuring the weight average molecular weight of each component and the method for measuring the glass transition temperature of the (E) component are as follows.

[0309] (Determination of weight average molecular weight)

[0310] The weight average molecular weight is a value determined in terms of standard polystyrene by a GPC method using the following apparatus, and is measured using a solution prepared by dissolving 0.5 mg of a polymer in 1 mL of tetrahydrofuran (THF).

[0311] Device name: HLC-8320GPC manufactured by Tosoh Corporation

[0312] Chromatographic columns: Gelpack R-420, R-430 and R-440 (connect 3 columns)

[0313] Detector: RI detector

[0314] Column temperature: 40°C

[0315] Eluent: THF

[0316] Flow rate: 1ml / min

[0317] Standard material: polystyrene

[0318] (Measurement of glass transition temperature of component (E))

[0319] As a pretreatment for measurement, the component (E) was heated at 120° C. for 3 hours and then cooled to prepare a sample.

[0320] 10 mg of the sample was measured using a differential scanning calorimeter (manufactured by Shimadzu Corporation, trade name: DSC-50) in a nitrogen stream at a temperature range of 25 to 200°C at a heating rate of 20°C / min, then cooled to 25°C and heated again under the same conditions. The temperature at which the baseline began to deviate was taken as the glass transition temperature.

[0321] (Examples 1 to 7 and Comparative Examples 1 to 2)

[0322] The composition was blended according to the blending composition shown in Table 1 (the unit of the numerical value in the table is part by mass, and in the case of a solution, it is the amount converted to solid content). The composition was kneaded using a three-roll mill to prepare a photosensitive resin composition. N,N-dimethylacetamide was added until the solid content concentration became 60% by mass, thereby obtaining a photosensitive resin composition.

[0323] Next, each evaluation was performed by the following method using the photosensitive resin composition obtained above. The evaluation results are shown in Table 1.

[0324] [Production of photosensitive resin film]

[0325] A 50 μm thick polyethylene terephthalate film (manufactured by TEIJIN LIMITED, trade name: A-4100) was used as a carrier film, and the photosensitive resin composition of the example and the comparative example was uniformly applied on the carrier film until the thickness after drying became 50 μm. Then, a hot air convection dryer was used to heat and dry the film at 100° C. for 15 minutes to form a photosensitive layer, thereby preparing a photosensitive resin film having a carrier film and a photosensitive layer.

[0326] [Evaluation of pattern forming properties (resolution)]

[0327] As substrates, a glass epoxy substrate having a copper surface (trade name: MCL-E-679FGB, manufactured by Hitachi Chemical Co., Ltd., hereinafter also referred to as a "Cu-containing substrate") and a substrate obtained by etching the copper of the above-mentioned glass epoxy substrate (hereinafter also referred to as a "Cu-free substrate") were prepared. On the above-mentioned substrate, a photosensitive resin film was stacked in a direction in which the photosensitive layer was located on the side of the glass epoxy substrate, and the carrier film was removed. Lamination was performed at 60°C using a laminator. Next, by the above-mentioned method, a photosensitive resin film was stacked again on the photosensitive layer, and the carrier film was removed. This operation was repeated 3 times, thereby obtaining a laminate having a photosensitive layer and a carrier film with a thickness of 200 μm on a glass epoxy substrate. Here, in Examples 2, 6 and 7, a heat treatment (first heating step) was performed in which the laminate prepared by the above-mentioned method was further heated at 90°C for 5 minutes.

[0328] Using a direct imaging exposure machine (Orbotech Ltd., trade name: Paragon9000) with a semiconductor laser as a light source and a main wavelength of 355 nm, the exposed portion shown in FIG. Figure 1 The imaging data with pattern shape (line spacing: 70μm, 50μm, 30μm, line width 12μm) was exposed. At this time, the laminate was divided into three areas, and the three areas were exposed at different exposure doses (120mJ / cm 2 、150mJ / cm 2 、180mJ / cm 2 ) was exposed. The exposed sample was heated on a 90°C hot plate for 1 minute. Figure 1 The imaging data shown has an exposed portion 10 and a non-exposed portion 20 , wherein the width W of the exposed portion 10 corresponds to the line width, and the width S of the non-exposed portion 20 corresponds to the line spacing.

[0329] After that, the carrier film was removed and immersed in a developer (cyclopentanone) for 20 minutes to develop. The developed pattern was dried at room temperature for 30 minutes and observed with a metal microscope to evaluate the pattern formation. The evaluation was performed according to the following criteria. Here, being able to form means that the unexposed portion is cleanly removed, the wireless portion (exposed portion) is twisted, and the space portion is buried. The evaluation results are shown in Table 1.

[0330] A: Can be formed with a line pitch of 30 μm.

[0331] B: Unable to form at a line pitch of 30 μm, but able to form at a line pitch of 50 μm.

[0332] C: Unable to form at a line pitch of 50 μm or less, but able to form at a line pitch of 70 μm.

[0333] D: No line spacing can be formed.

[0334] Furthermore, the resolution mismatch elimination property was evaluated based on the following criteria. The evaluation result of A or B was considered acceptable. When the evaluation result was A, it can be judged that excellent pattern formation can be achieved on both the surface of the portion having a copper surface and the portion not having a copper surface of the substrate under the same exposure conditions.

[0335] A: In both the Cu-containing substrate and the Cu-free substrate, there was an exposure amount at which the pattern formability was evaluated as A at the same exposure amount.

[0336] B: In both the Cu-containing substrate and the Cu-free substrate, there was an exposure amount at which the pattern formability was evaluated as A or B at the same exposure amount.

[0337] C: In both the Cu-containing substrate and the Cu-free substrate, the pattern formability did not reach the exposure amount that resulted in the A evaluation or the B evaluation at the same exposure amount.

[0338] [Evaluation of Development Residue on Glass Epoxy Substrate with Copper Surface]

[0339] In the evaluation of pattern formation, the copper surface of the part where the photosensitive layer was removed by development was observed with a metal microscope for the prepared Cu-containing substrate after development, thereby evaluating the development residue. The copper surface when exposed and developed at an exposure amount with a line pitch of 70 μm and the best pattern formation was observed, and evaluated according to the following criteria. The case where the evaluation result was A was considered qualified. The evaluation results are shown in Table 1.

[0340] A: The color tone of the copper surface itself is shown. This means that there is almost no residue.

[0341] B: Interference fringes (rainbow colors) were observed. This indicates the presence of a small amount of residue.

[0342] C: Residual organic matter (white) was observed. This indicates that a large amount of residue exists.

[0343]

[0344] The details of each material in Table 1 are as follows.

[0345] [(A) ingredient]

[0346] UN-954: Urethane acrylate (Negami Chemical Industrial Co., Ltd., trade name, number of functional groups: 6, weight average molecular weight (Mw): 4,500)

[0347] [(B) ingredient]

[0348] A-9300: Isocyanuric acid ethylene oxide-modified triacrylate (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., molecular weight: 423, a compound represented by the above formula (7-1), corresponding to the component (B1))

[0349] TMCH-5R: Urethane acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name, number of functional groups: 2, weight average molecular weight (Mw): 950, a compound having an acryloyl group (photopolymerizable functional group), a urethane bond (carbon-nitrogen bond), a chain hydrocarbon skeleton and an alicyclic hydrocarbon skeleton in the molecule, corresponding to the component (B2))

[0350] [(C) ingredient]

[0351] I-184: "IRGACURE-184" (trade name, manufactured by BASF Corporation) which is 1-hydroxy-cyclohexyl-phenyl-ketone

[0352] [(D) ingredient]

[0353] BT: Benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: 1,2,3-benzotriazole)

[0354] [(E) ingredient]

[0355] Z250: CYCLOMER P (ACA) Z250 (manufactured by DAICEL-ALLNEX LTD., a resin composed of three structural units represented by the above formula (XI) produced by reaction of an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound (weight average molecular weight: 19,000 to 25,000)).

[0356] [(F)INGREDIENT]

[0357] KBM-503: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name)

[0358] KBM-803: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name)

[0359] According to Table 1, it is confirmed that the photosensitive resin compositions of Examples 1 to 7 have excellent pattern forming properties on the copper surface of the Cu-containing substrate by adjusting the exposure amount, can eliminate the mismatch of pattern forming properties on the Cu-free substrate and the Cu-containing substrate, and can reduce the development residue on the Cu surface after development.

Claims

1. A photosensitive resin composition comprising: (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; (C) component: a photopolymerization initiator; and Component (D): triazole compound.

2. The photosensitive resin composition according to claim 1, wherein The component (D) includes a benzotriazole compound.

3. The photosensitive resin composition according to claim 1 or 2, wherein The content of the component (D) is 0.1 to 10% by mass based on the total solid content of the photosensitive resin composition.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein The component (A) contains a high molecular weight body having a (meth)acryloyl group as a photopolymerizable functional group.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein The component (A) contains a high molecular weight body having a urethane bond as a carbon-nitrogen bond.

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein The component (A) includes a high molecular weight body having 6 or more ethylenically unsaturated groups as photopolymerizable functional groups and having a weight average molecular weight of 2,500 or more.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein The component (A) comprises a high molecular weight body having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein The component (B) includes at least one selected from the group consisting of a low molecular weight body having a urethane bond, a low molecular weight body having an isocyanurate ring, and a low molecular weight body having an alicyclic skeleton.

9. The photosensitive resin composition according to any one of claims 1 to 7, wherein The component (B) includes a low molecular weight body having at least one (meth)acryloyl group and a urethane bond.

10. The photosensitive resin composition according to any one of claims 1 to 9, wherein The component (C) includes a compound represented by the following general formula (C1) or a compound represented by the following general formula (C2), R C1 , R C2 and R C3 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R C4 and R C5 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R other than a hydrogen atom C1 ~R C5 may have a substituent, respectively, R C6 represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an amino group, and R C7 and R C8 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, and R C7 With R C8 They can be bonded to each other to form a ring structure having 3 to 16 carbon atoms, and R other than hydroxyl and hydrogen atoms C6 ~R C8 Each of the amino groups may have a substituent, and the substituents of the amino group having a substituent may be bonded to each other to form a ring structure having 3 to 12 carbon atoms. C9 Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an organic group having 1 to 10 carbon atoms which may contain one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom. 11 . The photosensitive resin composition according to claim 1 , further comprising component (E): a high molecular weight body having a glass transition temperature of 70 to 150° C. and having no carbon-nitrogen bond. 12 . The photosensitive resin composition according to claim 1 , further comprising component (F): a silane compound. 13 . A photosensitive resin film comprising a photosensitive layer using the photosensitive resin composition according to claim 1 .

14. A method for producing a solidified product, comprising: A step of providing a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 12 or the photosensitive resin film according to claim 13; A step of irradiating at least a portion of the photosensitive layer with active light to form a photocured portion; and A step of removing at least a portion of the photosensitive layer except for the photocured portion to form a resin pattern. 15 . The method for producing a cured product according to claim 14 , further comprising the step of heating the resin pattern.

16. The method for producing a cured product according to claim 14 or 15, wherein: The resin pattern has a thickness of 70 μm or more and 300 μm or less.

17. The method for producing a cured product according to any one of claims 14 to 16, further comprising: A step of providing a photosensitive layer on a substrate and then heating the photosensitive layer. 18 . A laminate comprising a cured product of the photosensitive resin composition according to claim 1 .

19. The laminate according to claim 18, wherein The cured product has a thickness of 70 μm or more and 300 μm or less. 20 . An electronic device comprising a cured product of the photosensitive resin composition according to claim 1 .

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