JP2021005033A - Photosensitive resin composition, photosensitive resin film, method for producing cured product, laminate, and electronic component - Google Patents

Abstract

To provide a photosensitive resin composition that achieves excellent patterning properties on a copper surface of a substrate and suppresses the occurrence of development residues on the copper surface.SOLUTION: A photosensitive resin composition 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 secondary thiol compound.SELECTED DRAWING: None

Description

The present disclosure relates to photosensitive resin compositions, photosensitive resin films, methods for producing cured products, laminates, and electronic components.

In the field of manufacturing semiconductor integrated circuits (LSIs) or wiring boards, photosensitive materials are used as resists for producing conductor patterns. For example, in the production of a wiring board, a resist is formed using a photosensitive resin composition, and then a conductor pattern, a metal post, or the like is formed by a plating process. More specifically, a photosensitive layer is formed on a support (substrate) using a photosensitive resin composition or the like, and the photosensitive layer is exposed through a predetermined mask pattern, followed by a conductor pattern and a metal post. A resist pattern (resist) is formed by developing so that the portion forming the above can be selectively removed (peeled). Next, a conductor such as copper is formed on the removed portion by a plating process, and then the resist pattern is removed to manufacture a wiring board provided with a conductor pattern, a metal post, or the like.

Conventionally, a thick conductor pattern and a metal post have been produced by growing a metal plating after removing a resist pattern. In order to meet such demands, for example, a photosensitive resist for a thick film having a thickness of about 30 μm and a thickness of about 65 μm has been used (see Patent Documents 1 and 2).

Further, in recent years, in order to further improve the performance, the conductor layer has a thickness of 150 μm by performing a plating treatment while selectively destroying a layer existing in the direction in which plating growth is desired among the metal ion dilute layers with a plating solution. Attempts have been made to form the film as thick as possible (see Patent Document 3).

Japanese Unexamined Patent Publication No. 2015-034926 Japanese Unexamined Patent Publication No. 2014-077774 Japanese Unexamined Patent Publication No. 2014-080674

However, in the conventional photosensitive resist for a thick film, for example, when the formation of a thick photosensitive layer of 70 μm or more is required, light may not easily pass to the bottom and the pattern shape may be deteriorated. Further, in the method described in Patent Document 3, since the plating proceeds while partially destroying the metal ion dilute layer, it is difficult to stably form an excellent pattern. Therefore, even when a photosensitive layer having a thickness of 70 μm, 150 μm thicker than the conventional one, or more (thickness in the direction perpendicular to the substrate) is formed, the photosensitive layer has excellent pattern forming properties. Resist is required.

Further, copper wiring is mounted on the substrate of electronic components such as inductors. When a resist pattern is formed on a substrate having such copper wiring, the photosensitive layer is required to realize excellent pattern forming property on the surface of the portion where the copper wiring is formed.

Further, when the unexposed portion of the photosensitive layer is removed by development to form a resist pattern, there is also a problem that a development residue is likely to be generated on the copper surface.

The present disclosure has been made in view of the above circumstances, and it is possible to realize excellent pattern forming property on the copper surface of the substrate and suppress the generation of development residue on the copper surface. To provide a photosensitive resin composition that can be produced, a photosensitive resin film using the same, a method for producing a cured product, a laminate, and electronic parts (hereinafter, may be referred to as "photosensitive resin composition or the like"). With the goal.

As a result of intensive studies to solve the above problems, the present inventors have found that the problems can be solved by a photosensitive resin composition or the like having the following constitution. The present disclosure provides the following photosensitive resin compositions and the like.

[1] Component (A): high molecular weight compound having a photopolymerizable functional group and carbon-nitrogen bond, component (B): low molecular weight compound having a photopolymerizable functional group, and component (C): initiation of photopolymerization. A photosensitive resin composition containing an agent and a component (D): a secondary thiol compound.
[2] The photosensitive resin composition according to the above [1], wherein the component (D) contains a polyfunctional secondary thiol compound having two or more secondary thiol groups.
[3] The photosensitive component according to the above [1] or [2], wherein the component (D) contains a secondary thiol compound having at least one skeleton selected from the group consisting of a pentaerythritol skeleton and an isocyanul ring skeleton. Resin composition.
[4] Any of the above [1] to [3], wherein the content of the component (D) is 0.02 to 1.0% by mass based on the total solid content of the photosensitive resin composition. The photosensitive resin composition according to the above.
[5] The photosensitive resin composition according to any one of the above [1] to [4], wherein the component (A) contains a high molecular weight substance having a (meth) acryloyl group as a photopolymerizable functional group.
[6] The photosensitive resin composition according to any one of the above [1] to [5], wherein the component (A) contains a high molecular weight substance having a urethane bond as a carbon-nitrogen bond.
[7] The above [1] to the above, wherein the component (A) contains a high molecular weight substance having 6 or more ethylenically unsaturated groups as a photopolymerizable functional group and having a weight average molecular weight of 2,500 or more. The photosensitive resin composition according to any one of [6].
[8] The above [1] to [8], wherein the component (A) contains 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. 7] The photosensitive resin composition according to any one of.
[9] The above component (B) contains 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 isocyanul ring, and a low molecular weight body having an alicyclic skeleton. 1] The photosensitive resin composition according to any one of [8].
[10] The photosensitive resin composition according to any one of the above [1] to [8], wherein the component (B) contains a low molecular weight body having at least one (meth) acryloyl group and a urethane bond.
[11] The above-mentioned any of [1] to [10], wherein the component (C) includes a compound represented by the following general formula (C1) or a compound represented by the following general formula (C2). Photosensitive resin composition.

[ ^RC1 , ^RC2 and ^RC3 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and ^RC4 and ^RC5 independently represent each other. It represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ^R C1 ^{to R C5} other than a hydrogen atom may have each a substituent. ]

[ ^RC6 represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an amino group, and ^RC7 and ^RC8 each independently have a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 6 to 12 carbon atoms. Or an alkoxy group having 1 to 8 carbon atoms. R ^C7 and ^{R C8} are linked to each other, they may form a cyclic structure of 3 to 16 carbon atoms. Hydroxyl and hydrogen atoms other than R ^C6 to R ^C8 may have each a substituent, an amino group having a substituent bonded to a substituent each other to each other, a cyclic structure having 3 to 12 carbon atoms It may be formed. Each ^RC9 may independently contain one or more atoms selected from a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an oxygen atom, a nitrogen atom and a sulfur atom, and has 1 to 10 carbon atoms. Indicates an organic group of. ]
[12] The component (E) according to any one of the above [1] to [11], further containing a high molecular weight substance having a glass transition temperature of 70 to 150 ° C. and no carbon-nitrogen bond. Photosensitive resin composition.
[13] The photosensitive resin composition according to any one of the above [1] to [12], which further contains a component (F): a silane compound having no secondary thiol group.
[14] A photosensitive resin film having a photosensitive layer using the photosensitive resin composition according to any one of the above [1] to [13].
[15] A step of providing a photosensitive layer on a substrate using the photosensitive resin composition according to any one of the above [1] to [13] or the photosensitive resin film according to the above [14]. Curing, which comprises, in order, a step of irradiating at least a part of the layer with active light to form a photocurable portion and a step of removing at least a part other than the photocurable portion of the photosensitive layer to form a resin pattern. How to make things.
[16] The method for producing a cured product according to the above [15], further comprising a step of heat-treating the resin pattern.
[17] The method for producing a cured product according to the above [15] or [16], wherein the thickness of the resin pattern is 70 μm or more and 300 μm or less.
[18] A laminate comprising a cured product of the photosensitive resin composition according to any one of the above [1] to [13].
[19] The laminate according to the above [18], wherein the thickness of the cured product is 70 μm or more and 300 μm or less.
[20] An electronic component comprising a cured product of the photosensitive resin composition according to any one of the above [1] to [13].

According to the present disclosure, there is provided a photosensitive resin composition or the like that can realize excellent pattern formation on the copper surface of a substrate and can suppress the generation of development residue on the copper surface. be able to.

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

Hereinafter, the present disclosure will be described in detail.
In the present specification, the numerical range indicated by using "~" indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively. Further, in the numerical range described stepwise in the present specification, the upper limit value or the lower limit value of the numerical range of one step may be replaced with the upper limit value or the lower limit value of the numerical range of another step. In the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.

As used herein, the term "(meth) acrylic acid" means at least one of "acrylic acid" and the corresponding "methacrylic acid", and the same applies to other similar expressions such as (meth) acrylate.

In the present specification, the "solid content" is a non-volatile content excluding volatile substances such as water and solvent contained in the photosensitive resin composition, and is volatile when the resin composition is dried. It shows the components that remain without vaporization, and also includes those that are liquid, candy-like, and wax-like at room temperature around 25 ° C.

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

According to the photosensitive resin composition of the present embodiment, the component (A) having the specific structure: the high molecular weight substance, the component (B) having the specific structure: the low molecular weight substance, and the component (C): By containing the photopolymerization initiator and the component (D): the secondary thiol compound, excellent pattern forming property on the copper surface of the substrate can be realized, and the development residue on the copper surface can be realized. Can be suppressed. The present inventors infer the reason why such an effect is obtained as follows. That is, the secondary thiol compound which is the component (D) functions as a chain transfer agent, increases the curing rate, and improves the adhesion of the cured product of the photosensitive resin composition to the copper surface to form a pattern. Can have the effect of improving. In particular, the secondary thiol compound easily reacts with the photopolymerizable functional groups of the components (A) and (B) and easily improves the curability, so that even if the film thickness is thickened with a thin line (high aspect). Even if it does not impair the curability, it is possible to impart excellent pattern-forming property to the photosensitive resin composition. Further, the secondary thiol compound has a large steric hindrance around the thiol group as compared with the primary thiol compound, so that it is difficult to coordinate to the copper surface, and the development residue can be reduced. Therefore, according to the above-mentioned photosensitive resin composition, excellent pattern forming property can be realized on the copper surface of the substrate even when a photosensitive layer of a thick film (for example, a thickness of 70 μm or more) is formed. Moreover, the generation of development residue on the copper surface can be suppressed.

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

<Component (A): high molecular weight body>
The photosensitive resin composition of the present embodiment contains a high molecular weight material having a photopolymerizable functional group and a carbon-nitrogen bond as the component (A). The "high molecular weight substance" means a compound having a weight average molecular weight (Mw) of 2,500 or more. In the present specification, the value of the weight average molecular weight (Mw) is a value obtained by the gel permeation chromatography (GPC) method using tetrahydrofuran (THF) in terms of standard polystyrene.

Examples of the photopolymerizable functional group contained in the component (A) include an ethylenically unsaturated group such as a (meth) acryloyl group; an alkenyl group such as a vinyl group and an allyl group. From the viewpoint of improving pattern formation, the component (A) may contain a high molecular weight substance having a (meth) acryloyl group as a photopolymerizable functional group, and further, a high molecular weight substance having a urethane bond as a carbon-nitrogen bond. May include. Examples of the high molecular weight substance having a (meth) acryloyl group include (meth) acrylate, and examples of those having a urethane bond as a carbon-nitrogen bond include, for example, a (meth) acrylate having a urethane bond (hereinafter, “meth) acrylate”. It may be referred to as "urethane (meth) acrylate"). In particular, when the photopolymerizable functional group is a (meth) acryloyl group, the reactivity between the (meth) acryloyl group and the secondary thiol group of the component (D) is high, so that the curability is further improved and the copper of the substrate is used. More excellent pattern formability can be realized on the surface. Further, the component (D) is easily incorporated into the resin having a (meth) acryloyl group, and the coordination of the secondary thiol group of the component (D) on the copper surface is hindered, so that the development residue is further reduced. be able to. The same effect can be obtained when the component (B) has a (meth) acryloyl group as a photopolymerizable functional group.

The component (A) has at least one of these photopolymerizable functional groups and at least one carbon-nitrogen bond. Further, the total number of photopolymerizable functional groups (number of functional groups) contained in the high molecular weight substance of the component (A) is 2 to 30, 2 to 24 in one molecule from the viewpoint of improving pattern forming property and heat resistance. It can be appropriately selected from 2 to 20 or 2 to 15, and from the viewpoint of stabilizing the physical properties and properties of the obtained cured product and reducing the tackiness, 6 to 12, 6 to 10 or 6 to 12, 6 to 10 or , 6 to 8 can be appropriately selected.

In addition, in this specification, "tack property" means surface adhesiveness of a photosensitive layer formed by using a photosensitive resin composition (when the liquid photosensitive resin composition is directly applied on a substrate, it is applied. And the surface adhesiveness of the coating film after drying). If the tackiness is high, the manufacturing equipment is easily contaminated, and the manufacturing may be interrupted to clean the equipment, or the photosensitive layer may be defective. Therefore, it is required to reduce the tackiness.

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

As the high molecular weight urethane (meth) acrylate, for example, a (meth) acrylate having a hydroxyl group is reacted with the terminal isocyanate group of a heavy adduct of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound. Examples thereof include the reaction products produced.

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) hexafluoropropane, bicycloheptanetriisocyanate and other alicyclic diisocyanate compounds; 1,4-phenylenediocyanate, 2,4-Tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, hydrogenated xylylene diisocyanate, Examples thereof include diisocyanate compounds such as aromatic diisocyanate compounds such as naphthalene-1,5-diisocyanate, and multimers such as uretdione-type dimerates, isocyanurate-type and biuret-type trimers of these diisocyanate compounds. These can be used alone or in combination of two or more, and the two or three isocyanate compounds constituting the multimer may be the same or different.
Above all, from the viewpoint of improving the pattern forming property, it may be appropriately selected from the alicyclic diisocyanate compound and the multimer of the diisocyanate compound, and in particular, isophorone diisocyanate and the isocyanurate type multimer (isocyanurate type polyisocyanate) are appropriately selected. You can select it.
The above isocyanate compounds can be used alone or in combination of two or more.

Examples of the diol compound include diol compounds having 1 to 20 carbon atoms, and specifically, ethylene glycol, diethylene glycol, propanediol, dipropylene glycol, butanediol, pentanediol, isopentyl glycol, and hexanediol. , Nonandiol, decanediol, dodecanediol, dimethyldodecanediol, octadecanediol and other linear or branched saturated diol compounds; butenediol, pentendiol, hexenediol, methylpentenediol, dimethylhexenediol and the like. Alternatively, branched unsaturated diol compounds; diol compounds having an alicyclic skeleton such as various cyclohexanediols, various cyclohexanedimethanols, various tricyclodecanedimethanols, hydride bisphenol A, and hydride bisphenol F can be mentioned. Here, the saturated diol compound and the unsaturated diol compound can be collectively referred to as a diol compound having a chain hydrocarbon skeleton.
The above diol compounds can be used alone or in combination of two or more.

The diol compound having a chain hydrocarbon skeleton has 1 to 20 carbon atoms and 2 to 16 carbon atoms from the viewpoint of improving the pattern forming property and increasing the glass transition point (Tg) after polymerization to improve the water resistance. , 2 to 14 saturated diol compounds may be appropriately selected, and more specifically, ethylene glycol and octadecane diol may be appropriately selected.

Further, the diol compound having an alicyclic skeleton has 5 to 20, 5 carbon atoms from the viewpoint of improving the pattern forming property and increasing the glass transition point (Tg) after polymerization to improve the water resistance. It may be appropriately selected from diol compounds having 18, 6 to 16 alicyclic skeletons, and more specifically, various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol, 1,3-. It may be appropriately selected from various cyclohexanedimethanols such as cyclohexanedimethanol and 1,4-cyclohexanedimethanol.

Examples of the (meth) acrylate having a hydroxyl group include a compound having at least one hydroxyl group and at least one (meth) acryloyl group in one molecule. More specifically, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- Hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl (meth) acrylate, 2-hydroxy-3- (1-naphthoxy) propyl (meth) acrylate, 2-hydroxy- Monofunctional (meth) acrylates such as 3- (2-naphthoxy) propyl (meth) acrylates, their ethoxylated forms, their propoxylates, their ethoxylated propoxylates, and their caprolactone variants; trimethylol Bifunctional (meth) acrylates such as propanedi (meth) acrylate, glycerindi (meth) acrylate, bis (2- (meth) acryloyloxyethyl) (2-hydroxyethyl) isocyanurate, these ethoxylated forms, these Propoxides of, these ethoxylated propoxys, and their caprolactone variants; cyclohexanedimethanol type epoxy di (meth) acrylate, tricyclodecanedimethanol type epoxy di (meth) acrylate, hydrogenated bisphenol A type epoxy di (meth). ) Acrylate, hydrogenated bisphenol F type epoxy di (meth) acrylate, hydroquinone type epoxy di (meth) acrylate, resorcinol type epoxy di (meth) acrylate, catechol type epoxy di (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type Bifunctional epoxy (meth) acrylates such as epoxy di (meth) acrylate, bisphenol AF type epoxy di (meth) acrylate, biphenol type epoxy di (meth) acrylate, fluorene bisphenol type epoxy di (meth) acrylate, and isocyanurate monoallyl type epoxy di (meth) acrylate. Trifunctional or higher functional (meth) acrylates such as ditrimethylol propantri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and ethoxylation thereof. The body, these propoxys, these ethoxylated propoxys, and these caprolactone variants; Trifunctional or higher functional epoxy (meth) acrylates such as enol novolac type epoxy (meth) acrylate, cresol novolac type epoxy poly (meth) acrylate, isocyanuric acid type epoxy tri (meth) acrylate; trimethylolpropane tri (meth) acrylate, ditri Examples thereof include hydroxypropylated products such as methylolpropanetetra (meth) acrylate.
These can be used alone or in combination of two or more.

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

A reaction product obtained by reacting a (meth) acrylate having a hydroxyl group with a terminal isocyanate group of a heavy adduct of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound is described by, for example, the following general formula ( Examples thereof include those having a structural unit represented by 1).

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 chain hydrocarbon skeleton or an alicyclic skeleton. Indicates a divalent organic group having. Further, when the component (A) has a plurality of the structural units, the plurality of X ¹ and Y ¹ may be the same or different. That is, as the component (A), 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 can be mentioned.

Examples of the divalent organic group of X ¹ include an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, and an organic group derived from an aromatic diisocyanate compound, that is, the above-mentioned isocyanate compound, which is exemplified as the compound having an isocyanate group. Examples thereof include a divalent organic group having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton, which is a residue excluding the isocyanate group. Further, the divalent organic group represented by X ¹ may be these residues themselves, or residues derived from an isocyanate compound derivative such as a heavy adduct of the isocyanate compound and the diol compound. You may.

From the viewpoint of improving the pattern forming property and improving the transparency, water resistance, and moisture resistance of the resin composition in a well-balanced manner, X ¹ is a divalent organic group having an alicyclic skeleton, among which the following formula is used. It may be a divalent organic group having an alicyclic skeleton, which is a residue of isophorone diisocyanate represented by (2).

Examples of the divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton of Y ¹ include a diol compound having a chain hydrocarbon skeleton and a diol having an alicyclic skeleton exemplified as the above diol compound. Examples thereof include an organic group derived from the 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 diol compound.

Among them, the divalent organic group having a chain hydrocarbon skeleton has 1 carbon atom from the viewpoint of improving the pattern forming property and increasing the glass transition point (Tg) after polymerization to improve the water resistance. It may be appropriately selected from the residues obtained by removing the hydroxyl groups from the saturated diol compounds of ~ 20, 2 to 16 and 2 to 14, and more specifically, it may be appropriately selected from the residues obtained by removing the hydroxyl groups from ethylene glycol and octadecanediol. Just do it. From the same viewpoint, as the divalent organic group having an alicyclic skeleton, the residue obtained by removing the hydroxyl group from the diol compound having an alicyclic skeleton having 5 to 20, 5 to 18, 6 to 16 carbon atoms. It may be appropriately selected from the groups, and more specifically, various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and the like. It may be appropriately selected from the residues obtained by removing the hydroxyl group from various cyclohexanedimethanol.

Specifically, as a reaction product obtained by reacting a (meth) acrylate having a hydroxyl group with a terminal isocyanate group of a heavy adduct of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound, for example, , Compounds represented by the following general formulas (3) and (4) can be mentioned.

In the general formulas (3) and (4), n ₁ and n ₂ each independently represent an integer of 3 to 20.

Further, as the reaction product when an isocyanurate-type trimer (isocyanurate-type triisocyanate), which is a trimer of diisocyanate, is used as the isocyanate compound, for example, the following general formulas (5) and (6) are used. Examples include the compounds shown.

In the general formulas (5) and (6), n ₃ and n ₄ each independently represent an integer of 2 to 20.

Examples of commercially available products containing urethane acrylate represented by the general formula (1) or (3) include UN-952 (number of functional groups: 10, Mw: 6,500 to 11,000) and UN-953 (functional). Cardinal number: 20, weight average molecular weight: 14,000-40,000), UN-954 (number of functional groups: 6, weight average molecular weight: 4,500), H-219 (number of functional groups: 9, weight average molecular weight: 25, 000 to 50,000) (all of the above are trade names, manufactured by Negami Kogyo Co., Ltd.). Further, as a commercially available product containing urethane acrylate represented by the general formula (6), for example, UN-905 (number of functional groups: 15, Mw: 40,000 to 200,000) (trade name, manufactured by Negami Kogyo Co., Ltd.). ) Etc. can be mentioned.
Among these, UN-952 and UN-954 are preferable, and UN-954 is more preferable, from the viewpoint of pattern formation and photosensitivity.
In the above description, the number of functional groups and Mw in parentheses are the total number of (meth) acryloyl groups contained in the urethane (meth) acrylate and the weight average molecular weight, respectively.

The total number of (meth) acryloyl groups (number of photopolymerizable functional groups) contained in the high molecular weight urethane (meth) acrylate is 2 to 30, 2 to 2 in one molecule from the viewpoint of improving pattern formation and heat resistance. It may be appropriately selected from 24, 2 to 20, or 2 to 15, and from the viewpoint of stabilizing the physical properties and properties of the obtained cured product and reducing the tackiness, 6 to 12, 6 to 10, Alternatively, it may be appropriately selected from 6 to 8.
When the number of photopolymerizable functional groups is 6 or more, it is possible to improve the pattern forming property, heat resistance, and rigidity of the cured product at high temperature. On the other hand, when the number of photopolymerizable functional groups is 30 or less, the rigidity of the cured product is improved and the adhesion to the substrate or the like is improved. In addition, a resin composition having an appropriate viscosity can be obtained, the coatability is improved, and when the resin composition after coating is irradiated with light, only the surface portion is easily photocured rapidly and the inside is easily cured. Can suppress the phenomenon that photocuring does not proceed sufficiently, and excellent resolution can be obtained. Therefore, excellent pattern formability can be obtained even when a thick photosensitive layer is formed. Further, after at least one of photo-curing and thermosetting is performed, the residual unreacted (meth) acryloyl group can be further reduced, and fluctuations in the physical properties and properties of the obtained cured product can be further suppressed.

The weight average molecular weight of the component (A) is 2,500 or more, and may be 3,000 or more from the viewpoint of improving the coatability and resolution of the resin composition, and further improving the developability and compatibility. From the viewpoint, it may be 3,500 or more. On the other hand, the upper limit of the weight average molecular weight may be 100,000 or less or 50,000 or less from the viewpoint of improving the coatability and resolvability of the resin composition, and further developability and compatibility. From the viewpoint of improvement, it may be 40,000 or less, or 20,000 or less.
When the weight average molecular weight is 2,500 or more, when it is applied on a substrate, the generation of dripping of the applied composition can be suppressed, so that excellent film formability can be obtained. In addition, it is possible to easily form a thick photosensitive layer, and it is possible to suppress the problem that the stress of the resin due to curing shrinkage increases and the reliability decreases.
On the other hand, when the weight average molecular weight is 100,000 or less, the coatability is improved, a thick photosensitive layer is easily formed, and the pattern formability is improved. In addition, since the solubility in a developing solution is also good, excellent resolution can be exhibited. Further, the transparency of the cured product is improved, and a cured product having an excellent transmittance required as a transparent material can be obtained.

From the above, in one embodiment of the present embodiment, the component (A) has an ethylenically unsaturated group of 6 to 30 as a photopolymerizable functional group, and has a weight average molecular weight of 2,500 to 100,000. It may be a photosensitive resin composition containing a certain high molecular weight substance. Further, the photosensitive resin composition in which the component (A) contains a high molecular weight substance having 6 to 8 ethylenically unsaturated groups as a photopolymerizable functional group and having a weight average molecular weight of 2,500 to 50,000. It may be a thing.

The content of the component (A) may be appropriately selected from 10% by mass or more, 20% by mass or more, or 30% by mass or more based on the total solid content of the photosensitive resin composition. When the content is 10% by mass or more, the coatability is improved, and excellent pattern forming property can be obtained even when a thick photosensitive layer is formed.
Considering the pattern formability and coatability 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 the component (A) is the solid content of the photosensitive resin composition. Based on the total amount, it may be appropriately selected from 95% by mass or less, 85% by mass or less, or 75% by mass or less.

The content of the high molecular weight urethane (meth) acrylate in the component (A) is 70 to 100% by mass, 80, based on the total solid content of the component (A) from the viewpoint of improving the pattern forming property. It may be appropriately selected from -100% by mass, 90 to 100% by mass, 95 to 100% by mass, or 100% by mass (total amount).

<Component (B): low molecular weight substance>
The photosensitive resin composition of the present embodiment contains a low molecular weight substance having a photopolymerizable functional group as the component (B). By "low molecular weight" is meant a compound having a weight average molecular weight of less than 2,500. Here, even when the low molecular weight substance having a photopolymerizable functional group has a silicon atom, the low molecular weight substance having a photopolymerizable functional group is used instead of the silane compound of the component (F) described later. Prioritize the existence and classify it into the component (B).

Examples of the photopolymerizable functional group contained in the component (B) include an ethylenically unsaturated group such as a (meth) acryloyl group; an alkenyl group such as a vinyl group and an allyl group. The component (B) may be a low molecular weight substance having at least one photopolymerizable functional group, and the component (B) may be a (meth) acryloyl group as a photopolymerizable functional group from the viewpoint of improving pattern formation. May have. The component (B) may have two or more photopolymerizable functional groups or may have two to five photopolymerizable functional groups from the viewpoint of improving the pattern forming property.

In the photosensitive resin composition of the present embodiment, as the component (B), the component (B1): a low molecular weight substance having an isocyanul ring, the component (B2): a low molecular weight substance having a urethane bond, and the component (B3): fat. It preferably contains at least one selected from the group consisting of low molecular weight bodies having a cyclic skeleton. When the photosensitive resin composition of the present embodiment contains at least one of these, the adhesion of the electronic component to the substrate or the like is improved, and excellent pattern forming property tends to be obtained. In the case of a low molecular weight substance having two or more of an isocyanul ring, a urethane bond, and an alicyclic skeleton, if it has at least an isocyanul ring, it is classified as a component (B1), and is also classified as a urethane bond. When it has an alicyclic skeleton, it is classified as a component (B2) with priority given to having a urethane bond. That is, a low molecular weight substance having an alicyclic skeleton without an isocyanul ring and a urethane bond is classified as the component (B3).

(Component (B1): low molecular weight substance having an isocyanul ring)
The component (B1) may have two or more photopolymerizable functional groups or two to five photopolymerizable functional groups from the viewpoint of improving the pattern forming property, and may have two or five photopolymerizable functional groups. It may have two or three sex functional groups, or it may have three.
The photopolymerizable functional group contained in the component (B1) has been described as the photopolymerizable functional group contained in the component (B) described above, and is used as the photopolymerizable functional group from the viewpoint of improving the pattern forming property. It may have a (meth) acryloyl group.

Examples of the component (B1) include a compound represented by the following general formula (7).

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

In the general formula (7), the alkylene group having 1 to 6 carbon atoms represented by R ⁴ , R ⁵ and R ⁶ may be an alkylene group having 1 to 4 carbon atoms, or an alkylene group having 1 to 3 carbon atoms. There may be.
Examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, an isopropylene group, an isobutylene group, a t-butylene group, a pentylene group, a hexylene group and the like. , It may be an ethylene group from the viewpoint of improving the pattern forming property.

In the general formula (7), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and may be a hydrogen atom from the viewpoint of improving the pattern forming property.

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

The compound represented by the general formula (7) may be at least one selected from the group consisting of the compound represented by the following formula (7-1) and the compound represented by the following formula (7-2). Often, from the viewpoint of improving the pattern forming property, the compound represented by the following formula (7-1) may be used.

The weight average molecular weight of the component (B1) is less than 2,500, and from the viewpoint of improving the pattern forming property, it may be appropriately selected from 200 to 1,500, 300 to 1,000, or 350 to 600. Good.

As the component (B1), a commercially available product may be used. Examples of commercially available products include "A-9300" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (compound represented by the above formula (7-1)) and "M-215" manufactured by Toagosei Co., Ltd. (the above formula (the above formula (the above formula)). Examples include the compound) represented by 7-2).
The component (B1) can be used alone or in combination of two or more.

(Component (B2): low molecular weight substance having urethane bond)
The component (B2) may have two or more photopolymerizable functional groups or two to six photopolymerizable functional groups from the viewpoint of improving the pattern forming property, and may have two or six photopolymerizable functional groups. It may have 2 to 4 sex functional groups or 2 photopolymerizable functional groups.

The photopolymerizable functional group contained in the component (B2) has been described as the photopolymerizable functional group contained in the component (B) described above, and is used as the photopolymerizable functional group from the viewpoint of improving the pattern forming property. It may have a (meth) acryloyl group.
In the present specification, the component (B2) having a (meth) acryloyl group as a photopolymerizable functional group may be simply referred to as "low molecular weight urethane (meth) acrylate".

Examples of the low molecular weight urethane (meth) acrylate include a reaction product of a (meth) acrylate having a hydroxyl group and an isocyanate compound having an isocyanate group. Here, examples of the (meth) acrylate having a hydroxyl group and the isocyanate compound include the acrylate having a hydroxyl group and the isocyanate compound exemplified as the raw materials used for producing the high molecular weight substance described in the description of the component (A) above. Be done. As the isocyanate compound, a monoisocyanate compound may be used in addition to the above. Examples of the monoisocyanate compound include aliphatic monoisocyanate compounds such as ethyl isocyanate, propyl isocyanate, butyl isocyanate, octadecyl isocyanate and 2-isocyanate ethyl (meth) acrylate; alicyclic monoisocyanate compounds such as cyclohexyl isocyanate; phenylisocyanate and the like. Aromatic monoisocyanate compounds and the like.
Here, as an example of what is appropriately selected from the viewpoint of improving pattern formation and the like, the same one which is appropriately selected as being used for producing a high molecular weight body from the same viewpoint is exemplified.

As the low molecular weight urethane (meth) acrylate, a (meth) acrylate having a hydroxyl group is reacted with the terminal isocyanate group of the heavy adduct of the isocyanate compound having at least two isocyanate groups in one molecule and the diol compound. Examples thereof include the reaction products produced. Here, as the isocyanate compound having at least two isocyanate groups in one molecule, the diol compound, and the (meth) acrylate having a hydroxyl group, each of them has an isocyanate group in one molecule exemplified as being used for producing a high molecular weight compound. Examples thereof include an isocyanate compound having at least two of them, a diol compound, and a (meth) acrylate having a hydroxyl group. Here, as an example of what is appropriately selected from the viewpoint of improving pattern formation and the like, the same one which is appropriately selected as being used for producing a high molecular weight body from the same viewpoint is exemplified.
Examples of this reaction product include those having a structural unit represented by the following general formula (8).

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 chain hydrocarbon skeleton or an alicyclic skeleton. Indicates a divalent organic group having. That is, as the component (B2), 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 can be mentioned. Examples of X ² and Y ² are the same as those of X ¹ and Y ¹ in the general formula (1), respectively.

From the viewpoint of improving the pattern forming property and improving the transparency, water resistance, and moisture resistance of the resin composition in a well-balanced manner, X ² is a divalent organic group having a chain hydrocarbon skeleton, which is branched. It may be appropriately selected from a divalent organic group having a chain hydrocarbon skeleton, a branched alkylene group having 2 to 12 carbon atoms, for example, a residue of the above aliphatic diisocyanate compound. From the same viewpoint, Y ² may be appropriately selected from the residues of a divalent organic group having an alicyclic skeleton, for example, the diol compound having the alicyclic skeleton.

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

In the above general formula (9), n ₅ represents an integer of 1 to 4. R ¹⁰ and R ¹¹ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a plurality of R ¹⁰ and R ¹¹ are each an alkyl group having at least 3 carbon atoms having 1 to 4 carbon atoms. ..

Among the urethane acrylates represented by the general formula (9), X ² of the general formula (8) is a residue of trimethylhexamethylene diisocyanate which is a divalent organic group having a chain hydrocarbon skeleton, and Y ^As a commercially available product containing urethane acrylate having a structural unit in which 2 is a residue of a divalent organic group cyclohexanedimethanol having an alicyclic skeleton, for example, TMCH-5R (trade name, number of functional groups: 2, Mw: 950, manufactured by Hitachi Kasei Co., Ltd.) and the like.

Further, as commercially available products containing urethane (meth) acrylate having a structural unit represented by the above general formula (8), KRM8452 (number of functional groups: 10, Mw: 1,200, manufactured by Daicel Ornex Co., Ltd.), UN Examples thereof include -3320HA (number of functional groups: 6, Mw: 1,500, manufactured by Negami Kogyo Co., Ltd.) and UN-3320HC (number of functional groups: 6, Mw: 1,500, manufactured by Negami Kogyo Co., Ltd.). In the above description, the number of functional groups and Mw in parentheses are the total number of (meth) acryloyl groups and the weight average molecular weight contained in the urethane (meth) acrylate, respectively.

The weight average molecular weight of the component (B2) is less than 2,500, may be 2,000 or less from the viewpoint of improving adhesion, and is 1,500 or less from the viewpoint of improving resolution. It may be 1,000 or less. On the other hand, the lower limit of the weight average molecular weight may be 500 or more, or 700 or more, from the viewpoint of film formability, although it can be appropriately used according to a desired purpose.
By containing the component (B2) as the component (B), the effect of improving the pattern forming property is enhanced.

(Component (B3): low molecular weight substance having an alicyclic skeleton)
The component (B3) may have two or more photopolymerizable functional groups or two or four photopolymerizable functional groups from the viewpoint of improving the pattern forming property, and may have two or four photopolymerizable functional groups. It may have two sex functional groups.
The photopolymerizable functional group contained in the component (B3) has been described as the photopolymerizable functional group contained in the component (B) described above, and is used as the photopolymerizable functional group from the viewpoint of improving the pattern forming property. It may have a (meth) acryloyl group.
The alicyclic skeleton contained in the component (B3) is not particularly limited, and examples thereof include an alicyclic hydrocarbon skeleton having 5 to 20 carbon atoms. The alicyclic hydrocarbon skeleton is at least one selected from the group consisting of a cyclopentane skeleton, a cyclohexane skeleton, a cyclooctane skeleton, a cyclodecane skeleton, a norbornane skeleton, a dicyclopentane skeleton, and a tricyclodecane skeleton. May be good. Among these, a tricyclodecane skeleton may be used from the viewpoint of improving pattern formation.

The weight average molecular weight of the component (B3) is less than 2,500, may be 2,000 or less from the viewpoint of improving adhesion, and is 1,500 or less from the viewpoint of improving resolution. It may be 1,000 or less, or 500 or less. On the other hand, the lower limit of the weight average molecular weight may be 150 or more, or 200 or more, from the viewpoint of film formability, although it can be appropriately used according to a desired purpose.

The component (B3) may be tricyclodecanedimethanol diacrylate from the viewpoint of pattern formation.

As the component (B3), a commercially available product may be used. Examples of commercially available products include A-DCP (tricyclodecanedimethanol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and the like.

The content (total content) of the component (B) is appropriately from 5% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more based on the total solid content of the photosensitive resin composition. You may choose. When the content of the component (B) is 5% by mass or more, excellent pattern forming property can be obtained even when a thick photosensitive layer is formed, and excellent rigidity of the cured product can also be obtained. From the same viewpoint as this, the upper limit of the content of the component (B) is appropriately from 70% by mass or less, 60% by mass or less, or 50% by mass or less based on the total solid content of the photosensitive resin composition. You can select it.

The total solid content of the component (A) and the component (E) (however, if the component (E) is not contained, only the component (A)) is based on 100 parts by mass, and the content of the component (B) is pattern-forming. From the viewpoint of improving the rigidity of the cured product, it may be appropriately selected from 20 to 120 parts by mass, 25 to 100 parts by mass, 30 to 80 parts by mass, or 40 to 80 parts by mass.

The total content of the components (B1) to (B3) in the component (B) is 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. It can be appropriately selected from 100% by mass.
When at least two or more of the above components (B1) to (B3) are used, the content of the component (B2) in the total solid content of the component (B) is 10% by mass or more and 15% by mass or more. , 20% by mass or more may be appropriately selected. When the content of the component (B2) is 10% by mass or more, excellent pattern forming property can be obtained even when a thick photosensitive layer is formed, and excellent rigidity of the cured product can also be obtained. From the same viewpoint as this, the upper limit value of the component (B2) may be appropriately selected from 90% by mass or less, 80% by mass or less, and 70% by mass or less.

<Component (C): Photopolymerization initiator>
The photosensitive resin composition of the present embodiment contains a photopolymerization initiator as the component (C). The component (C) is not particularly limited as long as it can polymerize at least one of the component (A) and the component (B), and can be appropriately selected from commonly used photopolymerization initiators. From the viewpoint of improving pattern formation, those that generate free radicals by active light, for example, acylphosphine oxide type, oxime ester type, aromatic ketone type, quinone type, alkylphenone type, imidazole type, acridine type, phenylglycine Examples thereof include photopolymerization initiators such as radicals and coumarins.

The acylphosphine oxide-based photopolymerization initiator has an acylphosphine oxide group [> P (= O) -C (= O) -R], and is, for example, (2,6-dimethoxybenzoyl) -2,4. , 6-Pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("IRGACURE-TPO" (BASF)), ethyl-2 , 4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphenyl oxide ("IRGACURE-819" (manufactured by BASF)), (2,5-dihydroxyphenyl) diphenylphosphine Examples thereof include oxides, (p-hydroxyphenyl) diphenylphosphine oxide, bis (p-hydroxyphenyl) phenylphosphine oxide, tris (p-hydroxyphenyl) phosphine oxide and the like.

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

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

Examples of the quinone-based photopolymerization initiator include 2-ethylanthraquinone, phenanthrenquinone, 2-t-butyl anthraquinone, octamethyl anthraquinone, 1,2-benz anthraquinone, 2,3-benz anthraquinone, 2-phenylanthraquinone, and 2 , 3-Diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, etc. Be done.

Examples of the alkylphenone-based photopolymerization initiator include benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin phenyl ether, and 2,2-dimethoxy-1,2-diphenylethane-1-. On ("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-propane-1-one ("IRGACURE-") 2959 ”(manufactured by BASF)), 2-Hirodoxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (“IRGACURE) -127 "(manufactured by BASF)) and the like.

Examples of the imidazole-based photopolymerization initiator as a 2,4,5-triarylimidazole dimer include 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl. -1,3-Diazole-2-yl] -4,5-diphenylimidazole and other 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, 2- (P-methoxyphenyl) -4,5-diphenylimidazole dimer and the like can be mentioned.

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

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

Examples of the coumarin-based photopolymerization initiator include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, and 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-diethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin , 4,6-diethyl-7-dimethylaminocoumarin, 2,3,6,7,10,11-hexanehydro-1H, 5H-cyclopenta [3,4] [1] benzopyrano- [6,7,8- ij] Kinolidine 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.

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

( ^RC1 , ^RC2 and ^RC3 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and ^RC4 and ^RC5 independently represent each other. hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ^R C1 ^{to R C5} other than a hydrogen atom, each have a substituent May be.)

( ^RC6 represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an amino group, and ^RC7 and ^RC8 each independently have a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 6 to 12 carbon atoms. aryl group, or .R ^C7 and R ^C8 to an alkoxy group having 1 to 8 carbon atoms may be bonded to each other to form a cyclic structure of 3 to 16 carbon atoms. other than hydroxyl and hydrogen atoms R ^C6 to R ^C8 may have each a substituent, an amino group having a substituent bonded to another substituent of each other, may form a cyclic structure having 3 to 12 carbon atoms Each ^RC9 may independently contain one or more atoms selected from a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an oxygen atom, a nitrogen atom and a sulfur atom, and has 1 to 1 carbon atoms. Shows 10 organic groups.)

In the general formula (C1), ^RC1 , ^RC2 and ^RC3 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
The alkyl group having 1 to 6 carbon atoms represented by ^RC1 , ^RC2 and ^RC3 may be an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 or 2 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-heptyl group, an n-hexyl group and the like.
The alkoxy group having 1 to 6 carbon atoms represented by ^RC1 , ^RC2 and ^RC3 may be an alkoxy group having 1 to 3 carbon atoms or an alkoxy group having 1 or 2 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, an n-butoxy group, a tert-butoxy group and the like.
Among these groups, ^RC1 , ^RC2 and ^RC3 may be methyl groups from the viewpoint of improving pattern formation.

In the general formula (C1), ^RC4 and ^RC5 each independently represent 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. ..
Alkoxy groups of the alkyl group and 1 to 6 carbon atoms having 1 to 6 carbon atoms which R ^C4 and ^{R C5} are ^represented, is described as in the case of R ^{C1, R C2} and ^{R C3.}
The aryl group having 6 to 12 carbon atoms represented by ^RC4 and ^RC5 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.

The R ^C1 to R ^C5 substituent which may be have, for example, a halogen atom, a carboxyl group, hydroxy group, an amino group, a mercapto group, an alkyl group having 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms Examples thereof include a group and an aryl group having 6 to 12 carbon atoms. Alkyl group R ^C1 to R ^C5 is the substituent which may have, an alkoxy group and aryl group, an alkyl group described as R ^C1 to R ^C5, are the same as those of the alkoxy group and an aryl group ..

In the general formula (C2), ^RC6 represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an amino group.
The alkoxy group represented by ^RC6 is described in the same manner as in the case of ^RC1 , ^RC2 and ^RC3 in the general formula (C1).
Among these groups, ^RC6 may be a hydroxyl group from the viewpoint of improving pattern formation.

In the general formula (C2), ^RC7 and ^RC8 independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ..
Alkyl groups R ^C7 and ^{R C8} are represented, alkoxy group and aryl group, an alkyl ^{group R} C1 ^{to R C5} in the general formula (C1) is represented, are the same as those of the alkoxy group and aryl group.
R ^C7 and ^{R C8} are bonded to each other, may form a cyclic structure of 3 to 16 carbon atoms.
The cyclic structure may be a cyclic structure having 4 to 10 carbon atoms or a cyclic structure having 5 to 8 carbon atoms.
The cyclic structure may be an alicyclic structure from the viewpoint of improving the pattern forming property, and examples of the alicyclic structure include a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. In addition, these alicyclic structures may contain carbon atoms to which ^RC7 and ^RC8 are directly bonded together.

The substituents R ^C6 to R ^C8 may have, ^R C1 ^{to R C5} in formula (C1) is explained similarly to the substituent which may have.
However, the amino group having a substituent may form a cyclic structure having 3 to 12 carbon atoms by bonding the substituents to each other.
The cyclic structure formed by the substituent of the amino group may be a cyclic structure having 3 to 10 carbon atoms or a cyclic structure having 3 to 5 carbon atoms.
The cyclic structure may be a 5 to 10-membered ring containing a nitrogen atom of an amino group, a 5 to 7-membered ring containing a nitrogen atom of an amino group, or a 6-membered ring containing a nitrogen atom of an amino group. It may be a ring. Furthermore, these cyclic structures may contain heteroatoms other than nitrogen atoms such as oxygen atoms. Specific examples of the cyclic structure formed by the substituent of the amino group include a structure (morpholino group) represented by the following formula (C3).

In the general formula (C2), each ^RC9 independently contains one or more atoms selected from a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an oxygen atom, a nitrogen atom and a sulfur atom. It shows a good organic group having 1 to 10 carbon atoms.
The organic group having 1 to 10 carbon atoms represented by ^RC9 may be an organic group having 1 to 6 carbon atoms or an organic group having 1 to 4 carbon atoms.
The organic group having 1 to 10 carbon atoms represented by ^RC9 may be a hydrocarbon group such as an alkyl group, an alkenyl group or an aryl group. These alkyl group, the alkenyl group and an aryl group, an alkyl group represented by R ^C1 to R ^C5 in formula (C1), those similar to the alkenyl group and aryl group.
Examples of the organic group having 1 to 10 carbon atoms containing an oxygen atom represented by ^RC9 include an alkoxy group having 1 to 10 carbon atoms.
Examples of the organic group having 1 to 10 carbon atoms containing a nitrogen atom represented by ^RC9 include a group represented by the above general formula (C3).
Examples of the organic group having 1 to 10 carbon atoms containing a sulfur atom represented by ^RC9 include an alkylthio group such as a methylthio group.

The content of the component (C) is such that the absorbance of the photosensitive layer formed by the photosensitive resin composition (thickness after drying) of 50 μm with respect to light having a wavelength of 365 nm is 0.35 or less, 0.3 or less. It may be appropriately selected from an amount of 0.2 or less, or an amount of 0.1 or less. With the above content, for example, even when a pattern is formed with a thick photosensitive layer of 70 μm or more, light can easily pass to the bottom of the photosensitive layer (the surface of the photosensitive layer on the substrate side), so that the pattern is formed. The sex can be improved. Here, the absorbance can be adjusted to a wavelength of 365 nm by using, for example, an ultraviolet-visible spectrophotometer (product name: “U-3310 Spectrophotometer”, manufactured by Hitachi High-Technologies Corporation) and using a polyethylene terephthalate film alone as a reference. The absorbance for light can be measured.

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

In addition to the above component (C), N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like are three. (C') photopolymerization initiators such as secondary amines can also be used alone or in combination of two or more.

<Component (D): Secondary thiol compound>
The photosensitive resin composition of the present embodiment contains a secondary thiol compound as the component (D). The secondary thiol compound is a compound having a secondary thiol group and functions as a chain transfer agent in the photosensitive resin composition.

The component (D) may contain a polyfunctional secondary thiol compound having two or more secondary thiol groups. By using the polyfunctional secondary thiol compound, it is easier to react with the photopolymerizable functional groups of the components (A) and (B), and it is easier to improve the curability, so that the pattern forming property can be further improved. It is possible to realize excellent pattern forming property on the copper surface of the substrate.

Further, the component (D) may contain a secondary thiol compound having at least one skeleton selected from the group consisting of a pentaerythritol skeleton and an isocyanul ring skeleton. By using a secondary thiol compound having these skeletons, odor can be suppressed, workability and handleability can be improved, storage stability can be improved, and the curability of the photosensitive resin composition can be improved. ..

Examples of the secondary thiol compound include secondary butane thiol, 2,3-butane dithiol, hexa-5-ene-3-thiol, secondary dodecane thiol, secondary heptane thiol, secondary hexane thiol, and secondary hexane thiol. Octadecanthiol, secondary octanethiol, 2-methyl-2-propanethiol and the like. Examples of the secondary thiol compound include compounds represented by the following formulas (10) to (14). In addition, the component (D) can be used alone or in combination of two or more.

The molecular weight of the secondary thiol compound is preferably 150 or more, more preferably 400 or more. The molecular weight of the secondary thiol compound is preferably 5000 or less, more preferably 2000 or less, and even more preferably 1000 or less. When the molecular weight is 150 or more, it tends to be difficult to volatilize during coating. On the other hand, when the molecular weight is 5000 or less, the collision frequency between the secondary thiol compound and the photopolymerizable functional groups of the components (A) and (B) increases, the reaction becomes easier, and the curability is further improved. Therefore, the pattern forming property tends to be further improved.

Further, from the viewpoint of workability at the time of production and handleability of the product, the molecular weight of the secondary thiol compound is more preferably 400 or more. When the molecular weight is less than 400, the odor is strong when the material is blended and when the product is handled, and the workability and handleability tend to be deteriorated. On the other hand, when the molecular weight is 400 or more, the odor is suppressed and the workability and handleability are improved.

The thiol equivalent of the secondary thiol compound is preferably 50 g / eq or more and 500 g / eq or less, and more preferably 120 g / eq or more and 400 g / eq or less. When the thiol equivalent is 50 g / eq or more, the pattern forming property tends to be further improved. On the other hand, when the thiol equivalent is 500 g / eq or less, the pattern forming property tends to be further improved while reducing the residue.

The content of the component (D) in the photosensitive resin composition is 0.02 to 1.0% by mass, 0.07 to 0.8% by mass, or 0.07 to 0.8% by mass, based on the total solid content of the photosensitive resin composition. It may be 0.1 to 0.5% by mass. When the content of the component (D) is 0.02% by mass or more, the resolution on the copper surface tends to be further improved, and when it is 1.0% by mass or less, the resolution is high with the residue reduced. It tends to be possible.

<Component (E): High Tg high molecular weight body>
The photosensitive resin composition of the present embodiment may contain a high molecular weight substance having a glass transition temperature of 70 to 150 ° C. and no carbon-nitrogen bond as the component (E). The “high molecular weight body” is the same as the definition in the above component (A). By containing the component (E), it has the effect of suppressing the tack of the photosensitive resin composition.

The component (E) may contain an ethylenically unsaturated group from the viewpoint of pattern forming property and reducing tack property. Examples of the ethylenically unsaturated group include a (meth) acryloyl group and a vinyl group, which may be a (meth) acryloyl group from the viewpoint of pattern formation.

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, from the viewpoint of pattern forming property and reduction of tackiness. From the viewpoint, it may contain a high molecular weight substance having an alicyclic skeleton.

The high molecular weight compound having an alicyclic skeleton includes, for example, a part of an acid group derived from an acid group-containing acrylic resin (e1) having no carbon-nitrogen bond and an alicyclic having no carbon-nitrogen bond. It can be produced by reacting with an epoxy group derived from the unsaturated compound (e2) containing an epoxy group.

The acid group-containing acrylic resin (e1) having no carbon-nitrogen bond is composed of an acid having an ethylenically unsaturated group and a monomer such as an ester of (meth) acrylic acid, a vinyl aromatic compound, or a polyolefin compound. A copolymer obtained by copolymerizing one or more selected types can be used. Specifically, an acid having an ethylenically unsaturated group such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and (anhydrous) maleic acid is used as an essential component. In addition, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl ( Esters of (meth) acrylic acids such as meth) acrylates; Vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and p-chlorostyrene; Monomers of polyolefin compounds such as butadiene, isoprene and chloroprene, and methyl Examples thereof include a copolymer obtained by copolymerizing one or more monomers selected from other monomers such as isopropenyl ketone, vinyl acetate, and vinyl propionate.

The acid value of the component (e1) may be 15 mgKOH / g or more, or 40 to 500 mgKOH / g. Since the component (e1) has such an acid value, a sufficient amount of acid groups remain in the component (E) even after the component (e1) is reacted with the component (e2) described later. Become.

As the alicyclic epoxy group-containing unsaturated compound (e2) having no carbon-nitrogen bond, a compound having one ethylenically unsaturated group and an alicyclic epoxy group in one molecule is preferable. Specifically, for example, a compound represented by any of the following formulas (I) to (X) can be mentioned.

Here, each ^RE1 is a hydrogen atom or a methyl group independently. Each of ^RE2 is an aliphatic saturated hydrocarbon group independently.
Examples of the aliphatic saturated hydrocarbon group R ^E2 represents a linear or branched alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, an arylene group having 6 to 14 carbon atoms and, Examples thereof include a divalent organic group composed of a combination of these. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group and a hexamethylene group. Examples of the cycloalkylene group include a cyclopentylene group, a cyclohexylene group, a cyclooctylene group and the like. Examples of the arylene group include a phenylene group and a naphthylene group. The divalent organic group comprising a combination thereof, for example, -CH ₂ - phenylene group _-CH 2 -, - CH ₂ - cyclohexylene group -CH ₂ - and the like.
^RE2 includes methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group and cyclohexylene from the viewpoint of pattern formation property and reduction of tack property. groups, -CH 2 _- phenylene group -CH 2 _- and a may well include a methylene group, an ethylene group, may be a propylene group, or may be a methylene group.

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

As the component (E), a commercially available product may be used, and examples thereof include (ACA) Z250 (manufactured by Daicel Ornex Co., Ltd., acid value 101.7 mgKOH / g) of the cyclomer P series. (ACA) Z250 is a resin composed of three structural units represented by the following formula (XI), which is produced by the reaction of an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound.

^{(Wherein, R E1} is ^{.R E3} represents a hydrogen atom or a methyl group represents an alkyl group or hydroxyalkyl group having 1 to 6 carbon atoms having 1 to 6 carbon atoms.)

The glass transition temperature of the component (E) is 70 to 150 ° C., but it 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.

(Method for measuring the glass transition temperature of component (E))
As a pretreatment for measurement, the component (E) is heated at 120 ° C. for 3 hours and then cooled to prepare a sample.
Using 10 mg of the sample, a differential scanning calorimeter (manufactured by Shimadzu Corporation, trade name: DSC-50) is used to raise the temperature in a temperature range of 25 to 200 ° C. and a heating rate of 20 ° C./min under a nitrogen stream. And eliminate the influence of solvent and the like. After cooling to 25 ° C., the temperature is raised again under the same conditions, and the temperature at which the baseline deviation starts is defined as the glass transition temperature.

Further, 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 tack suppressing effect tends to be large, and if it is 50,000 or less, the resolution tends to be improved.

When the photosensitive resin composition of the present embodiment contains the component (E), the content of the component (E) is the component (A) and the component (E) from the viewpoint of pattern formation and reduction of tackiness. It may be 5 to 60 parts by mass, 10 to 40 parts by mass, or 10 to 30 parts by mass with respect to 100 parts by mass of the total components.

<Component (F): Silane compound>
Further, the photosensitive resin composition of the present embodiment can further contain (F) a silane compound having no secondary thiol group. A silane compound having a secondary thiol group is classified into the component (D). As the component (F), a known silane coupling agent can be used. The component (F) can improve the adhesiveness of the electronic component to the substrate, and in particular, when the substrate contains silicon (for example, a glass substrate, a silicon wafer, an epoxy resin impregnated glass cloth substrate, etc.). Is valid. Examples of the silane coupling agent include alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; (meth) acryloxypropyltrimethoxysilane and (meth) acryloxipropylmethyldimethoxysilane. Etc. (meth) acryloyl group-containing alkoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1, 3-Dimethylbutylidene) Amine-based alkoxysilanes such as propylamine; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidoxypropylmethyldi Glycydoxy group-containing alkoxysilanes such as isopropenoxysilane; alicyclic epoxy group-containing alkoxysilanes such as 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane; ureido group-containing alkoxy such as 3-ureidopropyltriethoxysilane Silane; mercapto group-containing alkoxysilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane; carbamate group-containing alkoxysilanes such as triethoxysilylpropylethylcarbamate; 3- (triethoxysilyl) propylsuccinate anhydride Examples thereof include alkoxysilane containing a polybasic acid anhydride group. These can be used alone or in combination of two or more.
From the viewpoint of further improving adhesiveness, (meth) acryloyl group-containing alkoxysilanes such as (meth) acryloxypropyltrimethoxysilane and (meth) acryloxypropylmethyldimethoxysilane, glycidoxypropyltrimethoxysilane, and glycidoxy A silane coupling agent having an ethylenically unsaturated group in the molecule, such as a glycidoxy group-containing alkoxysilane such as propylmethyldiethoxysilane and glycidoxypropylmethyldiisopropenoxysilane, may be used.

When the photosensitive resin composition of the present embodiment contains the component (F), the content of the component (F) is 0.05 to 15% by mass, 0, based on the total solid content of the photosensitive resin composition. .1 to 10% by mass, 0.1 to 7% by mass, 1 to 7% by mass, or 1 to 5% by mass may be appropriately selected. By setting the content as described above, deterioration of the resist shape can be suppressed and pattern forming property can be improved.

<Component (G): Thermal radical polymerization initiator>
In addition, the photosensitive resin composition of the present embodiment can further contain (G) a thermal radical polymerization initiator. The component (G) is not particularly limited, and for example, α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumylperoxide, t-butylcumylperoxide, di-t-butylperoxide and the like. Dialkyl peroxides; ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide; 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy)- 2-Methylcyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexyl) Peroxy) -3,3,5-Peroxyketal such as trimethylcyclohexane; Hydroperoxide such as p-menthanhydroperoxide; Diacylper such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide, benzoyl peroxide, etc. Oxide: Peroxy such as bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutylperoxydicarbonate, etc. Carbonate; t-butylperoxypivalate, t-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-Ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylper Oxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurylate, t-butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate , T-Butylperoxybenzoate, t-Hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, peroxides such as peroxyesters such as t-butylperoxyacetate Polymerization initiator, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2' Examples thereof include azo-based polymerization initiators such as -azobis (4-methoxy-2'-dimethylvaleronitrile).

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

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

<(H) component: inorganic filler>
The photosensitive resin composition of the present embodiment may contain the component (H) for the purpose of further improving various properties such as adhesiveness between the photosensitive resin composition and the substrate, heat resistance, and rigidity of the cured product. it can.

Examples of the component (H) include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TIO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), and silicon nitride (Si ₃ N). ₄ ), barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), magnesium carbonate (MgCO ₃ ), aluminum hydroxide (Al (OH) ₃ ), magnesium hydroxide (Mg (OH) ₂ ), titanium Lead Acid Acid (PbO · TiO ₂ ), Lead Titanium Zirconate (PZT), Lead Titanium Zirconate (PLZT), Gallium Oxide (Ga ₂ O ₃ ), Spinel (MgO · Al ₂ O ₃ ), Murite (3Al) ₂ O ₃ · 2SiO _2), cordierite _{(2MgO · 2Al 2 O 3 ·} 5SiO 2), talc _{(3MgO · 4SiO 2 · H 2} O), aluminum titanate _{(TiO 2 · Al 2 O 3} ), yttria-containing Zirconia (Y ₂ O ₃ · ZrO ₂ ), barium silicate (BaO · 8SiO ₂ ), boron nitride (BN), calcium carbonate (CaCO ₃ ), barium sulfate (BaSO ₄ ), calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO · TiO ₂ ), hydrotalcite, mica, calcined kaolin, carbon (C) and the like can be used. These inorganic fillers can be used alone or in combination of two or more.

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 from the viewpoint of improving adhesiveness, heat resistance, and rigidity of the cured product. Just do it. Here, the average particle size of the component (H) is the average particle size of the inorganic filler dispersed in the photosensitive resin composition, and is a value obtained by measuring as follows. First, the photosensitive resin composition is diluted (or dissolved) 1000 times with methyl ethyl ketone, and then it conforms to the international standard ISO13321 using a submicron particle analyzer (manufactured by Beckman Coulter, Inc., trade name: N5). Then, the particles dispersed in the solvent are measured at a refractive index of 1.38, and the particle size at an integrated value of 50% (volume basis) in the particle size distribution is taken as the average particle size. Further, the component (H) contained in the photosensitive layer or the cured film of the photosensitive resin composition provided on the carrier film is also diluted (or dissolved) 1000 times (volume ratio) with a solvent as described above. After that, it can be measured by using the above-mentioned submicron particle analyzer.

When the photosensitive resin composition of the present embodiment contains the component (H), the upper limit of the content is 10% by mass or less, 5% by mass or less, or based on the total solid content of the photosensitive resin composition. It may be appropriately selected from 1, 1% by mass or less, the lower limit may be appropriately selected from more than 0% by mass, and may be 0% by mass (that is, it may not be included). As described above, by substantially not containing the component (H), the permeability of the photosensitive resin composition is improved, and for example, even when a pattern is formed by a thick photosensitive layer of 70 μm or more, the photosensitive layer is formed. Since light can easily pass through to the bottom of the photosensitive layer (the surface of the photosensitive layer on the substrate side), the pattern forming property is improved.

<Other additives>
The photosensitive resin composition of the present embodiment further contains additives such as a sensitizer, a heat-resistant high molecular weight substance, a heat-crosslinking agent, and an adhesive auxiliary other than the above component (F), if necessary. Can be done.

Examples of the sensitizer include sensitizers such as pyrazolines, anthracenes, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stillbens, triazines, thiophenes and naphthalimides. Agents can be mentioned. These can be used alone or in combination of two or more.

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

The thermal cross-linking agent includes, for example, an epoxy resin, a phenol resin in which the α-position is substituted with a methylol group and an alkoxymethyl group, and a group consisting of a methylol group and an alkoxymethyl group at the N-position, from the viewpoint of improving the rigidity of the cured product. Examples thereof include a melamine resin and a urea resin substituted with at least one selected. These can be used alone or in combination of two or more.

The content of these other additives is not particularly limited as long as it does not impair the effect of the photosensitive resin composition of the present embodiment, and is, for example, 0 based on the total solid content of the photosensitive resin composition. .1 to 10% by mass, 0.3 to 5% by mass, or 0.5 to 5% by mass may be appropriately selected.

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

The amount of the diluent used may be appropriately selected from an amount such that the total amount of solids in the photosensitive resin composition is 50 to 90% by mass, 60 to 80% by mass, or 65 to 75% by mass. That is, when a diluent is used, the content of the diluent in the photosensitive resin composition may be appropriately selected from 10 to 50% by mass, 20 to 40% by mass, or 25 to 35% by mass. By setting the amount of the diluent used within the above range, the coatability of the photosensitive resin composition is improved, and a higher-definition pattern can be formed.

Further, for example, when forming a photosensitive layer having a thickness of 70 μm or more, in consideration of the ease of forming the photosensitive layer, the amount of the diluent used is such that the viscosity of the photosensitive resin composition at 25 ° C. is 0. The amount can be 5 to 20 Pa · s, or 1 to 10 Pa · s.

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

The photosensitive resin composition of the present embodiment may be used as a liquid or as a film.

When used as a liquid, the method for applying the photosensitive resin composition of the present embodiment is not particularly limited, and examples thereof include a printing method, a spin coating method, a spray coating method, a jet dispensing method, an inkjet method, and a dip coating method. Various coating methods can be mentioned. Among these, from the viewpoint of more easily forming a thick photosensitive layer, a printing method or a spin coating method may be appropriately selected.

When used in the form of a film, 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 with a laminator or the like.

The absorbance of the photosensitive layer formed by the photosensitive resin composition of the present embodiment with respect to light having a wavelength of 365 nm at a thickness (thickness after drying) of 50 μm is 0.35 or less, 0.3 or less, 0.2 or less, or. It can be appropriately selected from 0.1 or less. When the absorbance of the photosensitive layer at a thickness of 50 μm is 0.35 or less, for example, even when a pattern is formed by a thick photosensitive layer of 70 μm or more, the bottom of the photosensitive layer (on the substrate side of the photosensitive layer). Since the light can easily pass to the surface), the pattern forming property can be improved. The absorbance of the photosensitive layer against light having a wavelength of 365 nm when the thickness is 50 μm can be obtained by converting the absorbance measured for the photosensitive layer having a thickness other than 50 μm into the absorbance having a thickness of 50 μm based on Lambertbert's law. it can.

[Photosensitive resin film]
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 the present specification, the term "layer" includes not only a structure having a shape formed on the entire surface but also a structure having a shape partially formed when observed as a plan view.

For the photosensitive resin film of the present embodiment, for example, the photosensitive resin composition of the present embodiment is applied onto a carrier film by the above-mentioned various coating methods to form a coating film, and the coating film is dried. , A photosensitive layer can be formed and manufactured. Further, when the photosensitive resin composition of the present embodiment contains a diluent, at least a part of the diluent may be removed at the time of drying.

For drying the coating film, a dryer using hot air drying, far infrared rays, or near infrared rays can be used, and the drying temperature is from 60 to 120 ° C., 70 to 110 ° C., or 90 to 110 ° C. It may be selected as appropriate. The drying time may be appropriately selected from 1 to 60 minutes, 2 to 30 minutes, or 5 to 20 minutes. When dried under the above conditions, when the photosensitive resin composition of the present embodiment contains a diluent, at least a part of the diluent can be removed.

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

The thickness of the carrier film may be appropriately selected from 10 μm to 3 mm or 10 to 200 μm in consideration of handleability and the like.

The thickness of the photosensitive layer may be appropriately selected from 1 to 500 μm, 10 to 300 μm, or 30 to 100 μm. By setting the thickness to 30 μm or more, for example, when forming a photosensitive layer having a thickness of 150 μm or more, the number of operations by laminating or the like can be further reduced. Further, by setting the thickness to 100 μm or less, when the photosensitive resin film is wound around the winding core, the deformation of the photosensitive layer due to the stress difference between the inside and the outside of the winding core can be further reduced. Considering the effect of the photosensitive resin composition of the present embodiment that excellent pattern forming property can be obtained even when a thick photosensitive layer is formed, the thickness of the photosensitive layer may be 70 μm or more. The thickness may exceed 100 μm. The photosensitive layer having a thickness of 70 μm or more may be formed by, for example, laminating a photosensitive layer formed on a carrier film and a photosensitive layer formed on a protective layer described later. .. Thereby, a photosensitive resin film including a carrier film, a thick photosensitive layer, and a protective layer in this order can be obtained.

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

[Manufacturing method of cured product]
The method for producing a cured product of the present embodiment includes a step of providing a photosensitive layer on a substrate using the photosensitive resin composition of the present embodiment or a photosensitive resin film (photosensitive layer forming step), and at least one of the photosensitive layers. A step of irradiating the portion with active light to form a photocurable portion (exposure step) and a step of removing at least a part of the photosensitive layer other than the photocurable portion to form a resin pattern (removal step). Have in order. Further, if desired, the resin pattern is further heat-treated (heating step). According to the method for producing a cured product of the present embodiment, a desired pattern can be formed, and even when a thick photosensitive layer of 70 μm or more is formed, the photosensitive layer of the present embodiment has excellent pattern forming properties. Taking advantage of the characteristics of the sex resin composition, for example, a desired pattern can be formed by a thick cured product having a thickness of 70 μm or more. In the present specification, the term "process" is used not only as an independent process but also as a "process" if the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. include.

(Photosensitive layer forming process)
In 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 the substrate, respectively.

Examples of the substrate include a glass substrate, a silicon wafer, a metal oxide insulator such as TiO ₂ and SiO ₂ , a silicon nitride, a ceramic piezoelectric substrate, an epoxy resin impregnated glass cloth substrate, and the like. Further, the substrate may be a substrate having a copper surface such as copper wiring as a part of the surface. According to the photosensitive resin composition of the present embodiment, when a resist pattern is formed on a substrate in which a part of such a surface is a copper surface, excellent pattern forming property on the copper surface of the substrate is realized. It is possible to suppress the generation of development residue on the copper surface.

When the photosensitive resin composition is applied to the substrate to form a photosensitive layer, the photosensitive resin composition dissolved in the above-mentioned diluent in the form of a solution may be applied to the substrate, and may be applied as necessary. The coating film thus obtained may be dried. The coating and drying may be carried out by the various coating methods described for the above-mentioned preparation of the photosensitive resin film and the method of drying the coating film.

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

The thickness of the photosensitive layer provided on the substrate varies depending on the forming method (coating method or laminating method), the solid content concentration and viscosity of the photosensitive resin composition, etc., but is used as the lower limit of the thickness of the photosensitive layer after drying. It may be appropriately selected from 10 μm or more, 30 μm or more, 50 μm or more, 70 μm or more, 100 μm or more, 100 μm or more, or 150 μm or more. The upper limit is not particularly limited as long as the resin pattern can be formed, but may be appropriately selected from, for example, 500 μm or less, 300 μm or less, or 250 μm or less. The thickness of the photosensitive layer may be appropriately selected from the above range according to the application, and when used for electronic components or the like, the lower limit may be appropriately selected from 70 μm or more, more than 100 μm, or 150 μm or more, and the upper limit may be 500 μm. Hereinafter, it may be appropriately selected from 300 μm or less or 250 μm or less.

In the method for producing a cured product of the present embodiment, since the photosensitive layer is formed by using the photosensitive resin composition of the present embodiment, it is possible to form a thick photosensitive layer. For example, when forming a photosensitive layer having a thickness of 150 μm or more, it is not formed by one coating (and drying if necessary) or by laminating, but is applied multiple times (and as necessary) until a desired thickness is obtained. Drying) or laminating may be repeated.

(Exposure process)
In the exposure step, at least a part of the photosensitive layer provided on the substrate in the photosensitive layer forming step is irradiated with active light as necessary, and the exposed portion is photocured to form a cured portion. When irradiating the active light beam, the photosensitive layer may be irradiated with the active light ray through a mask having a desired pattern, or an LDI (Laser Direct Imaging) exposure method, a DLP (Digital Light Processing) exposure method, or the like. Active light may be irradiated by the direct drawing exposure method.

Further, from the viewpoint of improving the pattern forming property, post-exposure heating (PEB: Post exposure break) may be performed after exposure using a hot plate, a dryer or the like. The drying conditions are not particularly limited, but the drying may be performed at a temperature of 60 to 120 ° C. or 70 to 110 ° C. for 15 seconds to 5 minutes or 30 seconds to 3 minutes.

Exposure amount of active ray ^{is, 10~2,000mJ / cm 2, 100~1,500mJ /} cm 2, or, may be suitably selected from 300~1,000mJ / cm ^2. Examples of the active light beam used include ultraviolet rays, visible light rays, electron beams, X-rays and the like. Further, as the light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a halogen lamp, or the like can be used.

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

Examples of the organic solvent include ethanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, N-methylpyrrolidone and the like. Above all, cyclopentanone can be used from the viewpoint of development speed. These can be used alone or in combination of two or more.
In addition, various additives that can be usually used may be added to the organic solvent used as the developing solution.

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

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

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

[Laminate]
The laminate of the present embodiment includes a cured product of the photosensitive resin composition of the present embodiment, and for example, various types such as a substrate used in the above-mentioned method for producing a cured product, a carrier film of a photosensitive resin film, and the like. Those having the cured product on the support can be mentioned. The cured product of the photosensitive resin composition of the present embodiment can be formed, for example, by the above-mentioned method for producing a cured product of the present embodiment.

The thickness of the cured product in the laminate of the present embodiment may be appropriately selected from 10 μm or more, 30 μm or more, 50 μm or more, 70 μm or more, 100 μm or more, 100 μm or more, or 150 μm or more as the lower limit, and 500 μm or less and 300 μm as the upper limit. The following, or 250 μm or less may be appropriately selected. The thickness of the cured product may be appropriately selected from the above range according to the application, and when used for electronic parts or the like, the lower limit may be appropriately selected from 70 μm or more, more than 100 μm, or 150 μm or more, and the upper limit may be 500 μm. Hereinafter, it may be appropriately selected from 300 μm or less or 250 μm or less.

The cured product provided on the substrate obtained by the above-mentioned method for producing a cured product uses the photosensitive resin composition of the present embodiment, and excellent pattern forming property can be obtained even in a thick photosensitive layer of, for example, 70 μm or more. Therefore, for example, it is possible to meet the demand for an electronic circuit board that requires a thick cured product to be provided on the substrate in a finer pattern due to the trend toward miniaturization and higher performance of electronic devices. .. Further, for example, in the plating treatment step in the manufacture of an electronic circuit substrate, by using the cured product formed by the photosensitive resin composition of the present embodiment as an insulating film, it is possible to suppress a decrease in yield due to a short circuit between wirings. it can.
Therefore, the laminate of this embodiment can be used as an electronic component such as an electronic circuit board in a mobile terminal such as a mobile phone, for example.

Further, according to the above-mentioned method for producing a cured product, when the photosensitive resin composition of the present embodiment is used to form a resist pattern on a substrate having a copper surface as a part of the surface such as copper wiring. It is possible to realize excellent pattern forming property on the copper surface of the substrate, and to suppress the generation of development residue on the copper surface.
Therefore, the laminate of this embodiment can be used as an electronic component such as an electronic circuit board such as an inductor.

Hereinafter, the purpose and advantages of this embodiment will be described more specifically based on Examples and Comparative Examples, but this embodiment is not limited to the following Examples. The method for measuring the weight average molecular weight of each component and the method for measuring the glass transition temperature of the component (E) are as follows.

(Measurement of weight average molecular weight)
The weight average molecular weight was a value obtained by standard polystyrene conversion by the GPC method using the following apparatus, and was measured using a solution of 0.5 mg of polymer in 1 mL of tetrahydrofuran (THF).
Device name: HLC-8320GPC manufactured by Tosoh Corporation
Columns: Gelpack R-420, R-430, and R-440 (three joints)
Detector: RI detector Column temperature: 40 ° C
Eluent: THF
Flow velocity: 1 ml / min Standard substance: Polystyrene

(Measurement of glass transition temperature of component (E))
As a pretreatment for the measurement, the component (E) was heated at 120 ° C. for 3 hours and then cooled to prepare a sample.
Using 10 mg of the sample, the temperature is raised in a temperature range of 25 to 200 ° C. and a heating rate of 20 ° C./min under a nitrogen stream using a differential scanning calorimeter (manufactured by Shimadzu Corporation, trade name: DSC-50). Then, the temperature was cooled to 25 ° C., and then the temperature was raised again under the same conditions, and the temperature at which the baseline deviation started was defined as the glass transition temperature.

(Examples 1 to 8 and Comparative Examples 1 to 8)
The composition is blended according to the blending composition shown in Table 1 or 2 (the unit of the numerical value in the table is a mass part, and in the case of a solution, it is a solid content equivalent amount), kneaded with a 3-roll mill, and the photosensitive resin. The composition was prepared. N, N-dimethylacetamide was added so that the solid content concentration became 60% by mass to obtain a photosensitive resin composition.

Next, each evaluation was performed by the method shown below using the photosensitive resin composition obtained above. The evaluation results are shown in Tables 1 and 2.

[Preparation of photosensitive resin film]
A polyethylene terephthalate film having a thickness of 50 μm (manufactured by Teijin Limited, trade name: A-4100) was used as a carrier film, and the photosensitive resin compositions of Examples and Comparative Examples were placed on the carrier film to a thickness of 50 μm after drying. It was applied evenly so as to become. Next, a photosensitive layer was formed by heating and drying at 100 ° C. for 15 minutes using a hot air convection dryer to prepare a photosensitive resin film having a carrier film and a photosensitive layer.

[Evaluation of pattern formation (resolution)]
As a substrate, a glass epoxy substrate having a copper surface (trade name: MCL-E-679FGB, manufactured by Hitachi Kasei Co., Ltd., hereinafter also referred to as “substrate with Cu”) was prepared. A photosensitive resin film was laminated on the substrate with the photosensitive layer facing the glass epoxy substrate side, and the carrier film was removed. Lamination was performed at 60 ° C. using a laminator. Next, the photosensitive resin film was re-laminated on the photosensitive layer by the above method, the carrier film was removed, and this was repeated three times to form the photosensitive layer and the carrier film having a thickness of 200 μm on the glass epoxy substrate. A laminate was obtained.

A resolution evaluation mask (line width: 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, 25 μm, all line spaces are 100 μm) having the pattern shape shown in FIG. 1 is placed on the carrier film of the laminated body as an exposed portion. Further, an i-line filter (manufactured by Asahi Spectral Co., Ltd., trade name: HB-0365) was placed and exposed using a high-precision parallel exposure machine (manufactured by Mikasa Co., Ltd.). In this case, by dividing the laminate into three regions, exposed to light weight different exposure three regions ^{(600mJ / cm 2, 800mJ /} cm 2, 1,000mJ / cm 2) , the wavelength 365 nm (i line) did. The exposed sample was heated after exposure for 1 minute on a hot plate at 90 ° C.

Then, the carrier film was removed, and the film was immersed in a developing solution (cyclopentanone) for 20 minutes for development. The pattern after development was dried at room temperature for 30 minutes and observed with a metallurgical microscope to evaluate the pattern forming property. The evaluation was performed according to the following criteria. Here, "formable" means that the unexposed portion is cleanly removed and there is no defect such as tilting in the line portion (exposed portion). The evaluation results are shown in Tables 1 and 2. If the evaluation result is A with one or more types of exposure, it is considered as acceptable.
A: It was possible to form with a line width of 5 to 10 μm.
B: It could not be formed with a line width of 5 to 10 μm, but it could be formed with a line width of 15 to 20 μm.
C: It could not be formed with a line width of 20 μm or less, or the photosensitive layer was peeled off after development.

[Evaluation of development residue on glass epoxy substrate with copper surface]
With respect to the developed substrate with Cu prepared in the evaluation of pattern formability, the development residue was evaluated by observing the copper surface of the portion where the photosensitive layer was removed by development with a metallurgical microscope. In the evaluation, the copper surface was observed between lines with a line width of 10 μm, between the minimum lines when 10 μm was not resolved, and when exposed and developed at the exposure amount with the best pattern formation. , The following criteria were used. The evaluation results are shown in Tables 1 and 2. If the evaluation result is A, it is considered as a pass.
A: Indicates the color of the copper surface itself. This indicates that there is almost no residue.
B: Interference fringes (rainbow color) are observed. This indicates that there is a small amount of residue.
C: Residual organic matter (white) is observed. This indicates that there is a large amount of residue.

Details of each material in Tables 1 and 2 are as follows.
[(A) component]
UN-954: Urethane acrylate (manufactured by Negami Kogyo Co., Ltd., trade name, number of functional groups: 6, weight average molecular weight (Mw): 4,500)

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

[Component (C)]
-I-184: 1-hydroxy-cyclohexyl-phenyl-ketone "IRGACURE-184" (manufactured by BASF, trade name)
I-819: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide "IRGACURE-819" (manufactured by BASF, trade name)

[(D) component]
-PE1: Pentaerythritol tetrakis (3-mercaptobutyrate) "Karensu MT PE1" (manufactured by Showa Denko KK, trade name)
NR1: 1,3,5-tris (3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione "Karens MT NR1" ( Showa Denko Corporation, product name)

[(E) component]
Z250: Cyclomer P (ACA) Z250 (manufactured by Daicel Ornex Co., Ltd., represented by the above formula (XI) produced by the reaction of an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound 3 A resin consisting of one structural unit (weight average molecular weight: 19,000 to 25,000).

[(F) component]
KBM-803: 3-mercaptopropyltrimethoxysilane (primary thiol compound, manufactured by Shin-Etsu Chemical Co., Ltd., trade name)
KBM-503: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name)

From Table 1, it was confirmed that the photosensitive resin compositions of Examples 1 to 8 can realize excellent pattern formation on the copper surface of the Cu-containing substrate and can reduce the development residue on the Cu surface after development. Was done.

Claims (20)

Component (A): high molecular weight compound having a photopolymerizable functional group and carbon-nitrogen bond, component (B): low molecular weight compound having a photopolymerizable functional group, and component (C): photopolymerization initiator. A photosensitive resin composition containing a component (D): a secondary thiol compound. The photosensitive resin composition according to claim 1, wherein the component (D) contains a polyfunctional secondary thiol compound having two or more secondary thiol groups. The photosensitive resin composition according to claim 1 or 2, wherein the component (D) contains a secondary thiol compound having at least one skeleton selected from the group consisting of a pentaerythritol skeleton and an isocyanul ring skeleton. The photosensitive according to any one of claims 1 to 3, wherein the content of the component (D) is 0.02 to 1.0% by mass based on the total solid content of the photosensitive resin composition. Resin composition. The photosensitive resin composition according to any one of claims 1 to 4, wherein the component (A) contains a high molecular weight substance having a (meth) acryloyl group as a photopolymerizable functional group. The photosensitive resin composition according to any one of claims 1 to 5, wherein the component (A) contains a high molecular weight substance having a urethane bond as a carbon-nitrogen bond. Any of claims 1 to 6, wherein the component (A) contains a high molecular weight substance having 6 or more ethylenically unsaturated groups as a photopolymerizable functional group and having a weight average molecular weight of 2,500 or more. The photosensitive resin composition according to item 1. Any one of claims 1 to 7, wherein the component (A) comprises a high molecular weight compound having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton. The photosensitive resin composition according to the section. Claims 1 to 8 include the component (B) 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 isocyanul ring, and a low molecular weight body having an alicyclic skeleton. The photosensitive resin composition according to any one of the above. The photosensitive resin composition according to any one of claims 1 to 8, wherein the component (B) contains a low molecular weight body having at least one (meth) acryloyl group and a urethane bond. The photosensitive resin composition according to any one of claims 1 to 10, wherein the component (C) contains a compound represented by the following general formula (C1) or a compound represented by the following general formula (C2). Stuff.

[ ^RC1 , ^RC2 and ^RC3 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and ^RC4 and ^RC5 independently represent each other. It represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ^R C1 ^{to R C5} other than a hydrogen atom, each may have a substituent. ]

[ ^RC6 represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an amino group, and ^RC7 and ^RC8 each independently have a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 6 to 12 carbon atoms. Or an alkoxy group having 1 to 8 carbon atoms. R ^C7 and ^{R C8} are linked to each other, they may form a cyclic structure of 3 to 16 carbon atoms. Hydroxyl and hydrogen atoms other than R ^C6 to R ^C8 may have each a substituent, an amino group having a substituent bonded to a substituent each other to each other, a cyclic structure having 3 to 12 carbon atoms It may be formed. Each ^RC9 may independently contain one or more atoms selected from a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an oxygen atom, a nitrogen atom and a sulfur atom, and has 1 to 10 carbon atoms. Indicates an organic group of. ] The photosensitive resin composition according to any one of claims 1 to 11, further comprising a component (E): a high molecular weight substance having a glass transition temperature of 70 to 150 ° C. and no carbon-nitrogen bond. Stuff. The photosensitive resin composition according to any one of claims 1 to 12, further containing a component (F): a silane compound having no secondary thiol group. A photosensitive resin film having a photosensitive layer using the photosensitive resin composition according to any one of claims 1 to 13. A step of providing a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 13 or the photosensitive resin film according to claim 14, at least a part of the photosensitive layer. A method for producing a cured product, which comprises, in order, a step of irradiating an active light beam to form a photocurable portion and a step of removing at least a part of the photosensitive layer other than the photocurable portion to form a resin pattern. The method for producing a cured product according to claim 15, further comprising a step of heat-treating the resin pattern. The method for producing a cured product according to claim 15 or 16, wherein the thickness of the resin pattern is 70 μm or more and 300 μm or less. A laminate comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 13. The laminate according to claim 18, wherein the thickness of the cured product is 70 μm or more and 300 μm or less. An electronic component comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 13.