JP6926398B2 - Photosensitive resin composition, photosensitive resin film, method for manufacturing cured product, laminate, and electronic components - Google Patents

Description

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

In the field of manufacturing semiconductor integrated circuits (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 a portion such as, etc. so that it can be selectively removed (peeled). Next, a conductor such as copper is formed on the removed portion by a plating treatment, 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, there is a demand for a photosensitive resist having excellent pattern-forming properties even when a photosensitive layer having a thickness of 70 μm, more than 150 μm, which is thicker than the conventional one, or more is formed.

Therefore, the problem to be solved by the present disclosure has been made in view of the above circumstances. For example, a photosensitive resin having excellent pattern forming property even when a thick photosensitive layer of 70 μm or more is formed. It is an object of the present invention to provide a composition, a photosensitive resin film, a method for producing a cured product, a laminate, and an electronic component (hereinafter, may be referred to as a "photosensitive resin composition or the like").

As a result of intensive studies to solve the above problems, the present inventors have found that the problem 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 silane compound containing a functional group reactive with the photopolymerizable functional group.
[2] A photosensitive resin film having a photosensitive layer using the photosensitive resin composition according to the above [1].
[3] A step of forming a photosensitive layer on a substrate by using the photosensitive resin composition according to the above [1] or the photosensitive resin film according to the above [2].
A step of irradiating at least a part of the photosensitive layer with active light to form a photocurable portion.
A method for producing a cured product, which comprises, in order, a step of removing at least a part of the photosensitive layer other than the photocurable portion to form a resin pattern.
[4] A laminate comprising a cured product of the photosensitive resin composition according to the above [1].
[5] An electronic component comprising a cured product of the photosensitive resin composition according to the above [1].

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

It is a schematic diagram which shows an example of the resolution evaluation mask 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.
The “(meth) acrylic acid” means at least one of “acrylic acid” and the corresponding “methacrylic acid”, and the same applies to other similar expressions such as (meth) acrylate.

[Photosensitive resin composition]
The photosensitive resin composition according to the embodiment of the present disclosure (hereinafter, may be simply referred to as the present embodiment) is a high molecular weight substance having a component (A): a photopolymerizable functional group and a carbon-nitrogen bond (hereinafter referred to as “the present embodiment”). , Simply referred to as "high molecular weight substance"), component (B): low molecular weight substance having a photopolymerizable functional group (hereinafter, may be simply referred to as "low molecular weight substance"), and ( A photosensitive resin composition containing a component C): a photopolymerization initiator, and a component (D): a silane compound containing a functional group reactive with the photopolymerizable functional group.
In the present specification, the "solid content" is a non-volatile component 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 being used, and also includes those that are liquid, starch syrup, and wax at room temperature. Here, the room temperature is 25 ° C. in the present specification. Hereinafter, each component 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 2,000 or more. The value of the weight average molecular weight in the present specification is a value measured by a gel permeation chromatography (GPC) method using tetrahydrofuran (THF).
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. That is, the component (A) has at least one of these functional groups and at least one carbon-nitrogen bond.
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").
The number of photopolymerizable functional groups contained in the component (A) may be selected from 2 to 24, and 4 to 15 or 6 to 12 from the viewpoint of stabilizing the physical properties and properties of the obtained cured product. good.
When the number of photopolymerizable functional groups is 2 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 24 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. As a result, excellent resolution can be obtained, so that excellent pattern forming property can be obtained even when a thick photosensitive layer is formed. Further, after at least one of photo-curing and thermosetting is performed, the amount of unreacted photopolymerizable functional groups remaining can be reduced, and fluctuations in the physical properties and properties of the obtained cured product can be further suppressed.
The component (A) may contain a high molecular weight body having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton.

Examples of the high 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.
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) acrylates, glycerindi (meth) acrylates, bis (2- (meth) acryloyloxyethyl) (2-hydroxyethyl) isocyanurates, ethoxylated products thereof, and the like. Propoxylated products, these ethoxylated propoxylated products, and their caprolactone modified products; cyclohexanedimethanol type epoxy di (meth) acrylate, tricyclodecane dimethanol type epoxy di (meth) acrylate, hydrogenated bisphenol A type epoxy di (meth). ) Acrylate, hydrogenated bisphenol F type epoxy di (meth) acrylate, hydroquinone type epoxy di (meth) acrylate, resorcinol type epoxy di (meth) acrylate, catechol type epoxy di (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type Bifunctional epoxy (meth) acrylates such as epoxy di (meth) acrylates, bisphenol AF type epoxy di (meth) acrylates, biphenol type epoxy di (meth) acrylates, fluorene bisphenol type epoxy di (meth) acrylates, and isocyanurate monoallyl type epoxy di (meth) acrylates. Trifunctional or higher functional (meth) acrylates such as ditrimethylol propantri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate, and ethoxylation of these. The body, these propoxylates, these ethoxylated propoxylates, 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.

Examples of the isocyanate compound having an isocyanate group include a compound having at least one isocyanate group in one molecule, and may be a compound having 1 to 3 isocyanate groups in one molecule. More specifically, aliphatic monoisocyanate compounds such as ethyl isocyanate, propyl isocyanate, butyl isocyanate, octadecyl isocyanate and 2-isocyanate ethyl (meth) acrylate; alicyclic monoisocyanate compounds such as cyclohexyl isocyanate; aromatics such as phenylisocyanate. Monoisocyanate compounds such as group monoisocyanate compounds, aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate; 1,3-bis (isocyanatomethyl) cyclohexane , Isophorone diisocyanate, 2,5-bis (isocyanatomethyl) norbornene, bis (4-isocyanatocyclohexyl) methane, 1,2-bis (4-isocyanatocyclohexyl) ethane, 2,2-bis (4-isocyanatocyclohexyl) Alicyclic diisocyanate compounds such as cyclohexyl) propane, 2,2-bis (4-isocyanatocyclohexyl) hexafluoropropane, bicycloheptanetriisocyanate; 1,4-phenylenediocyanate, 2,4-tolylene diisocyanate, 2,6 Fragrances such as -tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, hydrogenated xylylene diisocyanate, naphthalene-1,5-diisocyanate, etc. Examples thereof include diisocyanate compounds such as diisocyanate compounds, and multimers such as uretdione-type dimer, isocyanurate-type, and biuret-type trimer 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.

Among them, from the viewpoint of improving the pattern forming property, a diisocyanate compound such as an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, an aromatic diisocyanate compound, and a multimer of these diisocyanate compounds may be appropriately selected, and in particular, hexamethylene diisocyanate. , Isophorone diisocyanate, 1,4-phenylenediocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, and isocyanurate-type multimer ( Isocyanurate type polyisocyanate) may be appropriately selected.

The reaction product of the (meth) acrylate having a hydroxyl group and the isocyanate compound described above has a (meth) acryloyl group as a photopolymerizable functional group and a urethane bond as a carbon-nitrogen bond. Specifically, for example, 1 to 5 (meth) residues obtained by removing the hydroxyl group from the (meth) acrylate having a hydroxyl group in the molecule (that is, the organic group derived from the (meth) acrylate having a hydroxyl group in the molecule (that is, the above-mentioned (meth) acrylate having a hydroxyl group). ) An organic group having an acryloyl group), a urethane bond, and an organic group derived from the above-mentioned isocyanate compound (that is, a residue obtained by removing the isocyanate group from the above-mentioned isocyanate compound), a chain hydrocarbon skeleton, and a fat. It can be said to have a cyclic skeleton or an organic group having an aromatic ring skeleton). These organic groups may be the same or different.

As the high molecular weight urethane (meth) acrylate, from the viewpoint of improving the pattern forming property, for example, 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 can be used. It may contain a reaction product obtained by reacting a (meth) acrylate having a hydroxyl group.

As the isocyanate compound used here having at least two isocyanate groups in one molecule, among the compounds exemplified as the above-mentioned isocyanate compounds, diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds and aromatic diisocyanate compounds are used. In addition, multimers such as uretdione-type dimer, isocyanurate-type, and biuret-type trimeric of these diisocyanate compounds can be mentioned.
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 pattern forming property and increasing the glass transition point (Tg) after polymerization to improve water resistance. , Or, it may be appropriately selected from 2 to 14 saturated diol compounds, and more specifically, it may be appropriately selected from ethylene glycol and octadecane diol.
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 18 or a diol compound having 6 to 16 alicyclic skeletons, and more specifically, various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol, 1, It may be appropriately selected from various cyclohexanedimethanols such as 3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol.

Further, as the (meth) acrylate having a hydroxyl group used here, those exemplified as the (meth) acrylate used for the reaction product of the above-mentioned (meth) acrylate having a hydroxyl group and the isocyanate compound having an isocyanate group are exemplified. Can be mentioned.

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 3).

In the general formula (3), 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.

As the _{divalent organic group of X 1} , from the organic group derived from the aliphatic diisocyanate compound, the alicyclic diisocyanate compound, and the aromatic diisocyanate compound exemplified as the compound having the above-mentioned isocyanate group, that is, the above-mentioned isocyanate compound. 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. 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, and among them, the following formula ( It may be a divalent organic group having an alicyclic skeleton, which is a residue of isophorone diisocyanate represented by 4).

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

Specific examples of the 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 include, for example. , Compounds represented by the following general formulas (5) and (6) can be mentioned.

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

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 (7) and (8) are used as reaction products. Examples include the compounds represented.

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

Examples of commercially available products containing urethane acrylate having the structural unit represented by the general formula (3) include UN-333 (number of functional groups: 2, Mw: 5,000) and UN-1255 (number of functional groups: 2, Mw: 8,000), UN-904 (number of functional groups: 10, Mw: 4,900), UN-2600 (number of functional groups: 2, Mw: 2,500), UN-6200 (number of functional groups: 2, Mw: 6,500), UN-9000PEP (number of functional groups: 2, Mw: 5,000), UN-9200A (number of functional groups: 2, Mw: 15,000), UN-3320HS (number of functional groups: 15, Mw: 4, 900), UN-6301 (number of functional groups: 2, Mw: 33,000), UN-954: (number of functional groups: 6, weight average molecular weight: 4,500), UN-953: (number of functional groups: 20, weight average) Molecular weight: 14,000 to 40,000), H-219 (number of functional groups: 9, weight average molecular weight: 25,000 to 50,000) (all above are trade names, manufactured by Negami Kogyo Co., Ltd.), EBECRYL8405 (urethane) Addition reaction product of acrylate / 1,6-hexanediol diacrylate = 80/20, number of functional groups: 4, Mw: 2,700) (trade name, manufactured by Daicel Ornex Co., Ltd.) and the like can be mentioned.
Further, as a commercially available product containing urethane methacrylate having a structural unit represented by the above general formula (3), for example, UN-6060PTM (number of functional groups: 2, Mw: 6,000, trade name, manufactured by Negami Kogyo Co., Ltd.) ) Etc. can be mentioned. 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.

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

The total number of (meth) acryloyl groups (number of photopolymerizable functional groups) contained in the high molecular weight urethane (meth) acrylate is 2 to 24 in one molecule from the viewpoint of improving pattern formation and heat resistance. From the viewpoint of stabilizing the physical properties and properties of the cured product, it may be appropriately selected from 4 to 15 or 6 to 12.

The weight average molecular weight of the component (A) is 2,000 or more, and may be 2,500 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 3,000 or more. On the other hand, the upper limit of the weight average molecular weight may be 40,000 or less or 30,000 or less from the viewpoint of improving the coatability and resolution of the resin composition, and further developability and compatibility. From the viewpoint of improvement, it may be 20,000 or less.
When the weight average molecular weight is 2,000 or more, when the resin composition is applied onto the substrate, the generation of dripping of the applied resin composition can be suppressed, so that excellent pattern forming property can be obtained. In addition, it is easy to 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 40,000 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.

The content of the component (A) may be appropriately selected from 10% by mass or more, 30% by mass or more, or 45% 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.
Further, the content of urethane (meth) acrylate in the component (A) is 70 to 100% by mass and 80 to 100% by mass based on the total solid content of the component (A) from the viewpoint of improving the pattern forming property. , 90 to 100% by mass, 95 to 100% by mass, or 100% by mass (total amount) may be appropriately selected.

<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 2,000.
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. From the viewpoint of improving the pattern forming property, the component (B) may have a (meth) acryloyl group as a photopolymerizable functional group.
The component (B) has at least one photopolymerizable functional group, and the number of photopolymerizable functional groups is 1 to 12, 2 to 10, or from the viewpoint of improving pattern formation. It may be appropriately selected from 2 to 6.

In the photosensitive resin composition of the present embodiment, as the component (B), the component (B1) is a low molecular weight substance having an isocyanul ring, the component (B2) is a low molecular weight substance having a urethane bond, and the component (B3) is a 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 and 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 a urethane bond and an alicyclic skeleton. When it has a cyclic 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 into the (B3) component.

(Component (B1): low molecular weight substance having an isocyanul ring)
The component (B1) is a low molecular weight substance having at least one photopolymerizable functional group and an isocyanul ring skeleton, and even if it has two or more photopolymerizable functional groups from the viewpoint of improving pattern forming property. It may have 2 to 5 photopolymerizable functional groups, 2 or 3 photopolymerizable functional groups, or 3 photopolymerizable functional groups.
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 (9).

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

(In the general formula (9), R ¹³ , R ¹⁴ and R ¹⁵ each independently represent an alkylene group having 1 to 8 carbon atoms, and R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group. , R ¹⁸ represents a hydrogen atom or a (meth) acryloyl group.)

In the general formula (9), ^{the alkylene group having 1 to 8 carbon atoms represented by R 13} , R ¹⁴ and R ¹⁵ may be an alkylene group having 1 to 4 carbon atoms, and may be an alkylene group having 1 to 3 carbon atoms. There may be.
Examples of the alkylene group having 1 to 8 carbon atoms include 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 (9), R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group, and may be a hydrogen atom from the viewpoint of improving sensitivity.
In the general formula (9), R ¹⁸ represents a hydrogen atom or a (meth) acryloyl group, and may be a (meth) acryloyl group from the viewpoint of improving pattern formation.

The compound represented by the general formula (9) may be at least one selected from the group consisting of the compound represented by the following formula (9-1) and the compound represented by the following formula (9-2). Often, from the viewpoint of improving the pattern forming property, it may be a compound represented by the following formula (9-1).

The weight average molecular weight of the component (B1) is less than 2,000, 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 (9-1)) and "M-215" manufactured by Toagosei Co., Ltd. (the above formula (the above formula (the above formula)). The compound) represented by 9-2) and the like can be mentioned.
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) is a low molecular weight substance having a photopolymerizable functional group and a urethane bond, and may have two or more photopolymerizable functional groups from the viewpoint of improving pattern forming property, and may have two or more photopolymerizable functional groups. It may have 2 to 6 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.

Examples of the component (B2) 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 (meth) acrylate having a hydroxyl group and an isocyanate compound exemplified as those used for producing the component (A). Here, as an example of what is appropriately selected from the viewpoint of improving the pattern forming property, the same one which is appropriately selected as being used for the generation of the component (A) from the same viewpoint is exemplified.

Further, as the component (B2), 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. Can be mentioned. 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, isocyanate in one molecule exemplified as being used for the production of the component (A), respectively. Examples thereof include isocyanate compounds having at least two groups, diol compounds, and (meth) acrylates having a hydroxyl group. Here, as an example of what is appropriately selected from the viewpoint of improving the pattern forming property, the same one which is appropriately selected as being used for the generation of the component (A) from the same viewpoint is exemplified.
Examples of this reaction product include urethane (meth) acrylate having a structural unit represented by the following general formula (10).

In the general formula (10), 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 (3), 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 and a branched chain. It may be appropriately selected from a divalent organic group having a state 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 component (B2) include urethane acrylate represented by the following general formula (11).

In the above general formula (11), n ₅ represents an integer of 1 to 4. R ¹⁹ and R ²⁰ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a plurality of R ¹⁹ and R ²⁰ 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 (11), X ₂ of the general formula (10) 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 (10), KRM8452 (number of functional groups: 10, Mw: 1,200, manufactured by Daicel Ornex Co., Ltd.), UN -3320HA (number of functional groups: 6, Mw: 1,500, manufactured by Negami Kogyo Co., Ltd.), UN-3320HC (number of functional groups: 6, Mw: 1,500, manufactured by Negami Kogyo Co., Ltd.) and the like can be mentioned. 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 weight average molecular weight of the component (B2) is less than 2,000, may be 1,500 or less from the viewpoint of improving adhesion, and is 1,000 or less from the viewpoint of improving resolution. May be good. On the other hand, the lower limit of the weight average molecular weight may be 500 or more from the viewpoint of film formability, although it can be appropriately used according to a desired purpose.

(Component (B3): low molecular weight substance having an alicyclic skeleton)
The component (B3) is a low molecular weight substance having a photopolymerizable functional group and an alicyclic skeleton, and may have two or more photopolymerizable functional groups from the viewpoint of improving pattern forming property. It may have 2 to 4 photopolymerizable functional groups, or may have two photopolymerizable 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 2,000, may be 1,500 or less from the viewpoint of improving adhesion, and is 1,000 or less from the viewpoint of improving resolution. It may be 500 or less. On the other hand, the lower limit of the weight average molecular weight may be 150 or more, or 200 or more, from the viewpoint of film formability, although it can be appropriately used according to a desired purpose.
The component (B3) may be tricyclodecanedimethanol diacrylate from the viewpoint of film formability.

The content of the component (B) may be appropriately selected from 3% by mass or more, 5% by mass or more, 10% by mass or more, or 20% by mass or more based on the total solid content of the photosensitive resin composition. .. 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 content of the component (B) based on 100 parts by mass of the total solid content of the component (A) is 20 to 120 parts by mass and 25 to 110 parts by mass from the viewpoint of improving the pattern forming property and the rigidity of the cured product. Alternatively, it may be appropriately selected from 30 to 100 parts by mass.

When the component (B) contains the component (B1), the content of the component (B1) in the total solid content of the component (B) is 15% by mass or more, 40% by mass or more, 70% by mass or more, 90. It may be appropriately selected from mass% or more or 95% by mass or more. When the content of the component (B1) is 15% 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 component (B1) is 100% by mass or less, and 100% by mass, that is, the total amount of the component (B) may be the component (B1).
When the component (B) contains the component (B2), the content of the component (B2) in the total solid content of the component (B2) is 20 to 90% by mass, 40 to 85% by mass, or 60 to 60 to It may be appropriately selected from 80% by mass.
When the component (B) contains the component (B3), the content of the component (B3) in the total solid content of the component (B) is 10 to 50% by mass, 15 to 40% by mass, or 20 to 20%. It may be appropriately selected from 30% by mass.

<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 quinones.

Acylphosphine oxide-based photopolymerization initiators have an acylphosphine oxide group (> P (= O) -C (= O) -group), and are, for example, (2,6-dimethoxybenzoyl) -2,4. , 6-Pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("IRGACURE-TPO" (manufactured by BASF)), ethyl-2 , 4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ("IRGACURE-819" (manufactured by BASF)), (2,5-dihydroxyphenyl) diphenylphosphine 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] esterone 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'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4 -Methyl-4'-dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one ("IRGACURE-651" (manufactured by BASF)), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one ("IRGACURE-369" (manufactured by BASF)), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one ("IRGACURE-907" (manufactured by BASF)) and the like.

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.

As the imidazole-based photopolymerization initiator, 2,4,5-triarylimidazole dimer is, for example, 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-Chienoki silk coumarin and the like.

Among these, from the viewpoint of improving the pattern forming property, the component (C) may contain a compound represented by the following general formula (1) or a compound represented by the following general formula (2).

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

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

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

(In the general formula (2), R ⁶ represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an amino group, and R ⁷ and R ⁸ are independently hydrogen atoms and alkyl having 1 to 8 carbon atoms, respectively. It represents a group, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. R ⁷ and R ⁸ may be bonded to each other to form a cyclic structure having 3 to 16 carbon atoms. ^{R 6 to} R ⁸ other than the hydroxyl group and the hydrogen atom may each have a substituent, and the amino group having a substituent has a cyclic structure having 3 to 12 carbon atoms in which the substituents are bonded to each other. R ⁹ each 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. Indicates an organic group having 1 to 10 carbon atoms which may be used.)

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

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

Examples of the substituent that R ^{1 to} R ⁵ may have include a halogen atom, a carboxy group, a hydroxy group, an amino group, a mercapto group, an alkyl group having 1 to 8 carbon atoms, and an alkoxy having 1 to 8 carbon atoms. Examples thereof include a group and an aryl group having 6 to 12 carbon atoms. Examples of the alkyl group, alkoxy group and aryl group which are substituents which R ^{1 to R 5} may have include the same as the alkyl group, alkoxy group and aryl group described as ^{R 1 to} R ^5. ..

In the general formula (2), R ⁶ represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an amino group.
The ^{alkoxy group represented by R 6} will be described in the same manner as in the case ^{of R 1} , R ² and R ³ in the general formula (1).
Among these groups, R ⁶ may be a hydroxyl group from the viewpoint of improving pattern formation.

In the general formula (2), R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ..
The alkyl group, alkoxy group and aryl group represented by ^{R 7} and R ⁸ are described in the same manner as in the case ^{of R 1 to} R ^{5 in the general formula (1).}
R ⁷ and R ⁸ may be bonded to each other to form a cyclic structure having 3 to 16 carbon atoms.
The cyclic structure may be a cyclic structure having 4 to 10 carbon atoms or 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. Further, these alicyclic structures may contain carbon atoms to which ^{R 7} and R ^{8 are directly bonded together.}

The ^{substituents that R 6 to} R ⁸ can have will be described in the same manner as the substituents that ^{R 1 to} R ⁵ in the general formula (1) 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 the structure represented by the following formula (12).

In the general formula (2) ^{, each of R 9} 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 an organic group having 1 to 10 carbon atoms.
The organic group having 1 to 10 carbon atoms represented by R ⁹ may be an organic group having 1 to 6 carbon atoms or an organic group having 1 to 4 carbon atoms.
The organic group having 1 to 10 carbon atoms represented by R ⁹ may be a hydrocarbon group such as an alkyl group, an alkenyl group or an aryl group. These alkyl groups, alkenyl groups and aryl groups will be described in the same manner as the alkyl groups, alkenyl groups and aryl groups represented by ^{R 1 to} R ^{5 in the general formula (1).}
Examples of the organic group having 1 to 10 carbon atoms containing an oxygen atom represented by R ^{9 include an alkoxy group and the like.}
Examples of the organic group having 1 to 10 carbon atoms containing a nitrogen atom represented by R ^{9 include a group represented by the above formula (12).}
Examples of the organic group having 1 to 10 carbon atoms containing a sulfur atom represented by R ^{9 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 with respect to light can be measured. Further, 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 Beer-Lambert's law. can.

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, 0.1 to 0% based on the total solid content of the photosensitive resin composition. It may be appropriately selected from 10% by mass or 0.15 to 5% 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 available. (C') photopolymerization initiators such as tertiary amines can also be used alone or in combination of two or more.

<Component (D): Silane compound containing a functional group reactive with a photopolymerizable functional group>
The photosensitive resin composition of the present embodiment has a functional group (hereinafter referred to as “reactive”) having reactivity with a photopolymerizable functional group contained in one or more selected from the component (A) and the component (B) as the component (D). , Also referred to as "reactive group for photopolymerizable functional group"). By containing the reactive group for the photopolymerizable functional group, the component (D) can improve the adhesiveness between the photosensitive resin composition of the present embodiment and the substrate of the electronic component, thereby improving the adhesiveness. It is considered that excellent pattern forming property can be obtained.

The reactive group for the photopolymerizable functional group contained in the component (D) may be appropriately selected depending on the type of the photopolymerizable functional group, and is selected from, for example, the component (A) and the component (B) 1. When the photopolymerizable functional group of the species or more is an ethylenically unsaturated group, a (meth) acryloyl group; an ethylenically unsaturated group such as an alkenyl group such as a vinyl group or an allyl group, an amino group, a thiol group and the like can be mentioned. Be done. Among these, a thiol group may be used from the viewpoint of improving the pattern forming property. In addition, in this embodiment, the compound corresponding to both the component (B) and the component (D) shall be classified into the component (D).

The component (D) may contain an alkoxysilyl group from the viewpoint of improving the pattern forming property. The carbon number of the alkoxy group bonded to the silicon atom of the alkoxysilyl group may be appropriately selected from 1 to 8, 1 to 5, or 1 to 3 from the viewpoint of improving the pattern forming property. Examples of the alkoxy group bonded to the silicon atom of the alkoxysilyl group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a t-butoxy group, and an n-pentyloxy group. Examples thereof include an n-hexyloxy group and an n-octyloxy group, which may be a methoxy group or an ethoxy group from the viewpoint of improving pattern forming property. The number of alkoxy groups bonded to the silicon atom of the alkoxysilyl group may be 1 to 3 or 2 or 3 from the viewpoint of improving the pattern forming property.
Examples of the component (D) include a compound represented by the following general formula (13).

In the general formula (13), R ²¹ independently represents an alkyl group having 1 to 8 carbon atoms, and R ²² independently represents a group or carbon containing a reactive group for a photopolymerizable functional group. It represents an alkyl group of the number 1-10, and n represents an integer of 1-3. However, when n is 1, R ²² is a group containing a reactive group for a photopolymerizable functional group, and when n is 2 or 3, at least one of ^{a plurality of R 22 existing is light.} It is a group containing a reactive group for a polymerizable functional group.

In the general formula (13) ^{, examples of the alkyl group having 1 to 8 carbon atoms represented by R 21} include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group. , N-Pentyl group, n-Hexyl group, n-octyl group and the like, and may be a methyl group or an ethyl group from the viewpoint of improving pattern forming property.

In the general formula (13), the ^{group containing the reactive group for the photopolymerizable functional group represented by R 22} may be an organic group having 1 to 20 carbon atoms, or an organic group having 1 to 15 carbon atoms. It may be an organic group having 1 to 10 carbon atoms. The reactive group for the photopolymerizable functional group of ^{R 22 is as described above.}
Specific examples of the group containing a reactive group for the photopolymerizable functional group represented by R ²² include an alkenyl group such as a vinyl group, an allyl group and a butenyl group, and a monovalent group represented by the following general formula (14). Organic groups of.

（一般式（１４）中、Ｒ^２３は、炭素数１〜１０の２価の炭化水素基を示し、Ｒ^２４は、（メタ）アクリロイル基、アミノ基、アルケニル基、又はチオール基を示す。）

(In the general formula (14), R ²³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ²⁴ represents a (meth) acryloyl group, an amino group, an alkenyl group, or a thiol group.)

Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R ²³ include an alkylene group having 1 to 10 carbon atoms and an arylene group having 6 to 10 carbon atoms.
The alkylene group having 1 to 10 carbon atoms represented by R ²³ may be an alkylene group having 1 to 8 carbon atoms or an alkylene group having 2 to 5 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group and the like.
Examples of the arylene group having 6 to 10 carbon atoms represented by R ^{23 include a phenylene group and a naphthylene group.}
Examples of the alkenyl group represented by R ²⁴ include the same alkenyl groups represented by R ^{22 in the} general formula (13).
R ²⁴ may be a thiol group from the viewpoint of improving pattern formation.

When the photopolymerizable functional group contained in one or more of the components (A) and (B) is an ethylenically unsaturated group, the component (D) includes, for example, vinyltrimethoxysilane or vinyltriethoxysilane. , P-Stylyltrimethoxysilane, alkenyl group-containing alkoxysilanes such as allyltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- (Meta) acryloyl group-containing alkoxysilanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane; amino group-containing alkoxysilanes such as 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane; 3 Examples thereof include thiol group-containing alkoxysilanes such as -mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. These can be used alone or in combination of two or more. Among these, a thiol group-containing alkoxysilane may be used from the viewpoint of improving the pattern forming property.

The content of the component (D) is 0.1 to 20% by mass, 0.1 to 7% by mass, 1 to 7% by mass, or 1 to 5% by mass based on the total solid content of the photosensitive resin composition. You can select from% as appropriate. When the content of the component (D) is within the above range, excellent pattern forming property can be obtained even when a thick photosensitive layer is formed.

<Component (E): Thermal radical polymerization initiator>
In addition, the photosensitive resin composition of the present embodiment can further contain (E) a thermal radical polymerization initiator. The component (E) is not particularly limited, and is, 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).

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

When the component (E) is contained, the content thereof is 0.1 to 10% by mass, 0.2 to 5% by mass, or 0.3 to 1% based on the total solid content of the photosensitive resin composition. It may be appropriately selected from 5% by 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.

<(F) component: inorganic filler>
The photosensitive resin composition of the present embodiment contains (F) an inorganic filler 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. Can be done.
Examples of the component (F) 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 (F) 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 (F) 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) 1,000-fold with methyl ethyl ketone, and then, using a submicron particle analyzer (manufactured by Beckman Coulter, Inc., trade name: N5), the international standard ISO13321 is met. According to this, 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 (F) contained in the photosensitive layer or the cured film of the photosensitive resin composition provided on the carrier film is also diluted (or dissolved) 1,000 times (volume ratio) with a solvent as described above. ), Then it can be measured by using the above-mentioned submicron particle analyzer.

The content of the component (F) may be appropriately selected from 10% by mass or less, 5% by mass or less, or 1% by mass or less, based on the total solid content of the photosensitive resin composition, and the lower limit is 0. It may be appropriately selected from more than mass%, and may be 0 mass% (not included). As described above, by substantially not containing the component (F), 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 adhesion aid other than the component (D), if necessary. Can be done.

Examples of the sensitizer include sensitizers such as pyrazolines, anthracenes, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbenes, 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 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.

Adhesive aids other than the component (D) include, for example, silanes that do not have a reactive group for photopolymerizable functional groups such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane. Examples include compounds.

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 to be 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, the viscosity of the photosensitive resin composition at 25 ° C. is 0.5 to 20 Pa · s, or 0.5 to 20 Pa · s, in consideration of the ease of forming the photosensitive layer. The amount can be 1 to 10 Pa · s.

The photosensitive resin composition of the present embodiment contains the above-mentioned components (A) to (D), as well as the components (E) and (F), other additives, and a diluent used as desired, in a roll mill. 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 as 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 light can easily pass to the surface), the pattern forming property can be improved. The absorbance can be measured by the method described above, and specifically, can be measured by the method described in Examples.

[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.

In 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. 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 polyester resin films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), and resin films such as polyolefin resin films such as polypropylene and polyethylene. A polyester resin film may be selected from the viewpoint of improving the mechanical strength and heat resistance of the photosensitive resin film.
The thickness of the carrier film may be appropriately selected from 10 μm to 3 mm or 10 to 200 μm 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, and by setting the thickness to 100 μm or less, the photosensitive resin film is wound around the core. It is possible to further reduce the deformation of the photosensitive layer due to the stress difference between the inside and the outside of the winding core when the film is wound around. 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 may be 70 μm or more, and the thickness may exceed 100 μm. There may be. The photosensitive layer having a thickness of 70 μm or more can 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 to obtain a carrier film. A photosensitive resin film including 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 a 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 when 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.

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, and an LDI (Laser Direct Imaging) exposure method, a DLP (Digital Light Processing) exposure method, or the like may be used. The 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 ray used include ultraviolet rays, visible 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, the temperature is 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. An example is one in which the cured product is provided on a support. 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. It may be appropriately selected from the following or 250 μm or less. 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. can.
Therefore, the laminate of this embodiment is used as an electronic component such as an electronic circuit board in a mobile terminal such as a mobile phone, for example.

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.

(Examples 1 to 12, Comparative Examples 1 to 2)
The composition is blended according to the compounding composition shown in Table 1 (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), and kneaded with a three-roll mill to prepare a photosensitive resin composition. Prepared. N, N-dimethylacetamide was added so that the solid content concentration became 60% by mass to obtain a photosensitive resin composition.

Next, using the photosensitive resin composition obtained above, each evaluation was performed under the conditions shown below.

[Preparation of photosensitive resin film]
A polyethylene terephthalate film having a thickness of 50 μm (manufactured by Teijin Limited, trade name: A-4100) is used as a carrier film, and the resin compositions of Examples and Comparative Examples are placed on the carrier film so that the thickness after drying is 50 μm. Was evenly applied to. 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.

[Measurement of absorbance]
With respect to the photosensitive resin film obtained in the above [Preparation of photosensitive resin film], the absorbance of the photosensitive layer with respect to light at a wavelength of 365 nm at a thickness of 50 μm (thickness after drying) was measured. Specifically, the absorbance (Abs) at a wavelength of 365 nm was measured using an ultraviolet-visible spectrophotometer (product name: “U-3310 Spectrophotometer”, manufactured by Hitachi High-Technologies Corporation). As a reference, a polyethylene terephthalate (PET) film alone was used. The measurement results are shown in Table 1.

[Evaluation of pattern formation]
A photosensitive resin film is placed on a glass epoxy substrate (MCL-E-679F (trade name, manufactured by Hitachi Kasei Co., Ltd.) by etching copper), and the photosensitive layer is oriented toward the glass epoxy substrate. And laminated, 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 mask for resolution evaluation having the pattern shape shown in FIG. 1 as an exposed portion on the carrier film of the laminated body (six types of line widths of 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, and 25 μm, and one type of line space of 200 μm). ) Was placed, and an i-line filter (manufactured by Asahi Spectral Co., Ltd .: HB-0365) was further placed and exposed using a high-precision parallel exposure machine (manufactured by Mikasa Co., Ltd.). At this time, the laminate was divided into four regions, and the four regions were exposed with light having a wavelength of 365 nm (i-line) ^{at different exposure amounts (300, 600, 1,000, 1,400 mJ / cm 2).} 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 developed pattern 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, the fact that the unexposed portion can be formed 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 Table 1.
A: It was possible to form with a line width of 5 to 10 μm.
B: Although it could not be formed with a line width of 5 to 10 μm, 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 insulation reliability]
Insulation reliability was evaluated by a high temperature and high humidity bias test. Thickness obtained in Examples 1 to 12 on a comb-shaped copper electrode of TEG (Test Element Group) (trade name: WALTS-KIT EM0101JY, manufactured by WALTS, L / S = 40 μm / 15 μm), which is an evaluation device. A 50 μm photosensitive resin film was attached at 60 ° C. using a laminator with the photosensitive layer oriented toward the comb-shaped copper electrode side. Then, after exposing with an i-line at an exposure amount of 1000 mJ / cm ² , the carrier film was removed after heating on a hot plate at 90 ° C. for 1 minute. Further, after heating in an oven at 200 ° C. for 1 hour, the sample was cooled to room temperature to obtain a measurement sample.
A lead wire was attached to the TEG electrode of the obtained measurement sample with solder, and a high-temperature and high-humidity bias test was performed (voltage; 5V (direct current), test time: 100 hours, 85 ° C., 85% RH (high-temperature and high-humidity)). Machine (manufactured by ESPEC) is used)). As a result, the measurement sample obtained by using the photosensitive resin films of Examples 1 to 12, the resistance in any test period (100 hours) is kept above 1.0 × 10 ⁷ Ω, sufficiently It was confirmed that the insulation reliability was excellent.

Details of each material in Table 1 are as follows.
[(A) component]
UN-952: Urethane acrylate (manufactured by Negami Kogyo Co., Ltd., trade name, number of functional groups: 10, weight average molecular weight: 9,000, reaction product of acrylate having a hydroxyl group and a diisocyanate compound, and an acryloyl group in the molecule. (Photopolymerizable functional group), urethane bond (carbon-nitrogen bond), chain hydrocarbon skeleton, and acryloyl hydrocarbon skeleton.)
-UN-954: Urethane acrylate (manufactured by Negami Kogyo Co., Ltd., trade name, number of functional groups: 6, weight average molecular weight: 4,500)
-UN-953: Urethane acrylate (manufactured by Negami Kogyo Co., Ltd., trade name, number of functional groups: 20, weight average molecular weight: 18,000)
H-219: Urethane acrylate (manufactured by Negami Kogyo Co., Ltd., trade name, number of functional groups: 9, weight average molecular weight: 35,000)
[(B) component]
A-9300: Ethylene oxide-modified diacrylate of isocyanuric acid (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name, compound represented by the above formula (7-1) and corresponding to component (B1))
-TMCH-5R: Urethane acrylate (manufactured by Hitachi Kasei Co., Ltd., trade name, number of functional groups: 2, weight average molecular weight: 950, acryloyl group (photopolymerizable functional group) in the molecule, urethane bond (carbon-nitrogen bond), It is a compound having a chain hydrocarbon skeleton and an alicyclic hydrocarbon skeleton, and corresponds to the component (B2).)
-A-DCP: Tricyclodecanedimethanol diacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name, corresponds to component (B3))
[(C) component]
-I-819: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide "IRGACURE-819" (manufactured by BASF, trade name)
-TPO: "IRGACURE-TPO" (trade name, manufactured by BASF), which is a 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
-I-184: "IRGACURE-184" which is a 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, trade name)
[(D) component]
KBM-803: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name)
KBM-503: Methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name)
[(D') component]
-KBM-103: Phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name)

From Table 1, it was confirmed that the photosensitive resin compositions of the present embodiments of Examples 1 to 12 had excellent pattern forming properties. On the other hand, a comparative example in which the resin composition of Comparative Example 1 containing no silane compound was used, or a silane compound not containing a functional group having reactivity with a photopolymerizable functional group was used. When the resin composition of No. 2 was used, the pattern forming property was poor at any exposure amount.

Claims (13)

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. Component (D): A photosensitive resin composition containing a silane compound containing a functional group reactive with the photopolymerizable functional group.
The component (D) contains a silane compound containing a thiol group as a functional group having reactivity with the photopolymerizable functional group.
The component (B) contains one or more selected from the group consisting of a low molecular weight body having a urethane bond, a low molecular weight body having an isocyanurate skeleton, and a low molecular weight body having an alicyclic skeleton .
A photosensitive resin composition in which the number of photopolymerizable functional groups contained in the component (A) is 4 to 24. The photosensitive resin composition according to claim 1, 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 claim 1 or 2, wherein the component (A) contains a high molecular weight substance having a urethane bond as a carbon-nitrogen bond. Any of claims 1 to 3, 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. The photosensitive resin composition according to item 1. The photosensitive according to any one of claims 1 to 4, wherein the component (C) contains a compound represented by the following general formula (1) or a compound represented by the following general formula (2). Resin composition.

(In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, and R ⁴ and R ⁵ respectively. Independently, it represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. R ^{1 to} R ⁵ other than the hydrogen atom are substituents, respectively. May have.)

(In the formula, R ⁶ represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an amino group, and R ⁷ and R ⁸ each independently have a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and a carbon number of carbons. It represents an aryl group of 6 to 12 or an alkoxy group having 1 to 8 carbon atoms. R ⁷ and R ⁸ may be bonded to each other to form a cyclic structure having 3 to 16 carbon atoms. Hydroxyl group and hydrogen. ^{R 6 to} R ⁸ other than the atom may each have a substituent, and the amino groups having a substituent are bonded to each other to form a cyclic structure having 3 to 12 carbon atoms. R ⁹ 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. The number 1 to 10 is shown.) The contents of the component (A), the component (B), the component (C), and the component (D) are 10 to 95% by mass and 3 to 70% by mass, respectively, based on the total solid content of the photosensitive resin composition. , 0.05 to 20% by mass, and 0.1 to 20% by mass, according to any one of claims 1 to 5. A photosensitive resin film having a photosensitive layer using the photosensitive resin composition according to any one of claims 1 to 6. A step of forming a photosensitive layer on a substrate by using the photosensitive resin composition according to any one of claims 1 to 6 or the photosensitive resin film according to claim 7.
A step of irradiating at least a part of the photosensitive layer with active light to form a photocurable portion.
A method for producing a cured product, which comprises, in order, 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 8, further comprising a step of heat-treating the resin pattern. The method for producing a cured product according to claim 8 or 9, wherein the thickness of the resin pattern is 70 to 300 μm. A laminate comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 6. The laminate according to claim 11, wherein the cured product has a thickness of 70 to 300 μm. An electronic component comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 6.

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