JP7073252B2 - 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 manufacture 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 via a predetermined mask pattern, followed by a conductor pattern and a metal post. A resist pattern (resist) is formed by developing so that the portion forming the above can be selectively removed (peeled). Next, a conductor such as copper is formed on the removed portion by plating, and then the resist pattern is removed, whereby a wiring board provided with a conductor pattern, a metal post, or the like can be manufactured.

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 a direction to be plated and grown 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. 2014-0777474 Japanese Unexamined Patent Publication No. 2014-08674

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

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, further 150 μm thicker than that of the conventional one, or thicker than that 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 properties 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 diligent research 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 body having photopolymerizable functional group and carbon-nitrogen bond, component (B): low molecular weight body having photopolymerizable functional group and carbon-nitrogen bond, (C) Component: A photosensitive resin composition containing a photopolymerization initiator and a low molecular weight substance having the component (B) as a photopolymerizable functional group having an acryloyl group.
[2] A photosensitive resin film having a photosensitive layer using the photosensitive resin composition according to the above [1].
[3] A step of providing a photosensitive layer on a substrate using the photosensitive resin composition according to the above [1] or the photosensitive resin film according to the above [2], active light rays on at least a part of the photosensitive layer. A method for producing a cured product, which comprises, in order, a step of forming a photocurable portion by irradiating the photosensitive layer and a step of removing at least a part of the photosensitive layer other than the photocured portion to form a resin pattern.
[4] A laminate comprising a cured product of the photosensitive resin composition 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 properties even when a thick photosensitive layer of 70 μm or more is formed.

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, and the minimum value and the minimum value described stepwise. The maximum value may be arbitrarily combined. 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 arbitrarily combined with the upper limit value or the lower limit value of the numerical range of another step. .. Further, 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.
"(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) comprises a component (A): a high molecular weight body having a photopolymerizable functional group and a carbon-nitrogen bond. A component (B): a low molecular weight substance having a photopolymerizable functional group and a carbon-nitrogen bond, and a component (C): a photopolymerization initiator are contained, and the component (B) is used as a photopolymerizable functional group. A photosensitive resin composition containing a low molecular weight substance having an acryloyl group.
In the present specification, the "solid content" is a non-volatile substance 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 liquid, water candy-like, and wax-like substances at room temperature (25 ° C.). Hereinafter, each component will be described.

<(A) component: high molecular weight body>
The photosensitive resin composition of the present embodiment contains a high molecular weight body having a photopolymerizable functional group and a carbon-nitrogen bond as the component (A). The "high molecular weight body" means a compound having a weight average molecular weight of 2,000 or more. In the present specification, the value of the weight average molecular weight (Mw) is a value obtained by the gel permeation chromatograph (GPC) method using tetrahydrofuran (THF) in terms of standard polystyrene.
Examples of the photopolymerizable functional group contained in the high molecular weight substance of the component (A) include a (meth) acryloyl group; an ethylenically unsaturated group such as an alkenyl group such as an allyl group and a vinyl group. From the viewpoint of improving the pattern forming property, 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 body having a urethane bond as a carbon-nitrogen bond. May include. Examples of the high molecular weight body having a (meth) acryloyl group as a photopolymerizable functional group include (meth) acrylate, and further, examples of the high molecular weight body having a urethane bond as a carbon-nitrogen bond include urethane (meth) acrylate. Be done.
Further, 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.

The component (A) has at least one of these photopolymerizable functional groups and at least one carbon-nitrogen bond. Further, the total number of photopolymerizable functional groups (number of functional groups) contained in the high molecular weight body of the component (A) can be obtained in 2 to 15 in one molecule from the viewpoint of improving pattern forming property and heat resistance. From the viewpoint of stabilizing the physical properties and properties of the cured product, it may be appropriately selected from 2 to 12 or 2 to 10.

Examples of the urethane (meth) acrylate of the component (A) 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 compounds 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 propoxysylated forms, these ethoxylated propoxyylated forms, and their caprolactone variants; trimethylol. Bifunctional (meth) acrylates such as propanedi (meth) acrylates, glycerindi (meth) acrylates, bis (2- (meth) acryloyloxyethyl) (2-hydroxyethyl) isocyanurate, these ethoxylated forms, these. Propoxifieds, these ethoxylated propoxys, and their caprolactone variants; cyclohexanedimethanol-type epoxydi (meth) acrylates, tricyclodecanedimethanol-type epoxydi (meth) acrylates, hydrogenated bisphenol A-type epoxydi (meth). ) Acrylate, hydrogenated bisphenol F type epoxy di (meth) acrylate, hydroquinone type epoxy di (meth) acrylate, resorcinol type epoxy di (meth) acrylate, catechol type epoxy di (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type Bifunctional epoxy (meth) acrylates such as epoxy di (meth) acrylate, bisphenol AF type epoxy di (meth) acrylate, biphenol type epoxy di (meth) acrylate, fluorene bisphenol type epoxy di (meth) acrylate, and isocyanuric acid monoallyl type epoxy di (meth) acrylate. Trifunctional or higher (meth) acrylates such as ditrimethylol propanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and ethoxylation thereof. The body, these propoxysylated, these ethoxylated propoxysylated, and these caprolactone variants; Trifunctional or higher functional epoxy (meth) acrylates such as enol novolac type epoxy (meth) acrylates, cresol novolac type epoxy poly (meth) acrylates, and isocyanuric acid type epoxy tri (meth) acrylates; trimethylolpropane tri (meth) acrylates, ditri Examples thereof include hydroxypropylated products such as trimethylolpropane tetra (meth) acrylate.
These can be used alone or in combination of two or more.

Here, the ethoxylated form, the propoxylated form, the ethoxylated propoxylated form, and the hydroxypropylated form of the (meth) acrylate are, for example, to 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 and propylene oxide groups, and those to which a hydroxypropyl group is added as a raw material.
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 a compound having one to three isocyanate groups in one molecule may be used. 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 diisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate; 1,3-bis (isocyanatomethyl) cyclohexane , Isophoron diisocyanate, 2,5-bis (isocyanatomethyl) norbornene, bis (4-isocyanatocyclohexyl) methane, 1,2-bis (4-isocyanatocyclohexyl) ethane, 2,2-bis (4-isocyanato) Alicyclic diisocyanate compounds such as cyclohexyl) propane, 2,2-bis (4-isocyanatocyclohexyl) hexafluoropropane, bicycloheptane triisocyanate; 1,4-phenylenediocyanate, 2,4-tolylene diisocyanate, 2,6 -Aromas 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.

Above all, 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-phenylenedi isocyanate, 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 organic group (that is, the above-mentioned (meth) acrylate having a hydroxyl group) derived from the (meth) acrylate having a hydroxyl group in the molecule. ) 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, 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.

The urethane (meth) acrylate as the component (A) may be, for example, 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 from the viewpoint of improving pattern forming property. , The reaction product obtained by reacting the (meth) acrylate having a hydroxyl group may be contained.

As the isocyanate compound used here having at least two isocyanate groups in one molecule, among the compounds exemplified as the above isocyanate compounds, diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds and aromatic diisocyanate compounds are used. Moreover, a multimer such as a uretdione type dimer, an isocyanurate type, and a biuret type trimer 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. Orbranched unsaturated diol compounds; examples thereof include diol compounds having an alicyclic skeleton such as various cyclohexanediols, various cyclohexanedimethanols, various tricyclodecanedimethanols, hydride bisphenol A, and hydride bisphenol F. .. Here, the saturated diol compound and the unsaturated diol compound can be collectively referred to as a diol compound having a chain hydrocarbon skeleton.
The above diol compounds can be used alone or in combination of two or more.

The diol compound having a chain hydrocarbon skeleton has 1 to 20 carbon atoms and 2 to 16 carbon atoms from the viewpoint of improving the pattern forming property and increasing the glass transition point (Tg) after polymerization to improve the water resistance. 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 to carbon atoms from the viewpoint of improving the pattern forming property and increasing the glass transition point (Tg) after polymerization to improve the water resistance. It may be appropriately selected from diol compounds having 18, 6 to 16 alicyclic skeletons, and more specifically, various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol, 1,3-. It may be appropriately selected from various cyclohexanedimethanols such as cyclohexanedimethanol and 1,4-cyclohexanedimethanol.

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.

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

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

The divalent organic group of X ₁ is derived from an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, and an organic group derived from an aromatic diisocyanate compound, which are exemplified as the above-mentioned compound having an 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. Further, the divalent organic group represented by X ₁ may be these residues themselves, or residues derived from an isocyanate compound derivative such as a heavy adduct of the isocyanate compound and the diol compound. May be.
From the viewpoint of improving the pattern forming property and improving the transparency, water resistance, and moisture resistance of the resin composition in a well-balanced manner, X ₁ is a divalent organic group having an alicyclic skeleton, among which, the following formula ( It may be a divalent organic group having an alicyclic skeleton, which is a residue of the isophorone diisocyanate represented by 2).

Examples of the divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton of Y ₁ include a diol compound having a chain hydrocarbon skeleton and a diol having an alicyclic skeleton exemplified as the above diol compound. Examples thereof include an organic group derived from the compound, that is, a divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton, which is a residue obtained by removing a hydroxyl group from the above diol compound.
Above all, 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 and 2 to 14, and more specifically, it may be appropriately selected from the residues obtained by removing the hydroxyl groups from ethylene glycol and octadecanediol. good. From the same viewpoint, as the divalent organic group having an alicyclic skeleton, the residue obtained by removing the hydroxyl group from the diol compound having an alicyclic skeleton having 5 to 20, 5 to 18 and 6 to 16 carbon atoms. It may be appropriately selected from the groups, and more specifically, various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and the like. It may be appropriately selected from the residues obtained by removing the hydroxyl group from various cyclohexanedimethanol.

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

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

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

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

Examples of commercially available products containing a urethane acrylate having a structural unit represented by the general formula (1) 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) (all of the above are trade names, manufactured by Negami Kogyo Co., Ltd.), EBECRYL8405 (urethane acrylate / 1,6-hexanediol diacrylate = 80 / Examples thereof include 20 addition reactants, number of functional groups: 4, Mw: 2,700) (trade name, manufactured by Daicel Ornex Co., Ltd.).
Further, as a commercially available product containing urethane methacrylate having a structural unit represented by the above general formula (1), for example, UN-6060PTM (number of functional groups: 2, Mw: 6,000, trade name, Negami Kogyo Co., Ltd.) Made) and the like. 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 (meth) acrylate represented by the above general formula (3), for example, UN-952 (number of functional groups: 10, Mw: 6,500 to 11,000) is a general formula ( Examples of commercially available products containing urethane (meth) acrylate represented by 6) include UN-905 (number of functional groups: 15, Mw: 40,000 to 200,000) (all of the above are trade names). , Made 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 functional groups) contained in the urethane (meth) acrylate of the component (A) is 2 to 15 in one molecule from the viewpoint of improving pattern formation and heat resistance, and the curing can be obtained. From the viewpoint of stabilizing the physical properties and characteristics of the substance, it may be appropriately selected from 2 to 12 or 2 to 10.
When the number of 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 functional groups is 15 or less, the rigidity of the cured product is improved and the adhesion to the substrate or the like is improved. Further, the resin composition having an appropriate viscosity can be obtained, the coatability is improved, and when the resin composition after coating is irradiated with light, only the surface portion is easily photocured rapidly and the inside is easily cured. Can suppress the phenomenon that photocuring does not proceed sufficiently, and excellent resolution can be obtained. Therefore, excellent pattern forming property can be obtained even when a thick photosensitive layer is formed. Further, after performing at least one of photo-curing and thermosetting, the residual unreacted (meth) acryloyl group can be further reduced, and fluctuations in the physical properties and properties of the obtained cured product can be further suppressed.

The weight average molecular weight of the high molecular weight substance 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 developability and phase. From the viewpoint of improving solubility, 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 it is applied on the substrate, the generation of dripping of the applied 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 50% 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 formability can be obtained even when a thick photosensitive layer is formed.
Considering the pattern moldability 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 body>
The photosensitive resin composition of the present embodiment contains a photopolymerizable functional group as a component (B) and a low molecular weight substance having a carbon-nitrogen bond, and the component (B) has an acryloyl group as a photopolymerizable functional group. Contains low molecular weight substances. By "low molecular weight" is meant a compound having a weight average molecular weight of less than 2,000.
The component (B) contains a low molecular weight substance having an acryloyl group as a photopolymerizable functional group. When the component (B) contains at least a low molecular weight substance having an acryloyl group, sufficiently excellent pattern forming property can be obtained. For example, when a compound containing a methacryloyl group and not an acryloyl group is used alone, it is difficult to sufficiently obtain pattern forming properties. The component (B) may contain urethane acrylate having a urethane bond as a carbon-nitrogen bond from the viewpoint of improving the pattern forming property. In general, a low molecular weight substance having an acryloyl group has a higher activation energy required for photopolymerization and improved sensitivity as compared with a low molecular weight substance having a methacryloyl group. Further, since the low molecular weight body further has a carbon-nitrogen bond, it can act as a chain transfer agent for radical polymerization, and excellent pattern forming property can be obtained.

The component (B) has at least one acryloyl group and at least one carbon-nitrogen bond. Further, the total number of acryloyl groups (number of functional groups) contained in the low molecular weight body of the component (B) is 2 to 15 in one molecule from the viewpoint of improving pattern formation and heat resistance, and the obtained cured product. From the viewpoint of stabilizing physical properties and properties, it may be appropriately selected from 2 to 12 or 2 to 10.

Examples of the urethane acrylate as the component (B) include a reaction product of an acrylate having a hydroxyl group and an isocyanate compound having an isocyanate group. Here, examples of the acrylate having a hydroxyl group and the isocyanate compound include an acrylate having a hydroxyl group and an isocyanate compound exemplified as those used for producing a high molecular weight compound. Here, as examples of the ones appropriately selected from the viewpoint of improving the pattern forming property, the same ones appropriately selected as those used for producing the high molecular weight body from the same viewpoint are exemplified.

Further, as the low molecular weight urethane acrylate, a reaction product obtained by reacting an 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 used. Can be mentioned. Here, as the isocyanate compound having at least two isocyanate groups in one molecule, the diol compound, and the acrylate having a hydroxyl group, at least two isocyanate groups are contained in one molecule exemplified as those used for producing a high molecular weight substance. Examples thereof include isocyanate compounds, diol compounds, and acrylates having a hydroxyl group. Here, as examples of the ones appropriately selected from the viewpoint of improving the pattern forming property, the same ones appropriately selected as those used for producing the high molecular weight body from the same viewpoint are exemplified.
Examples of this reaction product include those having a structural unit represented by the following general formula (7).

In the general formula (7), 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 (B), 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 above general formula (1), respectively.
From the viewpoint of improving the pattern forming property and improving the transparency, water resistance, and moisture resistance of the resin composition in a well-balanced manner, X ₂ is a divalent organic group having a chain hydrocarbon skeleton 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 urethane acrylate that can be used as the component (B) include compounds represented by the following general formula (8).

In the above general formula (8), n ₅ represents an integer of 1 to 4. R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a plurality of R ⁴ and R ⁵ 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 (8), X2 of the general formula (7) is a residue of trimethylhexamethylene diisocyanate which is a _divalent organic group having a chain hydrocarbon skeleton and is Y. As a commercial product containing urethane acrylate having a structural unit in which ₂ is a residue of cyclohexanedimethanol, which is a divalent organic group having an alicyclic skeleton, for example, TMCH-5R (trade name, number of functional groups: 2, Mw: 950, manufactured by Hitachi Chemical Co., Ltd.) and the like.
Further, as a commercially available product containing a urethane acrylate having a structural unit represented by the above general formula (7), 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), 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 number of functional groups and the weight average molecular weight of urethane acrylate, respectively.

The weight average molecular weight of the low molecular weight substance of the component (B) is less than 2,000, may be 1,800 or less from the viewpoint of improving adhesion, and further 1,500 from the viewpoint of improving resolution. It may be as follows. 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.

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 is 3% 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 selected from 70% by mass or less, 60% by mass or less, or 50% by mass or less based on the total solid content of the photosensitive resin composition. do it.
The content of the component (B) based on the total solid content of the component (A) is 25 to 90% by mass, 30 to 80% by mass, or 35 from the viewpoint of improving the pattern forming property and the rigidity of the cured product. It may be appropriately selected from ~ 65% by mass.
In the present embodiment, a low molecular weight substance having a photopolymerizable functional group other than the acryloyl group can be contained, depending on the desired purpose. The content of the low molecular weight substance having an acryloyl group as a photopolymerizable functional group based on the total solid content of the component (B) is 70% by mass or more, 80% by mass or more, 90% by mass or more, or. It may be appropriately selected from 95% by mass or more. When the content is 70% 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 low molecular weight substance having an acryloyl group as a photopolymerizable functional group is 100% by mass or less, that is, 100% by mass, that is, the total amount of the component (B) is photopolymerizable. It may have an acryloyl group as a functional group.

<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, aclysine type, phenylglycine. Examples thereof include photopolymerization initiators such as radicals and quinones.

The acylphosphine oxide-based photopolymerization initiator has an acylphosphine oxide group (> P (= O) -C (= O) -group), and is, for example, (2,6-dimethoxybenzoyl) -2,4. , 6-Pentylphosphinoxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide, 2,4,6-trimethylbenzoyldiphenylphosphinoxide (trade name: IRGACURE-TPO, manufactured by BASF), ethyl-2 , 4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphin oxide (trade name: IRGACURE-819, manufactured by BASF), (2,5-dihydroxyphenyl) diphenylphosphine Examples thereof include oxide, (p-hydroxyphenyl) diphenylphosphine oxide, bis (p-hydroxyphenyl) phenylphosphin oxide, tris (p-hydroxyphenyl) phosphin oxide and the like.

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

Examples of the aromatic ketone-based 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-diphenylethan-1-one (trade name: IRGACURE-651, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-Morphorinophenyl) -butane-1-one (trade name: IRGACURE-369, manufactured by BASF), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one (Product name: IRGACURE-907, manufactured by BASF) and the like.

Examples of the quinone-based photopolymerization initiator include 2-ethylanthraquinone, phenanthrenquinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 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; 2,2-dimethoxy-1,2-diphenylethane-1-. On (trade name: IRGACURE-651, manufactured by BASF), 1-hydroxy-cyclohexyl-phenylketone (trade name: IRGACURE-184, manufactured by BASF), 2-hydroxy-2-methyl-1-phenylpropan-1- On (trade name: IRGACURE-1173, manufactured by BASF), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1 on (trade name: IRGACURE-2959) , BASF), 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one (trade name: IRGACURE-127, BASF) and the like.

The imidazole-based photopolymerization initiator includes, for example, 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl as the 2,4,5-triarylimidazole dimer. -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) -on, 7-diethylamino-5', 7'-dimethoxy-3,3'-carbonylbiscoumarin, 3,3'-carbonylbis [7- (diethylamino) coumarin], 7-diethylamino -3-Chienoki silk marine and the like can be mentioned.

From the viewpoint of improving the photocurability and sensitivity and improving the pattern forming property, it can be appropriately selected from the acylphosphine oxide-based photopolymerization initiators. The above component (C) can be used alone or in combination of two or more. Further, as the component (C), one synthesized by a conventional method may be used, or a commercially available product may be obtained and used.

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 is 0.35 or less with respect to light having a wavelength of 365 nm, or 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 easily passes to the bottom of the photosensitive layer (the surface of the photosensitive layer on the substrate side), so that the pattern is formed. It is possible to improve the sex. Here, the absorbance is determined with respect to light having 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 single polyethylene terephthalate film as a reference. Absorbance can be measured. Further, the absorbance for light having a wavelength of 365 nm when the thickness of the photosensitive layer is 50 μm can be obtained by converting the absorbance of 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.

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

As described above, 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 based on the total solid content of the photosensitive resin composition. It may be appropriately selected from 0.1 to 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.

<Component (D): Thermal radical polymerization initiator>
Further, the photosensitive resin composition of the present embodiment can further contain (D) a thermal radical polymerization initiator. The component (D) 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 and the like Oxide; Peroxy such as bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-3-methoxybutylperoxycarbonate, 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-ethylhexylmonocarbonate , T-butylperoxybenzoate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, peroxyesters such as t-butylperoxyacetate, etc. 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 (D) include a peroxide-based polymerization initiator and a dialkyl peroxide-based polymerization initiator from the viewpoint of improving pattern-forming property, and among them, dicumyl peroxide can be selected. In addition, the component (D) can be used alone or in combination of two or more.

When the component (D) 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.

<(E) component: inorganic filler>
The photosensitive resin composition of the present embodiment may contain the component (E) 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.
Examples of the component (E) include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TIO ₂ ), titanium 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) _{2O 3.2SiO 2} ), Cordierite (2MgO ・ 2Al 2O3.5SiO ₂ ), Talk (3MgO ・_{4SiO 2}・_H2O ), Aluminum Titanium _{( TIO2}・_Al2O3 ) _, Itria 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 (E) may be appropriately selected from 0.01 to 3 μm, 0.01 to 2 μm, or 0.02 to 1 μm from the viewpoint of improving adhesiveness, heat resistance, and rigidity of the cured product. Just do it. Here, the average particle size of the component (E) 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 the international standard ISO13321 is used using a submicron particle analyzer (trade name: N5, manufactured by Beckman Coulter Co., Ltd.). The particles dispersed in the solvent are measured at a refractive index of 1.38, and the particle size at the integrated value of 50% (volume basis) in the particle size distribution is taken as the average particle size. Further, the component (E) contained in the photosensitive layer provided on the carrier film or the cured film of the photosensitive resin composition is also diluted (or by volume) 1,000 times (or volume ratio) with a solvent as described above. After dissolution), it can be measured by using the above-mentioned submicron particle analyzer.

The content of the component (E) 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 (E), the permeability of the photosensitive resin composition is improved, and for example, even when the pattern is formed by a thick photosensitive layer of 70 μm or more, the photosensitive layer is formed. Since it is easy for light to pass through to the bottom of the photosensitive layer (the surface of the photosensitive layer on the substrate side), the pattern formability is improved.

<Other additives>
The photosensitive resin composition of the present embodiment may further contain additives such as a silane coupling agent, a sensitizer, a heat-resistant high molecular weight substance, a thermal cross-linking agent, and an adhesive aid, if necessary. ..

The silane coupling agent can improve the adhesiveness of electronic components to the substrate, and in particular, when the substrate contains silicon (for example, a glass substrate, a silicon wafer, an epoxy resin impregnated glass cloth substrate, etc.). Is valid. Examples of the silane coupling agent include alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane, (meth) acryloxypropyltrimethoxysilane, and (meth) acryloxipropylmethyldimethoxysilane. (Meta) acryloyl group-containing alkoxysilane, aminopropyltrimethoxysilane, amine-based alkoxysilane such as aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidoxypropyl Examples thereof include glycidoxy group-containing alkoxysilanes such as methyldiisopropenoxysilane. These can be used alone or in combination of two or more.
From the viewpoint of further improving the adhesiveness, (meth) acryloyl group-containing alkoxysilanes such as (meth) acryloxypropyltrimethoxysilane and (meth) acryloxypropylmethyldimethoxysilane, glycidoxypropyltrimethoxysilane, and glycidoxy A silane coupling agent having an ethylenically unsaturated group in the molecule, such as a glycidoxy group-containing alkoxysilane such as propylmethyldiethoxysilane and glycidoxypropylmethyldiisopropenoxysilane, may be used.

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

As the heat-resistant high molecular weight material, for example, 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 substituted with a methylol group at the α-position and an alkoxymethyl group, and a group consisting of a methylol group and an alkoxymethyl group at the N-position from the viewpoint of improving the rigidity of the cured product. Examples thereof include a melamine resin and a urea resin substituted with at least one selected. These can be used alone or in combination of two or more.

The adhesion aid can be used as desired to improve the adhesion between the photosensitive resin composition and the substrate, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-. Glycydoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, triethoxysilylpropylethylcarbamate, 3- (triethoxysilyl) propylkohaku Acid anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, 2- (3) , 4-Epylcyclohexyl) Organic silane compounds such as ethyltrimethoxysilane. These can be used alone or in combination of two or more.

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

<Diluent>
A diluent can be used in the photosensitive resin composition of the present embodiment, if necessary. Examples of the diluent include alcohols having 1 to 6 carbon atoms such as isopropanol, isobutanol and t-butanol; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; dimethyl. Sulfur atom-containing substances such as sulfoxide and sulfolane; esters such as γ-butyrolactone and dimethyl carbonate; cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate. , Esters such as propylene glycol monoethyl ether acetate, and the like. 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 solid content in the photosensitive resin composition is 50 to 90% by mass, 60 to 80% by mass, or 65 to 75% by mass. That is, 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 to be 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.

In the photosensitive resin composition of the present embodiment, the above-mentioned components (A) to (C), and optionally used components (D), (E), other additives, and a diluent are used 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 in the form of a film, for example, it can be used in the form of a photosensitive resin film described later, and in this case, a photosensitive layer having a desired thickness can be formed by laminating using a laminator or the like.

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

[Photosensitive resin film]
The photosensitive resin film of the present embodiment has a photosensitive layer using the photosensitive resin composition of the present embodiment. Moreover, the photosensitive resin film of this embodiment may have a carrier film. As used herein, the term "layer" includes not only a structure having a shape formed on the entire surface but also a structure having a shape partially formed when observed as a plan view.

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

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

Examples of the carrier film include a polyester resin film such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), and a resin film such as a polyolefin resin film such as polypropylene and polyethylene. A polyester resin film may be selected from the viewpoint of improving the mechanical strength and heat resistance of the photosensitive resin film.
The thickness of the carrier film may be appropriately selected from 10 μm to 3 mm or 10 to 200 μm in consideration of handleability and the like.

The thickness of the photosensitive layer may be appropriately selected from 1 to 500 μm, 10 to 300 μm, or 30 to 100 μm. When the thickness is 30 μm or more, for example, when a photosensitive layer having a thickness of 150 μm or more is formed, the number of operations by laminating or the like can be further reduced, and when the thickness is 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 obtained by bonding, for example, a carrier film having a photosensitive layer formed on the carrier film and a photosensitive layer having a photosensitive layer formed on a protective layer described later. A photosensitive resin film having a thick photosensitive layer and a protective layer in this order can be obtained.

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

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

(Photosensitive layer forming process)
In the formation of 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 a 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 in 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 10 μm as the lower limit of the thickness of the photosensitive layer after drying. It may be appropriately selected from the above, 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-time application (and drying if necessary) or by laminating, but is applied multiple times (and as necessary) until the desired thickness is obtained. Drying) or laminating may be repeated.

(Exposure process)
In the exposure step, the photosensitive layer provided on the substrate in the photosensitive layer forming step is irradiated with active light rays at least partially as needed, 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. 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.

The exposure amount of the active light may be appropriately selected from 10 to 2,000 mJ / cm ² , 100 to 1,500 mJ / cm ² , or 300 to 1,000 mJ / 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 portion (unexposed portion) other than the cured portion of the photosensitive layer formed in the exposure step is removed to form a resin pattern. The 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.
Further, 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 developer, wash (rinse) with water, methanol, ethanol, alcohol such as isopropyl alcohol, n-butyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether acetate, etc., if necessary. 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 raising the temperature stepwise. 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, heat treatment is performed for 10 to 50 minutes or 20 to 40 minutes at least at least around 120 ° C. and 160 ° C., and then 30 to 100 at around 220 ° C. The heat treatment may be performed 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.

[Laminates and electronic components]
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.

As the cured product provided on the substrate obtained by the above-mentioned method for producing a cured product, the photosensitive resin composition of the present embodiment is used, and excellent pattern forming properties can be obtained even with 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 in a finer pattern on the substrate 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 board, by using the cured product formed from 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 the present embodiment is not limited to the following examples.

(Synthesis Example 1; Synthesis of Resin P-1)
Methyl methacrylate (635 g), butyl acrylate (30 g), butyl acrylate (245 g), and 2-hydroxyethyl methacrylate (75 g) were mixed to obtain a monomer mixture. 0.9 g of 2,2'-azodiisobutyronitrile was dissolved in the obtained monomer mixture to prepare a mixed solution. The above mixture was added to a 1 L autoclave equipped with a stirrer and a condenser while adding 1030 g of propylene glycol monomethyl ether acetate as a solvent and stirring. Then, the mixture was polymerized at 90 ° C. for 6 hours under a stirring rotation speed of 100 min ^-1 and a nitrogen atmosphere to obtain an acrylic resin solution (resin P-1). The weight average molecular weight of the obtained acrylic resin was 43,370. Here, the weight average molecular weight was a value obtained by GPC method standard polystyrene conversion using the following apparatus, and was measured using a solution in which 0.5 mg of the polymer was dissolved in 1 mL of tetrahydrofuran (THF).
Device name: HLC-8320GPC manufactured by Tosoh Corporation
Columns: Gelpack R-420, R-430, and R-440 (three joints)
Detector: RI detector Column temperature: 40 ° C
Eluent: THF
Flow rate: 1 ml / min Standard material: Polystyrene

(Examples 1 to 5, Comparative Examples 1 to 8)
The compositions are blended according to the compounding composition shown in Table 1 (the numerical values in the table indicate the mass part of each material, and in the case of a solution, the mass part in terms of solid content), kneaded with a three-roll mill, and the photosensitive resin. The composition was prepared. N, N-dimethylacetamide was added so that the solid content concentration became 60% by mass to obtain a photosensitive resin composition.

Details of each material in Table 1 are as follows.
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 acryloyl in the molecule. It has a group (photopolymerizable functional group), a urethane bond (carbon-nitrogen bond), a chain hydrocarbon skeleton, and an alicyclic hydrocarbon skeleton.)
-Resin P-1: Acrylic resin produced in Synthesis Example 1 (weight average molecular weight: 43,370)
Z250: Cyclomer P (ACA) Z250 (manufactured by Daicel Ornex Co., Ltd., trade name, has an acryloyl group (photopolymerizable functional group) in the molecule, but does not have a carbon-nitrogen bond).
TMCH-5R: Urethane acrylate (manufactured by Hitachi Chemical Co., Ltd., 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) , Has a chain hydrocarbon skeleton, and an acryloyl hydrocarbon skeleton.)
FA-324A: EO-modified bisphenol A diacrylate (manufactured by Hitachi Kasei Co., Ltd., trade name, number of functional groups: 2, weight average molecular weight: 512)
FA-7220M: Amide bond-containing methacrylate (manufactured by Hitachi Kasei Co., Ltd., trade name)
-I-819: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, (manufactured by BASF, trade name)
・ Park Mill D: Dicumyl Peroxide (manufactured by NOF CORPORATION, trade name)
KBM-503: Methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name)
・ AY43-031: Silane coupling agent (manufactured by Toray Dow Corning Co., Ltd., trade name)

Next, using the photosensitive resin composition obtained above, each evaluation was performed under the conditions shown below. The evaluation results are shown in Table 2.

[Preparation of photosensitive resin film]
A polyethylene terephthalate film having a thickness of 50 μm (trade name: A-4100, manufactured by Teijin Limited) is used as a carrier film, and the resin compositions of Examples and Comparative Examples are placed on the carrier film to a thickness of 50 μm after drying. It was applied evenly. Then, it was heated and dried at 100 ° C. for 15 minutes using a hot air convection dryer to form a photosensitive layer, and a photosensitive resin film having a carrier film and a photosensitive layer was prepared.

[Evaluation of pattern formation]
The direction in which the photosensitive layer of the photosensitive resin film is located on the glass epoxy substrate side (MCL-E-679F (trade name, manufactured by Hitachi Chemical Co., Ltd.) by etching copper). 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. Obtained a laminate to be provided.
A mask for resolution evaluation (details will be described later) is placed on the carrier film of the laminated body, and an i-line filter (trade name: HB-0365, manufactured by Asahi Spectral Co., Ltd.) is placed on the mask for high-precision parallel exposure. Exposure was performed using a machine (manufactured by Mikasa Co., Ltd.). At this time, the laminate was divided into three regions, and the three regions were exposed with light having a wavelength of 365 nm (i-line) at different exposure amounts (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 developed by immersing it in a developing solution (cyclopentanone) for 20 minutes. The developed pattern was dried at room temperature for 30 minutes and observed with a metallurgical microscope to evaluate the pattern formation property. The evaluation was performed according to the following criteria. Here, "formable" means that the unexposed portion is cleanly removed and there is no defect such as tilting in the line portion (exposed portion). Table 2 shows the evaluation results using the photosensitive resin compositions of Examples 1 to 5, and Table 3 shows the evaluation results using the resin compositions of Comparative Examples 1 to 7.
A: 6-1 to 6-8, 7-1 to 7-6, and 8-1 to 8-5 could be formed.
B: 7-7 to 7-8 and 8-6 to 8-8 could be formed.
C: A pattern having a line width of 30 μm or less could not be formed, or the photosensitive layer was peeled off after development.

Here, the mask for resolution evaluation is a mask having a predetermined line-to-line pitch, a line width, an L-shaped pattern shown in FIG. 1, and a linear pattern (in FIG. 1, the unit of numerical values is μm). be.). FIG. 1 is a schematic diagram showing a resolution evaluation mask having an L-shaped and linear line-to-line pitch of 200 μm and a line width of 30 μm among the resolution evaluation masks. In this embodiment, a mask having several combinations of the line-to-line pitch and the line width is used, and AB (A is a numerical value according to the line-to-line pitch, B) according to the line-to-line pitch and the line width. Is indicated by a numerical value according to the line width.), Where the pitch between lines is 100, 150, 200 μm, A is 6, 7, 8 respectively, and the line width is 5, 8, 10, 12, 15, Those of 20, 25, and 30 μm are referred to as B, 1 to 8, respectively (see Table 4). For example, a line-to-line pitch of 100 μm and a line width of 5 μm is referred to as 6-1. A line-to-line pitch of 200 μm and a line width of 30 μm shown in FIG. 1 is referred to as 8-8. Therefore, it can be said that the smaller the values of A and B are, the more difficult it is to form a pattern. It can be said that it has.

From Table 2, it was confirmed that the photosensitive resin compositions of the present embodiments of Examples 1 to 5 had excellent pattern forming properties. On the other hand, when the resin compositions of Comparative Examples 1 and 2 containing the component (B) were used, even the pattern could not be formed at an exposure amount of 600 (mJ / cm ² ), and the component (A) and the component (A) and (B) When the resin compositions of Comparative Examples 3 and 4 containing no component were used, the pattern could not be formed even if the exposure amount was increased to 1400 (mJ / cm ² ). When the resin compositions of Comparative Examples 5 to 7 containing the component (B) but not the component (A) were used, the resin composition of Comparative Example 6 was used and the exposure amount was 1400 (mJ / cm ² ). At that time, the pattern could be formed, but in other cases, the pattern could not be formed. Further, when the resin composition of Comparative Example 8 containing the component (A) but not containing the low molecular weight substance having an acryloyl group as the photopolymerization functional group was used, no pattern could be formed.

[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 light having a wavelength of 365 nm was measured at a thickness of 50 μm (thickness after drying). 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 5.

From the results in Table 5, the photosensitive resin compositions of the present embodiment of Examples 1 to 5 had an absorbance of 0.35 or less with respect to light having a wavelength of 365 nm at a thickness of the photosensitive layer (thickness after drying) of 50 μm. It was confirmed that excellent pattern formation was exhibited because the light was as small as 3 or less or 0.2 or less and the light passed to the bottom of the photosensitive layer (the surface of the photosensitive layer on the substrate side). On the other hand, the resin compositions of Comparative Examples 3 to 7 had an absorbance of more than 0.36.

[Evaluation of insulation reliability]
Obtained in Examples 1 to 5 on a comb-shaped copper electrode of the evaluation device TEG (Test Element Group) (WALTZ-KIT EM0101JY (trade name, manufactured by WALTZ, L / S = 40 μm / 15 μm)). A photosensitive resin film having a thickness of 50 μm was laminated with the photosensitive layer oriented toward the comb-shaped copper electrode side. Lamination was performed at 60 ° C. using a laminator. Then, after exposure 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 samples obtained by using the photosensitive resin films of Examples 1 to 5 all maintained a resistance value of 1.0 × ¹⁰⁷ or more during the test time (100 hours), which is sufficient. It was confirmed that the insulation reliability was excellent.

Claims (14)

(A) Component: A high molecular weight body having a photopolymerizable functional group and a carbon-nitrogen bond and having a weight average molecular weight of 2,000 to 30,000,
Component (B): A low molecular weight substance having a photopolymerizable functional group and a carbon-nitrogen bond and having a weight average molecular weight of less than 2,000.
(C) component: contains a photopolymerization initiator and
The component (A) contains a high molecular weight substance having a (meth) acryloyl group as a photopolymerizable functional group.
The content of the component (A) is 50% by mass or more based on the total solid content in the photosensitive resin composition.
The component (B) contains a low molecular weight substance having an acryloyl group as a photopolymerizable functional group and a urethane bond as a carbon-nitrogen bond.
The content of the component (C) is 0.05 to 20% by mass based on the total amount of solids in the photosensitive resin composition (however, the (A) carboxyl group-containing resin, (B). A photosensitive resin composition comprising () a urethane (meth) acrylate having 6 or more functional groups, (C) a photopolymerization initiator, and (D) titanium oxide; at least (A) in the molecule. Urethane bond and carboxyl group-containing resin substantially free of radically polymerizable group, (B) Urethane bond and carboxyl group-containing resin containing radically polymerizable group in the molecule, (C) Radical polymerizable compound, (D) It contains (E) a photopolymerization initiator, (F) rutyl-type titanium oxide, and (G) phosphinate, a reactive group-containing compound that is reactive with a carboxyl group that does not substantially contain an aromatic ring in the molecule. White photosensitive resin compositions characterized by substantially no silicon-containing organic compounds; excluding curable compositions containing silica particles having ethylenically unsaturated groups). The photosensitive resin composition according to claim 1, wherein the component (A) contains a high molecular weight body having a urethane bond as a carbon-nitrogen bond. The invention according to claim 1 or 2, wherein the component (A) contains a high molecular weight substance having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton. Photosensitive resin composition. The photosensitive resin composition according to any one of claims 1 to 3, wherein the component (C) contains an acylphosphine oxide-based photopolymerization initiator. Any of claims 1 to 4, wherein the contents of the component (A) and the component (B) are 50 to 95% by mass and 3 to 70% by mass, respectively, based on the total solid content in the photosensitive resin composition. The photosensitive resin composition according to item 1. The photosensitive resin composition according to any one of claims 1 to 5, further comprising a component (D): a thermal radical polymerization initiator. The photosensitive resin composition according to any one of claims 1 to 6, wherein the absorbance to light having a wavelength of 365 nm at a thickness of 50 μm is 0.35 or less. A photosensitive resin film having a photosensitive layer using the photosensitive resin composition according to any one of claims 1 to 7. A step of providing a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 7 or the photosensitive resin film according to claim 8, on at least a part of the photosensitive layer. A method for producing a cured product, which comprises, in order, a step of irradiating an active light beam to form a photocurable portion and a step of removing at least a part of the photosensitive layer other than the photocurable portion to form a resin pattern. The method for producing a cured product according to claim 9, further comprising a step of heat-treating the resin pattern. The method for producing a cured product according to claim 10, wherein the thickness of the resin pattern is 70 μm or more and 300 μm or less. A laminate comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 7. The laminate according to claim 12, wherein the cured product has a thickness of 70 μm or more and 300 μm or less. An electronic component comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 7.

Images