WO2017168697A1 - Photosensitive resin composition, photosensitive resin film, method for producing cured product, laminate, and electronic component - Google Patents

Abstract

Provided are: a photosensitive resin composition which exhibits excellent pattern forming properties even when forming a photosensitive layer having a thickness of at least 70 µm; a photosensitive resin film; a method for producing a cured product; a laminate; and an electronic component. The present invention relates to a photosensitive resin composition which includes: component (A), namely a high molecular weight polymer having photopolymerizable functional groups and carbon-nitrogen bonds; component (B), namely a low molecular weight polymer having photopolymerizable functional groups and carbon-nitrogen bonds; and component (C), namely a photopolymerization initiator. Component (B) includes a low molecular weight polymer having acryloyl groups as the photopolymerizable functional groups. The present invention also relates to: a photosensitive resin film which uses said photosensitive resin composition; a method for producing a cured product; a laminate; and an electronic component.

Description

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

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, and the like are formed by plating. More specifically, a photosensitive layer is formed on a support (substrate) using a photosensitive resin composition, the photosensitive layer is exposed through a predetermined mask pattern, and then a conductor pattern, a metal post A resist pattern (resist) is formed by developing so that a portion for forming a film 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 having a conductor pattern, a metal post, and the like can be manufactured.

Conventionally, a thick conductor pattern and a metal post have been produced by growing a metal plating after removing the resist pattern. In order to meet such a demand, for example, a thick photosensitive resist having a thickness of about 30 μm and a photosensitive layer having a thickness of about 65 μm has been used (see Patent Documents 1 and 2).
Also, in recent years, the conductor layer has a thickness of 150 μm by performing plating while destroying the layer existing in the direction in which selective plating growth is desired among the dilute metal ion layers with a plating solution in order to further improve the performance. Attempts have been made to make the film as thick as possible (see Patent Document 3).

Japanese Patent Laying-Open No. 2015-034926 JP 2014-074744 A JP 2014-080674 A

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

However, in the conventional thick-film photosensitive resist, for example, when formation of a thick photosensitive layer of 70 μm or more is required, light may hardly pass to the bottom portion, and the pattern shape may be deteriorated. In addition, in the method described in Patent Document 3, since the plating proceeds while partially destroying the diluted metal ion layer, it is difficult to stably form an excellent pattern. Therefore, there is a demand for a photosensitive resist having an excellent pattern forming property even when a photosensitive layer having a thickness of 70 μm or even 150 μm thicker than the conventional one 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 an excellent pattern forming property even when a thick photosensitive layer of 70 μm or more is formed. It is to provide a composition, a photosensitive resin film, a method for producing a cured product, a laminate, and an electronic component (hereinafter sometimes referred to as “photosensitive resin composition etc.”).

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 having the following constitution. The present disclosure provides the following photosensitive resin composition and the like.

[1] Component (A): high molecular weight body having a photopolymerizable functional group and a carbon-nitrogen bond, (B) component: low molecular weight body having a photopolymerizable functional group and a carbon-nitrogen bond, and (C) A photosensitive resin composition comprising: a component: a photopolymerization initiator, wherein the component (B) includes a low molecular weight body having an acryloyl group as a photopolymerizable functional group.
[2] A photosensitive resin film having a photosensitive layer using the photosensitive resin composition according to [1].
[3] A step of providing a photosensitive layer on the substrate using the photosensitive resin composition according to the above [1] or the photosensitive resin film according to the above [2], and at least a part of the photosensitive layer having an actinic ray , To form a photocured part, and at least a part of the photosensitive layer other than the photocured part is removed to form a resin pattern in order.
[4] A laminate comprising a cured product of the photosensitive resin composition according to [1].
[5] An electronic component comprising a cured product of the photosensitive resin composition according to [1].

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

Hereinafter, the present disclosure will be described in detail.
In this specification, the numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. The maximum values may be arbitrarily combined. In addition, in the numerical ranges described stepwise in this specification, the upper limit value or lower limit value of a numerical range of a certain step may be arbitrarily combined with the upper limit value or lower limit value of the numerical range of another step. . Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
“(Meth) acrylic acid” means at least one of “acrylic acid” and “methacrylic acid” corresponding thereto, and the same applies to other similar expressions such as (meth) acrylate.

[Photosensitive resin composition]
A photosensitive resin composition according to an embodiment of the present disclosure (hereinafter may be simply referred to as the present embodiment) includes (A) component: a high molecular weight body having a photopolymerizable functional group and a carbon-nitrogen bond, (B) component: a low molecular weight substance having a photopolymerizable functional group and a carbon-nitrogen bond, and (C) component: a photopolymerization initiator, wherein the (B) component is a photopolymerizable functional group It is the photosensitive resin composition containing the low molecular weight body which has an acryloyl group.
In the present specification, the “solid content” is a non-volatile content excluding volatile substances such as water and solvent contained in the photosensitive resin composition, and is volatilized when the resin composition is dried. Ingredients which remain without being included, and also include those which are liquid, syrupy and waxy 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 includes a high molecular weight body having a photopolymerizable functional group and a carbon-nitrogen bond as the component (A). “High molecular weight body” means a compound having a weight average molecular weight of 2,000 or more. In addition, in this specification, the value of a weight average molecular weight (Mw) is the value calculated | required by standard polystyrene conversion using tetrahydrofuran (THF) by the gel permeation chromatograph (GPC) method.
Examples of the photopolymerizable functional group of the high molecular weight component (A) include (meth) acryloyl groups; ethylenically unsaturated groups such as alkenyl groups such as allyl groups and vinyl groups. From the viewpoint of improving pattern formation, the component (A) may contain a high molecular weight body having a (meth) acryloyl group as a photopolymerizable functional group, and further a high molecular weight body having a urethane bond as a carbon-nitrogen bond. May be included. Examples of the high molecular weight substance having a (meth) acryloyl group as a photopolymerizable functional group include (meth) acrylate, and an example of the high molecular weight substance having a urethane bond as a carbon-nitrogen bond is urethane (meth) acrylate. It is done.
In addition, the component (A) may include 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. In addition, the total number (number of functional groups) of the photopolymerizable functional groups contained in the high molecular weight component of component (A) is 2 to 15 per molecule from the viewpoint of improving pattern formation and heat resistance. From the viewpoint of stabilizing the physical properties and characteristics of the cured product, it may be appropriately selected from 2 to 12, or 2 to 10.

As a urethane (meth) acrylate of (A) component, the reaction product of the (meth) acrylate which has a hydroxyl group, and the isocyanate compound which has an isocyanate group is mentioned, for example.
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 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) acrylate, ethoxylated products thereof, propoxylated products thereof, ethoxylated propoxylated products thereof, and caprolactone modified products thereof; trimethylol Propane (meta) acrelan , Difunctional (meth) acrylates such as glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) (2-hydroxyethyl) isocyanurate, ethoxylated products thereof, propoxylated products thereof, these Ethoxylated propoxylated products thereof, and modified caprolactone thereof: 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 (medium) ) Acrylate, bisphenol F type epoxy di (meth) acrylate, bisphenol AF type epoxy di (meth) acrylate, biphenol type epoxy di (meth) acrylate, fluorene bisphenol type epoxy di (meth) acrylate, isocyanuric acid monoallyl type epoxy di (meth) acrylate, etc. Functional epoxy (meth) acrylate; trifunctional or higher (meth) such as ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Acrylates, ethoxylated products thereof, propoxylated products thereof, ethoxylated propoxylated products thereof, and modified products of caprolactone thereof; Three or more functional epoxy (meth) acrylates such as a novolac type epoxy (meth) acrylate, a cresol novolac type epoxy poly (meth) acrylate, an isocyanuric acid type epoxy tri (meth) acrylate; trimethylolpropane tri (meth) acrylate, ditri And hydroxypropylated compounds such as methylolpropane tetra (meth) acrylate.
These can be used alone or in combination of two or more.

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

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 phenyl isocyanate Monoisocyanate compounds such as aliphatic monoisocyanate compounds, aliphatic diisocyanate compounds 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) propane, 2,2-bis (4-isocyanatocyclohexyl) ) Alicyclic diisocyanate compounds such as hexafluoropropane and bicycloheptane triisocyanate; 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4′-diphenylmethane diisocyanate, 4, Diisocyanates such as aromatic diisocyanate compounds such as 4'-diphenylmethane diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, hydrogenated xylylene diisocyanate, naphthalene-1,5-diisocyanate Over DOO compound, uretdione dimer of these diisocyanate compounds, isocyanurate type, and the like multimers such as biuret-type trimer. 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 pattern forming properties, it may be appropriately selected from diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, aromatic diisocyanate compounds, and multimers of these diisocyanate compounds, and in particular, hexamethylene diisocyanate. , Isophorone diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, and isocyanurate type multimers ( What is necessary is just to select suitably from isocyanurate type polyisocyanate).

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

As the urethane (meth) acrylate of the component (A), from the viewpoint of improving pattern formation, for example, the terminal isocyanate group of a polyaddition product of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound is used. A reaction product obtained by reacting a (meth) acrylate having a hydroxyl group may be included.

Diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds among the compounds exemplified as the isocyanate compound as the isocyanate compound having at least two isocyanate groups in one molecule used here. Moreover, multimers such as uretdione type dimers, isocyanurate types and biuret type trimers of these diisocyanate compounds may 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. Specific examples include ethylene glycol, diethylene glycol, propanediol, dipropylene glycol, butanediol, pentanediol, isopentylglycol, hexanediol. , Nonanediol, decanediol, dodecanediol, dimethyldodecanediol, octadecanediol, and other linear or branched saturated diol compounds; butenediol, pentenediol, hexenediol, methylpentenediol, dimethylhexenediol, etc. Or branched unsaturated diol compounds; various cyclohexanediols, various cyclohexanedimethanols, various tricyclodecanedimethanols, hydrogenated bisphenol A, hydrogenated bis Such as a diol compound having an alicyclic skeleton phenol F, and the like. Here, the saturated diol compound and the unsaturated diol compound are 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 water resistance by increasing the glass transition point (Tg) after polymerization. It may be appropriately selected from 2 to 14 saturated diol compounds, and more specifically, may be appropriately selected from ethylene glycol and octadecanediol.
In addition, the diol compound having an alicyclic skeleton has 5 to 20, 5 to 5 carbon atoms from the viewpoint of improving pattern formation and increasing the glass transition point (Tg) after polymerization to improve water resistance. A diol compound having an alicyclic skeleton of 18, 6 to 16 may be appropriately selected. More specifically, various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol, What is necessary is just to select suitably from various cyclohexane dimethanols, such as cyclohexane dimethanol and 1, 4- cyclohexane dimethanol.

Examples of the (meth) acrylate having a hydroxyl group used herein include those exemplified as the (meth) acrylate used in the reaction product of the above-mentioned (meth) acrylate having a hydroxyl group and an isocyanate compound having an isocyanate group. Can be mentioned.

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

In 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. The divalent organic group which has. Moreover, when (A) component has two or more said structural units, several X < ₁ >, Y < ₁ > may be the same or different. That is, examples of the component (A) include those 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 divalent organic group of X _1, exemplified as the compound having the isocyanate groups, aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and organic radical derived from an aromatic diisocyanate compound, i.e., from the above isocyanate compounds 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 an isocyanate group. Further, the divalent organic group represented by X ₁ may be these residues themselves, or a residue derived from an isocyanate compound derivative such as a polyaddition product of the above isocyanate compound and a diol compound. May be.
X ₁ is a divalent organic group having an alicyclic skeleton from the viewpoints of improving pattern formation and improving the transparency, water resistance, and moisture resistance of the resin composition in a balanced manner. It may be a divalent organic group having an alicyclic skeleton, which is a residue of isophorone diisocyanate represented by 2).

As the divalent organic group having a chain hydrocarbon skeleton of Y ₁ or an alicyclic skeleton, a diol compound having a chain hydrocarbon skeleton exemplified as the diol compound, and a diol having an alicyclic skeleton An organic group derived from a 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, as a divalent organic group having a chain hydrocarbon skeleton, from the viewpoint of improving the pattern forming property and improving the water resistance by increasing the glass transition point (Tg) after polymerization, the divalent organic group having 1 to It may be appropriately selected from residues obtained by removing hydroxyl groups from 20, 2 to 16, 2 to 14 saturated diol compounds, and more specifically, selected from residues obtained by removing hydroxyl groups from ethylene glycol and octadecandiol. Good. From the same viewpoint, the divalent organic group having an alicyclic skeleton is a residue obtained by removing a hydroxyl group from a diol compound having an alicyclic skeleton having 5 to 20, 5 to 18, or 6 to 16 carbon atoms. May be appropriately selected from the group, and more specifically, various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and the like. What is necessary is just to select suitably from the residue remove | excluding the hydroxyl group from various cyclohexanedimethanol.

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

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

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

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

Examples of commercially available products containing urethane acrylate having the structural unit represented by the general formula (1) include UN-333 (functional group number: 2, Mw: 5,000), UN-1255 (functional group number: 2, Mw: 8,000), UN-904 (functional group number: 10, Mw: 4,900), UN-2600 (functional group number: 2, Mw: 2,500), UN-6200 (functional group number: 2, Mw: 6,500), UN-9000PEP (functional group number: 2, Mw: 5,000), UN-9200A (functional group number: 2, Mw: 15,000), UN-3320HS (functional group number: 15, Mw: 4, 900), UN-6301 (number of functional groups: 2, Mw: 33,000) (all are trade names, manufactured by Negami Kogyo Co., Ltd.), EBECRYL 8405 (urethane acrylate / 1,6-hexanedio) An addition reaction product of diacrylate = 80/20, number of functional groups: 4, Mw: 2,700) manufactured (trade name, manufactured by Daicel-Orunekusu Ltd.) and the like.
In addition, as a commercial product containing urethane methacrylate having the structural unit represented by the general formula (1), for example, UN-6060PTM (functional group number: 2, Mw: 6,000, trade name, Negami Industrial Co., Ltd.) Manufactured) and the like. In the above description, the number of functional groups in parentheses and Mw are the total number and weight average molecular weight of (meth) acryloyl groups contained in urethane (meth) acrylate, respectively.

Moreover, as a commercially available product containing the urethane (meth) acrylate represented by the general formula (3), for example, UN-952 (number of functional groups: 10, Mw: 6,500 to 11,000) is represented by the 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) and the like. , Manufactured by Negami Kogyo Co., Ltd.).
Among these, UN-952 is particularly preferable from the viewpoint of pattern formability and photosensitivity.

The total number (functional group) of (meth) acryloyl groups contained in the urethane (meth) acrylate of the component (A) is 2 to 15 in one molecule from the viewpoint of improving pattern forming properties and heat resistance. From the viewpoint of stabilizing the physical properties and characteristics of the material, it may be appropriately selected from 2 to 12, or 2 to 10.
If the number of functional groups is 2 or more, the heat resistance and the rigidity of the cured product at high temperatures can be improved along with pattern formation. On the other hand, if the number of functional groups is 15 or less, the rigidity of the cured product is improved and the adhesion to the substrate and the like is improved. Moreover, it can be set as a resin composition having an appropriate viscosity, the coatability is improved, and when the resin composition after application is irradiated with light, only the surface portion is easily photocured rapidly and the inside Can suppress the phenomenon that photocuring does not proceed sufficiently, and an excellent resolution can be obtained. Therefore, even when a thick photosensitive layer is formed, an excellent pattern formability can be obtained. Furthermore, after at least one of photocuring and thermal curing is performed, the remaining of unreacted (meth) acryloyl groups can be reduced, and fluctuations in physical properties and characteristics of the obtained cured product can be further suppressed.

The weight average molecular weight of the high molecular weight component (A) is 2,000 or more, and may be 2,500 or more from the viewpoint of improving the coating property and resolution of the resin composition. 3,000 or more may be sufficient from a viewpoint of a soluble improvement. 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 coating property 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, since the occurrence of dripping of the applied composition can be suppressed when applied on a substrate, excellent pattern formability can be obtained. Moreover, 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 coating property is improved, a thick photosensitive layer is easily formed, and the pattern forming property is improved. Moreover, since the solubility with respect to a developing solution also becomes favorable, the outstanding resolution can be expressed. Furthermore, the transparency of the cured product is improved, and a cured product having excellent transmittance required as a transparent material can be obtained.

What is necessary is just to select content of (A) component suitably from 10 mass% or more, 30 mass% or more, or 50 mass% or more on the basis of the solid content whole quantity of the photosensitive resin composition. If content is 10 mass% or more, applicability | paintability will improve and even if it is a case where a thick photosensitive layer is formed, the outstanding pattern formation property will be obtained.
In consideration of the pattern moldability and coating properties of the resulting resin composition, and the physical properties and characteristics required for the cured product of the resin composition, the upper limit of the content of component (A) is the solid content of the photosensitive resin composition. What is necessary is just to select suitably from 95 mass% or less, 85 mass% or less, or 75 mass% or less on the basis of the whole quantity.
Further, the content of the urethane (meth) acrylate in the component (A) is 70 to 100% by mass, 80 to 100% by mass based on the total solid content of the component (A) from the viewpoint of improving the pattern formability. 90 to 100% by mass, 95 to 100% by mass, or 100% by mass (total amount).

<(B) component: low molecular weight body>
The photosensitive resin composition of the present embodiment includes a low molecular weight substance having a photopolymerizable functional group and a carbon-nitrogen bond as the component (B), and the component (B) has an acryloyl group as the photopolymerizable functional group. Includes low molecular weight products. The “low molecular weight body” means a compound having a weight average molecular weight of less than 2,000.
(B) A component contains the low molecular weight body which has an acryloyl group as a photopolymerizable functional group. When the component (B) contains a low molecular weight substance having at least an acryloyl group, a sufficiently excellent pattern forming property can be obtained. For example, when a compound containing a methacryloyl group and not containing an acryloyl group is used alone, it is difficult to obtain sufficient pattern formability. The component (B) may contain a urethane acrylate having a urethane bond as a carbon-nitrogen bond from the viewpoint of improving pattern formation. In general, a low molecular weight body having an acryloyl group has a higher activation energy required for photopolymerization and a higher sensitivity than a low molecular weight body having a methacryloyl group. Further, since the low molecular weight substance further has a carbon-nitrogen bond, it can function as a chain transfer agent for radical polymerization, and an excellent pattern forming property can be obtained.

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

Examples of the urethane acrylate of 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 the acrylate having a hydroxyl group and the isocyanate compound exemplified as those used for producing a high molecular weight compound. Here, examples of the one that is appropriately selected from the viewpoint of improving the pattern formability include the same one that is appropriately selected as the one used for the production of the high molecular weight from the same viewpoint.

In addition, as a low molecular weight urethane acrylate, there is a reaction product obtained by reacting a hydroxyl group-containing acrylate with a terminal isocyanate group of a polyaddition product of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound. Can be mentioned. Here, as an isocyanate compound having at least two isocyanate groups in one molecule, a diol compound, and an acrylate having a hydroxyl group, at least two isocyanate groups are exemplified in one molecule exemplified for use in the production of high molecular weight compounds. An isocyanate compound, a diol compound, and an acrylate having a hydroxyl group. Here, examples of the one that is appropriately selected from the viewpoint of improving the pattern formability include the same one that is appropriately selected as the one used for the production of the high molecular weight from the same viewpoint.
As this reaction product, what has a structural unit represented by following General formula (7) is mentioned, for example.

In 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. The divalent organic group which has. That is, examples of the component (B) include those 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 X ₂ and Y ₂ are the same as X ₁ and Y ₁ in the general formula (1).
From the viewpoint of improving pattern formation and improving the transparency, water resistance, and moisture resistance of the resin composition in a balanced manner, X ₂ represents a divalent organic group having a chain hydrocarbon skeleton, a branched chain. A divalent organic group having a skeleton-like hydrocarbon skeleton, a branched alkylene group having 2 to 12 carbon atoms, for example, a residue of the aliphatic diisocyanate compound may be appropriately selected. From the same viewpoint, Y ₂ may be appropriately selected from a divalent organic group having an alicyclic skeleton, for example, a residue of a 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 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 1 to 4 carbon atoms. . Among the urethane acrylates represented by the general formula (8), X _{2 in the} general formula (7) is a residue of trimethylhexamethylene diisocyanate, which is a divalent organic group having a chain hydrocarbon skeleton, ₂ has a structural unit is the residue of a divalent organic group cyclohexanedimethanol having an alicyclic skeleton, as commercially available products containing a urethane acrylate, for example, TMCH-5R (trade name, number of functional groups: 2, Mw: 950, manufactured by Hitachi Chemical Co., Ltd.).
Moreover, as a commercial item containing the urethane acrylate which has a structural unit represented by the said General formula (7), KRM8452 (the number of functional groups: 10, Mw: 1,200, Daicel Ornex Co., Ltd. product), UN-3320HA (Functional group number: 6, Mw: 1,500), UN-3320HC (functional group number: 6, Mw: 1,500, manufactured by Negami Kogyo Co., Ltd.) and the like. In the above description, the number of functional groups and Mw in parentheses are the number of functional groups and weight average molecular weight of urethane acrylate, respectively.

The weight average molecular weight of the low molecular weight component (B) is less than 2,000, and may be 1,800 or less from the viewpoint of improving adhesion, and 1,500 from the viewpoint of improving resolution. It may be the following. On the other hand, the lower limit of the weight average molecular weight may be appropriately used according to the desired purpose, but may be 500 or more from the viewpoint of film formability.

(B) Content of a component may be suitably selected from 3 mass% or more, 5 mass% or more, 10 mass% or more, or 20 mass% or more on the basis of the total solid content of the photosensitive resin composition. . When the content is 3% by mass or more, excellent pattern formability can be obtained even when a thick photosensitive layer is formed, and excellent rigidity of the cured product can be obtained. From the same viewpoint, the upper limit value 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) on the basis of 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 formability and the rigidity of the cured product. It may be appropriately selected from ˜65 mass%.
In the present embodiment, a low molecular weight body having a photopolymerizable functional group other than an acryloyl group can be included depending on a 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 You may select from 95 mass% or more suitably. When the content is 70% by mass or more, excellent pattern formability can be obtained even when a thick photosensitive layer is formed, and excellent rigidity of the cured product can be obtained. From the same viewpoint, 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, and 100% by mass, that is, the total amount of the component (B) is photopolymerizable. It may have an acryloyl group as a functional group.

<(C) component: photopolymerization initiator>
The photosensitive resin composition of this embodiment contains a photoinitiator as (C) component. The component (C) is not particularly limited as long as it can polymerize at least one of the components (A) and (B), and can be appropriately selected from commonly used photopolymerization initiators. . From the viewpoint of improving pattern formation, those that generate free radicals with actinic rays, such as acylphosphine oxides, oxime esters, aromatic ketones, quinones, alkylphenones, imidazoles, acridines, phenylglycines And photopolymerization initiators such as coumarins and coumarins.

The acylphosphine oxide photopolymerization initiator has an acylphosphine oxide group (> P (═O) —C (═O) — group), for example, (2,6-dimethoxybenzoyl) -2,4 , 6-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name: IRGACURE-TPO, manufactured by BASF), ethyl-2 , 4,6-Trimethylbenzoylphenyl phosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE-819, manufactured by BASF), (2,5-dihydroxyphenyl) diphenylphosphine Oxide, (p-hydroxypheny ) Diphenylphosphine oxide, bis (p- hydroxyphenyl) phenylphosphine oxide, tris (p- hydroxyphenyl) phosphine oxide, and the like.

The oxime ester photopolymerization initiator is a photopolymerization initiator having an oxime ester bond. For example, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) ( Trade name: OXE-01, manufactured by BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) (trade name: OXE) -02, manufactured by BASF), 1-phenyl-1,2-propanedione-2- [O- (ethoxycarbonyl) oxime] (trade name: Quantacure-PDO, manufactured by Nippon Kayaku Co., Ltd.), etc. .

Examples of the aromatic ketone photopolymerization initiator include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4 -Methoxy-4'-dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: IRGACURE-651, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (trade name: IRGACURE-369, manufactured by BASF), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (Trade name: IRGACURE-907, manufactured by BASF).

Examples of the quinone photopolymerization initiator include 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2 , 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, etc. It is done.

Examples of the alkylphenone photopolymerization initiator include benzoin 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-phenyl ketone (trade name: IRGACURE-184, manufactured by BASF), 2-hydroxy-2-methyl-1-phenylpropane-1- ON (trade name: IRGACURE-1173, manufactured by BASF), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name: IRGACURE-2959) , Manufactured by BASF), 2 And hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one (trade name: IRGACURE-127, manufactured by BASF) .

Examples of imidazole photopolymerization initiators include 2,4,5-triarylimidazole dimers such as 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl. -1,3-diazol-2-yl] -4,5-diphenylimidazole, 2- (o-chlorophenyl) -4,5-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- And (p-methoxyphenyl) -4,5-diphenylimidazole dimer.

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

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

Examples of the coumarin 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-he Sanhydro-1H, 5H-cyclopenta [3,4] [1] benzopyrano- [6,7,8-ij] quinolizine 12 (9H) -one, 7-diethylamino-5 ′, 7′-dimethoxy-3,3 ′ -Carbonylbiscoumarin, 3,3′-carbonylbis [7- (diethylamino) coumarin], 7-diethylamino-3-thienoxysilkine, and the like.

From the viewpoint of improving photocurability and sensitivity and improving pattern forming properties, it can be appropriately selected from acylphosphine oxide photopolymerization initiators. The said (C) component can be used individually or in combination of 2 or more types. Moreover, what was synthesize | combined by the conventional method may be used for (C) component, and a commercial item may be obtained and used.

The content of the component (C) is such that the absorbance with respect to light having a wavelength of 365 nm is 0.35 or less at a thickness of the photosensitive layer formed by the photosensitive resin composition (thickness after drying) of 50 μm, 0.3 or less. May be appropriately selected from the amount that becomes 0.2, the amount that becomes 0.2 or less, or the amount that becomes 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, the light can easily pass to the bottom of the photosensitive layer (the surface of the photosensitive layer on the substrate side). Can be improved. Here, the absorbance is measured 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 polyethylene terephthalate film alone as a reference. Absorbance can be measured. Further, the absorbance to 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 of 50 μm in thickness based on Lambert Beer's law.

Further, in addition to the above component (C), three compounds such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. Photopolymerization initiation assistants such as secondary amines can be used as the component (C ′). 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 depending on the absorbance at a thickness of 50 μm of the photosensitive layer, and is usually 0.05 to 20% by mass based on the total solid content of the photosensitive resin composition. What is necessary is just to select suitably from 0.1-10 mass% or 0.15-5 mass%. By setting it as the said content, the sensitivity of the photosensitive resin composition can be improved, the deterioration of a resist shape can be suppressed, and pattern formation property can be improved.

<(D) component: thermal radical polymerization initiator>
Moreover, the photosensitive resin composition of this embodiment can contain (D) thermal radical polymerization initiator further. The component (D) is not particularly limited, and examples thereof include α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide. 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-trimethylcyclohexane and other peroxy Tar; hydroperoxide such as p-menthane hydroperoxide; diacyl peroxide such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide, benzoyl peroxide; bis (4-t-butylcyclohexyl) peroxydicarbonate, Peroxycarbonates such as di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutyl peroxycarbonate; t-butyl peroxypivalate, t-hexyl peroxypi Valate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t-hexylperoxy -2-Ethyl hex Sanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, 2,5-dimethyl-2 , 5-bis (benzoylperoxy) hexane, peroxide-based polymerization initiators such as peroxyesters such as t-butylperoxyacetate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2'-azo Scan (4-methoxy-2'-dimethylvaleronitrile) azo polymerization initiators, and the like.

(D) As a component, from a viewpoint of improving pattern formation property, a peroxide type polymerization initiator and a dialkyl peroxide type | system | group polymerization initiator are mentioned, Especially, a dicumyl peroxide can be selected. Moreover, (D) component can be used individually or in combination of 2 or more types.

When the component (D) is included, the content is 0.1 to 10% by mass, 0.2 to 5% by mass, or 0.3 to 1.% by mass based on the total solid content of the photosensitive resin composition. What is necessary is just to select suitably from 5 mass%. By setting it as the above content, 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 a component (E) for the purpose of further improving various properties such as adhesion between the photosensitive resin composition and the substrate, heat resistance, and rigidity of the cured product. it can.
Examples of the component (E) 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 oxide (PbO · TiO ₂ ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga ₂ O ₃ ), spinel (MgO · Al ₂ O ₃ ), mullite (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), etc. Can be used. These inorganic fillers can be used alone or in combination of two or more.

The average particle diameter of the component (E) 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. That's fine. Here, the average particle diameter of (E) component is an average particle diameter of the inorganic filler in the state disperse | distributed in the photosensitive resin composition, and is set as the value obtained by measuring as follows. First, after diluting (or dissolving) the photosensitive resin composition 1,000 times with methyl ethyl ketone, using a submicron particle analyzer (trade name: N5, manufactured by Beckman Coulter, Inc.), an international standard ISO 13321 is used. In accordance with the above, particles dispersed in a solvent with a refractive index of 1.38 are measured, and the particle size at an integrated value of 50% (volume basis) in the particle size distribution is taken as the average particle size. In addition, 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 1,000 times (volume ratio) using a solvent as described above (or (Dissolution) and then by using the 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 with respect to the total solid content of the photosensitive resin composition, and the lower limit is 0. What is necessary is just to select suitably from more than mass%, and 0 mass% (it does not contain) may be sufficient. Thus, the component (E) does not substantially contain, thereby improving the transparency of the photosensitive resin composition. For example, even when a pattern is formed with a thick photosensitive layer of 70 μm or more, the photosensitive layer Since the light easily passes through to the bottom of the substrate (the surface on the substrate side of the photosensitive layer), the pattern formability is improved.

<Other additives>
The photosensitive resin composition of the present embodiment can further contain additives such as a silane coupling agent, a sensitizer, a heat-resistant high molecular weight body, a thermal cross-linking agent, and an adhesion assistant as necessary. .

The silane coupling agent can improve the adhesion of the electronic component to the substrate, and in particular, when the substrate contains silicon (for example, a glass substrate, a silicon wafer, an epoxy resin-impregnated glass cloth substrate, etc.). Is valid. Silane coupling agents include: methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and other alkoxysilanes, (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropylmethyldimethoxysilane (Meth) acryloyl group-containing alkoxysilanes such as, aminopropyltrimethoxysilane, amine-based alkoxysilanes such as aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidoxypropyl Examples 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 adhesiveness, (meth) acryloyl group-containing alkoxysilanes such as (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropylmethyldimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxy Silane coupling agents having an ethylenically unsaturated group in the molecule, such as glycidoxy group-containing alkoxysilanes such as propylmethyldiethoxysilane and glycidoxypropylmethyldiisopropenoxysilane, may be used.

Examples of the sensitizer include sensitization of pyrazolines, anthracenes, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbenes, triazines, thiophenes, naphthalimides, etc. Agents. These can be used alone or in combination of two or more.

Examples of the heat-resistant high molecular weight substance include polyoxazole and precursors thereof, phenol novolac, cresol novolac and other novolac resins, polyamide, 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.

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

The adhesion assistant can be used as desired in order to improve the adhesion between the photosensitive resin composition and the substrate. For example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, triethoxysilylpropylethylcarbamate, 3- (triethoxysilyl) propyl succinate Acid anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, 2- (3 , 4-Epoxycyclohexyl) Eth Organic silane compounds such as trimethoxysilane. 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 inhibit 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. It may be appropriately selected from 1 to 10% by mass, 0.3 to 5% by mass, or 0.5 to 5% by mass.

<Diluent>
A diluent can be used in the photosensitive resin composition of the present embodiment as 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; Sulfur atom-containing compounds 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 And polar solvents such as esters such as propylene glycol monoethyl ether acetate. These can be used alone or in combination of two or more.

The amount of the diluent used may be appropriately selected from the amount that makes the total solid content in the photosensitive resin composition 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 making the usage-amount of a diluent into the said range, the applicability | paintability of the photosensitive resin composition improves and formation of a higher definition pattern is attained.
For example, when a photosensitive layer having a thickness of 70 μm or more is to be formed, the viscosity of the photosensitive resin composition at 25 ° C. is 0.5 to 20 Pa · s, considering the ease of forming the photosensitive layer, or 1 to 10 Pa · s.

The photosensitive resin composition of the present embodiment comprises the above components (A) to (C), a component (D), a component (E), other additives, and a diluent that are used as desired. 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 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 ink jet method, and a dip coating method. Various coating methods are mentioned. Among these, a printing method or a spin coating method may be appropriately selected from the viewpoint of forming a thick photosensitive layer more easily.
Moreover, when using as a film form, it can use in the form of the photosensitive resin film mentioned later, for example, In this case, a photosensitive layer of desired thickness can be formed by laminating | stacking using a laminator etc.

The absorbance with respect to light having a wavelength of 365 nm at a thickness (thickness after drying) of the photosensitive layer formed by the photosensitive resin composition of the present embodiment is 0.35 or less, 0.3 or less, 0.2 or less, or It can be suitably 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 with 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 easily passes to the surface), the pattern forming property can be improved.

[Photosensitive resin film]
The photosensitive resin film of this embodiment has a photosensitive layer using the photosensitive resin composition of this embodiment. Moreover, the photosensitive resin film of this embodiment may have a carrier film. In this specification, the term “layer” includes not only a structure having a shape formed on the entire surface but also a structure having a shape formed on a part when observed as a plan view.

The photosensitive resin film of the present embodiment is formed by, for example, applying the photosensitive resin composition of the present embodiment on a carrier film by the above various coating methods to form a coating film, and then drying the coating film. A photosensitive layer can be formed and manufactured. Moreover, when the photosensitive resin composition of this embodiment contains a diluent, you may remove at least one part of this diluent in the case of drying.

The coating film can be dried using hot air drying, a far-infrared or near-infrared dryer, and the drying temperature is suitably from 60 to 120 ° C., 70 to 110 ° C., or 90 to 110 ° C. Just choose. The drying time may be appropriately selected from 1 to 60 minutes, 2 to 30 minutes, or 5 to 20 minutes. If it is 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 resin films such as polyester resin films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), and polyolefin resin films such as polypropylene and polyethylene. From the viewpoint of improving the mechanical strength and heat resistance of the photosensitive resin film, a polyester resin film may be selected.
The thickness of the carrier film may be appropriately selected from 10 μm to 3 mm or 10 to 200 μm in consideration of handling properties 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 lamination or the like can be further reduced, and by setting the thickness to 100 μm or less, the photosensitive resin film can be wound around the core. When it is wound, the deformation of the photosensitive layer due to the difference in stress between the inside and the outside of the core can be further reduced. Considering the effect that the photosensitive resin composition of this embodiment has an excellent pattern forming property even when a thick photosensitive layer is formed, it may be 70 μm or more, and the thickness exceeds 100 μm. There may be. In addition, the photosensitive layer having a thickness of 70 μm or more is, for example, by bonding a film formed with a photosensitive layer on a carrier film and a film formed with a photosensitive layer on a protective layer to be 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 this 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. Moreover, the same resin film as the carrier film mentioned above may be used, and a different resin film may be used.

[Method for producing cured product]
The method for producing a cured product according to the present embodiment includes a step of providing a photosensitive layer using a photosensitive resin composition or a photosensitive resin film of the present embodiment on a substrate (photosensitive layer forming step), and at least one of the photosensitive layers. A step of irradiating the part with actinic rays to form a photocured portion (exposure step), and a step of removing at least a portion other than the photocured portion of the photosensitive layer to form a resin pattern (removal step) Have in order. Moreover, it has the process (heating process) which heat-processes the said resin pattern further as needed. The method for producing a cured product according to this embodiment makes it possible to form a desired pattern. For example, even if a thick photosensitive layer of 70 μm or more is formed, the photosensitive material according to this embodiment has excellent pattern formability. For example, a desired pattern can be formed by a thick cured product having a thickness of 70 μm or more. In this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, if the intended action of the process is achieved, the “process” 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 photosensitive resin film of the present embodiment on a substrate.
Examples of the substrate include glass substrates, silicon wafers, metal oxide insulators such as TiO ₂ and SiO ₂ , silicon nitride, ceramic piezoelectric substrates, and epoxy resin impregnated glass cloth substrates.

When a photosensitive resin composition is applied to a substrate to form a photosensitive layer, the photosensitive resin composition dissolved in the above diluent and in the form of a solution may be applied to the substrate, and applied as necessary. The resulting coating film may be dried. Application | coating and drying may be performed with the various application | coating methods described about preparation of said photosensitive resin film, and the drying method of a coating film.
In the case of using a photosensitive resin film, 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. As described above, it may be appropriately selected from 30 μm or more, 50 μm or more, 70 μm or more, 100 μm or more, more than 100 μm, or 150 μm or more. The upper limit is not particularly limited as long as 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 depending on the application, and when used for an electronic component 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, a photosensitive layer is formed using the photosensitive resin composition of the present embodiment, so that a thick photosensitive layer can be formed. For example, when a photosensitive layer having a thickness of 150 μm or more is formed, it is not formed by a single application (and drying if necessary) or by lamination, but is applied a plurality of times (and as necessary) until a desired thickness is obtained. Drying) or lamination may be repeated.

(Exposure process)
In the exposure step, at least part of the photosensitive layer provided on the substrate in the photosensitive layer forming step is irradiated with actinic rays as necessary, and the exposed portion is photocured to form a cured portion. When irradiating with actinic rays, the photosensitive layer may be irradiated with actinic rays through a mask having a desired pattern. Moreover, such as LDI (Laser Direct Imaging) exposure method, DLP (Digital Light Processing) exposure method, etc. Actinic rays may be irradiated by a direct drawing exposure method.
Moreover, you may perform post-exposure heating (PEB: Post exposure bake) after exposure using a hotplate, a dryer, etc. from a viewpoint of improving pattern formation property. The drying conditions are not particularly limited, and may be performed at a temperature of 60 to 120 ° C. or 70 to 110 ° C. for a time of 15 seconds to 5 minutes or 30 seconds to 3 minutes.

The exposure dose of actinic rays 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 actinic rays used include ultraviolet rays, visible rays, electron beams, and X-rays. 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 removal step, at least a part of the portion (unexposed portion) other than the cured portion of the photosensitive layer formed in the exposure step is removed to form a resin pattern. The removal of the unexposed portion may be performed using a developer such as an organic solvent.
Examples of the organic solvent include ethanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, N-methylpyrrolidone and the like. Among these, cyclopentanone can be used from the viewpoint of development speed. These can be used alone or in combination of two or more.
Further, various commonly used additives may be added to the organic solvent used as the developer.

After removing the unexposed areas with a developer, if necessary, wash with water, alcohol such as methanol, ethanol, isopropyl alcohol, n-butyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether acetate, etc. (rinse) May be.

(Heating process)
A heating process is a process employ | adopted as needed, and is a process of heat-processing the resin pattern formed at the removal process, and forming hardened | cured material. The heat treatment is preferably performed for 1 to 2 hours while selecting the heating temperature and gradually increasing the temperature. The heating temperature may be appropriately selected from 120 to 240 ° C, 140 to 230 ° C, or 150 to 220 ° C. In the case where the temperature is raised stepwise, for example, at least one of around 120 ° C. and around 160 ° C., for 10 to 50 minutes, or after 20 to 40 minutes, after heat treatment, around 220 ° C. and 30 to 100 Heat treatment may be performed for a minute or for 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 suitably 10 μm or more, 30 μm or more, 50 μm or more, 70 μm or more, 100 μm or more, more than 100 μm, or 150 μm or more. What is necessary is just to select, and what is necessary is just to select suitably from 500 micrometers or less, 300 micrometers or less, or 250 micrometers or less as an upper limit. The thickness of the resin pattern may be appropriately selected from the above range depending on the application, and when used for an electronic component 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 is provided with a cured product of the photosensitive resin composition of the present embodiment. For example, various types of substrates, such as a substrate used in the method for producing the cured product and a carrier film of the photosensitive resin film, are used. The thing provided with this hardened | cured material on a support body is mentioned. The cured product of the photosensitive resin composition of the present embodiment can be formed by, for example, the above-described 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, more than 100 μm, or 150 μm or more as the lower limit, and the upper limit is 500 μm or less, 300 μm. What is necessary is just to select suitably below or 250 micrometers or less. The thickness of the cured product may be appropriately selected from the above range depending on the application, and when used for an electronic component 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-described method for producing a cured product uses the photosensitive resin composition of the present embodiment. For example, even with a thick photosensitive layer of 70 μm or more, excellent pattern formability can be obtained. Therefore, for example, with the trend toward downsizing and higher performance of electronic devices, it is possible to meet the demand for electronic circuit boards that require a thick cured product to be provided in a finer pattern on the substrate. . In addition, for example, in a plating process in the manufacture of an electronic circuit board, a decrease in yield due to a short circuit between wirings can be suppressed by using a cured product formed from the photosensitive resin composition of the present embodiment as an insulating film. it can.
Therefore, the laminated body of this embodiment is used as an electronic component such as an electronic circuit board in a mobile terminal such as a mobile phone.

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

(Synthesis Example 1; Synthesis of Resin P-1)
635 g of methyl methacrylate, 30 g of butyl acrylate, 245 g of butyl methacrylate, and 75 g of 2-hydroxyethyl methacrylate were mixed to obtain a monomer mixture. In the resulting monomer mixture, 0.9 g of 2,2′-azodiisobutyronitrile was dissolved to prepare a mixed solution. To a 1 L autoclave equipped with a stirrer and a condenser, 1030 g of propylene glycol monomethyl ether acetate was added as a solvent and the mixture was added while stirring. Next, the mixture was polymerized at 90 ° C. for 6 hours in a nitrogen atmosphere at a stirring speed of 100 min ⁻¹ 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 is a value determined by GPC standard polystyrene conversion using the following apparatus, and was measured using a solution in which 0.5 mg of polymer was dissolved in 1 mL of tetrahydrofuran (THF).
Device name: HLC-8320GPC manufactured by Tosoh Corporation
Column: Gelpack R-420, R-430, and R-440 (three-piece connection)
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 composition is blended according to the composition shown in Table 1 (the numerical values in the table indicate parts by mass of each material, and in the case of a solution, the parts by mass in terms of solid content), kneaded with a three-roll mill, and photosensitive resin. A composition was prepared. N, N-dimethylacetamide was added so that the solid content concentration was 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, a reaction product of an acrylate having a hydroxyl group and a diisocyanate compound, and acryloyl in the molecule Group (photopolymerizable functional group), urethane bond (carbon-nitrogen bond), chain hydrocarbon skeleton, and alicyclic hydrocarbon skeleton.)
Resin P-1: Acrylic resin prepared in Synthesis Example 1 (weight average molecular weight: 43,370)
Z250: Cyclomer P (ACA) Z250 (manufactured by Daicel Ornex Co., Ltd., trade name, having an acryloyl group (photopolymerizable functional group) in the molecule but no 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) , Having a chain hydrocarbon skeleton and an alicyclic hydrocarbon skeleton.)
FA-324A: EO-modified bisphenol A diacrylate (manufactured by Hitachi Chemical Co., Ltd., trade name, number of functional groups: 2, weight average molecular weight: 512)
FA-7220M: Amide bond-containing methacrylate (trade name, manufactured by Hitachi Chemical Co., Ltd.)
I-819: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name, manufactured by BASF)
・ Park mill D: Dicumyl peroxide (manufactured by NOF Corporation, trade name)
KBM-503: Methacryloxypropyltrimethoxysilane (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ AY43-031: Silane coupling agent (trade name, manufactured by Toray Dow Corning Co., Ltd.)

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

[Preparation of photosensitive resin film]
A polyethylene terephthalate film (trade name: A-4100, manufactured by Teijin Ltd.) having a thickness of 50 μm is used as a carrier film, and the resin compositions of Examples and Comparative Examples are dried on the carrier film to a thickness of 50 μm. Was applied uniformly. Subsequently, it dried by heating for 15 minutes at 100 degreeC using a hot air convection dryer, and formed the photosensitive resin film which formed the photosensitive layer and has a carrier film and a photosensitive layer.

[Evaluation of pattern formability]
Orientation where the photosensitive layer of the photosensitive resin film is located on the glass epoxy substrate side on the glass epoxy substrate (obtained by etching copper of MCL-E-679F (trade name, manufactured by Hitachi Chemical Co., Ltd.)) And the carrier film was removed. Lamination was performed at 60 ° C. using a laminator. Next, the photosensitive resin film is again laminated on the photosensitive layer by the above-described method, the carrier film is removed, and this is repeated three times to form a photosensitive layer having a thickness of 200 μm and the carrier film on the glass epoxy substrate. The laminated body provided was obtained.
A mask for resolution evaluation (details will be described later) is placed on the carrier film of the laminate, and an i-line filter (trade name: HB-0365, manufactured by Asahi Spectroscopy Co., Ltd.) is further placed on the carrier film for high precision parallel exposure. Exposure was performed using a machine (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 sample after exposure was heated after exposure for 1 minute on a hot plate at 90 ° C.
Thereafter, the carrier film was removed, and development was performed by immersing in a developer (cyclopentanone) for 20 minutes. The developed pattern was dried at room temperature for 30 minutes and observed with a metal microscope to evaluate the pattern formability. Evaluation was performed according to the following criteria. Here, “formable” means that the unexposed part is removed cleanly and the line part (exposed part) does not have a defect such as a fall. 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, 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 resolution evaluation mask is a mask having a L-shaped pattern and a linear pattern shown in FIG. 1 having a predetermined line pitch and line width (the unit of numerical values in FIG. 1 is μm). is there.). FIG. 1 is a schematic diagram showing a resolution evaluation mask having a L-shaped and straight 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 inter-line pitch and the line width is used. Depending on the inter-line pitch and the line width, AB (A is a numerical value corresponding to the inter-line pitch, B Is a numerical value according to the line width), and 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 designated as 1 to 8 as B (see Table 4). For example, a line pitch of 100 μm and a line width of 5 μm is referred to as 6-1, and a 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 pattern formation becomes more difficult as the values of A and B are smaller. That is, the photosensitive resin composition that can form a pattern using a mask having a numerical value of A and B is more excellent in pattern formation. 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 that did not contain the component (B) were used, the pattern could not be formed even at an exposure amount of 600 (mJ / cm ² ). When the resin compositions of Comparative Examples 3 and 4 not containing the component (B) 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 ). However, in other cases, the pattern could not be formed. In addition, when the resin composition of Comparative Example 8 containing the component (A) but not containing a low molecular weight substance having an acryloyl group as a photopolymerizable functional group was used, no pattern was formed.

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

From the results of Table 5, the photosensitive resin compositions of the present embodiments of Examples 1 to 5 have an absorbance with respect to light having a wavelength of 365 nm at a photosensitive layer thickness (thickness after drying) of 50 μm of 0.35 or less. Since the light passes to the bottom of the photosensitive layer (the surface on the substrate side of the photosensitive layer) as small as 3 or less or 0.2 or less, it was confirmed that excellent pattern forming properties were exhibited. On the other hand, the resin compositions of Comparative Examples 3 to 7 had an absorbance greater than 0.36.

[Evaluation of insulation reliability]
The evaluation device obtained in Examples 1 to 5 on a comb-type copper electrode of 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 in such a direction that the photosensitive layer was positioned on the comb copper electrode side. Lamination was performed at 60 ° C. using a laminator. Subsequently, after exposing with i line | wire with the exposure amount of 1000 mJ / cm < ² >, after heating for 1 minute on a 90 degreeC hotplate, the carrier film was removed. Furthermore, 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 portion of the obtained measurement sample with solder, and a high temperature and high humidity bias test was performed (voltage: 5 V (direct current), test time: 100 hours, 85 ° C., 85% RH (high temperature and high humidity). Machine (made by ESPEC)))). As a result, each of the measurement samples obtained using the photosensitive resin films of Examples 1 to 5 had a resistance value of 1.0 × 10 ⁷ or more during the test time (100 hours), and was sufficiently It was confirmed that the insulation reliability was excellent.

Claims (16)

1. (A) component: high molecular weight body having a photopolymerizable functional group and a carbon-nitrogen bond, (B) component: low molecular weight body having a photopolymerizable functional group and a carbon-nitrogen bond, and (C) component: light And a polymerization initiator, and the component (B) comprises a low molecular weight substance having an acryloyl group as a photopolymerizable functional group.
2. The photosensitive resin composition according to claim 1, wherein the component (A) contains a high molecular weight body having a (meth) acryloyl group as a photopolymerizable functional group.
3. 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.
4. The component (A) contains a high molecular weight polymer having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton. 2. The photosensitive resin composition according to item 1.
5. 5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the component (B) contains a low molecular weight substance having a urethane bond as a carbon-nitrogen bond.
6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the component (C) contains an acylphosphine oxide photopolymerization initiator.
7. The content of the component (A), the component (B), and the component (C) is 10 to 95% by mass, 3 to 70% by mass, and 0.05%, respectively, based on the total solid content in the photosensitive resin composition. The photosensitive resin composition according to any one of Claims 1 to 6, which is -20% by mass.
8. The photosensitive resin composition according to any one of claims 1 to 7, further comprising (D) component: a thermal radical polymerization initiator.
9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the absorbance to light having a wavelength of 365 nm at a thickness of 50 µm is 0.35 or less.
10. A photosensitive resin film having a photosensitive layer using the photosensitive resin composition according to any one of claims 1 to 9.
11. A step of forming a photosensitive layer using the photosensitive resin composition according to any one of claims 1 to 9 or the photosensitive resin film according to claim 10 on a substrate, and at least a part of the photosensitive layer A method for producing a cured product, which comprises a step of irradiating actinic rays to form a photocured portion, and a step of removing at least a portion other than the photocured portion of the photosensitive layer and forming a resin pattern.
12. Furthermore, the manufacturing method of the hardened | cured material of Claim 11 which has the process of heat-processing the said resin pattern.
13. The manufacturing method of the hardened | cured material of Claim 12 whose thickness of the said resin pattern is 70 micrometers or more and 300 micrometers or less.
14. A laminate comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 9.
15. The laminate according to claim 14, wherein the cured product has a thickness of 70 μm or more and 300 μm or less.
16. An electronic component comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 9.

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