JPWO2017168700A1 - Photosensitive resin composition, photosensitive resin film, method for producing cured product, laminate, and electronic component - Google Patents

Abstract

(A) component: a photosensitive resin composition containing a compound having a photopolymerizable functional group, and when the thickness of the photosensitive resin composition is 50 μm, the absorbance with respect to light having a wavelength of 365 nm is less than 0.45. A photosensitive resin composition for forming a thick film.

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, 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

  However, in the conventional thick-film photosensitive resist, for example, when formation of a thick photosensitive layer of 70 μm or more is required, it is difficult for light to pass to the bottom, and the pattern shape may deteriorate. 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] A photosensitive resin composition containing component (A): a compound having a photopolymerizable functional group. When the thickness of the photosensitive resin composition is 50 μm, the absorbance with respect to light having a wavelength of 365 nm is 0. The photosensitive resin composition for thick film formation which is less than 45.
[2] A photosensitive resin film for forming a thick film having a photosensitive layer using the photosensitive resin composition according to [1].
[3] A step of forming a photosensitive layer having a thickness of 70 μm or more on the substrate using the photosensitive resin composition according to the above [1] or the photosensitive resin film according to the above [2].
Irradiating at least a part of the photosensitive layer with actinic rays to form a photocured portion;
The manufacturing method of hardened | cured material which has the process of removing at least one part other than the photocuring part of this photosensitive layer, and forming a resin pattern in order.
[4] A photosensitive resin composition containing component (A): a compound having a photopolymerizable functional group. When the thickness of the photosensitive resin composition is 50 μm, the absorbance with respect to light having a wavelength of 365 nm is 0. A laminate comprising a photosensitive resin composition that is less than 45.
[5] A photosensitive resin composition containing component (A): a compound having a photopolymerizable functional group. When the thickness of the photosensitive resin composition is 50 μm, the absorbance with respect to light having a wavelength of 365 nm is 0. A laminate comprising a cured product of a photosensitive resin composition that is less than 45.
[6] An electronic component comprising the laminate according to [5].

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

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

Hereinafter, the present disclosure will be described in detail.
In the present specification, numerical ranges indicated using “to” indicate ranges including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In addition, in the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. In the numerical range 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 for thick film formation]
A photosensitive resin composition according to an embodiment of the present disclosure (hereinafter may be simply referred to as the present embodiment) is a photosensitive resin composition containing (A) component: a compound having a photopolymerizable functional group. And when the thickness of the photosensitive resin composition is 50 μm, the photosensitive resin composition for forming a thick film has an absorbance with respect to light having a wavelength of 365 nm of less than 0.45.
In the present embodiment, “for thick film formation” means an application for forming a photosensitive layer in which the photosensitive resin composition has a thickness of 70 μm or more (and 150 μm thicker than the conventional one). Hereinafter, the photosensitive resin composition for forming a thick film of the present embodiment is also simply referred to as “photosensitive resin composition of the present embodiment”.
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 that remain without being included, and also include those that are liquid, syrupy, and waxy at room temperature. Here, room temperature in this specification indicates 25 ° C.

The photosensitive resin composition of this embodiment has an absorbance of less than 0.45 for light having a wavelength of 365 nm when the thickness of the photosensitive resin composition is 50 μm. The photosensitive resin composition of the present embodiment has excellent pattern formability when the absorbance is less than 0.45. Usually, when the thickness of the photosensitive layer is increased, it becomes difficult for light to appropriately pass through the bottom of the photosensitive layer (the surface on the substrate side of the photosensitive layer), so that the pattern formability tends to be remarkably deteriorated. However, since the photosensitive resin composition of the present embodiment has the specific absorbance, light easily passes to the bottom of the photosensitive layer, so that excellent pattern formability can be obtained even with a thick photosensitive layer. It is done. That is, the photosensitive resin composition of the present embodiment is particularly suitable for forming a thick photosensitive layer, and when the pattern of the thick photosensitive layer is formed, the effect is particularly easily exhibited effectively.
From the same viewpoint, the absorbance of the photosensitive resin composition of the present embodiment is suitably 0.40 or less, 0.30 or less, 0.25 or less, 0.20 or less, 0.15 or less, or 0.10 or less. You can choose. The lower limit of the absorbance can be appropriately selected from, for example, 0.001 or more, 0.005 or more, or 0.008 or more.
In addition, the light absorbency of the photosensitive resin composition can be suitably adjusted with the kind and content of the compound which has a photopolymerizable functional group mentioned later, a photoinitiator, an inorganic filler, etc.
The absorbance is, for example, an absorbance for light having a wavelength of 365 nm by using a UV-visible spectrophotometer (product name: “U-3310 Spectrophotometer”, manufactured by Hitachi High-Technologies Corporation) and using a polyethylene terephthalate film alone as a reference. Can be measured. Specifically, it can be measured by the method described in the examples.
The absorbance with respect to light having a wavelength of 365 nm when the thickness of the photosensitive resin composition is 50 μm is the absorbance measured with respect to the photosensitive resin composition having a thickness other than 50 μm, based on the Lambert Beer law. It can also be obtained by conversion.

<(A) component: a compound having a photopolymerizable functional group>
The photosensitive resin composition of this embodiment contains the compound which has a photopolymerizable functional group as (A) component. Examples of the photopolymerizable functional group contained in the component (A) include (meth) acryloyl groups; ethylenically unsaturated groups such as alkenyl groups such as vinyl groups and allyl groups. Among these, (A) component may contain the compound which has a (meth) acryloyl group as a photopolymerizable functional group from a viewpoint of improving pattern formation property.
Moreover, (A) component may contain the compound which has a carbon-nitrogen bond from a viewpoint of improving pattern formation property, and may contain the compound which has a urethane bond as a carbon-nitrogen bond. . In addition, from the viewpoint of improving pattern formability when a thick photosensitive layer of 70 μm or more is formed, the lower limit of the content of the compound having a photopolymerizable functional group and a urethane bond is the total solid content of the photosensitive resin composition. May be appropriately selected from 70% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, or 95% by mass or more. The upper limit is not particularly limited in consideration of the pattern forming properties of the resulting resin composition, the coating properties, and the physical properties and characteristics required for the cured product of the resin composition, but based on the total solid content of the photosensitive resin composition Can be appropriately selected from 100% by mass or less, 99% by mass or less, 95% by mass or less, 85% by mass or less, or 80% by mass or less.
Examples of the compound having a (meth) acryloyl group include (meth) acrylate, and examples of the compound having a urethane bond as a carbon-nitrogen bond include a (meth) acrylate having a urethane bond (hereinafter, “urethane ( May be referred to as “meth) acrylate”.
The number of photopolymerizable functional groups that the component (A) has is 1 to 24 from the viewpoint of pattern formation, and 2 to 15 or 2 from the viewpoint of stabilizing the physical properties and characteristics of the resulting cured product. What is necessary is just to select from ~ 12 suitably.
The photosensitive resin composition of the present embodiment may contain, as a component (A), a component (A1): a high molecular weight body having a photopolymerizable functional group, from the viewpoint of improving pattern formation. (A2) component: You may contain the low molecular weight body which has a photopolymerizable functional group.
(A1) component and (A2) component are demonstrated in order below.

((A1) component: high molecular weight compound having a photopolymerizable functional group)
The component (A1) is a high molecular weight body having a photopolymerizable functional group. “High molecular weight body” means a compound having a weight average molecular weight (Mw) of 2,500 or more. In addition, the value of the weight average molecular weight in this specification is the value measured using tetrahydrofuran (THF) by the gel permeation chromatograph (GPC) method.
The (A1) component has a photopolymerizable functional group that has been described as a photopolymerizable functional group contained in the above-described component (A). From the viewpoint of improving pattern formability, It may have a (meth) acryloyl group.
The number of photopolymerizable functional groups that the component (A1) has is 2 to 24 from the same viewpoint as described above, and 4 to 15 or 6 from the viewpoint of stabilizing the physical properties and characteristics of the obtained cured product. What is necessary is just to select from ~ 12 suitably.
If the number of photopolymerizable functional groups is 2 or more, the heat resistance and rigidity of the cured product at a high temperature can be improved together with pattern formation. On the other hand, if the number of photopolymerizable functional groups is 24 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. As a result, excellent resolution can be obtained, so that excellent pattern formability can be obtained even when a thick photosensitive layer is formed. Furthermore, after at least one of photocuring and heat curing is performed, the remaining unreacted photopolymerizable functional groups can be further reduced, and fluctuations in physical properties and characteristics of the obtained cured product can be further suppressed.
The component (A1) may include 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, and the absorbance of the photosensitive resin composition. From the viewpoint of reducing the above, a high molecular weight product having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton and an alicyclic skeleton may be included.

Examples of the urethane (meth) acrylate as the component (A1) 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) acrylate, ethoxylated forms thereof, propoxylated forms thereof, ethoxylated propoxylated forms thereof, and caprolactone modified forms 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; Tri- or more functional epoxy (meth) acrylates such as enolol novolac type epoxy (meth) acrylate, cresol novolac type epoxy poly (meth) acrylate, 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 a phenol compound) that is a raw material for the (meth) acrylate with ε-caprolactone, for example.

  Examples of the isocyanate compound having an isocyanate group include compounds having at least one isocyanate group in one molecule, and may be compounds having 1 to 3 isocyanate groups in one molecule. More specifically, aliphatic monoisocyanate compounds such as ethyl isocyanate, propyl isocyanate, butyl isocyanate, octadecyl isocyanate, 2-isocyanatoethyl (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, Diisodies such as aromatic diisocyanate compounds such as 4'-diphenylmethane diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, hydrogenated xylylene diisocyanate, naphthalene-1,5-diisocyanate Aneto 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, and more Specifically, for example, an organic group derived from a (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 as the component (A1), 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, biuret type trimers of these diisocyanate compounds, and the like 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, specifically, ethylene glycol, diethylene glycol, propanediol, dipropylene glycol, butanediol, pentanediol, isopentylglycol, hexanediol. Linear or branched saturated diol compounds such as nonanediol, decanediol, dodecanediol, dimethyldodecanediol, and octadecanediol; linear such as butenediol, pentenediol, hexenediol, methylpentenediol, and dimethylhexenediol Or branched unsaturated diol compounds; various cyclohexanediols, various cyclohexanedimethanols, various tricyclodecanedimethanols, hydrogenated bisphenol A, hydrogenated bisphenols Diol compound having an alicyclic skeleton such Lumpur 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 formation and increasing the glass transition point (Tg) after polymerization to improve water resistance. Alternatively, it may be appropriately selected from 2 to 14 saturated diol compounds, and more specifically, may be appropriately selected from ethylene glycol and octadecanediol.
Moreover, as a diol compound which has an alicyclic skeleton, it is C5-C20, 5-C5 from a viewpoint which improves pattern formation property and raises the glass transition point (Tg) after superposition | polymerization and improves water resistance. The diol compound having an alicyclic skeleton of 18 or 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 3-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. When the component (A1) has a plurality of the above structural units, the plurality of X ₁ and Y ₁ may be the same or different. That is, examples of the component (A1) 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 these, as a divalent organic group having a chain hydrocarbon skeleton, from the viewpoint of improving pattern formation and increasing the glass transition point (Tg) after polymerization to improve water resistance, What is necessary is just to select suitably from the residue remove | excluding the hydroxyl group from 20, 2-16, or 2-14 saturated diol compound, More specifically, it selects suitably from the residue remove | excluding the hydroxyl group from ethylene glycol and octadecandiol. do it. From the same viewpoint, the divalent organic group having an alicyclic skeleton is a hydroxyl group removed from a diol compound having an alicyclic skeleton having 5 to 20, 5 to 18, or 6 to 16 carbon atoms. And more specifically, various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol What is necessary is just to select suitably from the residue remove | excluding the hydroxyl group from various cyclohexanedimethanols, such as.

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

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

As a commercial item containing the urethane acrylate which has a structural unit represented by the said General formula (1), 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), UN-954: (number of functional groups: 6, weight average molecular weight: 4,500), UN-953: (number of functional groups: 20, weight average) Molecular weight: 4,000 to 40,000), H-219 (functional group number: 9, weight average molecular weight: 25,000 to 50,000) (all are trade names, manufactured by Negami Kogyo Co., Ltd.), EBECRYL 8405 (urethane acrylate / 1,6-hexanediol diacrylate = 80/20 addition reaction product, number of functional groups: 4, Mw: 2,700) (trade name, manufactured by Daicel Ornex Co., Ltd.) and the like.
Moreover, as a commercial item containing the urethane methacrylate which has a structural unit represented by the said General formula (1), UN-6060PTM (functional group number: 2, Mw: 6,000, a brand name, Negami Kogyo Co., Ltd. make, for example) ) 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 commercial item containing the urethane acrylate represented by the said General formula (3), UN-952 (functional group number: 10, Mw: 6,500-11,000) is, for example, General Formula (4) As a commercial item containing the urethane acrylate represented, UN-905 (The number of functional groups: 15, Mw: 40,000-200,000) etc. are mentioned, for example (all are brand names and the Negami Industrial Co., Ltd. product). ).
Among these, UN-952 is particularly preferable from the viewpoints of pattern formability and photosensitivity.

  The total number of (meth) acryloyl groups (number of photopolymerizable functional groups) contained in the urethane (meth) acrylate as the component (A1) is 2 to 24 in one molecule from the viewpoint of improving pattern formation and heat resistance. What is necessary is just to select suitably from 4-15 or 6-12 from a viewpoint of stabilizing the physical property and characteristic of the hardened | cured material obtained.

The weight average molecular weight of the component (A1) is 2,500 or more, and may be 3,000 or more from the viewpoint of improving the coating property and resolution of the resin composition, and further improving developability and compatibility. From the viewpoint, it may be 3,500 or more. On the other hand, the upper limit of the weight average molecular weight may be 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 2,500 or more, since the occurrence of dripping of the applied resin 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.

When the photosensitive resin composition of this embodiment contains the component (A1), the content of the component (A1) is 10% by mass or more and 30% by mass or more based on the total solid content of the photosensitive resin composition. Or, what is necessary is just to select suitably from 40 mass% or more. 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 forming property, coating property, and physical properties and characteristics required for the cured product of the resin composition, the upper limit of the content of the component (A1) 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.
Moreover, content of urethane (meth) acrylate in (A1) component is 70-100 mass% and 80-100 mass% on the basis of the solid content whole quantity of (A1) component from a viewpoint of improving pattern formation property. 90-100% by mass, 95-100% by mass, or 100% by mass (total amount).

((A2) component: low molecular weight substance having a photopolymerizable functional group)
The component (A2) is a low molecular weight body having a photopolymerizable functional group. The “low molecular weight body” means a compound having a weight average molecular weight of less than 2,500.
The photopolymerizable functional group of the component (A2) is described as the photopolymerizable functional group contained in the component (A) described above, and as a photopolymerizable functional group from the viewpoint of improving pattern formability. It may have a (meth) acryloyl group.
The component (A2) has at least one photopolymerizable functional group, and from the viewpoint of improving pattern formability, the number of photopolymerizable functional groups is 1 to 12, 2 to 10, or 2 to 2. What is necessary is just to select from 6 suitably.

  From the viewpoint of pattern formation, the photosensitive resin composition of the present embodiment includes (A2-1) component: a low molecular weight body having a photopolymerizable functional group and an isocyanuric ring, (A2-2) as the component (A2). ) Component: a low molecular weight body having a photopolymerizable functional group and a urethane bond; and (A2-3) component: at least one selected from the group consisting of a low molecular weight body having a photopolymerizable functional group and an alicyclic skeleton. It may contain seeds. When the photosensitive resin composition of the present embodiment contains at least one of these, the adhesiveness of the electronic component with the substrate or the like tends to be improved, and excellent pattern formability tends to be obtained. In addition, in the case of a low molecular weight substance having two or more of an isocyanuric ring, a urethane bond, and an alicyclic skeleton, it is classified as a component (A2-1) if it has at least an isocyanuric ring, and a urethane bond. And an alicyclic skeleton, it is classified as component (A2-2) with priority given to having a urethane bond. That is, a low molecular weight substance having an alicyclic skeleton without having an isocyanuric ring and a urethane bond is classified as the component (A2-3).

[(A2-1) component: low molecular weight body having an isocyanuric ring]
The component (A2-1) is a low molecular weight substance having a photopolymerizable functional group and an isocyanuric ring skeleton, and may have two or more photopolymerizable functional groups from the viewpoint of improving pattern formation. , 2 to 5 photopolymerizable functional groups may be included, two or three photopolymerizable functional groups may be included, or three photopolymerizable functional groups may be included.
The photopolymerizable functional group of the component (A2-1) has been described as the photopolymerizable functional group contained in the component (A) described above. From the viewpoint of improving pattern formability, the photopolymerizable functional group is included. You may have a (meth) acryloyl group as a group.
Examples of the component (A2-1) include compounds represented by the following general formula (7).

（一般式（７）中、Ｒ^１３、Ｒ^１４及びＲ^１５は、各々独立に炭素数１〜８のアルキレン基を示し、Ｒ^１６及びＲ^１７は、各々独立に水素原子、又はメチル基を示し、Ｒ^１８は水素原子、又は（メタ）アクリロイル基を示す。）

(In the general formula (7), R ¹³ , R ¹⁴ and R ¹⁵ each independently represent an alkylene group having 1 to 8 carbon atoms, and R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group. R ¹⁸ represents a hydrogen atom or a (meth) acryloyl group.

In General Formula (7), the alkylene group having 1 to 8 carbon atoms represented by R ¹³ , R ^14, and R ¹⁵ may be an alkylene group having 1 to 4 carbon atoms, or an alkylene group having 1 to 3 carbon atoms. There may be.
Examples of the alkylene group having 1 to 8 carbon atoms include methylene group, ethylene group, propylene group, butylene group, isopropylene group, isobutylene group, t-butylene group, pentylene group, and hexylene group. Among these, From the viewpoint of improving pattern formability, an ethylene group may be used.
In General Formula (7), R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group, and may be a hydrogen atom from the viewpoint of improving sensitivity.
In the general formula (7), R ¹⁸ represents a hydrogen atom or a (meth) acryloyl group, and may be a (meth) acryloyl group from the viewpoint of improving pattern formation.

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

  The weight average molecular weight of the component (A2-1) is less than 2,500, and is appropriately selected from 200 to 1,500, 300 to 1,000, or 350 to 600 from the viewpoint of improving pattern formation. May be.

As the component (A2-1), a commercially available product may be used. Examples of commercially available products include “A-9300” (compound represented by the above formula (7-1)) manufactured by Shin-Nakamura Chemical Co., Ltd., and “M-215” manufactured by Toagosei Co., Ltd. (the above formula ( 7-2)) and the like.
(A2-1) A component can be used individually or in combination of 2 or more types.

[(A2-2) component: low molecular weight substance having urethane bond]
The component (A2-2) is a low molecular weight body having a photopolymerizable functional group and a urethane bond, and may have two or more photopolymerizable functional groups from the viewpoint of improving pattern formation. It may have 2 to 6 photopolymerizable functional groups and may have 2 photopolymerizable functional groups.
The photopolymerizable functional group (A2-2) has been described as the photopolymerizable functional group contained in the component (A) described above, and from the viewpoint of improving pattern formability, the photopolymerizable functional group. You may have a (meth) acryloyl group as a group.

  Examples of the component (A2-2) include a reaction product of a (meth) acrylate having a hydroxyl group and an isocyanate compound having an isocyanate group. Here, examples of the (meth) acrylate having a hydroxyl group and the isocyanate compound include a (meth) acrylate having a hydroxyl group and an isocyanate compound exemplified as those used for producing the component (A1). Here, examples of the appropriate selection from the viewpoint of improving the pattern formability are the same as those appropriately selected as those used for generating the component (A1) from the same viewpoint.

As the component (A2-2), a reaction in which a (meth) acrylate having a hydroxyl group is reacted 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. Products. Here, as the isocyanate compound having at least two isocyanate groups in one molecule, the diol compound, and the (meth) acrylate having a hydroxyl group, isocyanates in one molecule exemplified as those used for the production of the component (A1) are used. Examples thereof include an isocyanate compound having at least two groups, a diol compound, and a (meth) acrylate having a hydroxyl group. Here, examples of the appropriate selection from the viewpoint of improving the pattern formability are the same as those appropriately selected as those used for generating the component (A1) from the same viewpoint.
Examples of the reaction product include urethane (meth) acrylate having a structural unit represented by the following general formula (8).

In General Formula (8), X ₂ represents a divalent organic group having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton, and Y ₂ represents a chain hydrocarbon skeleton or an alicyclic skeleton. The divalent organic group which has. That is, examples of the component (A2-2) 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. What is necessary is just to select suitably from the bivalent organic group which has the shape-like hydrocarbon skeleton, the branched C2-C12 alkylene group, for example, the residue of the said aliphatic diisocyanate compound. 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 component (A2-2) include urethane acrylate represented by the following general formula (9).

In the general formula (9), _{n 5} is an integer of 1-4. R ¹⁹ and R ²⁰ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a plurality of R ¹⁹ and R ²⁰ are each at least three of which are alkyl groups having 1 to 4 carbon atoms. .
Among the urethane acrylates represented by the general formula (9), X _{2 in the} general formula (8) is a residue of trimethylhexamethylene diisocyanate, which is a divalent organic group having a chain hydrocarbon skeleton, _As a commercial product containing urethane acrylate having a structural unit in which 2 is a residue of a divalent organic group cyclohexanedimethanol having an alicyclic skeleton, for example, TMCH-5R (trade name, number of functional groups: 2, Mw: 950, manufactured by Hitachi Chemical Co., Ltd.).
Moreover, as a commercial item containing the urethane (meth) acrylate which has a structural unit represented by the said General formula (8), KRM8452 (the number of functional groups: 10, Mw: 1,200, Daicel Ornex Co., Ltd. make), UN -3320HA (functional group number: 6, Mw: 1,500, manufactured by Negami Industrial Co., Ltd.), UN-3320HC (functional group number: 6, Mw: 1,500, manufactured by Negami Industrial Co., Ltd.), 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.

  The weight average molecular weight of the component (A2-2) is less than 2,500, and may be 1,500 or less from the viewpoint of improving adhesion, and 1,000 or less from the viewpoint of improving resolution. There may be. 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.

[(A2-3) component: low molecular weight product having an alicyclic skeleton]
The component (A2-3) is a low molecular weight substance having a photopolymerizable functional group and an alicyclic skeleton, and may have two or more photopolymerizable functional groups from the viewpoint of improving pattern formation. In addition, 2 to 4 photopolymerizable functional groups may be included, or two photopolymerizable functional groups may be included.
The photopolymerizable functional group (A2-3) has been described as the photopolymerizable functional group contained in the component (A) described above, and from the viewpoint of improving pattern formability, the photopolymerizable functional group. You may have a (meth) acryloyl group as a group.
Although it does not restrict | limit especially as an alicyclic skeleton which (A2-3) component has, For example, a C5-C20 alicyclic hydrocarbon skeleton is mentioned. The alicyclic hydrocarbon skeleton is at least one selected from the group consisting of a cyclopentane skeleton, a cyclohexane skeleton, a cyclooctane skeleton, a cyclodecane skeleton, a norbornane skeleton, a dicyclopentane skeleton, and a tricyclodecane skeleton. Also good. Among these, a tricyclodecane skeleton may be used from the viewpoint of improving pattern formability.

The weight average molecular weight of the component (A2-3) is less than 2,500, may be 1,500 or less from the viewpoint of improving adhesion, and is 1,000 or less from the viewpoint of improving resolution. It may be 500 or less. On the other hand, the lower limit of the weight average molecular weight can be appropriately used according to the desired purpose, but may be 150 or more or 200 or more from the viewpoint of film formability.
The component (A2-3) may be tricyclodecane dimethanol diacrylate from the viewpoint of film formability.

  When the photosensitive resin composition of the present embodiment contains the component (A2), the content of the component (A2) is 3% by mass or more and 5% by mass or more based on the total solid content of the photosensitive resin composition. You may select suitably from 10 mass% or more or 20 mass% or more. When the content of the component (A2) 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 (A2) is suitably 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. Just choose.

  When the photosensitive resin composition of this embodiment contains the component (A1) and the component (A2), the content of the component (A2) based on 100 parts by mass of the total solid content of the component (A1) What is necessary is just to select suitably from 20-120 mass parts, 25-110 mass parts, or 30-100 mass parts from a viewpoint of improving the rigidity of formability and hardened | cured material.

When the component (A2) contains the component (A2-1), the content of the component (A2-1) in the total solid content of the component (A2) is 15% by mass or more, 40% by mass or more, and 70% by mass. % Or more, 90% by mass or more, or 95% by mass or more. When the content of the component (A2-1) is 15% 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 component (A2-1) is 100% by mass or less, and 100% by mass, that is, the total amount of the component (A2) may be the component (A2-1).
When the component (A2) contains the component (A2-2), the content of the component (A2-2) in the total solid content of the component (A2) is 20 to 100% by mass, 40 to 95% by mass, Or what is necessary is just to select suitably from 50-90 mass%.
When the component (A2) contains the component (A2-3), the content of the component (A2-3) in the total solid content of the component (A2) is 10 to 50% by mass, 15 to 40% by mass, Or what is necessary is just to select suitably from 20-30 mass%.

<(B) component: Photopolymerization initiator>
The photosensitive resin composition of this embodiment may contain a photopolymerization initiator as the component (B).
The component (B) is not particularly limited as long as it can polymerize a photosensitive resin, 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. Among these, the component (B) may contain at least one selected from the group consisting of alkylphenone photopolymerization initiators and acylphosphine oxide photopolymerization initiators.

  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 ("IRGACURE-TPO" (manufactured by BASF)), ethyl-2 , 4,6-trimethylbenzoylphenyl phosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“IRGACURE-819” (manufactured by BASF)), (2,5-dihydroxyphenyl) diphenylphosphine Oxide, (p-hydroxyphenyl) Phenylphosphine 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: Quanture-PDO, manufactured by Nippon Kayaku Co., Ltd.), and the like.

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

  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 (“IRGACURE-651” (manufactured by BASF)), 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE-184” (manufactured by BASF)), 2-hydroxy-2-methyl-1-phenyl-propane- 1-one (“IRGACURE-1173” (manufactured by BASF)), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (“IRGACURE- 2959 "(manufactured by BASF)), 2-H Doxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (“IRGACURE-127” (manufactured by BASF)) and the like Can be mentioned.

  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, and N-ethyl-N-phenylglycine.

  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-hex Hydro-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.

  Among these, from the viewpoint of improving pattern formability, the component (B) is at least selected from the group consisting of a compound represented by the following general formula (10) and a compound represented by the following general formula (11). You may contain 1 type.

（一般式（１０）中、Ｒ^１、Ｒ^２及びＲ^３は、各々独立に、水素原子、炭素数１〜８のアルキル基、又は炭素数１〜８のアルコキシ基を示し、Ｒ^４及びＲ^５は、各々独立に、水素原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、又は炭素数６〜１２のアリール基を示す。水素原子以外のＲ^１〜Ｒ^５は、各々置換基を有していてもよい。）

(In General Formula (10), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, and R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R ^{1 to} R ⁵ other than a hydrogen atom are , Each may have a substituent.)

（一般式（１１）中、Ｒ^６は、水酸基、炭素数１〜８のアルコキシ基、又はアミノ基を示し、Ｒ^７及びＲ^８は、各々独立に、水素原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、又は炭素数６〜１２のアリール基を示す。Ｒ^７とＲ^８は、互いに結合して、炭素数３〜１６の環状構造を形成していてもよい。水酸基及び水素原子以外のＲ^６〜Ｒ^８は、各々置換基を有していてもよく、置換基を有するアミノ基は、置換基同士が互いに結合して、炭素数３〜１２の環状構造を形成していてもよい。Ｒ^９は、各々独立に、水素原子、ハロゲン原子、水酸基、アミノ基、メルカプト基、又は酸素原子、窒素原子及び硫黄原子から選ばれる１種以上の原子を含んでいてもよい炭素数１〜１０の有機基を示す。）

(In General Formula (11), R ⁶ represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an amino group, and R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl having 1 to 8 carbon atoms. Group, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, R ⁷ and R ⁸ may be bonded to each other to form a cyclic structure having 3 to 16 carbon atoms. R ^{6 to} R ⁸ other than a hydroxyl group and a hydrogen atom may each have a substituent, and the amino group having a substituent is a cyclic structure having 3 to 12 carbon atoms, in which the substituents are bonded to each other. R ⁹ each independently contains a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or one or more atoms selected from an oxygen atom, a nitrogen atom and a sulfur atom. An organic group having 1 to 10 carbon atoms that may be present.

In General Formula (10), R ¹ , R ^2, and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.
The alkyl group having 1 to 8 carbon atoms represented by R ¹ , R ² and R ³ may be an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 or 2 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-heptyl group, an n-hexyl group, and an n-octyl group.
The alkoxy group having 1 to 8 carbon atoms represented by R ¹ , R ² and R ³ may be an alkoxy group having 1 to 4 carbon atoms, or may be an alkoxy group having 1 or 2 carbon atoms. Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, n-heptyloxy group, n-hexyloxy group, n-octyloxy and the like. Can be mentioned.
Among these groups, R ¹ , R ² and R ³ may be methyl groups from the viewpoint of improving resolution.

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

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

In General Formula (11), R ⁶ represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an amino group.
The alkoxy group represented by R ⁶ is explained in the same manner as in the case of R ¹ , R ² and R ³ in the general formula (10).
Among these groups, R ⁶ may be a hydroxyl group or a methoxy group from the viewpoint of improving pattern forming properties.

In General Formula (11), R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. .
The alkyl group, alkoxy group and aryl group represented by R ⁷ and R ⁸ are explained in the same manner as in R ^{1 to} R ⁵ in the general formula (10).
R ⁷ and R ⁸ may be bonded to each other to form a cyclic structure having 3 to 16 carbon atoms.
The cyclic structure may be a C4-10 cyclic structure or a C5-8 cyclic structure.
The cyclic structure may be an alicyclic structure from the viewpoint of improving pattern forming properties, and examples of the alicyclic structure include a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. These alicyclic structures may contain a carbon atom to which R ⁷ and R ⁸ are directly bonded.

The substituents that R ^{6 to} R ⁸ may have are described in the same manner as the substituents that R ^{1 to} R ⁵ in General Formula (10) may have.
However, in the amino group having a substituent, the substituents may be bonded to each other to form a cyclic structure having 3 to 12 carbon atoms.
The cyclic structure formed by the substituent of the amino group may be a cyclic structure having 3 to 10 carbon atoms or a cyclic structure having 3 to 5 carbon atoms.
The cyclic structure may be a 5- to 10-membered ring containing a nitrogen atom of the amino group, a 5- to 7-membered ring containing a nitrogen atom of the amino group, or a 6-membered ring containing the nitrogen atom of the amino group. It may be a ring. Furthermore, these cyclic structures may contain hetero atoms other than nitrogen atoms such as oxygen atoms. A specific example of the cyclic structure formed by the substituent of the amino group includes a structure represented by the following formula (12).

In general formula (11), each R ⁹ independently contains one or more atoms selected from a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an oxygen atom, a nitrogen atom, and a sulfur atom. Or an organic group having 1 to 10 carbon atoms.
The organic group having 1 to 10 carbon atoms represented by R ⁹ may be an organic group having 1 to 6 carbon atoms or an organic group having 1 to 4 carbon atoms.
The organic group having 1 to 10 carbon atoms represented by R ⁹ may be a hydrocarbon group such as an alkyl group, an alkenyl group, and an aryl group. These alkyl group, alkenyl group and aryl group are explained in the same manner as the alkyl group, alkenyl group and aryl group represented by R ^{1 to} R ⁵ in the general formula (10).
The organic group having 1 to 10 carbon atoms containing an oxygen atom which R ⁹ represents, for example, an alkoxy group, and the like.
Examples of the organic group having 1 to 10 carbon atoms containing a nitrogen atom represented by R ⁹ include a group represented by the formula (12).
The organic group having 1 to 10 carbon atoms containing a sulfur atom R ⁹ represents, for example, alkylthio groups such as methylthio group.

Moreover, the photosensitive resin composition of this embodiment contains the photoinitiator whose molar absorption coefficient with respect to the light of wavelength 365nm is less than 5.0 * 10 < ³ > L / mol * cm as (B) component. It may be.
By setting the molar extinction coefficient of the photopolymerization initiator within the above range, the absorbance of the photosensitive resin composition can be kept low, and light appropriately passes to the bottom of the photosensitive layer (surface on the substrate side of the photosensitive layer). Since it becomes easy, pattern formation property can be improved. In addition, the progress of the photopolymerization reaction other than the exposed portion can be suppressed, and thereby excellent pattern forming properties can be obtained.
Hereinafter, when simply described as “molar extinction coefficient”, it means “molar extinction coefficient with respect to light having a wavelength of 365 nm”, and when simply described as “absorbance”, “when the thickness of the photosensitive resin composition is 50 μm”. , “Absorbance with respect to light having a wavelength of 365 nm”.
The molar extinction coefficient of the component (B) is 4.5 × 10 ³ L / mol · cm or less, 4.0 × 10 ³ L / mol · cm or less, 3.5 × 10, from the viewpoint of improving pattern formation. ^{What is} necessary is just to select suitably from below ³ L / mol * cm or below 3.2 * 10 < ³ > L / mol * cm. The lower limit value of the molar extinction coefficient of the component (B) is not particularly limited, and may be appropriately selected from, for example, 1 L / mol · cm or more, 5 L / mol · cm or more, or 10 L / mol · cm or more.
The molar extinction coefficient of (B) component can be measured by the method as described in an Example using an ultraviolet visible spectrophotometer, for example.

  As the content of the component (B), when the thickness of the photosensitive resin composition of the present embodiment is 50 μm, the amount of absorbance with respect to light having a wavelength of 365 nm is less than 0.45, the amount of 0.40 or less, 0 .. 30 or less, 0.25 or less, 0.20 or less, 0.15 or less, or 0.10 or less. By setting the component (B) to the above content, for example, even when a pattern is formed with a thick photosensitive layer of 70 μm or more using the photosensitive resin composition of the present embodiment, the bottom of the photosensitive layer (photosensitive layer) Since the light can easily pass to the surface of the layer on the substrate side, the pattern formability can be improved.

  The content of the component (B) may be appropriately determined in consideration of the molar extinction coefficient of the component (B) and the absorbance of the photosensitive resin composition. Usually, based on the total solid content of the photosensitive resin composition, What is necessary is just to select suitably from 0.01-30 mass%, 0.05-20 mass%, or 0.08-15 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.

  Further, in addition to the above component (B), three compounds such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. (B ′) photopolymerization initiation assistants such as secondary amines may be used alone or in combination of two or more.

Further, the content of the component (B) may be determined according to the molar extinction coefficient, molecular weight, etc. of the (B) component, and is obtained from the following formula obtained from the molar extinction coefficient, molecular weight, and content of the photopolymerization initiator. The value P represented by the above may be appropriately selected from an amount of 0.1 or more, 0.2 or more, or 0.3 or more, and is 3 or less, 2 or less, or 1.3 or less. What is necessary is just to select suitably from quantity. When P represented by the formula (i) is within the above range, excellent pattern formability can be obtained.
P = A × B / C (i)
A: The molar extinction coefficient (L / mol · cm) of the photopolymerization initiator for light having a wavelength of 365 nm
B: Content (mass%) of the photopolymerization initiator with respect to the total amount of the photosensitive resin composition (however, when the photosensitive resin composition contains filler, the mass of filler is excluded)
C: Molecular weight of photopolymerization initiator

<(C) component: silane compound>
Moreover, the photosensitive resin composition of this embodiment can contain the (C) silane compound further.
As the component (C), a known silane coupling agent can be used. The component (C) 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. Examples of the silane coupling agent include: alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropylmethyldimethoxysilane (Meth) acryloyl group-containing alkoxysilanes such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1, Amine-based alkoxysilanes such as 3-dimethylbutylidene) propylamine; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, Glycidoxy group-containing alkoxysilanes such as sidoxypropylmethyldiisopropenoxysilane; Alicyclic epoxy group-containing alkoxysilanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-ureidopropyltriethoxysilane Ureido group-containing alkoxysilanes; mercapto group-containing alkoxysilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane; carbamate group-containing alkoxysilanes such as triethoxysilylpropylethylcarbamate; 3- (triethoxysilyl) And polybasic acid anhydride group-containing alkoxysilanes such as propyl succinic anhydride. 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.

  When the photosensitive resin composition contains the component (C), the content of the component (C) is 0.05 to 15% by mass, 0.1 to 10 based on the total solid content of the photosensitive resin composition. What is necessary is just to select suitably from the mass%, 0.1-7 mass%, 1-7 mass%, or 1-5 mass%. By setting it as the said content, deterioration of a resist shape can be suppressed and pattern formation property can be improved.

<(D) component: high Tg high molecular weight body>
The photosensitive resin composition of this embodiment may contain a high molecular weight body having a glass transition temperature of 70 to 150 ° C. and having no carbon-nitrogen bond as the component (D). The “high molecular weight body” has the same definition as in the component (A1). By containing the component (D), the photosensitive resin composition has a tack suppressing effect.
The component (D) may contain an ethylenically unsaturated group from the viewpoints of pattern forming properties and tackiness. Examples of the ethylenically unsaturated group include a (meth) acryloyl group and a vinyl group. From the viewpoint of pattern formation, a (meth) acryloyl group may be used.
The component (D) may contain a high molecular weight polymer having at least one skeleton selected from the group consisting of an alicyclic skeleton and an aromatic ring skeleton, which reduces pattern formation and reduces tackiness. From a viewpoint, you may contain the high molecular weight body which has an alicyclic skeleton.

The high molecular weight body having an alicyclic skeleton includes, for example, part of an acid group derived from an acid group-containing acrylic resin (d1) having no carbon-nitrogen bond and an alicyclic ring having no carbon-nitrogen bond. It can manufacture by making the epoxy group derived from a formula epoxy group containing unsaturated compound (d2) react.
Examples of the acid group-containing acrylic resin (d1) having no carbon-nitrogen bond include an acid having an ethylenically unsaturated group and monomers such as an ester of (meth) acrylic acid, a vinyl aromatic compound, and a polyolefin compound. A copolymer obtained by copolymerizing one or two or more selected ones can be used. Specifically, an acid having an ethylenically unsaturated group such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, (anhydrous) maleic acid, and the like as an essential component. Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl ( Esters of (meth) acrylic acid such as (meth) acrylate; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene; monomers of polyolefin compounds such as butadiene, isoprene, chloroprene, and methyliso Ropeniruketon, vinyl acetate, one or two or more monomers by copolymerizing a copolymer selected from other monomers such as vinyl propionate.
(D1) The acid value of a component may be 15 mgKOH / g or more, and may be 40-500 mgKOH / g. Since the component (d1) has such an acid value, a sufficient amount of acid groups remains in the component (D) even after the reaction between the component (d1) and the component (d2) described later. Become.

  As the alicyclic epoxy group-containing unsaturated compound (d2) having no carbon-nitrogen bond, a compound having one ethylenically unsaturated group and an alicyclic epoxy group in one molecule is preferable. Specific examples include compounds represented by any of the following formulas (I) to (X).

Here, R ^D1 is independently a hydrogen atom or a methyl group. R ^D2 is independently an aliphatic saturated hydrocarbon group.
As the aliphatic saturated hydrocarbon group represented by R ^D2 , a linear or branched alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, an arylene group having 6 to 14 carbon atoms, and Examples thereof include divalent organic groups composed of these combinations. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, and a hexamethylene group. Examples of the cycloalkylene group include a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group. Examples of the arylene group include a phenylene group and a naphthylene group. The divalent organic group comprising a combination thereof, for example, -CH ₂ - phenylene group _-CH 2 -, - CH ₂ - cyclohexylene group -CH ₂ - and the like.
^RD2 is a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, or a cyclohexylene from the viewpoints of pattern formation and reduction of tackiness. Group, —CH ₂ -phenylene group —CH ₂ —, methylene group, ethylene group, propylene group or methylene group may be used.

The alicyclic epoxy group-containing unsaturated compound (d2) having no carbon-nitrogen bond may be a compound represented by the formula (III) from the viewpoint of pattern formation.
As the component (D), a commercially available product may be used, and examples thereof include (ACA) Z250 (acid value 101.7 mgKOH / g, manufactured by Daicel Ornex Co., Ltd.) of the cyclomer P series. (ACA) Z250 is a resin composed of three structural units represented by the following formula, which is generated by a reaction between an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound.

（式中、Ｒ^Ｄ１は水素原子又はメチル基を表す。Ｒ^Ｄ３は炭素数１〜６のアルキル基、又は炭素数１〜６のヒドロキシアルキル基を表す。）

(In the formula, R ^D1 represents a hydrogen atom or a methyl group. R ^D3 represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms.)

(D) Although the glass transition temperature of a component is 70-150 degreeC, 100-150 degreeC may be sufficient, 115-150 degreeC may be sufficient, and 125-150 degreeC may be sufficient. Here, the glass transition temperature of (D) component is the value measured by the following method.
(Measurement method of glass transition temperature of component (D))
As a pretreatment for the measurement, the component (D) is heated at 120 ° C. for 3 hours and then cooled to prepare a sample.
Using 10 mg of the sample, the temperature was raised at a temperature range of 25 to 200 ° C. and a heating rate of 20 ° C./min under a nitrogen stream with a differential scanning calorimeter (trade name: DSC-50, manufactured by Shimadzu Corporation). And the influence of solvents and the like is eliminated. After cooling to 25 ° C., the temperature is raised again under the same conditions, and the temperature at which the baseline starts to be offset is defined as the glass transition temperature.

  Further, the weight average molecular weight of the component (D) may be 3,000 to 50,000, 4,000 to 40,000, or 5,000 to 30,000. . If it is 3,000 or more, the tack suppression effect tends to increase, and if it is 50,000 or less, the resolution tends to improve.

  When the photosensitive resin composition of the present embodiment contains the component (D), the content of the component (D) is the components (A1) and (D) from the viewpoints of pattern formability and tackiness. 5-60 mass parts may be sufficient with respect to a total of 100 mass parts of a component, 10-40 mass parts may be sufficient, and 10-30 mass parts may be sufficient.

<(E) component: thermal radical polymerization initiator>
Moreover, the photosensitive resin composition of this embodiment can contain (E) thermal radical polymerization initiator further. There is no restriction | limiting in particular as (E) component, For example, (alpha), (alpha) '-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, t-butyl cumyl peroxide, di-t-butyl peroxide, etc. 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-ethylhexyl 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.

  Examples of the component (E) include peroxide polymerization initiators, dialkyl peroxide polymerization initiators, and the like from the viewpoint of improving pattern formability. Among them, dicumyl peroxide can be selected. Moreover, (E) component can be used individually or in combination of 2 or more types.

  When the component (E) 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.

<(F) component: inorganic filler>
The photosensitive resin composition of the present embodiment contains (F) an inorganic filler for the purpose of further improving various properties such as adhesion between the photosensitive resin composition and the substrate, heat resistance, and rigidity of the cured product. Can do.
Examples of the component (F) include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), and silicon nitride (Si ₃ N). ₄ ), barium titanate (BaO.TiO ₂ ), barium carbonate (BaCO ₃ ), magnesium carbonate (MgCO ₃ ), aluminum hydroxide (Al (OH) ₃ ), magnesium hydroxide (Mg (OH) ₂ ), titanium Lead 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 size of the component (F) is appropriately selected from 0.01 to 3 μm, 0.01 to 2 μm, or 0.02 to 1 μm from the viewpoint of improving the adhesiveness, heat resistance, and rigidity of the cured product. That's fine. Here, the average particle diameter of the component (F) is the average particle diameter of the inorganic filler in a state dispersed in the photosensitive resin composition, and is a value obtained by measurement 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.), the international standard ISO 13321 is used. In conformity, 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 (F) contained in the photosensitive layer provided on the carrier film or the cured film of the photosensitive resin composition is also diluted (or dissolved) 1,000 times (volume ratio) using a solvent as described above. ) And then using the submicron particle analyzer.

  The content of the component (F) may be appropriately selected from 10% by mass or less, 5% by mass or less, or 1% by mass or less 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, by substantially not containing the component (F), the transparency of the photosensitive resin composition is improved. 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 improves.

<Other additives>
The photosensitive resin composition of the present embodiment further contains additives such as a sensitizer, a heat-resistant high molecular weight material, a thermal crosslinking agent, and an adhesion assistant other than the component (C) as necessary. Can do.

  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 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. What is necessary is just to select suitably from 0.1-10 mass%, 0.3-5 mass%, or 0.5-5 mass%.

  In addition, content of (A) component in the photosensitive resin composition of this embodiment, (B)-(F) component used as needed, and other additives is the photosensitive resin composition of this embodiment. When the thickness of the object is 50 μm, it is appropriately determined within a range where the absorbance with respect to light having a wavelength of 365 nm is less than 0.45.

<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.

What is necessary is just to select the usage-amount of a diluent suitably from the quantity from which content of the solid content total amount in the photosensitive resin composition will be 50-90 mass%, 60-80 mass%, or 65-75 mass%. That is, what is necessary is just to select suitably content of the diluent in the photosensitive resin composition in the case of using a diluent from 10-50 mass%, 20-40 mass%, or 25-35 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 at 25 ° C. of the photosensitive resin composition is 0.5 to 20 Pa · s in consideration of ease of formation of the photosensitive layer, or The amount can be 1 to 10 Pa · s.

  In the photosensitive resin composition of the present embodiment, the above component (A), components (B) to (F) used as desired, other additives, and a diluent are uniformly kneaded with a roll mill, a bead mill or the like. Can be obtained by mixing.

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, from the viewpoint of forming a thick photosensitive layer more easily, a printing method or a spin coating method may be selected as appropriate.
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.

[Photosensitive resin film for thick film formation]
The photosensitive resin film for forming a thick film of the present embodiment (hereinafter sometimes simply referred to as “photosensitive resin film of the present embodiment”) is a photosensitive layer using the photosensitive resin composition of the present embodiment. Have. 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 ray, or a dryer using near infrared rays, and the drying temperature is from 60 to 120 ° C., 70 to 110 ° C., or from 90 to 110 ° C. What is necessary is just to select suitably. Moreover, what is necessary is just to select suitably from 1 to 60 minutes, 2 to 30 minutes, or 5 to 20 minutes as drying time. 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 handleability and the like.

  The thickness of the photosensitive layer may be appropriately selected from 1 to 500 μm, 10 to 300 μm, or 30 to 100 μm. By setting the thickness to 30 μm or more, for example, when forming a photosensitive layer having a thickness of 150 μm or more, the number of operations by 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.

  Moreover, the photosensitive resin film of this embodiment can also laminate | stack a protective layer on the surface on the opposite side to the surface which contact | connects the carrier film of a photosensitive layer. 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 lamination method), the solid content concentration and viscosity of the photosensitive resin composition, etc., but as the lower limit of the thickness of the photosensitive layer after drying, What is necessary is just to select suitably from 70 micrometers or more, 100 micrometers or more, more than 100 micrometers, or 150 micrometers 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, 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, but 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.

Exposure amount of active ray ^{is, 10~2,000mJ / cm 2, 100~1,500mJ /} cm 2, or, may be suitably selected from 300~1,000mJ / cm ^2. Examples of 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. What is necessary is just to select heating temperature suitably from 120-240 degreeC, 140-230 degreeC, or 150-220 degreeC. In addition, when the temperature is raised stepwise, for example, at least one of around 120 ° C. and around 160 ° C., after heat treatment for 10 to 50 minutes or 20 to 40 minutes, at around 220 ° C., 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 dried photosensitive layer, and the lower limit may be appropriately selected from 70 μm or more, 100 μm or more, more than 100 μm, or 150 μm or more, and the upper limit is 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 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.

[Laminate]
The laminated body of this embodiment is the following (1) first laminated body and (2) second laminated body.
(1) (A) component: a photosensitive resin composition containing a compound having a photopolymerizable functional group, and when the thickness of the photosensitive resin composition is 50 μm, the absorbance with respect to light having a wavelength of 365 nm is 0. A laminate comprising a photosensitive resin composition that is less than 45.
(2) Component (A): a photosensitive resin composition containing a compound having a photopolymerizable functional group. When the thickness of the photosensitive resin composition is 50 μm, the absorbance with respect to light having a wavelength of 365 nm is 0. A laminate comprising a cured product of a photosensitive resin composition that is less than 45.
The photosensitive resin composition used in the first and second laminates of the present embodiment is a photosensitive resin composition containing (A) component: a compound having a photopolymerizable functional group, and the photosensitive resin composition. When the thickness of the photosensitive resin composition is 50 μm, there is no particular limitation as long as it is a photosensitive resin composition having an absorbance with respect to light having a wavelength of 365 nm of less than 0.45. Can be used.
Examples of the first laminate include those having a photosensitive resin composition on various supports such as a substrate used in the method for producing the cured product and a carrier film used in the photosensitive resin film. . A 1st laminated body can be manufactured by the method similar to the photosensitive layer formation process in the manufacturing method of the said hardened | cured material.
A 2nd laminated body can be manufactured by performing the exposure process in the manufacturing method of the said hardened | cured material, a removal process, a heating process, etc. with respect to said 1st laminated body, for example.

The first laminate of the present embodiment can provide excellent pattern formability even with a thick photosensitive layer of, for example, 70 μm or more. Further, the second laminate of the present embodiment has a fine pattern even with a photosensitive layer as thick as 70 μm or more, for example. Therefore, in response to the demand for an electronic circuit board that requires a thick cured product to be provided in a finer pattern on the substrate with the trend toward miniaturization and higher performance of electronic devices, the first and second of the present embodiment. It is possible to cope with such a laminate.
Further, for example, in a plating process in the manufacture of an electronic circuit board, by using a cured product obtained from the first laminate of the present embodiment or the second laminate of the present embodiment as an insulating film, Yield reduction due to short circuit can be suppressed.
Therefore, the 1st and 2nd laminated body of this embodiment is used as electronic components, such as an electronic circuit board in mobile terminals, such as a mobile phone, for example.

  Hereinafter, although the objective and advantage of this embodiment will be described more specifically based on examples and comparative examples, this embodiment is not limited to the following examples.

(Measurement method of weight average molecular weight)
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

(Measurement method of molar extinction coefficient)
The absorbance of the photopolymerization initiator was measured using an ultraviolet-visible spectrophotometer (trade name: U-3010, manufactured by Hitachi High-Technologies Corporation) and a quartz cell having a thickness of 1 cm. Specifically, 0.001 g of a photopolymerization initiator was dissolved in 0.01 L of methanol to obtain a 0.1% by mass sample solution. Furthermore, the obtained 0.1 mass% sample solution was diluted 10 times and 100 times, respectively, to prepare 0.01 mass% and 0.001 mass% sample solutions, respectively. The absorbance of each sample solution at a wavelength of 365 nm was measured, and the molar extinction coefficient was calculated from the slope when the horizontal axis represents the molar concentration and the vertical axis represents the absorbance.

(Examples 1 to 25, Comparative Example 1)
The composition is blended according to the blending composition shown in Tables 1 and 2 (the unit of numerical values in the table is parts by mass, and in the case of a solution, it is a solid content conversion amount), kneaded with a three roll mill, and photosensitive resin composition. A product was prepared. N, N-dimethylacetamide was added so that the solid content concentration was 60% by mass to obtain a photosensitive resin composition.

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

[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 so that the thickness after drying becomes 50 μm. Was applied uniformly. Subsequently, the photosensitive layer was formed by heating and drying at 100 degreeC for 15 minute (s) using a hot air convection dryer, and the photosensitive resin film which has a carrier film and a photosensitive layer was produced.

[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. The measurement results are shown in Tables 1 and 2.

[Evaluation of pattern formability]
On the glass epoxy substrate (obtained by etching copper of MCL-E-679F (trade name, manufactured by Hitachi Chemical Co., Ltd.)), the photosensitive resin film is oriented so that the photosensitive layer is located on the glass epoxy substrate side. And the carrier film was removed. Lamination was performed at 60 ° C. using a laminator. Next, the photosensitive resin film 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.
On the carrier film of the laminate, a mask for resolution evaluation (6 types of line widths (5 μm, 8 μm, 10 μm, 15 μm, 20 μm, 25 μm) and 5 types of line spaces (as shown in FIG. 1) as an exposed portion High-precision parallel exposure machine (Mikasa Co., Ltd.) on which an i-line filter (manufactured by Asahi Spectroscopy Co., Ltd .: HB-0365) is further placed, and 50 μm, 80 μm, 100 μm, 150 μm, and 200 μm) are combined. Ltd.) was used to exposure at an exposure dose of 300 mJ / cm ² of light having a wavelength of 365 nm (i line). 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. The evaluation results are shown in Tables 1 and 2. In addition, “line (μm) / space (μm)” described in the table has the narrowest line space among the patterns that can be formed, and among the patterns having the line space, It means the line width value (μm) / line space value (μm) of the pattern having the narrowest line width that could be formed.
A: A pattern having a line width of 15 μm or less or a pattern having a line space of 150 μm or less could be formed (hereinafter, these patterns are referred to as “pattern A”).
B: The pattern A could not be formed, but a pattern having a line width of 20 to 25 μm or a pattern having a line space of 200 μm could be formed (hereinafter, these patterns are referred to as “pattern B”). .
C: Not all patterns could be formed.

[Evaluation of insulation reliability]
The insulation reliability was evaluated by a high temperature and high humidity bias test. The thickness obtained in Examples 1 to 25 on the comb-shaped copper electrode of TEG (Test Element Group) (trade name: WALTS-KIT EM0101JY, manufactured by WALTS, L / S = 40 μm / 15 μm) which is an evaluation device. A 50 μm photosensitive resin film was attached at 60 ° C. using a laminator so that the photosensitive layer was positioned on the comb copper electrode side. Next, after exposure with i-line at an exposure amount of 1,000 mJ / cm ² , the carrier film was removed after heating on a hot plate at 90 ° C. for 1 minute. 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 (manufactured by ESPEC)))). As a result, each of the measurement samples obtained using the photosensitive resin films of Examples 1 to 25 had a resistance value of 1.0 × 10 ⁷ Ω or more during the test time (100 hours), and was sufficient. It was confirmed that the insulation reliability was excellent.

（式中、Ｒ^Ｄ１は水素原子又はメチル基を表す。Ｒ^Ｄ３は炭素数１〜６のアルキル基、又は炭素数１〜６のヒドロキシアルキル基を表す。）Details of each material in Tables 1 and 2 are as follows.
[(A1) component]
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 an acryloyl group in the molecule (It has a photopolymerizable functional group), a urethane bond (carbon-nitrogen bond), a chain hydrocarbon skeleton, and an alicyclic hydrocarbon skeleton.)
UN-954: urethane acrylate (manufactured by Negami Kogyo Co., Ltd., trade name, number of functional groups: 6, weight average molecular weight: 4,500)
[(A2) component]
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), (It is a compound having a chain hydrocarbon skeleton and an alicyclic hydrocarbon skeleton, and corresponds to the component (A2-2).)
A-9300: Isocyanuric acid ethylene oxide modified triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, molecular weight: 423, a compound represented by the above formula (7-1) and corresponding to the component (A2-1) To do.)
UN-3320HA: urethane (meth) acrylate (manufactured by Negami Kogyo Co., Ltd., trade name, number of functional groups: 6, weight average molecular weight: 1,500, urethane having a structural unit represented by the above general formula (8) (meta ) Acrylate, corresponding to component (A2-2).)
A-DCP: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, corresponding to component (A2-3))
[Component (B)]
TPO: “IRGACURE-TPO” (trade name, manufactured by BASF) which is 2,4,6-trimethylbenzoyldiphenylphosphine oxide
I-651: “IRGACURE-651” (trade name, manufactured by BASF) which is 2,2-dimethoxy-1,2-diphenylethane-1-one
I-184: “IRGACURE-184” (trade name, manufactured by BASF) which is 1-hydroxy-cyclohexyl-phenyl-ketone
OXE-01: “IRGACURE-OXE-01” (trade name, manufactured by BASF) which is 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime)
I-819: “IRGACURE-819” (trade name, manufactured by BASF) which is bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
[Component (C)]
KBM-803: 3-mercaptopropyltrimethoxysilane (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-503: Methacryloxypropyltrimethoxysilane (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
[(D) component]
Z250: Cyclomer P (ACA) Z250 (Daicel Ornex Co., Ltd., trade name, 3 represented by the following formula generated by reaction of an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound) Resin comprising one structural unit (weight average molecular weight: 19,000 to 25,000)).

^{(Wherein, R D1} is ^{.R D3} represents a hydrogen atom or a methyl group represents an alkyl group, or hydroxyalkyl group having 1 to 6 carbon atoms having 1 to 6 carbon atoms.)

  From Table 1 and 2, it was confirmed that the photosensitive resin composition of this embodiment of Examples 1-25 has the outstanding pattern formation property. On the other hand, the resin composition of Comparative Example 1 having an absorbance of 0.45 or more had a buried pattern and poor pattern formation.

Claims (17)

  (A) component: a photosensitive resin composition containing a compound having a photopolymerizable functional group, and when the thickness of the photosensitive resin composition is 50 μm, the absorbance with respect to light having a wavelength of 365 nm is less than 0.45. A photosensitive resin composition for forming a thick film.   The photosensitive resin composition for forming a thick film according to claim 1, further comprising a component (B): a photopolymerization initiator. The photosensitivity for thick film formation of Claim 2 containing the photoinitiator whose molar absorption coefficient with respect to the light of wavelength 365nm is less than 5.0 * 10 < ³ > L / mol * cm as said (B) component. Resin composition.   The photosensitive resin composition for thick film formation of Claim 2 or 3 whose content of the said (B) component is 0.01-30 mass% on the basis of the solid content whole quantity in the photosensitive resin composition. object.   The photosensitive resin composition for thick film formation of any one of Claims 1-4 in which the said (A) component contains the compound which has a (meth) acryloyl group as a photopolymerizable functional group.   The photosensitive resin composition for thick film formation of any one of Claims 1-5 in which the said (A) component contains the compound which has a carbon-nitrogen bond.   The photosensitive resin composition for thick film formation of Claim 6 in which the said (A) component contains the compound which has a urethane bond as a carbon-nitrogen bond.   The photosensitive resin composition for thick film formation of any one of Claims 1-7 containing (A1) component: High molecular weight body which has a photopolymerizable functional group as said (A) component.   The photosensitive resin composition for thick film formation of any one of Claims 1-8 containing (A2) component: The low molecular weight body which has a photopolymerizable functional group as said (A) component.   As the component (A), the component (A1): a high molecular weight body having a photopolymerizable functional group, the component (A2): a low molecular weight body having a photopolymerizable functional group, and the component (B): a photopolymerization initiator. The content of the component (A1), the component (A2), and the component (B) is 10 to 95% by mass and 3 to 70%, respectively, based on the total solid content in the photosensitive resin composition. The photosensitive resin composition for thick film formation of any one of Claims 1-9 which is a mass% and 0.01-30 mass%.   The photosensitive resin film for thick film formation which has a photosensitive layer using the photosensitive resin composition of any one of Claims 1-10. The process of forming a photosensitive layer 70 micrometers or more in thickness using the photosensitive resin composition of any one of Claims 1-10 on the board | substrate, or the photosensitive resin film of Claim 11. ,
Irradiating at least a part of the photosensitive layer with actinic rays to form a photocured portion;
The manufacturing method of hardened | cured material which has the process of removing at least one part other than the photocuring part of this photosensitive layer, and forming a resin pattern in order.   (A) component: a photosensitive resin composition containing a compound having a photopolymerizable functional group, and when the thickness of the photosensitive resin composition is 50 μm, the absorbance with respect to light having a wavelength of 365 nm is less than 0.45. A laminate comprising a photosensitive resin composition, wherein the photosensitive resin composition has a thickness of 70 μm or more.   The laminated body of Claim 13 whose said photosensitive resin composition is the photosensitive resin composition for thick film formation of any one of Claims 1-10.   (A) component: a photosensitive resin composition containing a compound having a photopolymerizable functional group, and when the thickness of the photosensitive resin composition is 50 μm, the absorbance with respect to light having a wavelength of 365 nm is less than 0.45. A laminate comprising a cured product of a certain photosensitive resin composition, wherein the thickness of the cured product is 70 μm or more.   The laminated body of Claim 15 whose said photosensitive resin composition is the photosensitive resin composition for thick film formation of any one of Claims 1-10.   An electronic component comprising the laminate according to claim 16.

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