JP6733266B2 - Photosensitive resin composition, photosensitive resin film, method for producing cured product, laminate, and electronic component - Google Patents

Description

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

In the field of manufacturing semiconductor integrated circuits (LSI) or wiring boards, a photosensitive material is used as a resist for forming a conductor pattern. For example, in manufacturing 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 or the like, the photosensitive layer is exposed through a predetermined mask pattern, and then a conductor pattern and a metal post are formed. A resist pattern (resist) is formed by performing a developing treatment so that a portion where the above is formed can be selectively removed (peeled). Next, a conductor such as copper is formed on the removed portion by a plating process, and then the resist pattern is removed, 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 film 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).
In addition, in recent years, in order to further improve the performance, a conductor layer having a thickness of 150 μm is formed by performing a plating process while destroying a layer existing in a direction in which metal plating is to be selectively grown by plating with a plating solution. Attempts have been made to form the film to a certain extent (see Patent Document 3).

JP, 2005-034926, A JP, 2014-074774, A JP, 2014-080674, A

However, in the conventional thick-film photosensitive resist, when it is required to form a thick photosensitive layer of 70 μm or more, it is difficult for light to pass to the bottom (the surface on the substrate side) and the pattern shape deteriorates. was there. Further, in the method described in Patent Document 3, since plating is advanced while the metal ion diluted layer is partially destroyed, it is difficult to form a stable and excellent pattern. Therefore, there is a demand for a photosensitive resist having excellent pattern formability even when a photosensitive layer having a thickness of 70 μm, further 150 μm, which is thicker than the conventional one, or more is formed.

In addition, when a pattern is formed using a photosensitive resin composition, a phenomenon in which the length of the bottom of the pattern becomes shorter than the length of the surface, that is, so-called bottom thinning may occur (note that " "Length" means the length of a "line" described below.). This phenomenon is particularly noticeable when it is required to form a thick photosensitive layer of 70 μm or more. However, with the method described in Patent Document 3, it is difficult to suppress the phenomenon of bottom thinning.

Therefore, the problems to be solved by the present disclosure have been made in view of the above circumstances. For example, even when a thick photosensitive layer having a thickness of 70 μm or more is formed, excellent pattern formability and suppression of bottom thinning phenomenon are achieved. By providing a photosensitive resin composition having a performance, 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.”). is there.

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

[1] Component (A): a high molecular weight polymer having a photopolymerizable functional group and a carbon-nitrogen bond, and (B) component: a low molecular weight polymer having a photopolymerizable functional group and a carbon-nitrogen bond, (C). Component: A photosensitive resin composition containing a photopolymerizable compound having no carbon-nitrogen bond, and (D) component: a photopolymerization initiator.
[2] A photosensitive resin film having a photosensitive layer using the photosensitive resin composition according to the above [1].
[3] A step of providing a photosensitive layer on the substrate using the photosensitive resin composition described in [1] or the photosensitive resin film described in [2],
Irradiating at least a part of the photosensitive layer with an actinic ray to form a photocured portion, and
A method for producing a cured product, which comprises a step of removing at least a part of the photosensitive layer other than a photo-cured portion and forming a resin pattern in that order.
[4] A laminate including the cured product of the photosensitive resin composition according to the above [1].
[5] An electronic component including the cured product of the photosensitive resin composition according to the above [1].

According to the present disclosure, for example, it is possible to provide a photosensitive resin composition or the like having excellent pattern formability and bottom thinning phenomenon suppressing performance even when a thick photosensitive layer having a thickness of 70 μm or more is formed.

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

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

[Photosensitive resin composition]
The photosensitive resin composition according to the embodiment of the present disclosure (hereinafter, may be simply referred to as the present embodiment) includes (A) component: a high molecular weight body having a photopolymerizable functional group and a carbon-nitrogen bond, Component (B): a low molecular weight compound having a photopolymerizable functional group and a carbon-nitrogen bond, component (C): a photopolymerizable compound having no carbon-nitrogen bond, and component (D): a photopolymerization initiator. It is a photosensitive resin composition containing.
In the present specification, the “solid content” is a non-volatile content obtained by removing volatile substances such as water and a solvent contained in the photosensitive resin composition, and when the resin composition is dried, it is volatilized. It shows the components that remain without any action, and also includes liquids, starch syrups, and waxes at room temperature (25°C). Hereinafter, each component will be described.

<(A) component: high molecular weight polymer>
The photosensitive resin composition of the present embodiment contains, as the component (A), at least one photopolymerizable functional group and a polymer having a carbon-nitrogen bond. The “high molecular weight substance” means a compound having a weight average molecular weight of 2,000 or more. In addition, in this specification, the value of a weight average molecular weight (Mw) is the value calculated|required by standard polystyrene conversion using tetrahydrofuran (THF) by the gel permeation chromatograph (GPC) method.

Examples of the photopolymerizable functional group contained in the high molecular weight component (A) include (meth)acryloyl groups; ethylenically unsaturated groups such as alkenyl groups such as vinyl groups and allyl groups. From the viewpoint of improving the pattern formability and bottom thinning phenomenon suppression performance, the component (A) may include a high molecular weight compound having a (meth)acryloyl group as a photopolymerizable functional group, and further, a urethane as a carbon-nitrogen bond. A high molecular weight compound having a bond may be included. Examples of the high molecular weight body having a (meth)acryloyl group as a photopolymerizable functional group include (meth)acrylate, and further examples of the high molecular weight body having a urethane bond as a carbon-nitrogen bond include urethane (meth)acrylate. To be
Further, the component (A) may include a high molecular weight substance having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton.

The component (A) has at least one of these photopolymerizable functional groups and at least one carbon-nitrogen bond. In addition, the total number of photopolymerizable functional groups (the number of functional groups) contained in the high molecular weight component (A) is 2 to 1 in one molecule from the viewpoint of pattern formability, bottom thinning phenomenon suppression performance, and heat resistance improvement. 15, and from the viewpoint of stabilizing the physical properties and characteristics of the obtained cured product, it may be appropriately selected from 2 to 12, or 2 to 10.

Examples of the urethane (meth)acrylate as the component (A) include reaction products 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, their ethoxylated products, their propoxylated products, their ethoxylated propoxylated products, and their caprolactone modified products; trimethylol Bifunctional (meth)acrylates such as propane di(meth)acrylate, glycerin di(meth)acrylate, bis(2-(meth)acryloyloxyethyl)(2-hydroxyethyl)isocyanurate, their ethoxylated products, these , A propoxylated product thereof, an ethoxylated propoxylated product thereof, and a caprolactone modified product 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(meth)acrylate, bisphenol F type Bifunctional epoxy (meth)acrylates such as epoxy di(meth)acrylate, bisphenol AF type epoxy di(meth)acrylate, biphenol type epoxy di(meth)acrylate, fluorene bisphenol type epoxy di(meth)acrylate, isocyanuric acid monoallyl type epoxy di(meth)acrylate, etc. Trifunctional or higher functional (meth)acrylates such as ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and ethoxylation thereof Body, propoxylated products thereof, ethoxylated propoxylated products thereof, and caprolactone-modified products thereof; Trifunctional or more functional epoxy (meth)acrylates such as enol novolac type epoxy (meth)acrylate, cresol novolac type epoxy poly(meth)acrylate, isocyanuric acid type epoxy tri(meth)acrylate; trimethylolpropane tri(meth)acrylate, ditri Examples thereof include hydroxypropylated products such as methylolpropane tetra(meth)acrylate.
These may be used alone or in combination of two or more.

Here, the ethoxylated product, the propoxylated product, the ethoxylated propoxylated product, and the hydroxypropylated product of (meth)acrylate are each, for example, an alcohol compound (or a phenol compound) which 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 a hydroxypropyl group added.
The caprolactone modified product is obtained, for example, by using, as a raw material, a product obtained by modifying an alcohol compound (or a phenol compound), which is a raw material of the (meth)acrylate, with ε-caprolactone.

The isocyanate compound having an isocyanate group includes a compound having at least one isocyanate group in one molecule, and may be a compound having 1 to 3 isocyanate groups in one molecule. More specifically, aliphatic monoisocyanate compounds such as ethyl isocyanate, propyl isocyanate, butyl isocyanate, octadecyl isocyanate, 2-isocyanate ethyl (meth)acrylate; alicyclic monoisocyanate compounds such as cyclohexyl isocyanate; aromatics such as phenyl isocyanate. Aliphatic diisocyanate compounds such as monoisocyanate compounds such as group monoisocyanate compounds, 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-isocyanato) Alicyclic diisocyanate compounds such as cyclohexyl)propane, 2,2-bis(4-isocyanatocyclohexyl)hexafluoropropane, bicycloheptane triisocyanate; 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6 -Aromatic aromatic compounds such as tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, hydrogenated xylylene diisocyanate, naphthalene-1,5-diisocyanate Examples thereof include diisocyanate compounds such as diisocyanate compounds, and multimers of these diisocyanate compounds such as uretdione type dimers, isocyanurate type and biuret type trimers. These may be used alone or in combination of two or more, and the two or three isocyanate compounds constituting the multimer may be the same or different.

Among them, from the viewpoint of improving the pattern formability and bottom thinning phenomenon suppression performance, an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, a diisocyanate compound such as an aromatic diisocyanate compound, and a multimer of these diisocyanate compounds may be appropriately selected. , Especially 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 It may be appropriately selected from isocyanurate type multimers (isocyanurate type polyisocyanate).

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

The high molecular weight urethane (meth)acrylate of the component (A) is, for example, an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound from the viewpoint of improving pattern formability and bottom thinning phenomenon suppressing performance. A reaction product obtained by reacting a (meth)acrylate having a hydroxyl group with the terminal isocyanate group of the polyaddition product of

The isocyanate compound having at least two isocyanate groups in one molecule, as used herein, is a diisocyanate compound such as an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, or an aromatic diisocyanate compound among the compounds exemplified as the above isocyanate compound. Further, multimers such as uretdione type dimers, isocyanurate type and biuret type trimers of these diisocyanate compounds can be mentioned.
The above isocyanate compounds can be used alone or in combination of two or more.

Examples of the diol compound include diol compounds having 1 to 20 carbon atoms, and specific examples include ethylene glycol, diethylene glycol, propanediol, dipropylene glycol, butanediol, pentanediol, isopentyl glycol, and hexanediol. , Linear or branched saturated diol compounds such as nonanediol, decanediol, dodecanediol, dimethyldodecanediol, octadecanediol; butenediol, pentenediol, hexenediol, methylpentenediol, dimethylhexenediol, etc. Or branched unsaturated diol compounds; various cyclohexanediols, various cyclohexanedimethanol, various tricyclodecanedimethanol, diol compounds having an alicyclic skeleton such as hydrogenated bisphenol A, hydrogenated bisphenol F, and the like. .. Here, the saturated diol compound and the unsaturated diol compound can be collectively referred to as a diol compound having a chain hydrocarbon skeleton.
The above diol compounds can be used alone or in combination of two or more.

The diol compound having a chain hydrocarbon skeleton has a carbon number of 1 from the viewpoint of improving the pattern formability and the ability to suppress the bottom thinning phenomenon, and increasing the glass transition point (Tg) after polymerization to improve the water resistance. -20, 2-16, and 2-14 saturated diol compounds may be appropriately selected, and more specifically, ethylene glycol and octadecanediol may be appropriately selected.
In addition, as the diol compound having an alicyclic skeleton, from the viewpoint of improving the pattern formability and the performance of suppressing the bottom thinning phenomenon, and increasing the glass transition point (Tg) after polymerization to improve the water resistance, It may be appropriately selected from diol compounds having an alicyclic skeleton of 5 to 20, 5 to 18 and 6 to 16, and more specifically, various cyclohexanes such as 1,3-cyclohexanediol and 1,4-cyclohexanediol. It may be appropriately selected from various cyclohexanedimethanols such as diol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol.

Moreover, as the (meth)acrylate having a hydroxyl group used here, 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 are exemplified. Can be mentioned.

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

In the general formula (1), X ₁ represents a divalent organic group having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton, and Y ₁ represents a chain hydrocarbon skeleton or an alicyclic skeleton. The divalent organic group contained therein is shown. Further, when the component (A) has a plurality of the structural units, a plurality of X ₁ and Y ₁ may be the same or different. That is, examples of the component (A) include those having at least one kind of skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton.

The divalent organic group of X ₁ is an organic group derived from the aliphatic diisocyanate compound, the alicyclic diisocyanate compound, and the aromatic diisocyanate compound exemplified as the compound having the above isocyanate group, that is, from the above isocyanate compound. Examples thereof include a divalent organic group having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton, which is a residue excluding the isocyanate group. The divalent organic group represented by X ₁ may be these residues themselves or residues derived from an isocyanate compound derivative such as a 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 the pattern formability and bottom thinning phenomenon suppressing performance, and improving the transparency, water resistance, and moisture resistance of the resin composition in a well-balanced manner. Above all, it may be a divalent organic group having an alicyclic skeleton, which is a residue of isophorone diisocyanate represented by the following formula (2).

The divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton of Y ₁ is a diol compound having a chain hydrocarbon skeleton and a diol having an alicyclic skeleton, which are exemplified as the above-mentioned diol compound. Examples thereof include a compound-derived organic group, that is, a divalent organic group having a chain hydrocarbon skeleton or an alicyclic skeleton, which is a residue obtained by removing a hydroxyl group from the above diol compound.
Among them, as a divalent organic group having a chain hydrocarbon skeleton, from the viewpoints of improving the pattern formability and the bottom thinning phenomenon suppressing performance, and increasing the glass transition point (Tg) after polymerization to improve the water resistance. May be appropriately selected from a residue obtained by removing a hydroxyl group from a saturated diol compound having 1 to 20, 2 to 16, and 2 to 14 carbon atoms, and more specifically, a residue obtained by removing a hydroxyl group from ethylene glycol or octadecanediol. It may be appropriately selected from the groups. From the same viewpoint, the divalent organic group having an alicyclic skeleton is the residue obtained by removing a hydroxyl group from a diol compound having an alicyclic skeleton having 5 to 20, 5 to 18, and 6 to 16 carbon atoms. It may be appropriately selected from the groups, and more specifically, various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and the like. It may be appropriately selected from residues obtained by removing a hydroxyl group from various cyclohexanedimethanols.

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

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

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

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

Examples of commercially available products containing the urethane acrylate having the structural unit represented by the general formula (1) include UN-333 (functional group number: 2, Mw: 5,000), UN-1255 (functional group number: 2, Mw: 8,000), UN-904 (functional group number: 10, Mw: 4,900), UN-2600 (functional group number: 2, Mw: 2,500), UN-6200 (functional group number: 2, Mw: 6,500), UN-9000PEP (functional group number: 2, Mw: 5,000), UN-9200A (functional group number: 2, Mw: 15,000), UN-3320HS (functional group number: 15, Mw: 4,). 900), UN-6301 (functional group number: 2, Mw: 33,000) (all above are trade names, manufactured by Negami Kogyo Co., Ltd.), EBECRYL8405 (urethane acrylate/1,6-hexanediol diacrylate=80/ 20 addition reaction products, the number of functional groups: 4, Mw: 2,700) (trade name, manufactured by Daicel-Ornex Co., Ltd.) and the like.
Moreover, as a commercially available product containing a urethane methacrylate having a structural unit represented by the general formula (1), for example, UN-6060PTM (functional group number: 2, Mw: 6,000, trade name, Negami Kogyo Co., Ltd.) Manufactured) and the like. In the above description, the number of functional groups in parentheses and Mw are the total number of (meth)acryloyl groups contained in urethane (meth)acrylate and the weight average molecular weight, respectively.

Moreover, as a commercial item containing the urethane (meth)acrylate represented by the above general formula (3), for example, UN-952 (functional group number: 10, Mw: 6,500 to 11,000) is represented by the general formula ( Examples of commercially available products containing the urethane (meth)acrylate represented by 6) include UN-905 (functional group number: 15, Mw: 40,000 to 200,000) and the like (the above are all trade names. , Manufactured by Negami Industry Co., Ltd.).
Among them, UN-952 is particularly preferable from the viewpoints of pattern formability, bottom thinning phenomenon suppressing performance, and photosensitivity.

The total number of (meth)acryloyl groups (the number of functional groups) contained in the urethane (meth)acrylate of the component (A) is 2 to 1 in one molecule from the viewpoint of pattern formability, bottom thinning phenomenon suppressing performance, and heat resistance improvement. 15, and from the viewpoint of stabilizing the physical properties and characteristics of the obtained cured product, it may be appropriately selected from 2 to 12, or 2 to 10.
When the number of functional groups is 2 or more, the heat resistance and the rigidity of the cured product at high temperature can be improved, as well as the pattern formability and the performance of suppressing the bottom thinning phenomenon. On the other hand, when the number of functional groups is 15 or less, the rigidity of the cured product is improved and the adhesion to the substrate or the like is improved. Further, a resin composition having an appropriate viscosity can be obtained, the coating property is improved, and when the resin composition after coating is irradiated with light, only the surface portion is easily photocured rapidly and Can suppress the phenomenon that the photo-curing does not proceed sufficiently and can obtain an excellent resolution. Therefore, even when a thick photosensitive layer is formed, excellent pattern formability and bottom thinning phenomenon suppressing performance can be obtained. Furthermore, after performing at least one of photo-curing and heat-curing, the unreacted (meth)acryloyl group remains less, and it is possible to further suppress variations in the physical properties and characteristics of the resulting cured product.

The weight average molecular weight of the high molecular weight component (A) is 2,000 or more, and may be 2,500 or more from the viewpoint of improving the coatability and resolution of the resin composition. From the viewpoint of improving the solubility, it may be 3,000 or more. On the other hand, the upper limit of the weight average molecular weight may be 40,000 or less, or 30,000 or less from the viewpoint of improving the coating property and resolution of the resin composition, and further, the developability and compatibility From the viewpoint of improvement, it may be 20,000 or less.
When the weight average molecular weight is 2,000 or more, it is possible to suppress the occurrence of dripping of the applied composition when applied on a substrate, and thus excellent pattern formability can be obtained. In addition, it is possible to easily form a thick photosensitive layer, and it is possible to suppress the problem that the stress of the resin due to curing shrinkage increases and the reliability decreases.
On the other hand, when the weight average molecular weight is 40,000 or less, the coatability is improved, the thick photosensitive layer is easily formed, and the pattern formability and the bottom thinning phenomenon suppression performance are improved. Further, since the solubility in the developing solution is also good, excellent resolution can be exhibited. Furthermore, the transparency of the cured product is improved, and a cured product having an excellent transmittance required as a transparent material can be obtained.

The content of the component (A) may be appropriately selected from 10% by mass or more, 30% by mass or more, or 50% by mass or more based on the total solid content of the photosensitive resin composition. When the content is 10% by mass or more, the coatability is improved, and even when a thick photosensitive layer is formed, excellent pattern formability and bottom thinning phenomenon suppression performance can be obtained.
Considering the pattern moldability and coatability of the obtained resin composition, and the physical properties and characteristics required for the cured product of the resin composition, the upper limit of the content of the component (A) is the solid content of the photosensitive resin composition. It may be appropriately selected from 95 mass% or less, 85 mass% or less, or 75 mass% or less based on the total amount.
Further, the content of the urethane (meth)acrylate in the component (A) is 70 to 100% by mass based on the total solid content of the component (A) from the viewpoint of improving pattern formability and performance of suppressing bottom thinning phenomenon. , 80 to 100% by mass, 90 to 100% by mass, 95 to 100% by mass, or 100% by mass (total amount).

<(B) component: low molecular weight substance>
The photosensitive resin composition of this embodiment contains a low molecular weight compound having a photopolymerizable functional group and a carbon-nitrogen bond as the component (B). By "low molecular weight" is meant a compound having a weight average molecular weight of less than 2,000.

As the photopolymerizable functional group of the low molecular weight component (B), the same as the photopolymerizable functional group of the high molecular weight component (A), a (meth)acryloyl group; an alkenyl such as an allyl group or a vinyl group. Examples thereof include ethylenically unsaturated groups such as groups. From the viewpoint of improving the pattern formability and bottom thinning phenomenon suppression performance, the component (B) may include a high molecular weight compound having a (meth)acryloyl group as a photopolymerizable functional group, and further, a urethane as a carbon-nitrogen bond. A high molecular weight compound having a bond may be included. Examples of the high molecular weight body having a (meth)acryloyl group as a photopolymerizable functional group include (meth)acrylate, and further examples of the high molecular weight body having a urethane bond as a carbon-nitrogen bond include urethane (meth)acrylate. To be When the low molecular weight component (B) has a photopolymerizable functional group and a carbon-nitrogen bond, it can function as a chain transfer agent for radical polymerization, and has excellent pattern formability and bottom thinning phenomenon suppressing performance. Can be obtained.

The component (B) has at least one of these photopolymerizable functional groups and at least one carbon-nitrogen bond. In addition, the total number of photopolymerizable functional groups (the number of functional groups) contained in the low molecular weight component (B) is 2 to 1 in one molecule from the viewpoint of pattern formability, bottom thinning phenomenon suppressing performance, and heat resistance improvement. 15, and from the viewpoint of stabilizing the physical properties and characteristics of the obtained cured product, it may be appropriately selected from 2 to 12, or 2 to 10.

Examples of the low molecular weight urethane (meth)acrylate as the component (B) include a reaction product of a (meth)acrylate having a hydroxyl group and an isocyanate compound having an isocyanate group. Here, as the (meth)acrylate having a hydroxyl group and the isocyanate compound, there may be mentioned the (meth)acrylate having a hydroxyl group and the isocyanate compound exemplified as those used for the production of the high molecular weight substance. Here, from the viewpoints of improving the pattern formability and the bottom thinning phenomenon suppressing performance, etc., the same ones as those appropriately selected as those used for producing the high molecular weight polymer from the same viewpoint are exemplified.

Further, as the low molecular weight urethane (meth)acrylate, a terminal (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. The reaction product thus obtained is included. 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, the isocyanate group in one molecule exemplified as those used for producing a high molecular weight compound Examples thereof include an isocyanate compound having at least two, a diol compound, and a (meth)acrylate having a hydroxyl group. Here, from the viewpoints of improving the pattern formability and the bottom thinning phenomenon suppressing performance, etc., the same ones as those appropriately selected as those used for producing the high molecular weight polymer from the same viewpoint are exemplified.
Examples of this reaction product include those having a structural unit represented by the following general formula (7).

In the general formula (7), X ₂ represents a divalent organic group having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton, and Y ₂ represents a chain hydrocarbon skeleton or an alicyclic skeleton. The divalent organic group contained therein is shown. That is, examples of the component (B) include those having at least one kind of 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 those of X ₁ and Y ₁ in the general formula (1).
From the viewpoint of improving the pattern formability and the bottom thinning phenomenon suppressing performance, and also improving the transparency, water resistance, and moisture resistance of the resin composition in a well-balanced manner, X ₂ is a divalent one having a chain hydrocarbon skeleton. It may be appropriately selected from an organic group, a divalent organic group having a branched chain hydrocarbon skeleton, and a branched alkylene group having 2 to 12 carbon atoms, for example, the residue of the above 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 urethane (meth)acrylate that can be used as the component (B) include compounds represented by the following general formula (8).

In the general formula (8), n ₅ represents an integer of 1 to 4. R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a plurality of R ⁴ and R ⁵ are each an alkyl group having at least 3 carbon atoms. .. In the urethane (meth)acrylate represented by the general formula (8), X _{2 in the} general formula (7) is a residue of trimethylhexamethylene diisocyanate, which is a divalent organic group having a chain hydrocarbon skeleton. As a commercially available product containing urethane (meth)acrylate, in which Y ₂ has a structural unit which is a residue of cyclohexanedimethanol having a divalent organic group having an alicyclic skeleton, for example, TMCH-5R (trade name) , Functional group number: 2, Mw: 950, manufactured by Hitachi Chemical Co., Ltd., and the like.
In addition, as a commercial product containing a urethane (meth)acrylate having a structural unit represented by the above general formula (7), KRM8452 (functional group number: 10, Mw: 1,200, manufactured by Daicel Ornex Co., Ltd.), UN-3320HA (functional group number: 6, Mw: 1,500), UN-3320HC (functional group number: 6, Mw: 1,500, manufactured by Negami Kogyo Co., Ltd.) and the like. In the above description, the number of functional groups and Mw in parentheses are the number of functional groups and the weight average molecular weight of urethane (meth)acrylate, respectively.

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

The content of the component (B) based on the total solid content of the photosensitive resin composition may be appropriately selected from 3% by mass or more, 5% by mass or more, 10% by mass or more, or 20% by mass or more. .. When the content is 3% by mass or more, excellent pattern formability and bottom thinning phenomenon suppressing performance can be obtained even when a thick photosensitive layer is formed, and excellent cured product rigidity can also be obtained. From the same viewpoint as this, the upper limit of the content of the component (B) is appropriately 70% by mass or less, 50% by mass or less, or 40% by mass or less based on the total solid content of the photosensitive resin composition. Just select it.
The content of the component (B) based on the total solid content of the component (A) is 25 to 90% by mass and 30 to 80% by mass from the viewpoint of improving pattern formability, bottom thinning phenomenon suppressing performance, and cured product rigidity. It may be appropriately selected from mass% or 35 to 65 mass %.
The content of the low molecular weight product having a (meth)acryloyl group as a photopolymerizable functional group based on the total solid content of the component (B) is 70% by mass or more, 80% by mass or more, 90% by mass or more. Alternatively, it may be appropriately selected from 95% by mass or more. When the content is 70% by mass or more, excellent pattern formability and bottom thinning phenomenon suppressing performance can be obtained even when a thick photosensitive layer is formed, and excellent cured product rigidity can also be obtained. From the same viewpoint as this, the upper limit of the content of the low molecular weight compound having an acryloyl group as a photopolymerizable functional group is 100% by mass or less, and 100% by mass, that is, the total amount of the component (B) is photopolymerizable. It may have a (meth)acryloyl group as a functional group.

<Component (C): Photopolymerizable compound having no carbon-nitrogen bond>
The photosensitive resin composition of the present embodiment contains a photopolymerizable compound having no carbon-nitrogen bond as the component (C). Since the photosensitive resin composition contains the component (C), light easily passes to the bottom of the photosensitive layer (the surface of the photosensitive layer on the substrate side) even when a pattern is formed in a photosensitive layer having a thickness of 70 μm or more. Therefore, the pattern formability and the bottom thinning phenomenon suppression performance can be improved. Further, if the photopolymerizable compound as the component (C) has a carbon-nitrogen bond, the pattern formability and the bottom thinning phenomenon suppressing performance cannot be obtained at the same time.

Examples of the photopolymerizable compound as the component (C) include compounds having a photopolymerizable functional group.
Examples of the photopolymerizable functional group contained in the component (C) include (meth)acryloyl group; alkenyl groups such as allyl group and vinyl group, as in the photopolymerizable functional groups contained in the components (A) and (B). And an ethylenically unsaturated group of From the viewpoint of improving the pattern formability and the bottom thinning phenomenon suppressing performance, the component (C) may contain a photopolymerizable compound having a (meth)acryloyl group as a photopolymerizable functional group, and as the photopolymerizable functional group, Is (meth)acrylate.

The component (C) has at least one of these photopolymerizable functional groups. The total number of photopolymerizable functional groups (the number of functional groups) contained in the photopolymerizable compound of the component (C) is 1 to 12 in one molecule from the viewpoint of pattern formability, bottom thinning phenomenon suppressing performance, and heat resistance improvement. Further, from the viewpoint of stabilizing the physical properties and characteristics of the obtained cured product, it may be appropriately selected from 2 to 6, 2 to 4, or 2 to 3.

Examples of the photopolymerizable compound as the component (C) include various propyl (meth)acrylates of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate (hereinafter, linear chain). , Branched, and (meth) acrylates having a predetermined carbon number including these isomers may be abbreviated as various.), various butyl (meth) acrylates, various pentyl (meth) acrylates, Various hexyl (meth)acrylates, various heptyl (meth)acrylates, various octyl (meth)acrylates, various nonyl (meth)acrylates, various decyl (meth)acrylates, various undecyl (meth)acrylates, various lauryl (meth)acrylates, various The carbon number of tridecyl (meth)acrylate, various tetradecyl (meth)acrylates, various pentadecyl (meth)acrylates, various hexadecyl (meth)acrylates, various stearyl (meth)acrylates, various behenyl (meth)acrylates, etc. is 2 to 24, or , 2 to 20 aliphatic mono(meth)acrylates; butoxyethyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, hydroxybutyl( Having in its molecule an oxygen atom derived from a functional group other than a (meth)acryloyl group such as a hydroxyl group such as (meth)acrylate, mono(2-(meth)acryloyloxyethyl)succinate, or the like, having 5 to 24 carbon atoms, or , 5 to 20 aliphatic mono(meth)acrylates; methoxypolyethylene glycol (meth)acrylate, ethoxypolyethyleneglycol (meth)acrylate, methoxypolypropyleneglycol (meth)acrylate, ethoxypolypropyleneglycol (meth)acrylate, etc. 9-80 or 9-60 polyalkylene glycol mono(meth)acrylate; cyclocyclopentyl(meth)acrylate, chlorhexyl(meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentenyl(meth)acrylate, isobornyl (Meth)acrylate, mono(2-(meth)acryloyloxyethyl)tetrahydrophthalate, mono(2-(meth)acryloyloxyethyl)hexahydrophthalate and the like having 8 to 24 carbon atoms or 8 to 20 alicyclic rings Formula mono(meth)acrylate; phenyl(meth)acrylate, benzyl(meth)acrylate, biphenyl(meth)acrylate, naphthyl(meth)acrylate, naphthyl(meth)acrylate, phenoxyethyl(meth)acrylate, cumylphenoxyethyl(meth ) Acrylate, phenylphenoxyethyl (meth)acrylate, naphthoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, phenoxypolypropylene glycol (meth)acrylate, hydroxyphenoxypropyl (meth)acrylate, 2-hydroxy-3-(o-phenylphenoxy)propyl(meth)acrylate, 2-hydroxy-3-(1-naphthoxy)propyl(meth)acrylate, 2-hydroxy-3-(2-naphthoxy)propyl(meth) Examples thereof include mono(meth)acrylates having one (meth)acryloyl group in the molecule, such as aromatic mono(meth)acrylates having 9 to 24 carbon atoms such as acrylate or 9 to 20 carbon atoms.

Examples of the photopolymerizable compound as the component (C) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di. Carbon such as (meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate Number 10-80 or 10-60 aliphatic alkylene glycol di(meth)acrylate and alkylene oxide-modified products thereof (for example, EO-modified polypropylene glycol di(meth)acrylate); butanediol di(meth)acrylate , Neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, hexanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di( An aliphatic polyol di(meth)acrylate having 10 to 24 carbon atoms or 10 to 20 carbon atoms such as (meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, glycerin di(meth)acrylate; 12 to 30 carbon atoms such as cyclohexanedimethanol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, hydrogenated bisphenol A type di(meth)acrylate, hydrogenated bisphenol F type di(meth)acrylate, or the like. , 12 to 24 alicyclic di(meth)acrylate, and modified products of these alkylene oxides (for example, when the alicyclic (meth)acrylate is cyclohexanedimethanol di(meth)acrylate, EO-modified cyclohexanedimethanol). Di(meth)acrylate, PO-modified cyclohexanedimethanol di(meth)acrylate, EO/PO-modified cyclohexanedimethanol di(meth)acrylate, etc.; EO-modified bisphenol A type di(meth)acrylate, PO-modified bisphenol A type di( (Meth)acrylate, EO/PO modified bisphenol A type di(meth)acrylate, EO modified bisphenol F type di(meth)acrylate, PO modified bisphenol F type di(meth)acrylate, EO/PO modified Bisphenol F type di(meth)acrylate, EO-modified bisphenol AF type di(meth)acrylate, PO-modified bisphenol AF type di(meth)acrylate, EO/PO-modified bisphenol AF type di(meth)acrylate, EO-modified fluorene type di( Aromatic di(meth)acrylates such as (meth)acrylate, PO-modified fluorene type di(meth)acrylate, EO/PO-modified fluorene type di(meth)acrylate; EO-modified isocyanuric acid di(meth)acrylate, PO-modified isocyanuric acid di Heterocyclic di(meth)acrylates such as (meth)acrylate, EO/PO-modified isocyanuric acid di(meth)acrylate, and caprolactone-modified products thereof; Aliphatic epoxy di(meth)acrylates such as neopentyl glycol type epoxy di(meth)acrylate ) Acrylate; alicyclic epoxy di(meth)acrylate such as cyclohexanedimethanol type epoxy di(meth)acrylate, hydrogenated bisphenol A type epoxy di(meth)acrylate, hydrogenated bisphenol F type epoxy di(meth)acrylate; resorcinol type epoxy di(meth) ) Molecules such as acrylate, aromatic epoxy di(meth)acrylates such as bisphenol A type epoxy di(meth)acrylate, bisphenol F type epoxy di(meth)acrylate, bisphenol AF type epoxy di(meth)acrylate, fluorene type epoxy di(meth)acrylate Among them are di(meth)acrylates having two (meth)acryloyl groups.

In addition, for example, EO-modified isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tri(2-(meth)acryloyloxyethyl)isocyanurate, etc. Tri(meth)acrylate having three (meth)acryloyl groups in the molecule; ditrimethylolpropane tetra(meth)acrylate, EO-modified pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. in the molecule. Tetra(meth)acrylate having four (meth)acryloyl groups; dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa Examples thereof include (meth)acrylates having 5 or more (meth)acryloyl groups in the molecule, such as (meth)acrylates.

Of these, commercially available products include, for example, hexanediol diacrylate (trade name: A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) and nonanediol diacrylate (commodity). Name: A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd., or trade name: FA-129AS, manufactured by Hitachi Chemical Co., Ltd., decanediol diacrylate (trade name: A-DOD-N, Shin-Nakamura Chemical Co., Ltd.) Industrial Co., Ltd.), tricyclodecane dimethanol diacrylate (trade name: A-DCP, Shin-Nakamura Chemical Co., Ltd.), EO-modified bisphenol A type diacrylate (trade name: FA-324A, Hitachi Chemical ( Co., Ltd.), EO-modified bisphenol A-type dimethacrylate (trade name: FA-321M, manufactured by Hitachi Chemical Co., Ltd.), etc., and di(meth)acrylate having two (meth)acryloyl groups in the molecule; EO-modified Isocyanuric acid triacrylate (trade name: A-9300, Shin-Nakamura Chemical Co., Ltd.), pentaerythritol tri(meth)acrylate (trade name: A-TMM-3, Shin-Nakamura Chemical Co., Ltd.), Tri(meth)acrylate having three (meth)acryloyl groups in the molecule, such as trimethylolpropane tri(meth)acrylate (trade name: A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.); Ditrimethylolpropane tetra (Meth)acrylate (trade name: AD-TMP, Shin-Nakamura Chemical Co., Ltd.), EO-modified pentaerythritol tetra(meth)acrylate (trade name: ATM-35E, Shin-Nakamura Chemical Co., Ltd.), Tetra(meth)acrylate having four (meth)acryloyl groups in the molecule, such as pentaerythritol tetra(meth)acrylate (trade name: A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.); dipentaerythritol Poly(meth)acrylate (trade name: A-9550, manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol hexa(meth)acrylate (trade name: A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.), Dipentaerythritol poly(meth)acrylate (trade name: A-9550, manufactured by Shin Nakamura Chemical Co., Ltd.), dipentaerythritol hexa(meth)acrylate (trade name: A-DPH, Shin Nakamura Chemical Co., Ltd. ()) and the like, and (meth)acrylates having 5 or more (meth)acryloyl groups in the molecule.

As the component (C), a photopolymerizable compound having an alicyclic skeleton, that is, the alicyclic mono(meth)acrylate and the alicyclic diamine described above are used from the viewpoint of improving the pattern formability and the performance of suppressing the bottom thinning phenomenon. It may be an alicyclic (meth)acrylate such as a (meth)acrylate, an alkylene oxide modified product thereof, or an alicyclic epoxy di(meth)acrylate, and among them, an alicyclic di(meth)acrylate Good. From the same viewpoint, the content of the photopolymerizable compound having an alicyclic skeleton is 10 parts by mass or more, 20 parts by mass or more, or 50 parts by mass with respect to 100 parts by mass of the solid content of the component (C). It may be appropriately selected from the parts by mass or more. When it is 10 parts by mass or more, the pattern formability tends to be improved. The upper limit of the photopolymerizable compound having an alicyclic skeleton may be 100 parts by mass or less.

The content of the component (C) based on the total solid content of the photosensitive resin composition may be appropriately selected from 1% by mass or more, 3% by mass or more, or 5% by mass or more. When the content is 1% by mass or more, excellent pattern formability and bottom thinning phenomenon suppressing performance can be obtained even when a thick photosensitive layer is formed, and excellent cured product rigidity can also be obtained. From the same viewpoint as this, the upper limit of the content of the component (C) is appropriately 30% by mass or less, 20% by mass or less, or 15% by mass or less based on the total solid content of the photosensitive resin composition. Just select it.

<(D) component: photopolymerization initiator>
The photosensitive resin composition of this embodiment contains a photopolymerization initiator as the component (D). The component (D) is not particularly limited as long as it is capable of polymerizing at least one of the component (A), the component (B), and the component (C). It can be appropriately selected. From the viewpoint of improving pattern formability, those that generate free radicals by actinic rays, for example, acylphosphine oxide-based, oxime ester-based, aromatic ketone-based, quinone-based, alkylphenone-based, imidazole-based, acridine-based, phenylglycine Examples thereof include photopolymerization initiators such as those based on coumarin and coumarin.

The acylphosphine oxide-based photopolymerization initiator has an acylphosphine oxide group (>P(=O)-C(=O)-group), and is, for example, (2,6-dimethoxybenzoyl)-2,4. ,6-Pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name: IRGACURE-TPO, manufactured by BASF), ethyl-2. ,4,6-Trimethylbenzoylphenylphosphineate, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (trade name: IRGACURE-819, manufactured by BASF), (2,5-dihydroxyphenyl)diphenylphosphine Oxides, (p-hydroxyphenyl)diphenylphosphine oxide, bis(p-hydroxyphenyl)phenylphosphine oxide, tris(p-hydroxyphenyl)phosphine oxide and the like can be mentioned.

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

Examples of the aromatic ketone photopolymerization initiator include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4 -Methoxy-4'-dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: IRGACURE-651, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)-butan-1-one (trade name: IRGACURE-369, manufactured by BASF), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one (Trade name: IRGACURE-907, manufactured by BASF) 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, and 2phenylanthraquinone. , 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone and 2,3-dimethylanthraquinone. To be

Examples of the alkylphenone-based photopolymerization initiator include benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin phenyl ether; 2,2-dimethoxy-1,2-diphenylethane-1- ON (trade name: IRGACURE-651, manufactured by BASF), 1-hydroxy-cyclohexyl-phenyl ketone (trade name: IRGACURE-184, manufactured by BASF), 2-hydroxy-2-methyl-1-phenylpropane-1- ON (trade name: IRGACURE-1173, manufactured by BASF), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (trade name: IRGACURE-2959) , Manufactured by BASF), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropan-1-one (trade name: IRGACURE-127, BASF Corporation) and the like.

Examples of the imidazole-based photopolymerization initiator 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 and other 2-(o-chlorophenyl)-4,5-diphenylimidazole dimers, 2-(o-chlorophenyl)-4,5- Di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2- (P-Methoxyphenyl)-4,5-diphenylimidazole dimer and the like.

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

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

Examples of the coumarin-based photopolymerization initiator include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin. , 7-ethylamino-4-methylcoumarin, 7-dimethylaminocyclopenta[c]coumarin, 7-aminocyclopenta[c]coumarin, 7-diethylaminocyclopenta[c]coumarin, 4,6-dimethyl-7-. Ethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin , 4,6-Diethyl-7-dimethylaminocoumarin, 2,3,6,7,10,11-hexanehydro-1H,5H-cyclopenta[3,4][1]benzopyrano-[6,7,8- ij]Quinolidin 12(9H)-one, 7-diethylamino-5′,7′-dimethoxy-3,3′-carbonylbiscoumarin, 3,3′-carbonylbis[7-(diethylamino)coumarin], 7-diethylamino -3-Thienoxy silk marine etc. are mentioned.

From the viewpoint of improving photocurability, sensitivity, and pattern formability, it can be appropriately selected from acylphosphine oxide-based photopolymerization initiators. The said (D)component can be used individually or in combination of 2 or more types. As the component (D), those synthesized by a usual method may be used, or commercially available products may be obtained and used.

The content of the component (D) is such that the absorbance at a wavelength of 365 nm at a thickness of the photosensitive layer formed by the photosensitive resin composition (thickness after drying) of 50 μm is 0.35 or less, 0.3 or less. The amount may be appropriately selected from the following amounts, an amount of 0.2 or less, or an amount of 0.1 or less. With the above content, for example, even when a pattern is formed with a thick photosensitive layer of 70 μm or more, light easily passes through to the bottom of the photosensitive layer (the surface of the photosensitive layer on the substrate side), so that the pattern is formed. It is possible to improve the sex. Here, the absorbance is, for example, using an ultraviolet-visible spectrophotometer (product name: U-3310 Spectrophotometer, manufactured by Hitachi High-Technologies Corporation), using a polyethylene terephthalate film alone as a reference, with respect to light having a wavelength of 365 nm. Absorbance can be measured. Further, the absorbance with respect to light having a wavelength of 365 nm when the thickness of the photosensitive layer is 50 μm can be obtained by converting the absorbance of the photosensitive layer having a thickness other than 50 μm into the absorbance of 50 μm based on Lambert-Beer's law.

In addition to the above component (D), N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like can be used. A photopolymerization initiation aid such as a primary amine can be used as the component (D'). These (D') components can be used alone or in combination of two or more kinds.

As described above, the content of the component (D) may be appropriately determined by the absorbance at a thickness of the photosensitive layer of 50 μm, and is usually 0.05 to 20% by mass based on the total solid content of the photosensitive resin composition. It may be appropriately selected from 0.1 to 10% by mass, 0.15 to 5% by mass, or 0.15 to 3% by mass. With the above content, the sensitivity of the photosensitive resin composition can be improved, deterioration of the resist shape can be suppressed, and pattern formability can be improved.

<(E) component: thermal radical polymerization initiator>
Further, the photosensitive resin composition of the present embodiment may further contain (E) a thermal radical polymerization initiator. The component (E) is not particularly limited and includes, for example, α,α′-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide and the like. Dialkyl peroxide; methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, and other ketone peroxides; 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 peroxyketals; p-menthane hydroperoxide and other hydroperoxides; octanoyl peroxide, lauroyl peroxide, stearyl peroxide, benzoyl peroxide and other diacyl peroxides Oxide; peroxy such as bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-3-methoxybutylperoxycarbonate Carbonate; t-butylperoxypivalate, t-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-Ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylper Oxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurylate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate Peroxides such as peroxyesters such as, t-butylperoxybenzoate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane and t-butylperoxyacetate Polymerization initiator; 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2' Examples thereof include azo-based polymerization initiators such as -azobis(4-methoxy-2'-dimethylvaleronitrile).

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

When the component (E) is contained, its content is 0.1 to 10% by mass, 0.2 to 5% by mass, or 0.3 to 3% by mass based on the total solid content of the photosensitive resin composition. It may be appropriately selected from %. With 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 may contain the component (F) for the purpose of further improving various properties such as adhesion between the photosensitive resin composition and the substrate, heat resistance, and rigidity of the cured product. it can.
Examples of the component (F) include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), silicon nitride (Si ₃ N ₃ ). 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) and the like can be used. These inorganic fillers may be used alone or in combination of two or more.

The average particle size of the component (F) may be appropriately selected from 0.01 to 3 μm, 0.01 to 2 μm, or 0.02 to 1 μm from the viewpoint of improving adhesiveness, heat resistance, and rigidity of the cured product. Good. Here, the average particle size of the component (F) is the average particle size of the inorganic filler dispersed in the photosensitive resin composition, and is a value obtained by the following measurement. First, after diluting (or dissolving) the photosensitive resin composition by 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 accordance with the above, particles having a refractive index of 1.38 and dispersed in a solvent are measured, and the particle diameter at an integrated value of 50% (volume basis) in the particle size distribution is taken as the average particle diameter. 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 1,000 times (volume ratio) with the solvent as described above (or It can be measured by using the submicron particle analyzer described above after the dissolution.

The content of the component (F) may be appropriately selected from the upper limit of 10% by mass or less, 5% by mass or less, or 1% by mass or less, and the lower limit of 0, based on the total solid content of the photosensitive resin composition. It may be appropriately selected from more than mass% and may be 0 mass% (not included). Thus, by substantially not containing the component (F), the permeability of the photosensitive resin composition is improved, and for example, even when a pattern is formed with a thick photosensitive layer of 70 μm or more, the photosensitive layer Since it becomes easy for light to properly pass through to the bottom (the surface of the photosensitive layer on the side of the substrate), pattern formability is improved.

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

The silane coupling agent can improve the adhesiveness of the electronic component to the substrate, and particularly 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, aminopropyltrimethoxysilane, aminopropyltriethoxysilane and other amine-based alkoxysilanes, glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidoxypropyl Examples thereof include glycidoxy group-containing alkoxysilanes such as methyldiisopropenoxysilane. These may be used alone or in combination of two or more.
From the viewpoint of further improving adhesiveness, (meth)acryloxypropyltrimethoxysilane, (meth)acryloxypropylmethyldimethoxysilane, and other (meth)acryloyl group-containing alkoxysilanes, glycidoxypropyltrimethoxysilane, glycidoxy A silane coupling agent having an ethylenically unsaturated group in the molecule such as glycidoxy group-containing alkoxysilane such as propylmethyldiethoxysilane and glycidoxypropylmethyldiisopropenoxysilane may be used.

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

As the heat-resistant high molecular weight material, for example, from the viewpoint of improving processability, it has high heat resistance and is used as an engineering plastic, polyoxazole and their precursors, phenol novolac, novolac resins such as cresol novolac, and polyamide. Examples thereof include imide and polyamide. These may 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, from the group consisting of an epoxy resin, a phenol resin substituted at the α-position with a methylol group, an alkoxymethyl group, a methylol group and an alkoxymethyl group at the N-position. Examples include melamine resins and urea resins substituted with at least one selected. These may be used alone or in combination of two or more.

The adhesion aid can be used as desired in order to improve the adhesion between the photosensitive resin composition and the substrate. For example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, triethoxysilylpropylethylcarbamate, 3-(triethoxysilyl)propylsuccinic acid Acid anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 2-(3 , 4-epoxycyclohexyl)ethyltrimethoxysilane and the like. These may be used alone or in combination of two or more.

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

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

The amount of the diluent to be used may be appropriately selected from the amount such that the total solid content of the photosensitive resin composition is 50 to 90% by mass, 60 to 80% by mass, or 65 to 75% by mass. That is, when the diluent is used, the content of the diluent in the photosensitive resin composition may be appropriately selected from 10 to 50% by mass, 20 to 40% by mass, or 25 to 35% by mass. When the amount of the diluent used is within the above range, the coatability of the photosensitive resin composition is improved and it becomes possible to form a finer pattern.
Further, for example, when a photosensitive layer having a thickness of 70 μm or more is to be formed, the viscosity of the photosensitive resin composition at 25° C. is 0.5 to 20 Pa·s, in consideration of the ease of forming the photosensitive layer, or The amount can be 1 to 10 Pa·s.

The photosensitive resin composition of the present embodiment comprises a roll mill, the components (A) to (D), the component (E), the component (F), other additives and diluents which are used as desired. It can be obtained by uniformly kneading and mixing with a bead mill or the like.

The photosensitive resin composition of this embodiment may be used in the form of 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 inkjet method, and a dip coating method. Various coating methods can be used. Among these, a printing method or a spin coating method may be appropriately selected from the viewpoint of forming a thick photosensitive layer more easily.
When it is used as a film, it can be used, for example, in the form of a photosensitive resin film described later, and in this case, a photosensitive layer having a desired thickness can be formed by laminating using a laminator or the like.

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

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

The photosensitive resin film of the present embodiment, for example, a photosensitive resin composition of the present embodiment is applied on a carrier film by the above various coating methods to form a coating film, and the coating film is dried. , A photosensitive layer can be formed and manufactured. When the photosensitive resin composition of the present embodiment contains a diluent, at least a part of the diluent may be removed during drying.

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

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

The thickness of the photosensitive layer may be appropriately selected from 1 to 500 μm, 10 to 300 μm, or 30 to 100 μm. By setting the thickness to 30 μm or more, for example, in the case of forming a photosensitive layer having a thickness of 150 μm or more, the number of operations such as lamination can be further reduced, and by setting the thickness to 100 μm or less, the photosensitive resin film is wound around the core. It is possible to further reduce the deformation of the photosensitive layer due to the stress difference between the inner side and the outer side of the winding core. Considering the effect of the photosensitive resin composition of the present embodiment that excellent pattern formability can be obtained even when a thick photosensitive layer is formed, it may be 70 μm or more, and a thickness of more than 100 μm. It may be. Note that the photosensitive layer having a thickness of 70 μm or more is, for example, a carrier film formed by laminating a photosensitive layer formed on a carrier film and a photosensitive layer formed on a protective layer described below, A photosensitive resin film having a thick photosensitive layer and a protective layer in this order can be obtained.

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

[Cured product manufacturing method]
The method for producing a cured product of the present embodiment includes a step of forming a photosensitive layer on the substrate using the photosensitive resin composition of the present embodiment or the photosensitive resin film (photosensitive layer forming step), and at least one of the photosensitive layers. A step of irradiating an actinic ray to a portion to form a photocured portion (exposure step), and a step of removing at least a part of the photosensitive layer other than the photocured portion to form a resin pattern (removing step). Have in order. Further, if desired, the method further includes a step of heating the resin pattern (heating step). The method for producing a cured product according to the present embodiment makes it possible to form a desired pattern. Further, even when a photosensitive layer having a thickness of, for example, 70 μm or more is formed, it has excellent pattern formability. Taking advantage of the characteristics of the resin composition, a desired pattern can be formed by using a thick cured product having a thickness of 70 μm or more, for example. In the present specification, the term "process" is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, it means "process" if the intended action of the process is achieved. include.

(Photosensitive layer forming step)
In forming the photosensitive layer, the photosensitive layer can be formed by applying or laminating the photosensitive resin composition or the photosensitive resin film of the present embodiment on a substrate, respectively.
Examples of the substrate include a glass substrate, a silicon wafer, a metal oxide insulator such as TiO ₂ and SiO ₂ , silicon nitride, a ceramic piezoelectric substrate, and an epoxy resin-impregnated glass cloth substrate.

When the photosensitive layer is formed by applying the photosensitive resin composition to the substrate, the photosensitive resin composition in the form of a solution dissolved in the above diluent may be applied to the substrate and applied as necessary. The coating film obtained in this way may be dried. The coating and drying may be carried out by the various coating methods described for the preparation of the above-mentioned photosensitive resin film and the coating film drying method.
When a photosensitive resin film is used, the photosensitive layer can be formed by a laminating method using a laminator or the like.

The thickness of the photosensitive layer provided on the substrate varies depending on the forming method (coating method or laminating method), the solid content concentration and viscosity of the photosensitive resin composition, etc., but the lower limit of the thickness of the photosensitive layer after drying is 10 μm. As described above, it may be appropriately selected from 30 μm or more, 50 μm or more, 70 μm or more, 100 μm or more, more than 100 μm, or 150 μm or more. The upper limit is not particularly limited as long as the resin pattern can be formed, but may be appropriately selected from, for example, 500 μm or less, 300 μm or less, or 250 μm or less. The thickness of the photosensitive layer may be appropriately selected from the above range depending on the application. When used in electronic parts and the like, the lower limit may be appropriately selected from 70 μm or more, 100 μm or more, or 150 μm or more, and the upper limit is 500 μm. Hereinafter, it may be appropriately selected from 300 μm or less, or 250 μm or less.
In the method for producing a cured product of the present embodiment, since the photosensitive layer is formed using the photosensitive resin composition of the present embodiment, it is possible to form a thick photosensitive layer. For example, when a photosensitive layer having a thickness of 150 μm or more is formed, the photosensitive layer is not applied once (and dried if necessary) or formed by lamination, and is applied multiple times until the desired thickness is obtained (and, if necessary, May be repeated).

(Exposure process)
In the exposure step, at least a part of the photosensitive layer provided on the substrate in the photosensitive layer forming step is irradiated with an actinic ray if necessary, and the exposed portion is photocured to form a cured portion. The active layer may be irradiated with the active ray through a mask having a desired pattern when the active ray is applied, and LDI (Laser Direct Imaging) exposure method, DLP (Digital Light Processing) exposure method and the like may be used. Actinic rays may be irradiated by a direct writing exposure method.
Further, from the viewpoint of improving the pattern formability, post-exposure heating (PEB: Post exposure bake) may be performed using a hot plate, a drier or the like after the exposure. 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 15 seconds to 5 minutes or 30 seconds to 3 minutes.

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

(Removal process)
In the removing step, at least a part of a portion (unexposed portion) other than the cured portion of the photosensitive layer formed in the exposing step is removed to form a resin pattern. The unexposed portion may be removed by using, for example, a developing solution such as an organic solvent.
Examples of the organic solvent include ethanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, N-methylpyrrolidone and the like. Among them, cyclopentanone can be used from the viewpoint of developing speed. These may be used alone or in combination of two or more.
In addition, various additives that are usually used may be added to the organic solvent used as the developing solution.

Further, after removing the unexposed portion with a developer, if necessary, washing with water, alcohol such as methanol, ethanol, isopropyl alcohol, n-butyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether acetate, etc. (rinse) You may.

(Heating process)
The heating step is a step that is adopted as necessary, and is a step of heating the resin pattern formed in the removing step to form a cured product. The heat treatment is preferably carried out for 1 to 2 hours while the heating temperature is selected and the temperature is raised stepwise. The heating temperature may be appropriately selected from 120 to 240°C, 140 to 230°C, or 150 to 220°C. When the temperature is raised stepwise, for example, after heat treatment for at least one of 120° C. and 160° C. for 10 to 50 minutes or 20 to 40 minutes, at 220° C. for about 30 to 100 minutes. The heat treatment may be performed for 5 minutes or 50 to 70 minutes.

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

[Laminates and electronic components]
The laminate of the present embodiment is provided with a cured product of the photosensitive resin composition of the present embodiment, and for example, various substrates such as a substrate used in the above-mentioned method for producing a cured product and a carrier film of a photosensitive resin film are used. The thing which equips a support with this hardened|cured material is mentioned. The cured product of the photosensitive resin composition of the present embodiment can be formed, for example, by the above-described method for producing a cured product of the present embodiment.

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

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

Hereinafter, the objects and advantages of the present embodiment will be described more specifically based on Examples and Comparative Examples, but the present embodiment is not limited to the following Examples.

(Examples 1 to 8, Comparative Examples 1 to 4)
The composition was blended according to the blending composition shown in Table 1 (numerical values in the table indicate parts by mass of each material) and kneaded with a three-roll mill to prepare a photosensitive resin composition. N,N-dimethylacetamide was added so that the solid content concentration was 60% by mass to obtain a photosensitive resin composition.

Details of each material in Table 1 are as follows.
UN-952: Urethane acrylate (manufactured by Negami Kogyo Co., Ltd., trade name, number of functional groups: 10, weight average molecular weight: 9,000, a reaction product of a hydroxyl group-containing acrylate and a diisocyanate compound, and acryloyl in the molecule (A component having a group (photopolymerizable functional group), a urethane bond (carbon-nitrogen bond), a chain hydrocarbon skeleton, and an alicyclic hydrocarbon skeleton.)
Cyclomer P: Cyclomer P (ACA) Z250 (manufactured by Daicel Ornex Co., Ltd., trade name, having an ethylenically unsaturated bond (acryloyl group) in the molecule, but having no carbon-nitrogen bond, acrylated It is an acrylate.)
TMCH-5R: urethane acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name, number of functional groups: 2, weight average molecular weight: 950, ethylenically unsaturated bond (acryloyl group), urethane bond (carbon-nitrogen bond) in the molecule , Which is a component (B) having a chain hydrocarbon skeleton and an alicyclic hydrocarbon skeleton.)
FA-324A: EO-modified bisphenol A diacrylate (manufactured by Hitachi Chemical Co., Ltd., trade name, number of functional groups: 2, weight average molecular weight: 512)
A-DCP: tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, number of functional groups: 2)
I-819: bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, (BASF, trade name: IRGACURE-819)
・Park Mill D: Dicumyl peroxide (trade name, manufactured by NOF CORPORATION)
KBM-503: Methacryloxypropyltrimethoxysilane (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)

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

[Preparation of photosensitive resin film]
A polyethylene terephthalate film (trade name: A-4100, manufactured by Teijin Ltd.) having a thickness of 50 μm was used as a carrier film, and the resin compositions of Examples and Comparative Examples were dried on the carrier film to have a thickness of 50 μm. So that it was applied uniformly. Then, a photosensitive layer was formed by heating and drying at 100° C. for 15 minutes using a hot air convection dryer to prepare a photosensitive resin film having a carrier film and a photosensitive layer.

[Measurement of absorbance]
With respect to the photosensitive resin film obtained in the above [Production of photosensitive resin film], the absorbance for 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). A polyethylene terephthalate (PET) film alone was used as a reference. The measurement results are shown in Table 2.

[Evaluation of pattern formability]
A glass epoxy substrate (MCL-E-679F (trade name, manufactured by Hitachi Chemical Co., Ltd.) obtained by etching copper) on which a photosensitive resin film is placed so that the photosensitive layer is located on the glass epoxy substrate side. Then, the carrier film was removed. Lamination was performed at 60° C. using a laminator. Then, the photosensitive resin film was laminated again on the photosensitive layer by the above method, the carrier film was removed, and this was repeated 3 times to obtain a 200 μm thick photosensitive layer and the carrier film on the glass epoxy substrate. The laminated body provided was obtained.
A mask for resolution evaluation (details will be described later) is placed on the carrier film of the laminated body, and an i-line filter (trade name: HB-0365, Asahi Spectroscopy Co., Ltd.) is placed thereon, and a high-precision parallel exposure machine is provided. (Mikasa Co., Ltd.) was used for exposure. At this time, the laminated body was divided into three regions, and the three regions were exposed with light having a wavelength of 365 nm (i-line) at different exposure doses (1,000, 1,400 mJ/cm ² ). The sample after exposure was subjected to post-exposure heating for 1 minute on a hot plate at 90°C.
Then, the carrier film was removed, and the film was developed by immersing it in a developing solution (cyclopentanone) for 20 minutes. The pattern after development was dried at room temperature for 30 minutes to obtain a sample for evaluation. The pattern formability was evaluated by observing the obtained sample using a metallurgical microscope. The evaluation was performed according to the following criteria. Here, "formable" means that the unexposed portion is removed cleanly, and the line portion (exposed portion) has no defects such as falling. The evaluation results are shown in Table 2.
A: 6-1 to 6-8, 7-1 to 7-6, 8-1 to 8-5 could be formed.
B: 7-7 to 7-8 and 8-6 to 8-8 could be formed.
C: A pattern having a line width of 30 μm or less could not be formed, or the photosensitive layer was peeled off after development.

Here, the resolution evaluation mask is a mask having an L-shaped pattern and a linear pattern shown in FIG. 1 having a predetermined line pitch and line width (the unit of numerical values in FIG. 1 is μm). is there.). FIG. 1 is a schematic diagram showing a resolution evaluation mask of the L-shaped and linear shapes having a line pitch of 200 μm and a line width of 30 μm among the resolution evaluation masks. In the present embodiment, a mask having several combinations of line pitches and line widths is used, and A-B (A is a numerical value corresponding to the line pitches, B is set according to the line pitches and line widths). Is a value corresponding to the line width, and the line pitch is 100, 150, 200 μm, A is 6, 7, 8 respectively, and the line width is 5, 8, 10, 12, 15, Those having a thickness of 20, 25, and 30 μm are referred to as B as 1 to 8 (see Table 3). For example, a line pitch of 100 μm and a line width of 5 μm is referred to as 6-1 and a line pitch shown in FIG. 1 of 200 μm and a line width of 30 μm is referred to as 8-8. Therefore, it can be said that the smaller the numerical values of A and B are, the more difficult it is to form a pattern, that is, the photosensitive resin composition that can be patterned even by using a mask of a small numerical value of A and B has a better pattern forming property. Can be said to have.

[Evaluation of bottom thinning phenomenon (difference in length between surface and bottom)]
A sample for evaluation was obtained in the same manner as the method performed in the above [Evaluation of pattern formability]. Measure the length (corresponding to the line width) between the bottom of the pattern (the surface on the substrate side) and the surface (the surface on the side opposite to the bottom) of the obtained sample using a scanning electron microscope. Then, the difference between the surface portion and the bottom portion of the pattern was evaluated by the ratio of the length of the bottom portion/the length of the surface portion. The evaluation was performed according to the following criteria. A larger ratio of the length of the bottom portion/the length of the surface portion means that the bottom thinning phenomenon is suppressed. The evaluation results are shown in Table 2.
A: The ratio of the length of the bottom portion/the length of the surface portion was 60% or more.
B: The ratio of the length of the bottom portion/the length of the surface portion was less than 60%.
C: The pattern could not be formed.

From Table 2, it was confirmed that the photosensitive resin compositions according to this embodiment of Examples 1 to 8 have excellent pattern formability and bottom thinning phenomenon suppression performance. On the other hand, the resin composition of Comparative Example 1 containing no component (A), the resin composition of Comparative Example 2 containing no component (B), and the comparative example containing no components (A) and (B). The resin composition of 3 did not satisfy both the pattern formability and the bottom thinning phenomenon suppressing performance. Further, the resin composition of Comparative Example 4 containing no component (C) had pattern formability, but did not satisfy the bottom thinning phenomenon suppression performance.

[Evaluation of insulation reliability]
Obtained in Examples 1 to 8 on a comb-shaped copper electrode of TEG (Test Element Group) (WALTZ-KIT EM0101JY (trade name, manufactured by WALTZ Co., L/S=40 μm/15 μm)) which is an evaluation device. A photosensitive resin film having a thickness of 50 μm was laminated with the photosensitive layer facing the comb-shaped copper electrode. Lamination was performed at 60° C. using a laminator. Then, the film was exposed with i-line at an exposure dose of 1000 mJ/cm ² , and then heated on a hot plate at 90° C. for 1 minute, and then the carrier film was removed. Furthermore, after heating in an oven at 200° C. for 1 hour, it was cooled to room temperature to obtain a measurement sample.
A lead wire was attached to the TEG electrode portion of the obtained measurement sample with solder, and a high temperature and high humidity bias test was performed (voltage: 5 V (direct current), test time: 100 hours, 85° C., 85% RH (high temperature and high humidity). Machine (made by ESPEC) is used)). As a result, the measurement samples obtained by using the photosensitive resin films of Examples 1 to 8 all had a resistance value of 1.0×10 ⁷ or more during the test time (100 hours), which was sufficient. It was confirmed that the insulation reliability was excellent.

Claims (17)

Component (A): a high molecular weight substance having a photopolymerizable functional group and a carbon-nitrogen bond, (B) component: a low molecular weight substance having a photopolymerizable functional group and a carbon-nitrogen bond, and (C) component: carbon. A photopolymerizable compound having no nitrogen bond, and a component (D): a photopolymerization initiator ,
The component (C) contains a photopolymerizable compound having an alicyclic skeleton,
The photosensitive resin composition, wherein the component (D) contains an acylphosphine oxide photopolymerization initiator . The photosensitive resin composition according to claim 1, wherein the component (A) contains a polymer having a (meth)acryloyl group as a photopolymerizable functional group. The photosensitive resin composition according to claim 1 or 2, wherein the component (A) contains a polymer having a urethane bond as a carbon-nitrogen bond. The said (A) component contains the high molecular weight body which has at least 1 sort(s) of skeleton selected from the group which consists of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton. Item 1. The photosensitive resin composition according to item 1. The said (B) component contains the low molecular weight body which has a (meth)acryloyl group as a photopolymerizable functional group, The photosensitive resin composition of any one of Claims 1-4. The said (B) component contains the low molecular weight body which has a urethane bond as a carbon-nitrogen bond, The photosensitive resin composition of any one of Claims 1-5. The component (C) contains a photopolymerizable compound having at least two photopolymerizable functional groups, the photosensitive resin composition according to any one of claims 1-6. The contents of the component (A), the component (B), the component (C), and the component (D) are each 10 to 95% by mass and 3 to 70% by mass based on the total solid content in the photosensitive resin composition. %, 30 wt%, and 0.05 to 20 wt%, the photosensitive resin composition according to any one of claims 1-7. Additionally, (E) component: containing thermal radical polymerization initiator, the photosensitive resin composition according to any one of claims 1-8. Absorbance with respect to light having a wavelength of 365nm in thickness 50μm The photosensitive resin composition according to any one of claims 1 to 9 0.35 or less. Having a photosensitive layer using the photosensitive resin composition according to any one of claims 1-10, the photosensitive resin film. The photosensitive resin composition according to any one of claims 1-10 onto a substrate, or, the step of providing a photosensitive layer using the photosensitive resin film according to claim 11, at least a portion of the photosensitive layer And a step of forming a resin pattern by irradiating the photosensitive layer with an actinic ray to form a photo-cured portion, and removing at least a part of the photosensitive layer other than the photo-cured portion. .. Furthermore, the manufacturing method of the hardened|cured material of Claim 12 which has the process of heat-processing the said resin pattern. The thickness of the resin pattern is 70μm or more 300μm or less, method for producing a cured product according to claim 12 or 13. Laminate comprising a cured product of the photosensitive resin composition according to any one of claims 1-10. The laminate according to claim 15 , wherein the cured product has a thickness of 70 μm or more and 300 μm or less. Electronic component comprising a cured product of the photosensitive resin composition according to any one of claims 1-10.