TW201928519A - Photosensitive resin composition, method for forming cured embossment pattern, and semiconductor device exhibiting good resolution even when a shift in focus depth occurs - Google Patents

Abstract

This invention provides a photosensitive resin composition, a method for forming a cured embossment pattern by using the photosensitive resin composition, and a semiconductor device having the cured embossment pattern; the photosensitive resin composition provides a cured embossment pattern that exhibits good resolution even when a shift in focus depth occurs, exhibits good chemical resistance, and suppresses deterioration of mold resin and adhesion. The photosensitive resin composition of the present invention is characterized by containing: (A) a polyimide precursor; and (B) a photopolymerization initiator, wherein a g-ray absorbance of a 0.001 wt% solution is 0.01 to 0.1 when using N-methyl-2-pyrrolidone as a solvent.

Description

Photosensitive resin composition, method for producing cured embossed pattern, and semiconductor device

The present invention relates to a photosensitive resin composition for forming an insulating material such as an electronic component and a embossed pattern of a passivation film, a buffer coating film, an interlayer insulating film, or the like of a semiconductor device, and a method of manufacturing a cured embossed pattern using the same And semiconductor devices.

Conventionally, a dielectric material, a passivation film, a surface protective film, an interlayer insulating film, and the like of a semiconductor device use a polyimide resin having excellent heat resistance, electrical properties, and mechanical properties. In the polyimine resin, the composition of the photosensitive polyimide precursor composition can be coated, exposed, developed, and cured by heat hydrazyl imidation of the composition. A heat-resistant embossed pattern film is easily formed. Such a photosensitive polyimide precursor composition has a feature that the step can be greatly shortened as compared with the prior non-photosensitive polyimide material.

However, a semiconductor device (hereinafter also referred to as "element") is packaged on a printed circuit board by various methods depending on the purpose. In general, the prior components were fabricated by wire bonding using thinner wires from the external terminals (pads) of the component to the leadframe. However, at present, as the speed of components increases, the operating frequency reaches GHz, and the difference in wiring length of each terminal in the package affects the operation of the component. Therefore, in the package of components for high-end use, the length of the package wiring must be accurately controlled, and it is difficult to meet this requirement by wire bonding.

Therefore, a flip chip package has been proposed in which a rewiring layer is formed on the surface of a semiconductor wafer, and bumps (electrodes) are formed thereon, and then the wafer is flipped (flip-chip) and directly packaged onto a printed substrate. The flip chip package is used for processing high-end signals for high-end applications because it can accurately control the wiring distance, or is used for mobile phones due to a small package size, and the demand is rapidly expanding. Further, a semiconductor chip packaging technology called a fan-out wafer level package (FOWLP) has recently been proposed, which performs dicing on a pre-processed wafer to fabricate a single wafer, and rearranges a single wafer on the support. The wafer is sealed with a mold resin to form a rewiring layer after peeling off the support (for example, Patent Document 1). The fan-out wafer level package has the advantages of not only making the package thinner, but also achieving high-speed transmission or low cost.
[Previous Technical Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-167191

[The problem that the invention wants to solve]

However, in recent years, since the package packaging technology is diversified, the types of the support are various, and the rewiring layer is multi-layered. Therefore, when the photosensitive resin composition is exposed, the depth of focus varies, and the resolution is largely large. The problem of deterioration. Therefore, there is a problem that the rewiring layer is broken due to the deterioration of the resolution, causing signal delay or causing a decrease in yield. In addition, when the desired resolution is not obtained when the rewiring layer is laminated, the layer is peeled off by the chemical liquid and laminated again. However, the film of the lower layer is damaged due to the chemical liquid, and the film thickness is increased. Reduce the problem. Further, in order to form a plurality of layers, the exposure step and the development step are repeated, which causes a problem of deterioration of the mold resin or a decrease in adhesion.

An object of the present invention is to provide a photosensitive resin composition, a method for forming a cured embossed pattern using the photosensitive resin composition, and a semiconductor device comprising the cured embossed pattern, the photosensitive resin composition providing even A hardened embossed pattern which exhibits good resolution and exhibits good chemical resistance and suppresses deterioration of the mold resin or a decrease in adhesion.
[Technical means to solve the problem]

The present inventors have found that the above object can be attained by combining a polyimine precursor with a specific initiator, thereby completing the present invention. That is, the present invention encompasses the following aspects.
[1] A photosensitive resin composition comprising: (A) a polyimide precursor; and
(B) A photopolymerization initiator having a g-ray absorbance of 0.01 to 0.1 in a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent.
[2] The photosensitive resin composition according to the above aspect 1, wherein the (b) photopolymerization initiator has a g-ray absorbance of from 0.015 to 0.04.
[3] The photosensitive resin composition according to the above aspect 1 or 2, wherein the (b) photopolymerization initiator has a g-ray absorbance of from 0.015 to 0.03.
[4] The photosensitive resin composition according to any one of the above aspects 1 to 3, wherein the (B) photopolymerization initiator is a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent The h-ray absorbance is 0.15~0.5.
[5] The photosensitive resin composition according to any one of the above aspects, wherein the (B) photopolymerization initiator has a fluorene structure.
[6] The photosensitive resin composition according to any one of the above aspects, wherein the (B) photopolymerization initiator is represented by the following formula (B1),
[Chemical 1]

In the formula, R ₆ to R ₈ each independently represent a one-valent organic group having 1 to 6 carbon atoms, and Ar is a direct bond or at least one selected from the group consisting of a stretching phenyl group, a stretching naphthyl group, and a thienyl group. Price base}.
[7] The photosensitive resin composition according to any one of the above aspects 1 to 6, further comprising (C) a crosslinking agent.
[8] The photosensitive resin composition according to any one of the above aspects, wherein the (A) polyimine precursor is applied as a separate solution and prebaked, The g-ray absorbance measured for the obtained film having a thickness of 10 μm was 0.001 to 0.1, and the h-ray absorbance was 0.001 to 0.5.
[9] The photosensitive resin composition according to any one of the above aspects, wherein the (A) polyimine precursor system comprises a polyfluorene having a structure represented by the following formula (A1). Imine precursor,
[Chemical 2]

Wherein X is a tetravalent organic group, Y is a divalent organic group, and R ₁ and R ₂ are each independently a hydrogen atom, and the following formula (R1)
[Chemical 3]

(in the formula (R1), R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, p is an integer selected from 2 to 10), or A saturated aliphatic group having 1 to 4 carbon atoms, wherein at least one of R ₁ and R ₂ is a monovalent organic group represented by the formula (R1)}.
[10] The photosensitive resin composition according to the above aspect 9, wherein the X includes the following structure:
[Chemical 4]
.
[11] The photosensitive resin composition according to the above aspect 9, wherein the X includes the following structure:
[Chemical 5]
.
[12] The photosensitive resin composition according to any one of the above aspects 9 to 11, wherein the Y comprises the following structure:
[Chemical 6]
.
[13] The photosensitive resin composition according to any one of the above aspects 9 to 11, wherein the Y comprises the following structure:
[Chemistry 7]
.
[14] The photosensitive resin composition according to the above aspect 9, wherein the X includes the following structure:
[化8]
,
The above Y contains the following structure:
[Chemistry 9]
.
[15] The photosensitive resin composition according to any one of the above aspects, wherein the total content of the (B) photopolymerization initiator and the (C) crosslinking agent is relative to the above (A) polyfluorene The imine precursor is used in an amount of 0.1 to 20 parts by mass.
[16] A photosensitive resin composition for a fan-out wafer level package, comprising: (A) a polyimide precursor; and
(B) A photopolymerization initiator having a g-ray absorbance of 0.01 to 0.1 in a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent.
[17] A photosensitive resin composition comprising: (A) a polyimide precursor, and
(B) a photopolymerization initiator represented by the following formula (B1),
[化10]

In the formula, R ₆ to R ₈ each independently represent a one-valent organic group having 1 to 6 carbon atoms, and Ar is a direct bond or at least one selected from the group consisting of a stretching phenyl group, a stretching naphthyl group, and a thienyl group. Price base}.
[18] The photosensitive resin composition according to the above aspect 17, wherein the (A) polyimine precursor contains a polyimine precursor having a structure represented by the following formula (A1),
[11]

Wherein X is a tetravalent organic group, Y is a divalent organic group, and R ₁ and R ₂ are each independently a hydrogen atom, and the following formula (R1):
[化12]

(in the formula (R1), R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an organic group of C ₁ to C ₃ , p is an integer selected from 2 to 10), or a saturated aliphatic group of C ₁ to C ₄ , wherein at least one of R ₁ and R ₂ is a monovalent organic group represented by the formula (R1)}.
[19] The photosensitive resin composition according to the above aspect 18, wherein the X includes the following structure:
[Chemistry 13]
.
[20] The photosensitive resin composition according to the above aspect 18, wherein the X includes the following structure:
[Chemistry 14]
.
[21] The photosensitive resin composition according to any one of the above aspects 18 to 20, wherein the Y comprises the following structure:
[化15]
.
The photosensitive resin composition as described in any one of the above aspects 18 to 20, wherein the above Y has the following structure:
[Chemistry 16]
.
[23] The photosensitive resin composition according to the above aspect 18, wherein the X includes the following structure:
[化17]
,
The above Y contains the following structure:
[化18]
.
[24] A method of manufacturing a hardened relief pattern, comprising the steps of:
(1) a coating step of applying the photosensitive resin composition according to any one of the above aspects 1 to 23 onto a substrate, and forming a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer with g rays and/or h rays;
(3) a developing step of developing the exposed photosensitive resin layer to form an embossed pattern;
(4) A heating step of forming a hardened relief pattern by heat-treating the embossed pattern.
[25] A semiconductor device comprising the hardened relief pattern obtained by the manufacturing method described in the above aspect 24.
[Effects of the Invention]

According to the present invention, there is provided a photosensitive resin composition, a method for forming a cured embossed pattern using the photosensitive resin composition, and a semiconductor device comprising the cured embossed pattern, the photosensitive resin composition providing even A hardened embossed pattern which exhibits good resolution and exhibits good chemical resistance and suppresses deterioration of the mold resin or a decrease in adhesion.

Hereinafter, this embodiment will be specifically described. Further, in the present specification, the structures represented by the same symbols in the general formula may be the same or different from each other when a plurality of structures are present in the molecule.

<Photosensitive Resin Composition>
The photosensitive resin composition of one aspect of the present invention contains (A) a polyimide intermediate and (B) a photopolymerization initiator. In one aspect, the (g) photopolymerization initiator has a g-ray absorbance of 0.01 to 0.1 in a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent. Further, the photosensitive resin composition may further contain (C) a crosslinking agent in addition to the above components.
According to such a photosensitive resin composition, a hardened relief pattern capable of improving the focus range and chemical resistance and suppressing deterioration of the epoxy resin as a mold resin or a decrease in adhesion can be obtained.

The photosensitive resin composition of one aspect of the present invention can be suitably used for a semiconductor device of a fan-out Wafer Level Package (FOWLP) type (also referred to as a fan-out type). The FOWLP refers to a package form in which a rewiring layer (having wiring and an insulating film) is formed to be larger than a semiconductor wafer (ie, fan out from a semiconductor wafer). In the fan-out type semiconductor device, it is necessary to make the insulating film of the rewiring layer adhere not only to the semiconductor wafer but also to the mold resin as the sealing material. The photosensitive resin composition of the present invention is particularly suitable as an insulating film for a rewiring layer because it can suppress deterioration of a mold resin and is in close contact with a mold resin. Therefore, in one aspect, the photosensitive resin composition of the present invention is a photosensitive resin composition for fan-out type wafer level encapsulation.

[(A) Polyimine precursor]
The (A) polyimine precursor of the present embodiment will be described.
The (A) polyimine precursor of the present embodiment is not limited as long as it can form a hardened embossed pattern by the action of (B) a photopolymerization initiator.
The (A) polyimine precursor of the present embodiment preferably has a g-ray absorbance measured for a film having a thickness of 10 μm after being applied as a separate solution and pre-baked. 0.001 to 0.1, and more preferably h-ray absorbance of 0.001 to 0.5.
The photosensitive resin composition of the present embodiment preferably contains a viewpoint of obtaining a broad focus range of the cured embossed pattern obtained from the photosensitive resin composition and exhibiting good chemical resistance. (A) Polyimine precursors satisfying the above-mentioned requirements.

The g-ray and h-ray absorbance of a film having a thickness of 10 μm after prebaking of the (A) polyimine precursor alone can be measured by a usual spectrophotometer on a film formed on quartz glass. When the thickness of the formed film is not 10 μm, the g-ray having a thickness of 10 μm can be obtained by converting the absorbance obtained for the film into a thickness of 10 μm according to the Lange-Beer law. Ray absorbance.
When the g-ray absorbance is 0.001 or more, it is preferable to sufficiently exhibit mechanical properties or thermal properties when forming a polyimide film having a polyimide precursor hardened. When the g-ray absorbance is 0.1 or less, the light reaches the bottom of the coating film. Therefore, for example, in the case of a negative type, the bottom portion tends to be sufficiently hardened, which is preferable. From the viewpoint of mechanical properties or development resolution, it is preferably 0.001 to 0.05, more preferably 0.005 to 0.03.
When the h-ray absorbance is 0.001 or more, it is preferable to sufficiently exhibit mechanical properties or thermal properties when forming a polyimide film having a polyimide precursor hardened. When the h-ray absorbance is 0.5 or less, the light reaches the bottom of the coating film. Therefore, for example, in the case of a negative type, the bottom portion tends to be sufficiently hardened, which is preferable. From the viewpoint of mechanical properties or development resolution, it is preferably 0.001 to 0.3, more preferably 0.005 to 0.2.

The (A) polyimine precursor of the present embodiment is preferably, for example, selected from the group consisting of polylysine, polyphthalate, polyamidate, and polyamidamine. At least one resin is used as a main component. Here, the main component means that the resin is contained in an amount of 60% by mass or more, and more preferably 80% by mass or more based on the total of the resin. Further, other resins may be contained as needed.

The weight average molecular weight of the (A) polyimine precursor is determined by the polystyrene conversion value obtained by gel permeation chromatography from the viewpoint of heat resistance and mechanical properties of the film obtained after the heat treatment. It is preferably 1,000 or more. More preferably 5,000 or more. The upper limit is preferably 100,000 or less. The weight average molecular weight is more preferably 50,000 or less from the viewpoint of solubility of the developer.

In the resin composition of the present embodiment, one of the most preferred (A) polyimine precursors contains an ester of the structure represented by the following formula (A1) from the viewpoint of heat resistance and photosensitivity. A type of polyimine precursor.

[Chemistry 19]

Wherein X is a tetravalent organic group, Y is a divalent organic group, and R ₁ and R ₂ are each independently a hydrogen atom, and the following formula (R1)
[Chemistry 20]

(wherein R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10), or a carbon number of 1~ a saturated aliphatic group of 4, but at least one of R ₁ and R ₂ is a monovalent organic group represented by the formula (R1)}

In the above formula (A1), the tetravalent organic group represented by X is preferably an organic group having 6 to 40 carbon atoms, and further preferably bonded to one of the -COOR ₁ group and the -CONH- group. An aromatic ring and a tetravalent aromatic group or an alicyclic aliphatic group in the ortho position. In the former case, the aromatic ring having a -COOR ₁ group and the aromatic ring having a -COOR ₂ group may be the same aromatic ring or a different aromatic ring. The aromatic ring in the context is preferably a benzene ring.

The tetravalent organic group represented by X is more preferably a formula:
[Chem. 21]

The structure represented by each of them is not limited to these. Further, the structure of X may be one type or a combination of two or more types.

In particular, the photosensitive resin composition is preferably in the above formula (A1), and the tetravalent organic group represented by X includes the following structure:
[化22]

Or the following structure:
[化23]
.
By having such a structure of the polyimide precursor, heat resistance and photosensitivity are improved, and in the obtained hardened relief pattern, the focus range and chemical resistance can be improved, and the epoxy resin as a mold resin can be suppressed. Deterioration or decrease in adhesion.

In the above formula (A1), the divalent organic group represented by Y is preferably an aromatic group of C ₆ to C ₄₀ , and examples thereof include the following formula:
[Chem. 24]

[化25]

In the above formula, A is each of a methyl group (-CH ₃ ), an ethyl group (-C ₂ H ₅ ), a propyl group (-C ₃ H ₇ ), or a butyl group (-C ₄ H ₉ ). Indicates the structure, but is not limited to these. Further, the structure of Y may be one type or a combination of two or more types.

R ₃ in the above formula (R1) is preferably a hydrogen atom or a methyl group, and from the viewpoint of photosensitivity, R ₄ and R ₅ are each preferably a hydrogen atom. From the viewpoint of the photosensitive property, p is preferably an integer of 2 or more and 10 or less, more preferably an integer of 2 or more and 4 or less.

In particular, the photosensitive resin composition is particularly preferably a polyimine precursor in the formula (A1), and the divalent organic group represented by Y contains the following structure:
[Chem. 26]

Or the following structure:
[化27]
.
By having such a structure of the polyimide precursor, heat resistance and photosensitivity are improved, and in the obtained hardened relief pattern, the focus range and chemical resistance can be improved, and the epoxy resin as a mold resin can be suppressed. Deterioration or decrease in adhesion.

The photosensitive resin composition is preferably in the above formula (A1),
X contains the following structure:
[化28]
,
Y contains the following structure:
[化29]
.
By having such a structure of the polyimide precursor, heat resistance and photosensitivity are further improved, and in the obtained hardened relief pattern, the focus range and chemical resistance can be further improved, and the mold can be further reliably suppressed. The deterioration of the epoxy resin of the resin or the decrease in the adhesion.

[(A) Preparation method of polyimine precursor]
The above ester-bonded polyimine precursor is, for example, first reacted with a tetracarboxylic dianhydride having a desired tetravalent organic group X and an alcohol having a photopolymerizable group (for example, an unsaturated double bond) to prepare a local portion. A tetracarboxylic acid (hereinafter also referred to as an acid/ester) which is esterified. Thereafter, it is obtained by subjecting the acid/ester body to a diamine having a divalent organic group Y to carry out guanamine polycondensation. Further, a saturated aliphatic alcohol may be used in combination with the above-mentioned alcohol having a photopolymerizable group.

(Preparation of acid/ester)
In the present invention, as the tetracarboxylic dianhydride having a tetravalent organic group X which is suitable for use in the preparation of an ester-bonded polyimine precursor, for example, pyromellitic dianhydride and diphenyl ether-3 may be mentioned. 3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3,'4,4'-tetracarboxylic dianhydride, biphenyl-3,3,'4,4'-tetracarboxylate Acid dianhydride, diphenyl hydrazine-3,3, '4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3,'4,4'-tetracarboxylic dianhydride, 2,2- Bis(3,4-phthalic anhydride) propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc. Not limited to these. Further, of course, these may be used alone or in combination of two or more.

In the present invention, as the alcohol having a photopolymerizable group which is suitable for use in the preparation of the ester-bonded polyimine precursor, for example, 2-propenyloxyethanol and 1-propenyloxy-3-propene are mentioned. Alcohol, 2-propenylamine ethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate , 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-cycloacrylate Hexyloxypropyl ester, 2-methylpropenyloxyethanol, 1-methylpropenyloxy-3-propanol, 2-methylpropenylamine ethanol, 2-hydroxy-3-methoxy methacrylate Propyl propyl ester, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, A 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, and the like.

The saturated aliphatic alcohol which can be used arbitrarily with the above-mentioned alcohol having a photopolymerizable group is preferably a saturated aliphatic alcohol having 1 to 4 carbon atoms. Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, and third butanol.

The above-mentioned tetracarboxylic dianhydride suitable for the present invention and the above alcohol are preferably present in a suitable reaction solvent at a temperature of 20 to 50 ° C in the presence of a basic catalyst such as pyridine. After stirring and mixing for 4 to 10 hours, an esterification reaction of an acid anhydride can be carried out to obtain a desired acid/ester body.

As the reaction solvent, it is preferred to completely dissolve the tetracarboxylic dianhydride and the alcohol of the raw material and the acid/ester as the product. More preferably, the polyimine precursor which is a polycondensation product of the acid/ester body and the diamine is also completely dissolved. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, tetramethyl urea, ketones, esters Classes, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and the like. As a specific example of these,
Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone;
Examples of the esters include methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, and the like;

Examples of the lactones include γ-butyrolactone and the like;
Examples of the ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and the like;
Examples of the halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, and the like;
Examples of the hydrocarbons include hexane, heptane, benzene, toluene, xylene, and the like. These may be used alone or in combination of two or more.

(Preparation of polyimine precursors)
In the above acid/ester body (typically in a solution state dissolved in the above reaction solvent), it is preferred to introduce an appropriate dehydrating condensing agent under ice cooling to make the acid/ester body a polyanhydride. Then, the addition of the diamine having a divalent organic group Y suitable for use in the present invention is additionally added or dispersed in a solvent, and the two are subjected to guanamine polycondensation, whereby the target aggregation can be obtained. A quinone imine precursor. It is also possible to use a diamine oxirane together with the above diamine having a divalent organic group Y.
Examples of the above-mentioned dehydrating condensing agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, and 1,1-carbonyldioxy- Bis-1,2,3-benzotriazole, N,N'-d-butylenediminocarbonate, and the like.
By the above manner, a polyanhydride compound as an intermediate is obtained.

In the present invention, as the diamine having a divalent organic group Y which is suitably used for the reaction with a polyanhydride compound obtained by the above-mentioned method, for example, p-phenylenediamine, m-phenylenediamine, 4,4- Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-di Aminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,4'-diaminodiphenylanthracene, 3,3' -diaminodiphenylanthracene, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diamino Benzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-di Aminodiphenylmethane, 3,3'-diaminodiphenylmethane,

1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, double [ 4-(4-Aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, 4,4-bis(4-aminophenoxy)biphenyl , 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)benzene Ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2 , 2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl Propane, 2,2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylmethylalkyl)benzene, o-linked Aniline, 9,9-bis(4-aminophenyl)anthracene, etc.;
And a part of the hydrogen atom on the benzene ring is substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen atom or the like;
And mixtures thereof, and the like.

Specific examples of the above-mentioned substituents include 3,3'-dimethyl-4,4'-diaminobiphenyl and 2,2'-dimethyl-4,4'-diamine linkage. Benzene, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3' - Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and the like; and mixtures thereof. The diamines are not limited to the above examples.

The diamino sulfoxane is used for the purpose of improving the adhesion between the coating film formed of the photosensitive resin composition and various substrates, and when preparing the (A) photosensitive polyimide precursor, The divalent organic group Y diamines are used in combination. Specific examples of such a diamine-based oxane include, for example, 1,3-bis(3-aminopropyl)tetramethyldioxane and 1,3-bis(3-aminopropyl). Base) tetraphenyldioxane, and the like.

After the polycondensation reaction of the guanamine is completed, the water-absorbent by-product of the dehydration condensing agent coexisting in the reaction solution is filtered as needed, and then a suitable poor solvent (for example, water or aliphatic) is added to the solution containing the polymer component. An alcohol, a mixed solution thereof, etc., the polymer is analyzed, and if necessary, the resin is refined by re-dissolving and reprecipitation and precipitation operations, and then vacuum-dried to thereby target the target polyimine precursor. The item is separated. In this case, an acid compound such as a carboxylic acid or a sulfonic acid, a salt compound such as a carboxylate or a sulfonate, or an alkali compound such as an aliphatic amine or an aromatic amine may be added for the purpose of improving storage stability or resolution. a salt compound such as an aliphatic amine salt or an aromatic amine salt. In order to improve the fine system, the anion and/or cation exchange resin may be swollen and filled into the column with a suitable organic solvent, and the solution of the polymer is passed through the column to remove ionic impurities.
Examples of the carboxylic acid include formic acid, oxalic acid, and maleic acid. Examples of the sulfonic acid include p-toluenesulfonic acid and methanesulfonic acid.
Examples of the carboxylate include sodium formate and sodium oxalate. Examples of the sulfonate include sodium p-toluenesulfonate and pyridinium p-toluenesulfonate.
Examples of the aliphatic amine include triethylamine and tributylamine. Examples of the aromatic amine include aniline and diphenylamine.
Examples of the aliphatic amine salt include triethylamine hydrochloride and tributylamine hydrochloride. Examples of the aromatic amine salt include aniline hydrochloride and diphenylamine hydrochloride.

The weight average molecular weight of the ester-bonded polyimine precursor is calculated from the polystyrene equivalent value obtained by gel permeation chromatography from the viewpoint of heat resistance and mechanical properties of the film obtained after the heat treatment. It is preferably 1,000 or more. More preferably 5,000 or more. The upper limit is preferably 100,000 or less. The weight average molecular weight is more preferably 50,000 or less from the viewpoint of solubility of the developer. As a developing solvent for gel permeation chromatography, tetrahydrofuran or N-methyl-2-pyrrolidone is recommended. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to select STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko.

Regarding the (A) polyimine precursor synthesized by this method, the g-ray and h-ray absorbance of the film formed by pre-baking separately formed take various values depending on the molecular structure. However, since the g-ray and h-ray absorbance of the mixture become the arithmetic mean of the g-ray and the h-ray absorbance of each component, two or more (A) polyimine precursors are combined at an appropriate ratio. The balance between mechanical properties and thermal properties is obtained, and the g-beam absorbance of the film having a thickness of 10 μm after prebaking of the (A) polyimide precursor is 0.001 to 0.1, and the h-ray absorbance is 0.001 to 0.5. .

[(B) Photopolymerization initiator]
Next, the photopolymerization initiator (B) of the present embodiment will be described.
In one aspect, the (g) photopolymerization initiator has a g-ray absorbance of 0.01 to 0.1 in a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent.
(B) Absorbance of photopolymerization initiator The compound was dissolved in N-methyl-2-pyrrolidone at a concentration of 0.001 wt%, and was measured using a 1 cm quartz cell using a usual spectrophotometer.
The g-ray absorbance of the 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent in the (B) photopolymerization initiator of the present embodiment is preferably in terms of the focus range and chemical resistance. It is 0.015 or more, preferably 0.020 or more. Further, the g-ray absorbance is preferably 0.09 or less, preferably 0.08 or less, preferably 0.07 or less, preferably 0.06 or less, preferably 0.05 or less, preferably 0.04 or less, or preferably 0.03 or less.
The (B) photopolymerization initiator of the present embodiment preferably has a h-ray absorbance of 0.15% by weight of a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent, from the viewpoint of the range of focus and chemical resistance. ~0.5. The h-ray absorbance is preferably from 0.15 to 0.4, more preferably from 0.15 to 0.3.
The photopolymerization initiator (B) of the present embodiment is not limited as long as it has the above absorbance, and from the viewpoint of chemical resistance, it is preferred to have a fluorene structure in the structure.
The (B) photopolymerization initiator of the present embodiment is not limited as long as the g-ray absorbance of the 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent is 0.01 to 0.1, and in one aspect, It is preferably a structure represented by the following formula (B1). In one aspect, the (B) photopolymerization initiator is a compound represented by the following formula (B1).
[化30]

In the formula, R ₆ to R ₈ each independently represent a one-valent organic group having 1 to 6 carbon atoms, and Ar is a direct bond or at least one selected from the group consisting of a stretching phenyl group, a stretching naphthyl group, and a thienyl group. Price base. }
In these, Ar is preferably a phenyl group, R ₇ and R _{8 are} preferably a one-valent organic group having 1 to 4 carbon atoms, and R _{6 is} preferably a one-valent organic group having 1 to 3 carbon atoms.

By using the (B) photopolymerization initiator having a g-ray absorbance of 0.01 to 0.1 in a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent of the present embodiment, the focusing range and chemical resistance are improved. The reason for the deterioration of the epoxy resin of the mold resin or the decrease in the adhesion is suppressed. The reason for this is not clear. For example, the inventors of the present invention considered the cause of deterioration of the epoxy resin or the adhesion.
It is considered that the i-ray or ghi ray which is usually used for exposure has higher energy than the g and h ray, and therefore, when it reaches the epoxy resin side through the polyimide film, the epoxy resin is damaged or damaged. One part of the damaged epoxy resin is volatilized, whereby gas is deposited in the boundary area between the polyimide and the epoxy resin, and the adhesion is lowered. Therefore, when exposure is performed using g-rays or h-rays, damage of the epoxy resin can be suppressed.
In the present embodiment, the reason why the chemical resistance is good is not clear. For example, when the g-ray or the h-ray has a specific absorbance, it is considered that the exposed portion is easily used in the case of the negative-type photosensitive resin composition. Cross-linking makes it easy to obtain a three-dimensional network structure and exhibits chemical resistance.

By using the photopolymerization initiator (B) of the present embodiment, the focus range and the chemical resistance are improved, and the deterioration of the epoxy resin as a mold resin or the decrease in the adhesion property is suppressed, and the tendency is particularly high. When the imine precursor has a g-ray absorbance of 0.01 to 0.1, it tends to be favorably exhibited.
The photopolymerization initiator (B) of the present embodiment is not limited as long as it has the above-mentioned absorbance, and the photosensitive resin composition is usually operated under yellow light having a wavelength of 500 nm or less, so that the absorbance at 500 nm is obtained. The lower the better. Specifically, the absorbance at 500 nm of a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent is preferably 0.1 or less, more preferably 0.05 or less, and still more preferably 0.02 or less.

Further, the photosensitive resin composition of one aspect of the present invention can also be expressed as follows.
The photosensitive resin composition contains (A) a polyimide precursor and (B) a photopolymerization initiator represented by the following formula (B1),
[化31]

In the formula, R ₆ to R ₈ each independently represent a one-valent organic group having 1 to 6 carbon atoms, and Ar is a direct bond or at least one selected from the group consisting of a stretching phenyl group, a stretching naphthyl group, and a thienyl group. Price base}. Further, the photosensitive resin composition may further contain (C) a crosslinking agent in addition to the above components.
According to such a photosensitive resin composition, a hardened relief pattern capable of improving the focus range and chemical resistance and suppressing deterioration of the epoxy resin as a mold resin or a decrease in adhesion can be obtained.

[(C) Crosslinker]
The (C) crosslinking agent which can be used arbitrarily in the present invention is exemplified by any compound having a plurality of functional groups in the molecule. Here, examples of the functional group include an acryloyl group, a methacryloyl group, an epoxy group, a methylol group, an allyl group, a vinyl group, and a maleimide group.

Examples of the crosslinking agent include ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, and ML-TBC having one crosslinkable group (the above is a trade name, the state Chemical Industry Co., Ltd.), Pa-type benzoxazine (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.), etc.; as DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP with two crosslinkable groups (above Trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML -OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML -Bis25X-PCHP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Ba-type benzoxazine, Bm-type benzoxazine (above, trade name, four Manufactured by Guohuacheng Industrial Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-di醯oxymethyl p-cresol or the like; TriML-P, TriML-35XL, TriML-TrisCR-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) having three crosslinkable groups; TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (with 4 crosslinkable bases) The above is the trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-280, Nikalac MX-270 (the above is the trade name, manufactured by Sanwa Chemical Co., Ltd.), etc.; as a HML with 6 crosslinkable bases. -TPPHBA, HML-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MW-390, Nikalac MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).

Among these, in the present invention, it is preferred to contain at least two crosslinkable groups, and particularly preferably: 46DMOC, 46DMOEP (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML -MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above For the trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Ba-type benzoxazine, Bm-type benzoxazine (above, trade name, Shikoku Chemical Industry Co., Ltd. Manufactured, 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethyloxymethyl-p-cresol Etc., TriML-P, TriML-35XL (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), TML-BP, TML- HQ, TML-pp-BPF, TML-BPA, TMOM-BP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-280, Nikalac MX-270 (above) , Sanwa Chemical Co., Ltd.), HML-TPPHBA, HML-TPHAP (trade names, Honshu Chemical Industry Co., Ltd.). Further, preferred examples thereof include Nikalac MX-290, Nikalac MX-280, Nikalac MX-270 (all the above are trade names, manufactured by Sanwa Chemical Co., Ltd.), Ba-type benzoxazine, and Bm-type benzoxazine (the above are trade names, Nippon Chemical Industry Co., Ltd., Nikalac MW-390, Nikalac MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).

The amount of the crosslinking agent (C) is preferably from 1 to 40 parts by mass, more preferably from 2 to 30 parts by mass, per 100 parts by mass of the (A) resin.

Further, in the photosensitive resin composition, the total content of the (B) photopolymerization initiator and the (C) crosslinking agent is preferably 0.1 to 20 based on 100 parts by mass of the (A) polyimine precursor component. Parts by mass.

[(D) Other ingredients]
The photosensitive resin composition may further contain components other than the above components (A) to (C).
Typically, the photosensitive resin composition is used in the form of a liquid photosensitive resin composition in which the above-mentioned respective components and any components which are used as needed are dissolved in a solvent to form a varnish. Therefore, as the other component (D), a solvent other than the above-mentioned (A) photosensitive polyimide intermediate, a sensitizer, and a monomer having a photopolymerizable unsaturated bond may be mentioned. Next, an auxiliary agent, a thermal polymerization inhibitor, an azole compound, a hindered phenol compound, and the like.

Examples of the solvent include polar organic solvents, alcohols, and the like.
As the solvent, it is preferred to use a polar organic solvent in terms of the solubility of the (A) photosensitive polyimide precursor. Specific examples thereof include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and dimethyl Kea, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-ethinyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazole The ketone ketone, N-cyclohexyl-2-pyrrolidone, etc. may be used alone or in combination of two or more.

The solvent in the present invention is preferably a solvent containing an alcohol in view of improving the storage stability of the photosensitive resin composition. The alcohol which can be suitably used is typically an alcohol having an alcoholic hydroxyl group in the molecule and having no olefinic double bond. Specific examples thereof include alkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and third butanol;
a lactate such as ethyl lactate;

Propylene glycol monomethyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1-(n-propyl) ether, propylene glycol-2-(n-propyl) ether, etc. Alkyl ethers;
Monools such as ethylene glycol methyl ether, ethylene glycol ether, and ethylene glycol n-propyl ether;
2-hydroxyisobutyrate;
Glycols such as ethylene glycol and propylene glycol. Among these, preferred are lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrate, and ethanol, and more preferably ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether. And propylene glycol-1-(n-propyl) ether.

The solvent may correspond to a desired coating film thickness and viscosity of the photosensitive resin composition, and is, for example, in the range of 30 to 1,500 parts by mass, preferably 100%, based on 100 parts by mass of the (A) polyimide precursor. Used within a range of ~1,000 parts by mass. When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in all the solvents is preferably from 5 to 50% by mass, more preferably from 10 to 30% by mass. When the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is good, and when it is 50% by mass or less, (A) The solubility of the amine precursor becomes good.

The photosensitive resin composition of the present embodiment may further contain a resin component other than the above (A) polyimine precursor. Examples of the resin component that can be contained include polyimine, polycarbazole, polycarbazole precursor, phenol resin, polyamine, epoxy resin, decane resin, and acrylic resin. The amount of the resin component to be added is preferably in the range of 0.01 to 20 parts by mass based on 100 parts by mass of the (A) polyimine precursor.

In order to enhance the photosensitivity, the sensitizer can be arbitrarily formulated in the photosensitive resin composition of the present embodiment. Examples of the sensitizer include: mireconone, 4,4'-bis(diethylamino)benzophenone, and 2,5-bis(4'-diethylaminobenzylidene) ring. Pentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminobenzylidene chlorin, p-dimethylene Aminobenzylidene indanone, 2-(p-dimethylaminophenyl-extension benzene)-benzothiazole, 2-(p-dimethylaminophenyl-vinyl)benzothiazole, 2-(pair Dimethylaminophenylvinylidene)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene) acetone,

3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-ethylindol-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylamine Bean, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino Coumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-carbolinylbenzophenone, dimethylamine Isoamyl benzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylamino) Styryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2- (p-Dimethylaminobenzimidyl)styrene, diphenylacetamide, benzamidine anilide, N-methylacetanilide, 3',4'-dimethylacetanilide, and the like. These may be used alone or in combination, for example, 2 to 5 types.

When the photosensitive resin composition contains a sensitizer for improving the photosensitivity, the amount of the compound is preferably 0.1 to 25 parts by mass based on 100 parts by mass of the (A) polyimine precursor.

In order to improve the resolution of the embossed pattern, a monomer having a photopolymerizable unsaturated bond may be arbitrarily formulated in the resin composition. As such a monomer, a (meth)acrylic compound which is subjected to radical polymerization by a photopolymerization initiator is preferred. In particular, mono or di(meth)acrylates of ethylene glycol or polyethylene glycol represented by diethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate;
Mono or di(meth)acrylate of propylene glycol or polypropylene glycol;
Mono, di or tri (meth) acrylate of glycerol;
Cyclohexane di(meth)acrylate;
Diacrylate of 1,4-butanediol and dimethacrylate, di(meth)acrylate of 1,6-hexanediol;

Di(meth)acrylate of neopentyl glycol;
Mono or di(meth)acrylate of bisphenol A;
Benzene trimethacrylate;
Isodecyl (meth)acrylate;
Acrylamide and its derivatives;
Methacrylamide and its derivatives;
Trimethylolpropane tri(meth)acrylate;
Di- or tri(meth)acrylate of glycerol;
a di-, tri- or tetra (meth) acrylate of pentaerythritol;
And a compound such as an ethylene oxide or a propylene oxide adduct of the above compounds, but is not limited thereto.

The photosensitive resin composition of the present embodiment contains a monomer having a photopolymerizable unsaturated bond for improving the resolution of the embossed pattern, and the amount of the photosensitive resin composition is relative to (A) the polyimide precursor 100. The mass part is preferably from 1 to 50 parts by mass.

In order to improve the adhesion between the film formed of the photosensitive resin composition of the present embodiment and the substrate, a bonding aid can be arbitrarily formulated in the photosensitive resin composition. Examples of the auxiliary auxiliary agent include γ-aminopropyl dimethoxydecane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxydecane, and γ-glycidol. Oxypropyl propyl dimethoxy decane, γ-mercaptopropyl methyl dimethoxy decane, 3-methyl propylene methoxy propyl dimethoxy methyl decane, 3-methyl propylene oxime Propyltrimethoxydecane, dimethoxymethyl-3-piperidinylpropylnonane, diethoxy-3-glycidoxypropylmethyldecane, N-(3-diethoxy Methyl decyl propyl) butyl quinone imine, N-[3-(triethoxydecyl)propyl] phthalic acid, benzophenone-3,3'-double (N -[3-triethoxydecylalkyl]propyl decylamine)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxydecyl]propyl decylamine a decane coupling agent such as -2,5-dicarboxylic acid, 3-(triethoxydecyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxy decane, and tris(acetonitrileacetate B) An aluminum-based secondary auxiliary agent such as aluminum, tris(acetonitrile)aluminum, ethyl acetate or ethyl diisopropylaluminate.

Among these secondary auxiliaries, a decane coupling agent is more preferably used in terms of adhesion. The amount of the photosensitive resin composition in the case where the auxiliary agent is contained is preferably in the range of 0.5 to 25 parts by mass based on 100 parts by mass of the (A) polyimine precursor.

In the case where the photosensitive resin composition of the present embodiment is in a state of a solution containing a solvent, in order to improve the viscosity at the time of storage and the stability of light sensitivity, thermal polymerization inhibition can be arbitrarily formulated in the photosensitive resin composition. Agent. As the thermal polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butyl catechol, morphine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-t-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitrogen 2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N- Phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, and the like.

The amount of the thermal polymerization inhibitor to be blended in the case of the photosensitive resin composition is preferably in the range of 0.005 to 12 parts by mass based on 100 parts by mass of the (A) photosensitive polyimide precursor.

When a substrate containing a copper or a copper alloy is used as the substrate to which the resin composition of the present embodiment is applied, the azole compound may be optionally formulated in order to suppress discoloration of the copper surface. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, and 5-phenyl group. -1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyl triazole, 5- Phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl -1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α- Dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5 -methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5' -T-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amine Base-1H-tetrazole, 1-methyl-1H-tetrazole, and the like. More preferably, it is one or more selected from the group consisting of tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in combination of two or more.

In the case where the photosensitive resin composition of the present embodiment contains the azole compound, the amount of the azole compound is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the (A) polyimine precursor, and the light sensitivity characteristic is used. More preferably, it is 0.5 to 5 parts by mass. When the amount of the azole compound is 0.1 parts by mass or more based on 100 parts by mass of the (A) polyimine precursor, when the photosensitive resin composition of the present embodiment is formed on copper or a copper alloy, The discoloration of the surface of the copper or copper alloy can be suppressed. On the other hand, when it is 10 parts by mass or less, the photosensitive resin composition can maintain excellent light sensitivity.

In order to suppress discoloration of the copper surface, a hindered phenol compound may be arbitrarily formulated in place of the above azole compound or together with the above azole compound. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and 3-(3,5-di-3). Octadecyl butyl-4-hydroxyphenyl)propionate, isooctyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoate, 4,4'-methylene Bis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3- Methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexyl Glycol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-di-extension ethyl bis[3-(3,5-di Third butyl-4-hydroxyphenyl)propionate],

N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-phenylpropanamide), 2,2'-methylene-bis(4-methyl-6- Tributylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), tetrakis[3-(3,5-di-t-butyl-4-hydroxybenzene) Pentaerythritol propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-iso-cyanate, 1,3,5-trimethyl-2,4,6 -Tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)- 1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-di Methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxyl -2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri[4-(1 -ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tris-2,4,6-(1H,3H,5H)-trione,

1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-trimethyl-2,4,6-(1H,3H ,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tris-2,4,6- (1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-three 𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethyl Benzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl- 3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-third Butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1 ,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-( 1H, 3H, 5H)-trione,

1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)- Triketone, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H ,3H,5H)-Trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine- 2,4,6-(1H,3H,5H)-trione or the like, but is not limited thereto. In these, it is especially preferred that 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4 , 6-(1H, 3H, 5H)-trione and the like.

The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the (A) polyimine precursor, and more preferably 0.5 to 10 parts by mass from the viewpoint of light sensitivity characteristics. When the amount of the hindered phenol compound relative to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, for example, when a photosensitive resin composition is formed on copper or a copper alloy, In the case where the content is 20 parts by mass or less, the photosensitive resin composition is excellent in light sensitivity.

<Method of Manufacturing Hardened Emboss Pattern>
Moreover, the present invention also provides a method of manufacturing a hardened relief pattern.
The method for producing a cured embossed pattern of the present invention is characterized by the following steps, for example, in the order described above:
(1) a coating step of applying the negative photosensitive resin composition of the present invention to a substrate, and forming a photosensitive resin layer on the substrate;
(2) an exposure step of exposing the photosensitive resin layer by using an exposed g-ray or h-ray;
(3) a developing step of developing the exposed photosensitive resin layer to form an embossed pattern;
(4) A heating step of forming a hardened relief pattern by heat-treating the embossed pattern.
Hereinafter, typical aspects of each step will be described.

(1) Coating step In this step, the photosensitive resin composition is applied onto a substrate, and if necessary, dried to form a photosensitive resin layer.
As the substrate, for example, a metal substrate including ruthenium, aluminum, copper, copper alloy or the like can be used;
a resin substrate such as epoxy, polyimide or polybenzoxazole;
a substrate on which a metal circuit is formed on the resin substrate;
A plurality of metals, or a substrate obtained by laminating a plurality of layers of a metal and a resin.
As the coating method, a method for coating a photosensitive resin composition from the prior art can be used, and for example, a spin coater, a bar coater, a knife coater, a curtain coater, or the like can be used. A method of coating by a screen printing machine or the like, a method of performing spray coating by a spray coater, and the like.

The photosensitive resin composition film may be dried as needed. As the drying method, air drying, heating drying using an oven or a hot plate, vacuum drying, or the like can be used. Further, it is preferred that the drying of the coating film is carried out under the conditions of imidization of the (A) polyimine precursor (polyphthalate) in the photosensitive resin composition. Specifically, in the case of air drying or heat drying, drying can be carried out at 20 ° C to 140 ° C for 1 minute to 1 hour. According to the above, the photosensitive resin layer can be formed on the substrate.

(2) Exposure step In this step, the photosensitive resin layer formed as described above is exposed. As the exposure device, for example, an exposure device such as a contact aligner, a mirror projector, or a stepper can be used. Exposure can be performed via a patterned reticle or reticle, or directly. The light used for the exposure is, for example, an ultraviolet light source or the like.

After the exposure, for the purpose of improving the light sensitivity, etc., post-exposure baking (PEB) and/or pre-development baking based on a combination of any temperature and time may be performed as needed. The range of the baking conditions is preferably 40 to 120 ° C and the time is 10 seconds to 240 seconds. However, the properties of the photosensitive resin composition of the present embodiment are not limited to these ranges.

(3) Developing Step In this step, the unexposed portion in the photosensitive resin layer after the exposure is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), a developing method using a previously known photoresist can be selected. For example, a rotary spray method, a liquid coating method, a dipping method accompanying ultrasonic treatment, and the like. Further, after development, for the purpose of adjusting the shape of the embossed pattern, etc., post-development baking based on a combination of any temperature and time may be performed as needed. The temperature after post-development baking can be, for example, 80 to 130 ° C, and the time can be, for example, 0.5 to 10 minutes.

The developer to be used for development is preferably a good solvent for the photosensitive resin composition or a combination of the good solvent and the poor solvent. As a good solvent, preferred are N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, As the poor solvent, α-ethinyl-γ-butyrolactone or the like is preferably toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, water or the like. When a good solvent and a poor solvent are used in combination, it is preferred to adjust the ratio of the poor solvent to the good solvent in accordance with the solubility of the polymer in the negative photosensitive resin composition. Further, two or more kinds of the respective solvents may be used in combination, for example, in combination of several kinds.

(4) Heating step In this step, the embossed pattern obtained by the above development is heated to volatilize the photosensitive component, and the (A) polyimine precursor is imidized and converted into a polyfluorene. Hardened relief pattern of imine.
As the method of heat curing, various methods such as a method using a hot plate, a method using an oven, and a method using a temperature-increasing oven capable of setting a temperature program can be selected. The heating can be carried out, for example, at 200 ° C to 400 ° C for 30 minutes to 5 hours. As the ambient gas during heat curing, air may be used, and an inert gas such as nitrogen or argon may be used.
By the above manner, a hardened relief pattern can be produced.

<semiconductor device>
Moreover, the present invention provides a semiconductor device having a cured embossed pattern obtained by the above-described method for producing a cured embossed pattern.
The semiconductor device may be, for example, a semiconductor device having a semiconductor element, and a semiconductor device having a cured embossed pattern formed by the method of manufacturing the cured embossed pattern on the substrate.
The semiconductor device can be manufactured, for example, by using a semiconductor element as a substrate and a method including a method of manufacturing the cured embossed pattern as a part of the steps. The semiconductor device can form a hardened relief pattern formed by the above-described hardened relief pattern manufacturing method as, for example, a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a semiconductor having a bump structure. The protective film or the like of the device is combined with a known method for manufacturing a semiconductor device to be manufactured.

In addition to the application to the semiconductor device as described above, the photosensitive resin composition of one aspect of the present invention also has interlayer insulation of a multilayer circuit, a coating coating for a flexible copper clad laminate, a solder resist film, a liquid crystal alignment film, and the like. Useful for use.
[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited thereto. The physical properties of the photosensitive resin composition in the examples, the comparative examples, and the production examples were measured and evaluated according to the following methods.

(1) Weight average molecular weight The weight average molecular weight (Mw) of each photosensitive resin is measured by gel permeation chromatography (standard polystyrene conversion). The column used for the measurement was a serial name of Shodex 805M/806M manufactured by Showa Denko Co., Ltd., and the standard monodisperse polystyrene was selected from Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd., and the solvent was N-methyl-2. Pyrrolidone, the detector was sold under the trade name Shodex RI-930 by Showa Denko.

(2) Absorbance measurement The absorbance of the photopolymerization initiator (B) was adjusted to 0.001 wt% of the NMP solution, and filled in a 1 cm quartz cell, and then scanned at a scanning speed using a UV-1800 device manufactured by Shimadzu Corporation. The measurement was carried out at a speed of 0.5 nm.
The absorbance of the polyimide precursor was applied to a quartz glass as a film having a thickness of 10 μm after prebaking, and the measurement was carried out. When the thickness of the formed film is not 10 μm, the g-ray and the h-ray having a thickness of 10 μm are obtained by converting the absorbance obtained for the film into a thickness of 10 μm according to the Lange-Beer law. Absorbance.

(3) The focus range was evaluated on a 6-inch wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625±25 μm) using a sputtering device (L-440S-FHL type, manufactured by Canon Anelva Co., Ltd.) A Cu wafer substrate having a thickness of 200 nm and a thickness of 400 nm is prepared.
The photosensitive resin composition was spin-coated on the sputtered Cu wafer substrate by a spin coating apparatus (D-spin 60A type, manufactured by SOKUDO Co., Ltd.), and dried by heating at 110 ° C for 180 seconds to prepare a film thickness of 10 μm ± 0.2. Spin coating film of μm.

For the spin coating film, a reticle with a test pattern having a circular pattern of a diameter of 6 μm was used, and an i-ray was mounted by an equal magnification projection exposure apparatus PrismaGHI S/N5503 (manufactured by Ultratech). The cut-off filter or the gh-ray cut filter was irradiated with g and h rays of energy of 40 mJ/cm ² in Examples 1 to 9, and irradiated with energy of 120 mJ/cm ² in Comparative Examples 1 and ² . Rays. At this time, for each exposure amount, the focus was moved in the direction of the film bottom direction in units of 4 μm with reference to the surface of the spin coating film, and exposure was performed.
Then, using a cyclopentanone, a coating film formed on a sputtered Cu wafer was spray-developed by a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Co., Ltd.), and washed with propylene glycol methyl ether acetate. Hollow concave embossed pattern of polyphthalate. Further, the development time of the spray development was defined as the time which was 1.4 times the minimum time of development of the resin composition of the unexposed portion in the above-mentioned 10 μm spin coating film.

Whether the opening of the hollow circular concave embossed pattern having the mask size of 6 μm obtained above is acceptable or not is determined by the following criteria (I) and (II), and the focus of the qualified pattern is provided. The thickness of the range is described in the results.
(I) The area of the pattern opening portion is 1/2 or more of the corresponding pattern mask opening area.
(II) The pattern profile is not trapezoidal, and no undercut or swelling or bridging occurs.

(4) Evaluation of chemical resistance The above-obtained pattern was heat-treated at 200 ° C for 2 hours by using a temperature-programming type curing oven (VF-2000 type, manufactured by Koyo Lindberg Co., Japan) under a nitrogen atmosphere. A hardened embossed pattern of polyimine having a thickness of about 7 to 8 μm is obtained on the wafer.
The embossed pattern was immersed in a chemical (DMSO: 70% by weight, 2-aminoethanol: 25% by weight, TMAH: 5% by weight) at 50 ° C for 5 minutes, and then Tencor P-15 type was used. The difference meter (manufactured by KLA-Tencor Co., Ltd.) was measured for film thickness and compared with that before the chemical treatment, thereby calculating the dissolution rate (nm/min).

(5) Sealing material deterioration test As the epoxy-based sealing material, the R4000 series manufactured by Nagase ChemteX Co., Ltd. was prepared.
Then, the sealing material was spin-coated on the tantalum wafer sputtered by aluminum to a thickness of about 150 μm, and thermally cured at 130 ° C to cure the epoxy-based sealing material.
The photosensitive resin composition produced in the examples and the comparative examples was applied to the epoxy-based cured film so that the final film thickness was 10 μm. The photosensitive resin composition to be applied was exposed to the entire surface in the exposure conditions of g and h rays of 100 mJ/cm ² in Examples 1 to 9, and in the comparative examples 1 and 2, the i-ray was 100 mJ. After the entire surface was exposed under exposure conditions of /cm ² , it was thermally cured at 200 ° C for 2 hours to prepare a first-layer cured film having a thickness of 10 μm.
The photosensitive resin composition used for forming the first layer cured film is applied onto the first layer cured film, and the entire surface is exposed to light under the same conditions as in the production of the first cured film, and then thermally cured. A second cured film having a thickness of 10 μm was produced.
After the cross-section of the test piece after the formation of the second-layer cured film was cut by a FIB apparatus (manufactured by JEOL Ltd., JIB-4000), it was confirmed whether or not the epoxy portion had a void, and the degree of deterioration was evaluated. When the void was not observed, it was set to ○, and it was observed that even one void was set to ×.

(6) Adhesion test with sealing material Epoxy resin was applied to the photosensitive resin cured film of the sample prepared in the sealing material deterioration test, and then the needle was raised, and a traction tester (SEBASTIAN, manufactured by Quad Group) was used. Type 5) Perform the adhesion test.
Evaluation: The strength is 70 MPa or more.
50 MPa or more and less than -70 MPa・・・Intimate force ○
30 MPa or more and less than -50 MPa・・・Intimate force Δ
Less than 30 MPa・・・Intimate force ×

<Manufacturing Example 1>
a. Synthesis of carbazole derivatives (ruthenium matrix)
[化32]

2.73 parts of p-xylylene chloride and 3.76 parts of AlCl ₃ were added to 5.00 parts of N-ethylcarbazole in 40 ml of CH ₂ Cl ₂ . After stirring at room temperature, 2.21 parts of ethyl chloroform and 3.76 parts of AlCl ₃ were added. The reaction mixture was stirred at room temperature for 4 hours. Then, the reaction mixture was poured into ice water. The product was extracted with ethyl acetate. The ethyl acetate layer was washed with a saturated aqueous NaHCO ₃ solution and brine, and then dried over anhydrous magnesium sulfate. After concentration of the solvent, 5.91 parts (76.3%) of a pale yellow-green solid was obtained. This solid was used in the following reaction in an unpurified state.

b. Synthesis of carcass
[化33]

To 3.0 parts of the oxime matrix obtained in a. of 30 ml of ethanol, 0.76 parts of hydroxyammonium chloride and 0.86 parts of pyridine were added. After refluxing for 10 hours, the reaction mixture was poured into ice water. The solid obtained was taken out by filtration, washed with water and dissolved in ethyl acetate. After drying over anhydrous magnesium sulfate, it was concentrated to give 2.80 parts (yield: 89%) as pale yellow white solid. This solid was used in the following reaction in an unpurified state.

c. Synthesis of oxime esters
[化34]

1.5 parts of the steroid obtained in b. was dissolved in 25 parts of DMF. 0.59 parts of ethyl hydrazine chloride was added to the solution, and then 0.78 parts of triethylamine was added dropwise at 10 ° C or lower. After stirring at room temperature for 4 hours, the reaction mixture was poured into water, and the precipitated solid was filtered. The filtrate was purified by silica gel column chromatography using CH ₂ Cl ₂ -hexane (2:1) to yield 1.05 (61.8%) of pale yellow solid (starter B1). The λmax is 345 nm and the melting point is 191 to 202 °C.
The starter B1 had a g-ray absorbance of 0.025 and an h-ray absorbance of 0.16.

<Manufacturing Example 2>
The compound (B2) having the following structure was synthesized by the same synthesis method as in Production Example 1. Λmax is 366 nm and the melting point is 205-218 °C. The g-ray absorbance was 0.024 and the h-ray absorbance was 0.17.
[化35]

In the formula, A represents a divalent organic group represented by the following formula, B and C represent an ethyl group, and D represents a methyl group}
[化36]

<Production Example 3> ((A) Synthesis of Polyimine Precursor (Polymer A-1))
Add 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) to a 2 liter separable flask, add 2-hydroxyethyl methacrylate (HEMA) 134.0 g and γ-butane 400 ml of the ester was added with 79.1 g of pyridine while stirring at room temperature to obtain a reaction mixture. After the endotherm of the reaction was completed, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.

Next, under ice cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes. A suspension obtained by suspending 4,4'-diaminodiphenyl ether (DADPE) 93.0 g in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate obtained by the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction liquid was added to 3 liters of ethanol to form a precipitate containing a crude polymer. The resulting crude polymer was taken out by filtration, dissolved in 1.5 liters of tetrahydrofuran, and then dissolved in p-toluenesulfonic acid pyridinium salt (2.0 g). The obtained crude polymer solution was purified by using a cation exchange resin (manufactured by Organo Co., Ltd.), and then dropped into 28 liters of water to precipitate a polymer, and the obtained precipitate was taken out by filtration, followed by vacuum drying to obtain a powder. Polymer A-1.
The weight average molecular weight (Mw) of the polymer A-1 was measured and found to be 20,000. The polymer had a g-ray absorbance of 0.01 and an h-ray absorbance of 0.04.

<Production Example 4> (Synthesis of Polyimine Precursor (Polymer A-2))
In the above Production Example 2, 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride, in addition to The reaction was carried out in the same manner as in the method described in Production Example 1, whereby Polymer A-2 was obtained.
The weight average molecular weight (Mw) of the polymer A-2 was measured and found to be 22,000. The polymer had a g-ray absorbance of 0.02 and an h-ray absorbance of 0.152.

<Manufacturing Example 5> (Synthesis of Polyimine Precursor (Polymer A-3))
In the above Production Example 2, 4,4'-diaminodiphenyl ether (DADPE) was replaced by 1,4-phenylenediamine (50.2 g), and the production example 1 was used. The reaction was carried out in the same manner, whereby Polymer A-3 was obtained.
The weight average molecular weight (Mw) of the polymer A-3 was measured and found to be 21,000. The polymer had a g-ray absorbance of 0.01 and an h-ray absorbance of 0.02.

Starting agent B3: Adeka Optomer NCI831 (g-ray: 0.001, h-ray: 0.127)
Starting agent B4: PBG305 (g-ray: 0.001, h-ray: 0.001)
[化37]

Crosslinker C1:
[化38]

<Example 1>
50 g of the polymer A-1 as the component (A) and 50 g of the polymer A-2, the starting agent B1 (4 g) as the component (B), and 16 g of tetraethylene as the other component The alcohol dimethacrylate is dissolved in a mixed solvent containing γ-butyrolactone and DMSO (75:25 by weight), and the amount of the solvent is adjusted so as to have a viscosity of about 35 poise, thereby preparing a photosensitive resin composition. Solution.
The composition was evaluated by the above method. The evaluation results are shown in Table 1.

<Examples 2 to 9 and Comparative Examples 1 to 2>
Evaluation was carried out in the same manner as in Example 1 except that the resin composition solution was prepared at the ratios shown in Table 1. The evaluation results are shown in Table 1.
[Table 1]

As is clear from Table 1, the (B) photopolymerization initiator has a structure of the formula (B1) and/or a photosensitive resin composition of Examples 1 to 9 having a g-ray absorbance of 0.01 to 0.1. The hardened embossed pattern can improve the focusing range and chemical resistance, and suppress deterioration or adhesion of the epoxy resin as a molding resin.

The embodiments of the present invention have been described above, but the present invention is not limited thereto, and may be appropriately modified without departing from the spirit of the invention.
[Industrial availability]

The photosensitive resin composition of the present invention can be suitably used in the field of photosensitive materials useful for the production of electrical/electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (25)

A photosensitive resin composition characterized by comprising: (A) a polyimide precursor; and (B) A photopolymerization initiator having a g-ray absorbance of 0.01 to 0.1 in a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent. The photosensitive resin composition of claim 1, wherein the (B) photopolymerization initiator has a g-ray absorbance of from 0.015 to 0.04. The photosensitive resin composition of claim 1 or 2, wherein the (B) photopolymerization initiator has a g-ray absorbance of from 0.015 to 0.03. The photosensitive resin composition according to any one of claims 1 to 3, wherein the (b) photopolymerization initiator has a h-ray absorbance of 0.15% by weight of a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent. ~0.5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the (B) photopolymerization initiator has a fluorene structure. The photosensitive resin composition according to any one of claims 1 to 5, wherein the (B) photopolymerization initiator is represented by the following formula (B1), [Chemical Formula 1] In the formula, R ₆ to R ₈ each independently represent a one-valent organic group having 1 to 6 carbon atoms, and Ar is a direct bond or at least one selected from the group consisting of a stretching phenyl group, a stretching naphthyl group, and a thienyl group. Price base}. The photosensitive resin composition according to any one of claims 1 to 6, which further contains (C) a crosslinking agent. The photosensitive resin composition according to any one of claims 1 to 7, wherein after the (A) polyimine precursor is coated as a separate solution and pre-baked, the obtained thickness is 10 μm. The g-ray absorbance measured by the film is 0.001 to 0.1, and the h-ray absorbance is 0.001 to 0.5. The photosensitive resin composition according to any one of claims 1 to 7, wherein the (A) polyimine precursor is a polyimine precursor comprising a structure represented by the following formula (A1), [ 2] Wherein X is a tetravalent organic group, Y is a divalent organic group, and R ₁ and R ₂ are each independently a hydrogen atom, and the following general formula (R1) [Chemical 3] (in the formula (R1), R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, p is an integer selected from 2 to 10), or A saturated aliphatic group having 1 to 4 carbon atoms, wherein at least one of R ₁ and R ₂ is a monovalent organic group represented by the formula (R1)}. The photosensitive resin composition of claim 9, wherein the above X comprises the following structure: [Chemical 4] . The photosensitive resin composition of claim 9, wherein the above X comprises the following structure: [Chemical 5] . The photosensitive resin composition according to any one of claims 9 to 11, wherein the above Y comprises the following structure: [Chem. 6] . The photosensitive resin composition according to any one of claims 9 to 11, wherein the above Y comprises the following structure: [Chem. 7] . The photosensitive resin composition of claim 9, wherein the above X comprises the following structure: [Chemical 8] , Y above contains the following structure: [Chem. 9] . The photosensitive resin composition according to any one of claims 1 to 14, wherein the total content of (B) photopolymerization initiator and (C) crosslinking agent is relative to the mass of the above (A) polyimine precursor 100 The serving is 0.1 to 20 parts by mass. A photosensitive resin composition for a fan-out type wafer level package, characterized by comprising: (A) a polyimide precursor; and (B) A photopolymerization initiator having a g-ray absorbance of 0.01 to 0.1 in a 0.001 wt% solution using N-methyl-2-pyrrolidone as a solvent. A photosensitive resin composition comprising: (A) a polyimide precursor; and (B) a photopolymerization initiator represented by the following formula (B1), [Chem. 10] In the formula, R ₆ to R ₈ each independently represent a one-valent organic group having 1 to 6 carbon atoms, and Ar is a direct bond or at least one selected from the group consisting of a stretching phenyl group, a stretching naphthyl group, and a thienyl group. Price base}. The photosensitive resin composition of claim 17, wherein the (A) polyimine precursor is a polyimine precursor comprising a structure represented by the following formula (A1), [Chem. 11] Wherein X is a tetravalent organic group, Y is a divalent organic group, and R ₁ and R ₂ are each independently a hydrogen atom, and the following general formula (R1): [Chemical 12] (in the formula (R1), R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an organic group of C ₁ to C ₃ , p is an integer selected from 2 to 10), or a saturated aliphatic group of C ₁ to C ₄ , wherein at least one of R ₁ and R ₂ is a monovalent organic group represented by the formula (R1)}. The photosensitive resin composition of claim 18, wherein the above X comprises the following structure: [Chem. 13] . The photosensitive resin composition of claim 18, wherein the above X comprises the following structure: [Chem. 14] . The photosensitive resin composition according to any one of claims 18 to 20, wherein the above Y comprises the following structure: [Chem. 15] . The photosensitive resin composition according to any one of claims 18 to 20, wherein the above Y comprises the following structure: [Chem. 16] . The photosensitive resin composition of claim 18, wherein the above X comprises the following structure: [Chem. 17] , Y above contains the following structure: [Chem. 18] . A method of manufacturing a hardened embossed pattern, comprising the steps of: (1) a coating step of applying the photosensitive resin composition according to any one of claims 1 to 23 onto a substrate, and forming a photosensitive resin layer on the substrate; (2) an exposure step of exposing the photosensitive resin layer with g rays and/or h rays; (3) a developing step of developing the exposed photosensitive resin layer to form an embossed pattern; (4) A heating step of heat-treating the embossed pattern to form a hardened relief pattern. A semiconductor device characterized by having a hardened relief pattern obtained by the manufacturing method of claim 24.