KR20120023545A - Photosensitive resin composition, method of producing cured relief pattern, and semiconductor device - Google Patents

Abstract

PURPOSE: A photo-sensitive resin composition, a cured relief pattern manufacturing method, and a semiconductor device are provided to mix purine derivatives into the photo-sensitive resin composition. CONSTITUTION: A photo-sensitive resin composition includes 100 parts by weight of resin, 0.01-10 parts by weight of purine derivatives, and 1-50 parts by weight of a photo-sensitive agent. The resin is at least one selected from a group polyamide acid, polyamide acid ester, polyhydroxyamide polyaminoamide, polyamide, polyamideimide, polyimide, polybenzooxaol, polybenzoimidazol, and polybenzthiazol. The resin is selected from a group including a polyimide precursor represented by chemical formula 1, polyamide represented by chemical formula 3, polyoxazol precursor represented by chemical formula 4, and polyimide represented by chemical formula 5. In chemical formula 2, the X1 is tetravalent organic group; the Y1 is divalent organic group; the n1 is the integer of 2 to 150; and the R1 and the R2 are respectively hydrogen element, monovalent organic group represented by chemical formula 2 or C1 to C4 saturated aliphatic group.

Description

Photosensitive resin composition, manufacturing method of hardening relief pattern, and semiconductor device {PHOTOSENSITIVE RESIN COMPOSITION, METHOD OF PRODUCING CURED RELIEF PATTERN, AND SEMICONDUCTOR DEVICE}

The present invention is, for example, an insulating material for an electronic component, a photosensitive resin composition used for forming a relief pattern such as a passivation film, a buffer coat film, and an interlayer insulating film in a semiconductor device, a method for producing a cured relief pattern using the same, and A semiconductor device.

DESCRIPTION OF RELATED ART Conventionally, the polyimide resin which combines the outstanding heat resistance, electrical characteristics, and mechanical characteristics is used for the insulating material of an electronic component, the passivation film of a semiconductor device, a surface protective film, an interlayer insulation film, etc. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor can easily form a heat resistant relief pattern film by application of the precursor, exposure, development, and thermal imidization treatment by curing. Such a photosensitive polyimide precursor has the feature that a significant process shortening is possible compared with the conventional non-photosensitive polyimide.

On the other hand, in recent years, the mounting method of the printed wiring board of a semiconductor device is also changing from a viewpoint of the improvement of an integration degree, a function, and the size reduction of a chip size. From conventional mounting methods using metal pins and lead-tin process handers, polyimide coatings directly contact the hander bumps, such as BGA (ball grid array) and CSP (chip size packaging), which are more densely mounted. Structures have been used. When forming such a bump structure, the said film requires high heat resistance and chemical resistance. The method of improving the heat resistance of a polyimide film or a polybenzoxazole film by adding a heat crosslinking agent to the composition containing a polyimide precursor or a polybenzoxazole precursor is disclosed (refer patent document 1).

Further, as the semiconductor device becomes more miniaturized, wiring resistance of the semiconductor device cannot be ignored. Therefore, the change from the gold or aluminum wiring which has been used so far to the wiring of copper or copper alloy with lower resistance is made. However, in the conventional photosensitive resin composition, since the compound in a composition is easy to react with copper or a copper alloy, there existed a problem that discoloration of copper or a copper alloy occurs.

As a means to solve the above, a method of suppressing discoloration and corrosion occurring in copper or a copper alloy is disclosed by adding a triazole or a derivative thereof to a composition containing a polyimide precursor (see Patent Document 2).

Moreover, the method of providing favorable adhesion | attachment of copper with respect to a polyimide by introducing an unsaturated heterocyclic group etc. in the terminal of a polyimide is disclosed (refer patent document 3).

Japanese Unexamined Patent Publication No. 2003-287889 Japanese Laid-Open Patent Publication 2005-010360 Japanese Patent Application Laid-open No. Hei 6-106678

However, the composition of patent document 2 had a problem that discoloration generate | occur | produces on copper or a copper alloy when a film thickness is made thick. Therefore, an object of this invention is to provide the photosensitive resin composition which gives the cured film which does not cause discoloration even on copper or a copper alloy, the manufacturing method of the hardening relief pattern which forms a pattern using this photosensitive resin composition, and a semiconductor device. .

MEANS TO SOLVE THE PROBLEM The present inventors discovered that by mix | blending a purine derivative in the photosensitive resin composition, the photosensitive resin composition which gives the cured film excellent in suppression of discoloration also on copper or a copper alloy was obtained, and came to complete this invention. That is, this invention is as follows.

[1] (A) Polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole which may be polyamic acid, polyamic acid ester, or polyoxazole precursor which is a polyimide precursor , At least one resin selected from the group consisting of polybenzoimidazole and polybenzthiazole: 100 parts by mass,

(B) Purine derivative: 0.01? Based on 100 parts by mass of the (A) resin. 10 parts by mass, and

(C) Photosensitive agent: 1? 50 parts by mass

Photosensitive resin composition containing.

[2] The resin (A) is represented by the following general formula (1):

[Formula 1]

(1)

(One)

In formula, X <_1> is a tetravalent organic group, Y <_1> is a divalent organic group, n <_1> is 2? An integer of 150, and R ₁ and R ₂ are each independently a hydrogen atom or the following general formula (2):

[Formula 2]

(2)

(2)

(In formula, R <_3> , R <_4> and R <_5> is respectively independently a hydrogen atom or a C1-C3 organic group, and m <_1> is an integer of 2-10.) Monovalent organic group represented by C1 or C1-C1 ? It is a saturated aliphatic group of 4. The polyimide precursor which has a structure represented by X, General formula (3) shown below:

(3)

(3)

(3)

In formula, X <_2> has 6? It is a trivalent organic group of 15, Y <_2> is C6? It is a 35-valent divalent organic group, may have the same structure, or may have multiple structure, and R <_6> is C3-C? It is an organic group which has at least 1 radically polymerizable unsaturated bond group of 20, and n <_2> is 1? An integer of 1000.

Polyamide having a structure represented by the following general formula (4):

[Formula 4]

(4)

(4)

In formula, Y <_3> is a tetravalent organic group which has a carbon atom, Y <_4> , X <_3> and X <_4> are each independently a divalent organic group which has 2 or more carbon atoms, and n <_3> is 1? Is an integer of 1000 and n ₄ is 0? An integer of 500, n ₃ / (n ₃ + n ₄ )> 0.5, and n ₃ dihydroxydiamide units comprising X ₃ and Y ₃ and n ₄ dia comprising X ₄ and Y ₄ The order of the mid units does not matter.

Polyoxazole precursor which has a structure represented by following, and following General formula (5):

[Chemical Formula 5]

(5)

(5)

In the formula, X ₅ is 4? 14 valence organic group, Y ₅ is 2? The divalent organic group, R ₇ and R ₈ each independently represent an organic group having at least one group selected from phenolic hydroxyl group, sulfonic acid group or thiol group, and n ₅ is 3? Is an integer of 200, and m <_2> and m <_3> are 0? Represents an integer of 10.

The photosensitive resin composition as described in [1] which is at least 1 sort (s) of resin chosen from the group which consists of polyimide which has a structure shown by the following.

[3] The (B) purine derivative is represented by the following general formula (6):

[Formula 6]

(6)

(6)

In formula, R <_9> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? An alkyl group or aromatic group of ₁₀ , and R ₁₀ represents a hydrogen atom, a halogen atom, or a carbon atom; 6 alkoxy group, hydroxyl group, hydroxyalkyl group or C1-C? It is an amino group which may be substituted by the alkyl group or aromatic group of 10. The compound represented by v, following general formula (7):

[Formula 7]

(7)

(7)

In formula, R <_11> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? An alkyl group or an aromatic group of 10, and R ₁₂ and R ₁₃ each independently represent a hydrogen atom, a hydroxyl group, a hydroxyalkyl group or a carbon atom; It is an alkyl group or aromatic group of 10. The compound represented by i, the following general formula (8):

[Formula 8]

(8)

(8)

In formula, R <_14> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? An alkyl group or an aromatic group of 10, and R ₁₅ represents a hydrogen atom, a halogen atom or C 1? 6 alkoxy group, hydroxyl group, hydroxyalkyl group or C1-C? It is an amino group which may be substituted by the alkyl group or aromatic group of 10. The compound represented by X and following General formula (9):

[Formula 9]

(9)

(9)

In formula, R <_16> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? An alkyl group or an aromatic group of 10, and R ₁₇ and R ₁₈ each independently represent a hydrogen atom, a hydroxyl group, a hydroxyalkyl group or a carbon atom; It is an alkyl group or aromatic group of 10. The photosensitive resin composition as described in [1] or [2] which is at least 1 sort (s) of purine derivatives chosen from the group which consists of a compound shown by (i).

[4] The (B) purine derivative is represented by the following general formula (10):

[Formula 10]

(10)

10

In formula, R <_19> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? It is an alkyl group or aromatic group of 10. The compound represented by v, following general formula (11):

[Formula 11]

(11)

(11)

In formula, R <_20> is a hydrogen atom, a hydroxyalkyl group, or C1-C? It is an alkyl group of 10. The compound represented by X, following General formula (12):

[Chemical Formula 12]

(12)

(12)

In formula, R <_21> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? It is an alkyl group or aromatic group of 10. The compound represented by X and following General formula (13):

[Formula 13]

(13)

(13)

In formula, R <_22> represents a hydrogen atom, a hydroxyalkyl group, or C1-C? It is an alkyl group of 10. [1] which is at least 1 sort (s) of purine derivatives chosen from the group which consists of a compound shown by (i). The photosensitive resin composition in any one of [3].

[5] [1], wherein the (B) purine derivative is at least one purine derivative selected from the group consisting of a compound represented by the general formula (12) and a compound represented by the general formula (13). The photosensitive resin composition in any one of [3].

[6] (D) Crosslinking agent: 0.5? Based on 100 parts by mass of the above (A) resin. [1] which further contains 20 parts by mass The photosensitive resin composition in any one of [5].

[7] The organic titanium compound (E): 0.05? Based on 100 parts by mass of the above (A) resin. [1] containing further 10 parts by mass The photosensitive resin composition in any one of [6].

[8] The photosensitive resin composition according to [7], wherein the organic titanium compound (E) is at least one compound selected from the group consisting of a titanium chelate compound, a tetraalkoxy titanium compound and a titanocene compound.

[9] (1) The above [1]? Forming the photosensitive resin layer on the substrate by applying the photosensitive resin composition according to any one of [8] onto the substrate;

(2) exposing the photosensitive resin layer,

(3) developing the photosensitive resin layer after the exposure to form a relief pattern;

(4) Process of forming hardening relief pattern by heat-processing the relief pattern

Method of producing a cured relief pattern comprising a.

[10] The method of [9], wherein the substrate is formed of copper or a copper alloy.

[11] A semiconductor device comprising a cured relief pattern obtained by the production method described in [9] or [10].

ADVANTAGE OF THE INVENTION According to this invention, by mix | blending a purine derivative in a photosensitive resin composition, the photosensitive resin composition which gives the cured film which does not cause discoloration also on copper or a copper alloy can be obtained, and also the hardening relief which forms a pattern using this photosensitive resin composition The manufacturing method of a pattern, and a semiconductor device can be provided.

This invention is demonstrated concretely below. In addition, throughout this specification, the structure represented by the same code | symbol in general formula may mutually be same or different, when there exist multiple.

<Photosensitive resin composition>

The present invention relates to polyhydroxyamides, polyaminoamides, polyamides, polyamideimides, polyimides, and polybenzoxazoles, which can be (A) polyamic acid, polyamic acid ester, and polyoxazole precursors which are polyimide precursors. , At least one resin selected from the group consisting of polybenzoimidazole and polybenzthiazole: 100 parts by mass, and (B) purine derivative: 0.01? Based on 100 parts by mass of (A) resin. 10 parts by mass, (C) Photosensitive agent: 1? Based on 100 parts by mass of (A) resin. 50 parts by mass is an essential component.

(A) resin

(A) resin used for this invention is demonstrated. The resin (A) of the present invention is polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzo, which can be polyamide acid, polyamic acid ester, polyoxazole precursor which is a polyimide precursor. The main component is at least one resin selected from the group consisting of oxazole, polybenzoimidazole and polybenzthiazole. Here, a main component means containing 60 mass% or more of these resin, and it is preferable to contain 80 mass% or more. Moreover, you may contain other resin as needed.

It is preferable that it is 1,000 or more in polystyrene conversion by gel permeation chromatography from a viewpoint of the heat resistance after heat processing and a mechanical characteristic of these resin, and 5,000 or more are more preferable. It is preferable that an upper limit is 100,000 or less, and when it is set as the photosensitive resin composition, 50,000 or less are more preferable from a viewpoint of the solubility to a developing solution.

In the present invention, the resin (A) is preferably a photosensitive resin in order to form a relief pattern. The photosensitive resin is a resin which is used together with the photosensitive agent (C) described later to form a photosensitive resin composition, and causes development of dissolution or undissolved in the subsequent development step.

Examples of the photosensitive resin include polyamic acid, polyamic acid ester, and polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and polyamide which are polyimide precursors. Among the benzoimidazoles and polybenzthiazoles, polyimide precursors, polyamides, polybenzoxazole precursors, and polyimides are preferably used in that the resin after the heat treatment is excellent in heat resistance and mechanical properties. Moreover, these photosensitive resin can be selected according to a desired use, such as which photosensitive resin composition of negative type or positive type is prepared with (C) photosensitive agent mentioned later.

[Polyimide Precursor]

In the photosensitive resin composition of this invention, one example of the most preferable (A) resin from a viewpoint of heat resistance and photosensitive characteristic is the said General formula (1):

[Formula 14]

(1)

(One)

In formula, X <_1> is a tetravalent organic group, Y <_1> is a divalent organic group, n <_1> is 2? It is an integer of 150, R <_1> and R <_2> is respectively independently a hydrogen atom or the said general formula (2):

[Formula 15]

(2)

(2)

(In formula, R <_3> , R <_4> and R <_5> is respectively independently a hydrogen atom or a C1-C3 organic group, and m <_1> is an integer of 2-10.) Monovalent organic group represented by C1 or C1-C1 ? It is a saturated aliphatic group of 4.

It is a polyimide precursor which has a structure shown by. The polyimide precursor is converted to polyimide by subjecting to heating (eg 200 ° C. or more) cyclization treatment. A polyimide precursor is suitable for the negative photosensitive resin composition.

In the said General formula (1), since the tetravalent organic group represented by X <_1> makes heat resistance and photosensitive characteristic compatible, Preferably it is C6? It is an organic group of 40, More preferably, -COOR ₁ group, -COOR ₂ group, and -CONH- group are an aromatic group or an alicyclic aliphatic group which is in an ortho position mutually. As a tetravalent organic group represented by X <_1> , Preferably it is C6-C6 containing an aromatic ring. It is 40 organic groups, More preferably, it is following formula (14):

[Formula 16]

(14)

(14)

Although the structure represented by is mentioned, it is not limited to these. Moreover, ₁ type may be sufficient as the structure of X <_1> , and 2 or more types of combinations may be sufficient as it. X ₁ having a structure represented by the formula (14) Group is especially preferable at the point which makes heat resistance and photosensitivity compatible.

In the said General formula (1), since the bivalent organic group represented by Y <_1> makes heat resistance and photosensitive characteristic compatible, Preferably it is C6-C? It is an aromatic group of 40, for example, following formula (15):

[Formula 17]

(15)

(15)

Structure represented by and following formula (16):

[Formula 18]

(16)

(16)

{Wherein, R ₂₃ and R ₂₄ represent each independently a methyl group (-CH _3), ethyl group (-C ₂ H _5), propyl (-C ₃ H ₇₎ or a butyl group (-C ₄ H ₉₎ .｝

Although the structure represented by is mentioned, it is not limited to these. In addition, _one structure may be sufficient as Y1, and 2 or more types of combinations may be sufficient as it. Y ₁ which has a structure represented by said Formula (15) and (16) The group is particularly preferred in that both the heat resistance and the photosensitivity are compatible.

R ₁ and R ₂ In terms of, R ₃ in General Formula (2) is preferably a hydrogen atom or a methyl group, and R ₄ and R ₅ are preferably hydrogen atoms from the viewpoint of photosensitivity. In addition, m ₁ is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less from the viewpoint of photosensitive characteristics.

When using a polyimide precursor as (A) resin, ester bonding type and an ion bonding type are mentioned as a system which gives photosensitivity to the photosensitive resin composition. The former is a method of introducing a photopolymerizable group, that is, a compound having an olefinic double bond, by an ester bond into the side chain of the polyimide precursor, and the latter is an amino group of a (meth) acryl compound having an carboxyl group and an amino group of the polyimide precursor. To a photopolymerizable group by bonding via ionic bond.

The ester-bonded polyimide precursor is, firstly, tetracarboxylic dianhydride containing the tetravalent organic group X ₁ described above, alcohols having a photopolymerizable unsaturated double bond, and optionally C 1? By reacting a saturated aliphatic alcohol of 4, a partially esterified tetracarboxylic acid (hereinafter referred to as acid / ester material is also known as) was prepared, and this, the above-described divalent organic group Y ₁ It is obtained by amide polycondensation of diamine containing these.

(Preparation of acid / ester)

In the present invention, as tetracarboxylic dianhydride containing tetravalent organic group X ₁ , which is preferably used to prepare an ester-bonded polyimide precursor, for example, pyromellitic anhydride, diphenyl ether- 3,3 ', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'- Tetracarboxylic dianhydride, diphenylsulfone-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, and the like. It is not limited to these. In addition, these may be used alone or may be used in combination of two or more thereof.

In the present invention, as the alcohols having a photopolymerizable unsaturated double bond, which are preferably used to prepare an ester-bonded polyimide precursor, for example, 2-acryloyloxyethyl alcohol and 1-acryloyl jade Cy-3-propyl alcohol, 2-acrylamideethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl Acrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-hydroxy-3-butoxypropylacrylate, 2-hydroxy-3-t-butoxypropylacrylate, 2-hydroxy-3 -Cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamide ethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl Ketone, 2-hydroxy-3-methoxypropylmethacryl 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3 -t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, etc. are mentioned.

Carbon number 1 to the above alcohols As the saturated aliphatic alcohol of 4, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like may be used in combination.

Tetracarboxylic dianhydride and the above alcohols preferred in the present invention described above are used at a temperature of 20 ° C. in a suitable reaction solvent in the presence of a basic catalyst such as pyridine. 4 at 50 ℃? By stirring and dissolving and mixing for 10 hours, esterification of an acid anhydride advances and a desired acid / ester body can be obtained.

As said reaction solvent, it is preferable to fully dissolve the polyimide precursor which is an acid / ester body and the amide polycondensation product of this and a diamine component, For example, N-methyl- 2-pyrrolidone, N, N -Dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma butyrolactone, etc. are mentioned.

Other reaction solvents include ketones, esters, lactones, ethers and halogenated hydrocarbons, and as the hydrocarbons, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o- Dichlorobenzene, hexane, heptane, benzene, toluene, xylene, etc. are mentioned. These may be used independently as needed, and may mix and use 2 or more types.

(Preparation of polyimide precursor)

A suitable dehydrating condensing agent such as dicyclocarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydro under ice cooling in the acid / ester body (typically a solution in the reaction solvent) After quinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidylcarbonate, etc. were added and mixed, the acid / ester was made into a polyacid anhydride, Divalent organic group Y ₁ used preferably in this invention for this. What melt | dissolved or disperse | distributed diamine containing these separately in the solvent was dripped, and the target polyimide precursor can be obtained by amide polycondensation.

As diamines containing the divalent organic group Y ₁ used preferably in the present invention, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4 ' -Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodi Phenylsulfide, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4 '-Diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4 '-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ( 4-aminophenoxy) benzene,

1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4-bis ( 4-aminophenoxy) biphenyl, 4,4-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) Phenyl] 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-aminopropyldimethylsilyl) benzene, ortho-tolidine sulfone, 9,9-bis (4-aminophenyl) fluorene, and these A part of hydrogen atoms on the benzene ring substituted with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., for example 3,3'-dimethyl-4, 4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl- 4,4'-diaminodiphenylmethane, 3,3'-dimethyloxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof Although it is mentioned, it is not limited to this.

Moreover, 1,3-bis (3-aminopropyl) at the time of preparation of a polyimide precursor for the purpose of improving the adhesiveness of the resin layer formed on a board | substrate and various board | substrates by apply | coating the photosensitive resin composition of this invention on a board | substrate. Diaminosiloxanes, such as tetramethyldisiloxane and 1, 3-bis (3-aminopropyl) tetraphenyl disiloxane, can also be copolymerized.

The polymer component which obtained the poor solvent, such as water, an aliphatic lower alcohol, or its liquid mixture, after filtering and separating the absorption by-product of the dehydration condensation agent which coexists in the said reaction liquid after completion | finish of an amide polycondensation reaction. The polymer is precipitated, and the polymer component is precipitated, and the polymer is further purified by re-dissolving and reprecipitation precipitation operation or the like, followed by vacuum drying to isolate the desired polyimide precursor. In order to improve the degree of purification, anionic and / or cation exchange resins may be swollen with a suitable organic solvent and passed through a solution of this polymer to remove ionic impurities.

On the other hand, the ion-bonded polyimide precursor is typically obtained by reacting diamine with tetracarboxylic dianhydride. In this case, R ₁ and R ₂ in the general formula (11) At least one of which is a hydroxyl group.

As tetracarboxylic dianhydride, the anhydride of the tetracarboxylic acid containing the structure of said Formula (14) is preferable, and as diamine, the diamine containing the structure of said Formula (15) or (16) is preferable. Do. By adding the (meth) acryl compound which has an amino group mentioned later to the obtained polyamide precursor, a photopolymerizable group is provided by the ionic bond of a carboxyl group and an amino group.

The molecular weight of the said ester bond type | mold and the ion bond type | mold polyimide precursor is 8,000 when it is measured by the polystyrene conversion weight average molecular weight by gel permeation chromatography. It is preferable that it is 150,000, and 9,000? It is more preferable that it is 50,000. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, when the weight average molecular weight is 150,000 or less, the dispersibility to the developer is good, and the resolution performance of the relief pattern is good. As a developing solvent of gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, a weight average molecular weight is calculated | required from the analytical curve created using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko.

[Polyamide]

Another example of preferable (A) resin in the photosensitive resin composition of this invention is following General formula (3):

[Formula 19]

(3)

(3)

In formula, X <_2> has 6? It is a trivalent organic group of 15, Y <_2> is C6? It is a 35-valent divalent organic group, may have the same structure, or may have multiple structure, and R <_6> is C3-C? It is an organic group which has at least 1 radically polymerizable unsaturated bond group of 20, and n <_2> is 1? An integer of 1000.

It is a polyamide which has a structure shown by these. This polyamide is suitable for the negative photosensitive resin composition.

As said group represented by R <_6> in the said General formula (3), since the photosensitive characteristic and chemical-resistance are compatible, the following General formula (17),

[Formula 20]

(17)

(17)

In formula, R <_25> has 2 carbon atoms? It is an organic group which has at least 1 radically polymerizable unsaturated bond group of 19.

It is preferable that it is group represented by.

As said trivalent organic group represented by X <_2> in the said General formula (3), carbon number is 6? It is preferable that it is a trivalent organic group which is 15, for example, following formula (18):

[Formula 21]

(18)

(18)

It is preferable that it is an aromatic group chosen from the group shown by, and it is more preferable that it is an aromatic group which removed the carboxyl group and the amino group from the amino-group substituted isophthalic acid structure.

In General Formula (3), examples of the divalent organic group represented by Y ₂ include 6 to 6 carbon atoms. It is preferable that it is 35 organic groups, and the aromatic ring or aliphatic ring which may be substituted may be 1? It is more preferable that they are a cyclic organic group which has 4, or an aliphatic group or siloxane group which does not have a cyclic structure. As a divalent organic group represented by Y <_2> , following General formula (15) and following General formula (19) and (20):

[Formula 22]

(15)

(15)

(23)

(19)

(19)

In formula, R ₂₆ and R ₂₇ are each independently a hydroxyl group, 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 ) 1 group selected from the group consisting of, and the propyl group and the butyl group include various isomers.

[Formula 24]

(20)

20

In the formula, m ₄ is 0? Is an integer of 8, and m ₅ and m ₆ are each independently 0? Is an integer of 3, and m ₇ and m ₈ are each independently 0? An integer of 10 and R ₂₈ and R ₂₉ Is a methyl group (-CH ₃ ), an ethyl group (-C ₂ H ₅ ), a propyl group (-C ₃ H ₇ ), a butyl group (-C ₄ H ₉ ) or an isomer thereof.

As an aliphatic group or siloxane group which does not have a cyclic structure, it is a following general formula (21):

[Formula 25]

(21)

(21)

In the formula, m ₉ is 2? Is an integer of 12 and m ₁₀ is 1? Is an integer of 3 and m ₁₁ is 1? An integer of 20, and R ₃₀ , R ₃₁ , R ₃₂ and R ₃₃ each independently represent 1? It is an alkyl group of 3 or the phenyl group which may be substituted. The｝ is mentioned as a preferable thing.

The polyamide resin of this invention can be synthesize | combined as follows, for example.

(Synthesis of Phthalic Acid Compound Seal)

First, at least one compound selected from the group consisting of a compound having a trivalent aromatic group X ₂ , for example, phthalic acid substituted with an amino group, isophthalic acid substituted with an amino group, and terephthalic acid substituted with an amino group (hereinafter, “ 1 mole of a compound reacting with an amino group and 1 mole of a compound reacting with an amino group, modified and sealed with a group containing a radical polymerizable unsaturated bond described later (hereinafter referred to as "phthalic acid compound sealing"). Sieve "). These may be individual or may be used in mixture.

When a phthalic acid compound is made into the structure which sealed with the group containing the said radically polymerizable unsaturated bond, negative photosensitive property (photocurability) can be provided to a polyamide resin.

As group containing a radically polymerizable unsaturated bond, C3-C? It is preferable that it is an organic group which has a radically polymerizable unsaturated bond group of 20, and the group containing a methacryloyl group or acryloyl group is especially preferable.

The phthalic acid compound sealing body mentioned above is an amino group of a phthalic acid compound, and C3-C? It can obtain by making acid radical, isocyanate, an epoxy compound, etc. which have at least 1 radically polymerizable unsaturated bonding group of 20 react.

Preferred acid chlorides include (meth) acryloyl chloride, 2-[(meth) acryloyloxy] acetyl chloride, 3-[(meth) acryloyloxy] propionyl chloride, 2-[(meth) acrylic Royloxy] ethylchloroformate, 3-[(meth) acryloyloxypropyl] chloroformate, and the like. Preferable isocyanates include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxymethyl] ethyl isocyanate, 2- [2- (meth) acryloyloxyethoxy] Ethyl isocyanate etc. are mentioned. As a preferable epoxy compound, glycidyl (meth) acrylate etc. are mentioned. Although these may be used independently and may be used in mixture, it is especially preferable to use methacryloyl chloride and / or 2- (methacryloyloxy) ethyl isocyanate.

Moreover, as these phthalic-acid compound sealing bodies, it is preferable that a phthalic-acid compound is 5-aminoisophthalic acid because it is excellent in the photosensitive characteristic and the polyamide excellent in the film | membrane characteristic after heat hardening can be obtained.

The said sealing reaction can be advanced by stirring, dissolving, and mixing a phthalic acid compound and a sealing agent in a solvent in presence of basic catalysts, such as pyridine, or tin-type catalysts, such as di-n-butyltin dilaurate.

As a reaction solvent, it is preferable to dissolve the phthalic acid compound sealing body which is a product completely, for example, N-methyl- 2-pyrrolidone, N, N- dimethylacetamide, N, N- dimethylformamide, dimethyl sulfoxide. Said, tetramethylurea, gamma-butyrolactone, etc. are mentioned.

Other reaction solvents include ketones, esters, lactones, ethers and halogenated hydrocarbons, and as the hydrocarbons, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o- Dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like. These solvents may be used alone or as a mixture, if necessary.

Depending on the type of sealant such as acid chloride, hydrogen chloride is by-produced in the course of the sealing reaction. In this case, in order to prevent contamination of the subsequent steps, purification is appropriately performed, for example, by reprecipitating with water and drying with water or passing through a column filled with an ion exchange resin to remove and reduce ionic components. desirable.

Synthesis of Polyamide

And the acid compound sealing member and divalent in the presence of a basic catalyst such as pyridine or triethylamine and a diamine compound having the organic group Y _2, it is possible to obtain the polyamide according to the present invention by mixing, and the amide condensation in a suitable solvent.

As the amide polycondensation method, the phthalic acid compound sealant is made into a symmetric polyacid anhydride using a dehydrating condenser, followed by mixing with a diamine compound, or after acid chlorideizing the phthalic acid compound sealant by a known method. The method of mixing with a compound, the method of mixing a dicarboxylic acid component and an active esterifying agent in the presence of a dehydrating condensation agent, making it active esterification, and mixing with a diamine compound etc. are mentioned.

As a dehydration condensing agent, For example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1'-carbonyldioxy-di-1,2 , 3-benzotriazole, N, N'-disuccinimidyl carbonate and the like can be cited as preferred ones.

Examples of the chloroating agent include thionyl chloride.

Examples of the active esterifying agent include N-hydroxysuccinimide or 1-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide and 2-hydroxyimino-2 Ethyl cyanoacetate, 2-hydroxyimino-2-cyanoacetic acid amide, and the like.

The diamine compound having an organic group Y ₂ is preferably at least one diamine compound selected from the group consisting of an aromatic diamine compound, an aromatic bisaminophenol compound, an alicyclic diamine compound, a linear aliphatic diamine compound, and a siloxane diamine compound. It is also possible to use a plurality in combination as desired.

As an aromatic diamine compound, p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenyl ether, 3,4'- diamino diphenyl ether, 3,3'- diamino diphenyl ether , 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3, 4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl methane,

3,3'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy ) Benzene, bis [4- (4-aminophenoxy) phenyl] sulphone, bis [4- (3-aminophenoxy) phenyl] sulphone, 4,4'-bis (4-aminophenoxy) biphenyl, 4 , 4'-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] 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] hexa Fluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, ortho-tolidine sulfone, 9,9-bis (4-aminophenyl) fluorene, and some of the hydrogen atoms on these benzene rings are methyl groups , Ethyl group, hydroxy Group, there may be mentioned a diamine compound substituted with at least one selected from the group consisting of hydroxy group and halogen atoms.

Examples of the diamine compound in which a hydrogen atom on the benzene ring is substituted include 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3, 3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyloxy-4,4'-diamino ratio Phenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, etc. are mentioned.

As an aromatic bisaminophenol compound, 3,3'- dihydroxybenzidine, 3,3'- diamino-4,4'- dihydroxy biphenyl, 3,3'- dihydroxy-4,4 ' -Diaminodiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3- Amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (3-hydroxy-4-aminophenyl) hexafluoropropane, bis- (3-hydroxy-4-aminophenyl) methane, 2,2-bis- (3-hydroxy-4-aminophenyl) propane, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 3,3'-dihydroxy-4,4 '-Diaminodiphenylether, 4,4'-dihydroxy-3,3'-diaminodiphenylether, 2,5-dihydroxy-1,4-diaminobenzene, 4,6-diamino Resorcinol, 1,1-bis (3-amino-4-hydroxyphenyl) cyclohexane, 4,4- (α-methylbenzylidene) -bis (2-aminophenol), and the like.

As an alicyclic diamine compound, 1, 3- diamino cyclopentane, 1, 3- diamino cyclohexane, 1, 3- diamino- 1-methyl cyclohexane, 3, 5- diamino- 1, 1- dimethyl Cyclohexane, 1,5-diamino-1,3-dimethylcyclohexane, 1,3-diamino-1-methyl-4-isopropylcyclohexane, 1,2-diamino-4-methylcyclohexane, 1 , 4-diaminocyclohexane, 1,4-diamino-2,5-diethylcyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2- (3-aminocyclopentyl) -2-propylamine, mensendiamine, isophoronediamine, norbornanediamine, 1-cyclohepten-3,7-diamine, 4,4'-methylenebis (cyclohexylamine), 4 , 4'-methylenebis (2-methylcyclohexylamine), 1,4-bis (3-aminopropyl) piperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetra Oxaspiro- [5,5] -undecane etc. are mentioned.

As a linear aliphatic diamine compound, 1, 2- diamino ethane, 1, 4- diamino butane, 1, 6- diamino hexane, 1, 8- diamino octane, 1, 10- diamino decane, 1, Hydrocarbon type diamines, such as 12-diaminododecane, or 2- (2-aminoethoxy) ethylamine, 2,2 '-(ethylenedioxy) diethylamine, bis [2- (2-aminoethoxy) Alkylene oxide type diamine, such as ethyl] ether, etc. are mentioned.

Dimethyl (poly) siloxane diamine, for example, Shin-Etsu Chemical Co., Ltd., brand names PAM-E, KF-8010, X-22-161A, etc. are mentioned as a siloxane diamine compound.

As a reaction solvent, the solvent which melt | dissolves the produced polymer completely is preferable, For example, N-methyl- 2-pyrrolidone, N, N- dimethylacetamide, N, N- dimethylformamide, dimethyl sulfoxide, Tetramethylurea, gamma butyrolactone, etc. are mentioned.

In addition, in some cases, ketones, esters, lactones, ethers, hydrocarbons and halogenated hydrocarbons may be used as the reaction solvent. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like.

After completion of the amide polycondensation reaction, precipitates derived from the dehydrating condensation agent precipitated in the reaction solution and the like are separated by filtration as necessary. Subsequently, a poor solvent of polyamide, such as water or aliphatic lower alcohol, or a mixture thereof, is added to the reaction solution to precipitate the polyamide. Further, the precipitated polyamide is redissolved in a solvent, purified by repeating the reprecipitation precipitation operation, and vacuum dried to isolate the desired polyamide. In order to further improve the degree of purification, a solution of this polyamide may be passed through a column filled with an ion exchange resin to remove ionic impurities.

Polystyrene conversion weight average molecular weight by gel permeation chromatography of polyamide (henceforth "GPC") is 7,000? Preferably 70,000, and 10,000? It is more preferable that it is 50,000. When the polystyrene reduced weight average molecular weight is 7,000 or more, the basic physical properties of the cured relief pattern are secured. Moreover, image development solubility at the time of forming a relief pattern is ensured that a polystyrene conversion weight average molecular weight is 70,000 or less.

Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as the eluent for GPC. In addition, a weight average molecular weight value is calculated | required from the analytical curve created using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to select from Showa Denko's organic solvent-based standard sample STANDARD SM-105.

[Polyoxazole Precursor]

Another example of preferable (A) resin in the photosensitive resin composition of this invention is following General formula (4):

[Formula 26]

(4)

(4)

In formula, Y <_3> is a tetravalent organic group which has a carbon atom, Preferably it is a tetravalent organic group which has 2 or more carbon atoms, Y <_4> , X <_3>, and X <_4> are respectively independently 2 or more carbon atoms It is a divalent organic group which has n <_{3>, and} is 1? Is an integer of 1000 and n ₄ is 0? An integer of 500, n ₃ / (n ₃ + n ₄ )> 0.5, and n ₃ dihydroxydiamide units comprising X ₃ and Y ₃ and n ₄ dia comprising X ₄ and Y ₄ The order of arrangement of the mid units is not a problem. A polyoxazole precursor having a structure represented by VII (hereinafter, the polyoxazole precursor represented by General Formula (4) may be simply referred to as a "polyoxazole precursor"). to be.

The polyoxazole precursor is a polymer having n ₃ dihydroxydiamide units (hereinafter may be simply referred to as dihydroxydiamide units) in the general formula (4), and in the general formula (4) n You may have _four diamide units (Hereinafter, it may only be called a diamide unit.).

The number of carbon atoms of X ₃ is preferably 2 or more and 40 or less for the purpose of obtaining photosensitivity properties, and the number of carbon atoms of X ₄ is preferably 2 or more and 40 or less for the purpose of obtaining photosensitivity, and the carbon of Y ₃ The number of atoms is preferably 2 or more and 40 or less for the purpose of obtaining photosensitivity, and the number of carbon atoms of Y ₄ is preferably 2 or more and 40 or less for the purpose of obtaining photosensitivity.

The dihydroxydiamide unit is a dicarboxylic acid having a structure of a diaminodihydroxy compound (preferably bisaminophenol) and X ₃ (COOH) ₂ having a structure of Y ₃ (NH ₂ ) ₂ (OH) ₂ . It can form by synthesis from an acid. Hereinafter, a typical embodiment will be described by taking the case where the diaminodihydroxy compound is bisaminophenol. The two sets of amino groups and the hydroxy groups of the bisaminophenol are each at the ortho position, and the dihydroxydiamide unit is about 250? It is ring-closed by heating at 400 degreeC, and changes into a heat resistant polyoxazole structure. N <_3> in General formula (3) is 1 or more in order to acquire a photosensitive characteristic, and 1000 or less for the purpose of obtaining a photosensitive characteristic. n ₃ is 2? The range of 1000 is preferable and 3? The range of 50 is more preferable, and 3? Most preferably, it is the range of 20.

In the polyoxazole precursor, n ₄ of the diamide units may be condensed as necessary. The diamide unit can be formed by synthesis from a diamine having a structure of Y ₄ (NH ₂ ) ₂ and a dicarboxylic acid having a structure of X ₄ (COOH) ₂ . N ₄ in general formula (3) is 0? And 500 range, a good sensitivity characteristic as the n being ₄ or less to 500 is obtained. n ₄ Is 0? The range of 10 is more preferable. If the ratio of the diamide unit to the dihydroxydiamide unit is too high, the solubility in the alkaline aqueous solution used as the developing solution is lowered, so the value of n ₃ / (n ₃ + n ₄ ) in the general formula (3) is 0.5 It is more than that, it is more preferable that it is 0.7 or more, and it is most preferable that it is 0.8 or more.

_{Y 3 (NH 2) 2 (} OH) as bisaminophenol as a diamino dihydroxy compound having the structure of ₂ is, for example, 3,3'-dihydroxy-benzidine, 3,3'-diamino -4 , 4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4 , 4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl Propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- ( 4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenylether, 3,3'-diamino-4,4 '-Dihydroxydiphenyl ether, 1,4 -Diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. are mentioned. These bisaminophenols can be used individually or in combination of 2 or more types. As the Y ₃ group in the bisaminophenol, the following formula (22):

[Formula 27]

(22)

(22)

It is preferable from the viewpoint of the photosensitive characteristic to represent.

In addition, Y as ₄ (NH ₂₎ a diamine having the structure of Figure _2, and the like aromatic diamine, a silicon diamine. Among these, as aromatic diamine, for example, m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl Ether, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3 ' -Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenyl Ketone, 4,4'-diaminodiphenylketone, 3,4'-diaminodiphenylketone, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (4-aminophenyl) Hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl -2,4-bis (4-aminophenyl) -1-pentene,

4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-aminobenzyl) benzene, imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl)- 1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4'-diaminoazobenzene, 4,4'-diaminodiphenylurea, 4,4'-bis (4-amino Phenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2 -Bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 4,4'-bis [4- (α, α-dimethyl- 4-aminobenzyl) phenoxy] benzophenone, 4,4'-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 4,4'-diaminobiphenyl,

4,4'-diaminobenzophenone, phenylindandiamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, o Toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-amino Phenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-di- (3-aminophenoxy) diphenyl At least one selected from the group consisting of sulfone, 4,4'-diaminobenzanilide, and the hydrogen atom of the aromatic nucleus of these aromatic diamines selected from the group consisting of chlorine atom, fluorine atom, bromine atom, methyl group, methoxy group, cyano group and phenyl group The compound substituted by the group or atom of is mentioned.

Moreover, silicone diamine can be selected as said diamine in order to improve adhesiveness with a base material. Examples of the silicone diamine include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane And 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane and the like.

Further, X ₃ (COOH) ₂ or X ₄ (COOH) in the desired dicarboxylic acid having the structure _2, X ₃ and X ₄ Is an aliphatic group or an aromatic group each having a linear, branched or cyclic structure. Especially, the organic group of 2 or more and 40 or less carbon atoms which may contain an aromatic ring or an aliphatic ring is preferable, and X <_3> and X <_4> are respectively following formula (23):

[Formula 28]

(23)

(23)

In formula, R ₃₄ is a divalent group selected from the group consisting of -CH _2- , -O-, -S-, -SO _2- , -CO-, -NHCO- and -C (CF ₃ ) _2- . ｝

It can select preferably from the aromatic group shown, and these are preferable at the point of photosensitive characteristic.

The polyoxazole precursor may be one in which the terminal group is sealed with a specific organic group. When using the polyoxazole precursor sealed by the sealing machine, it is anticipated that the mechanical property (especially elongation) of the coating film after heat-hardening of the photosensitive resin composition of this invention, and hardening relief pattern shape will become favorable. As a preferable example of such a sealing machine, following formula (24):

[Formula 29]

(24)

(24)

The thing represented by is mentioned.

Polystyrene conversion weight average molecular weight by gel permeation chromatography of polyoxazole precursor was 3,000? It is preferable that it is 70,000, and 6,000? It is more preferable that it is 50,000. As for this weight average molecular weight, 3,000 or more are preferable from a viewpoint of the physical property of a hardening relief pattern. Moreover, from a viewpoint of resolution, 70,000 or less are preferable. As a developing solvent of gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. Moreover, molecular weight is calculated | required from the analytical curve created using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko.

[Polyimide]

Another example of preferable (A) resin in the photosensitive resin composition of this invention is the said General formula (5):

[Formula 30]

(5)

(5)

(Wherein X ₅ represents a 4-14 valent organic group, Y ₅ represents a 2-12 valent organic group, R ₇ and R ₈ represent an organic group having at least one group selected from phenolic hydroxyl groups, sulfonic acid groups or thiol groups). And may be the same or different, n ₅ is an integer of 3 to 200, and m ₂ and m ₃ are integers of 0 to 10. Resin represented by General formula (5) is especially preferable at the point which is suitable for the process at low temperature, since chemical change is not needed in the process of heat processing in expressing sufficient film | membrane characteristic.

X <_5> in the structural unit represented by the said General formula (5) is C4? 4 of 40? It is preferable that it is a 14-valent organic group, and since it is compatible with heat resistance and photosensitivity, it is 5-5 carbon atoms containing an aromatic ring or an aliphatic ring. It is more preferable that it is 40 organic groups.

The polyimide represented by the said General formula (5) can be obtained by making tetracarboxylic acid, the corresponding tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, etc. react with diamine, the corresponding diisocyanate compound, and trimethylsilylated diamine. have. Polyimide can generally be obtained by dehydrating and ring-closing polyamic acid which is one of the polyimide precursors obtained by making tetracarboxylic dianhydride and diamine react by heating or chemical treatment with an acid or a base.

As preferable tetracarboxylic dianhydride, a pyromellitic dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, 2,3,3', 4'-biphenyl tetracarboxylic Acid dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3 '-Benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1 -Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2 , 3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarb Acid dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene acid dianhydride,

9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorene acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6- Aromatic tetracarboxes such as pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride Aliphatic tetracarboxylic dianhydrides such as acid dianhydride or butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,3 ', 4,4' -Diphenylsulfontetracarboxylic dianhydride and the following general formula (25):

[Formula 31]

(25)

(25)

{Wherein, R ₃₅ is an oxygen _{atom, C (CF 3) 2,} C (CH 3) 2 or represents a group selected from SO _2, and R ₃₆ and R ₃₇ can be the same or different, and a hydrogen atom, The group chosen from a hydroxyl group or a thiol group is shown. The compound shown by (i) is mentioned.

Among them, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3' -Biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2, 2-bis (3,4-dicarboxyphenyl) propane 2 anhydride, 2,2-bis (2,3-dicarboxyphenyl) propane 2 anhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane 2 Anhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis ( 3,4-dicarboxyphenyl) sulfone 2 anhydride,

Bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 3,3 ', 4,4'-diphenylsulfontetracar Acid dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene acid dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorene acid dianhydride And the following general formula (26)

[Formula 32]

(26)

(26)

{Wherein, R ₃₈ is an oxygen _{atom, C (CF 3) 2,} C (CH 3) 2 or represents a group selected from SO _2, and R ₃₉ and R ₄₀ May be same or different and represents group selected from a hydrogen atom, a hydroxyl group, or a thiol group. The acid dianhydride of the structure shown by (i) is preferable. These are used individually or in combination of 2 or more types.

Y <_5> of the said General formula (5) represents the structural component of a diamine, As this diamine, _2-5 containing an aromatic ring or an aliphatic ring is mentioned. It represents a 12-valent organic group, Especially, it is C5? 40 organic groups are preferable.

Specific examples of the diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4- Bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, P-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobi Phenyl,

3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 4,4 ' -Tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene Or a compound substituted with an alkyl group or a halogen atom in these aromatic rings, or an aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the following general formula (27):

[Formula 33]

(27)

(27)

In the formula, R ₄₁ represents an oxygen atom, a group selected from C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R ₄₂ ? R ₄₅ May be same or different and represents group selected from a hydrogen atom, a hydroxyl group, or a thiol group. The diamine etc. of the structure shown by (i) are mentioned.

Among them, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4 '-Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, m-phenylenediamine, P -Phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, and the following general formula (28):

[Formula 34]

(28)

(28)

In the formula, R ₄₆ represents an oxygen atom, a group selected from C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R ₄₇ ? R ₅₀ May be the same or different and further represents a group selected from a hydrogen atom, a hydroxyl group or a thiol group.

Diamine of the structure shown by is preferable.

Among them, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4 '-Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 1,4-bis (4-aminophenoxy) benzene, and the following general formula (29):

[Formula 35]

(29)

(29)

In the formula, R ₅₁ Represents an oxygen atom, a group selected from C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R ₅₂ and R ₅₃ May be the same or different and further represents a group selected from a hydrogen atom, a hydroxyl group or a thiol group.

Diamine of the structure shown by is especially preferable. These are used individually or in combination of 2 or more types.

R <_7> and R <_8> of General formula (5) represents a phenolic hydroxyl group, a sulfonic acid group, or a thiol group. In this invention, a phenolic hydroxyl group, a sulfonic acid group, and / or a thiol group can be mixed as R <_7> and R <_8> .

Since the dissolution rate with respect to aqueous alkali solution changes by controlling the quantity of the alkali-soluble group of R <_7> and R <_8> , this adjustment can obtain the photosensitive resin composition which has a suitable dissolution rate.

Moreover, in order to improve adhesiveness with a board | substrate, you may copolymerize the aliphatic group which has a siloxane structure as X <_5> , Y <_5> in the range which does not reduce heat resistance. Specifically, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, or the like is used as the diamine component. 10 mol% copolymerized thing etc. are mentioned.

The polyimide is, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (some of which are substituted with a terminal sealer which is a monoamine) at low temperature, and tetracarboxylic dianhydride (part of an acid anhydride or mono at low temperature). A method of reacting a diamine compound with a diamine compound, a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then a diamine (some of which are substituted with a terminal sealer which is a monoamine). ), A method of reacting in the presence of a condensing agent, to obtain a diester with tetracarboxylic dianhydride and an alcohol, and then to acid chloride the remaining dicarboxylic acid, and to replace the diamine (some with a monoamine terminal sealer). ) To obtain a polyimide precursor using a method such as A method of completely imidizing using the true imidation reaction method, or a method of stopping the imidation reaction and introducing a part of the imide structure on the way, and further, by partially blending the fully imidized polymer and the polyimide precursor. Synthesis can be carried out using a method of introducing a DE structure.

It is preferable that the said polyimide has polyimide so that the imidation ratio may be 15% or more with respect to the whole polymer which comprises the photosensitive resin composition. More preferably, it is 20% or more. Here, an imidation ratio refers to the ratio of the imidation which exists in the whole polymer which comprises the photosensitive resin composition. When the imidation ratio is less than 15%, the shrinkage amount at the time of thermosetting becomes large, and it is not suitable for thick film preparation.

The imidation ratio can be computed easily with the following method. First, the infrared absorption spectrum of a polymer is measured and the presence of the absorption peak (near 1780 cm <^-1> and 1377 cm <^-1> ) of the imide structure resulting from a polyimide is confirmed. Next, this polymer is heat-treated at 350 degreeC for 1 hour, the infrared absorption spectrum after heat processing is measured, and the imidation ratio in a polymer before heat processing is computed by comparing the peak intensity of around 1377 cm <^-1> with the intensity before heat processing.

The molecular weight of the said polyimide is 3,000? When measured by the polystyrene conversion weight average molecular weight by gel permeation chromatography. It is preferable that it is 200,000, and 5,000? It is more preferable that it is 50,000. When the weight average molecular weight is 3,000 or more, the mechanical properties are good, and when the weight average molecular weight is 50,000 or less, the dispersibility to the developer is good, and the resolution performance of the relief pattern is good.

As a developing solvent of gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. Moreover, molecular weight is calculated | required from the analytical curve created using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko.

(B) purine derivatives

The (B) purine derivative used for this invention is demonstrated. The purine derivative (B) is a compound having a purine ring as a basic skeleton, and a compound derived from the skeleton is referred to as a purine derivative. By using the (B) purine derivative, the discoloration suppression effect is excellent also on copper or a copper alloy. Although the chemical mechanism of the excellent discoloration suppression effect on copper or a copper alloy is not certain, the purine derivative which contains a nitrogen atom in a molecule | numerator, and (A) resin containing hetero atoms, such as an oxygen atom or a nitrogen atom, are a hydrogen bond etc. By moderate interaction, it is inferred that excessive interaction of resin and copper is suppressed and discoloration on copper is prevented.

Specific examples of the (B) purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, and 2-hydroxyadenine. , 2-methyladenine, 1-methyladenine, N-methyladenine, N, N-dimethyladenine, 2-fluoroadenine, 9- (2-hydroxyethyl) adenine, guanoxoxime, N- (2-hydroxy Ethyl) adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyldenine, N-methylguanine, 7- (2-hydroxyethyl Guanine, N- (3-chlorophenyl) guanine, N- (3-ethylphenyl) guanine, 2-azadenine, 5-azadenine, 8-azadenine, 8-azaguanine, 8-azapurin, 8- Azaxanthin, 8-azahypoxanthin and the like and derivatives thereof.

Moreover, (B) a purine derivative has the following general formula (6):

[Formula 36]

(6)

(6)

In formula, R <_9> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? An alkyl group or aromatic group of ₁₀ , and R ₁₀ represents a hydrogen atom, a halogen atom, or a carbon atom; 6 alkoxy group, hydroxyl group, hydroxyalkyl group or C1-C? It is an amino group which may be substituted by the alkyl group or aromatic group of 10. The compound represented by v, following general formula (7):

[Formula 37]

(7)

(7)

In formula, R <_11> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? An alkyl group or an aromatic group of 10, and R ₁₂ and R ₁₃ each independently represent a hydrogen atom, a hydroxyl group, a hydroxyalkyl group or a carbon atom; It is an alkyl group or aromatic group of 10. The compound represented by i, the following general formula (8):

[Formula 38]

(8)

(8)

In formula, R <_14> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? An alkyl group or an aromatic group of 10, and R ₁₅ represents a hydrogen atom, a halogen atom or C 1? 6 alkoxy group, hydroxyl group, hydroxyalkyl group or C1-C? It is an amino group which may be substituted by the alkyl group or aromatic group of 10. The compound represented by X and following General formula (9):

[Formula 39]

(9)

(9)

In formula, R <_16> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? An alkyl group or an aromatic group of 10, and R ₁₇ and R ₁₈ each independently represent a hydrogen atom, a hydroxyl group, a hydroxyalkyl group, or a carbon atom; It is an alkyl group or an aromatic group of 10. It is preferable from a viewpoint of the discoloration suppression on copper or a copper alloy which is at least 1 sort (s) of purine derivatives chosen from the group which consists of a compound represented by X.

General formula (6) above? Specifically as a compound represented by (9), Purine, adenine, guanine, 2, 6- diaminopurine, 2-hydroxy adenine, 2-methyl adenine, N-methyl adenine, N, N-dimethyl adenine, 2 -Fluoroadenine, N- (2-hydroxyethyl) adenine, guanoxoxime, N- (2-hydroxyethyl) adenine, N-ethyladenine, N-methylguanine, N- (3-ethylphenyl) guanine, 8-azadenine, 8-azaguanine, 8-azapurin, etc. are mentioned.

Especially, following General formula (10):

[Formula 40]

(10)

10

In formula, R <_19> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? It is an alkyl group or aromatic group of 10. The compound represented by v, following general formula (11):

[Formula 41]

(11)

(11)

In formula, R <_20> is a hydrogen atom, a hydroxyalkyl group, or C1-C? It is an alkyl group of 10. The compound represented by X, following General formula (12):

[Formula 42]

(12)

(12)

In formula, R <_21> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? It is an alkyl group or aromatic group of 10. The compound represented by X and following General formula (13):

[Formula 43]

(13)

(13)

In formula, R <_22> represents a hydrogen atom, a hydroxyalkyl group, or C1-C? It is an alkyl group of 10. At least 1 sort (s) of purine derivatives chosen from the group which consists of a compound shown by v is more preferable at the point of the discoloration suppression on copper or a copper alloy.

General formula (10) above? Specifically as a compound represented by (13), Purine, adenine, guanine, 2, 6- diaminopurine, 2-hydroxy adenine, 2-methyl adenine, 2-fluoro adenine, 8- aza adenine, 8- Azaguanine, 8-azapurin, and the like.

The purine derivative is particularly preferably at least one compound selected from the group consisting of a compound represented by the general formula (12) and a compound represented by the general formula (13) in view of adhesion to copper or a copper alloy phase. And from the viewpoint of better adhesion, most preferably 8-azadenine or 8-azaguanine.

The blending amount of the (B) purine derivative is 0.01? To 100 parts by mass of the resin (A). 10 parts by mass, preferably 0.05? 2 parts by mass. When the said compounding quantity is 0.01 mass part or more, discoloration on copper or a copper alloy is expressed, and when it is 10 mass parts or less, it is excellent in storage stability.

(C) photosensitizer

(C) Photosensitive agent used for this invention is demonstrated. (C) The photosensitive agent is the photosensitive resin composition of this invention is a negative type mainly using a polyimide precursor and / or a polyamide as (A) resin, for example, (A) resin, for example, mainly poly It depends on whether it is positive type using an oxazole precursor and / or soluble polyimide, etc.

(C) The compounding quantity of the photosensitive agent in the photosensitive resin composition is 1 to 100 mass parts of (A) photosensitive resin. 50 parts by mass. The said compounding quantity is 1 mass part or more from a light sensitivity or patterning viewpoint, and is 50 mass parts or less from a viewpoint of the hardenability of the photosensitive resin composition or the physical property of the photosensitive resin layer after hardening.

First, the case where a negative type is desired is demonstrated. In this case, a photoinitiator and / or a photo-acid generator are used as a photosensitive agent (C), It is preferable that it is an optical radical polymerization initiator as a photoinitiator, Benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4'-methyl Acetophenones such as benzophenone derivatives such as diphenyl ketone, dibenzyl ketone, and fluorenone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone Thioxanthone derivatives such as derivatives, thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, diethyl thioxanthone, benzyl, benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal derivative,

Benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- ( o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) Oximes such as oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime, N N-arylglycines such as phenylglycine, peroxides such as benzoyl perchloride, aromatic biimidazoles, titanocenes, and mineral acids such as α- (n-octanesulfonyloxyimino) -4-methoxybenzyl cyanide Although generators etc. are mentioned preferably, It is not limited to these. In said photoinitiator, oxime is especially preferable from a light sensitivity viewpoint.

When using a photo-acid generator as a photosensitive agent (C) for a negative photosensitive resin composition, while exhibiting acidity by irradiation of actinic light, such as an ultraviolet-ray, by the effect, the crosslinking agent which is (D) component mentioned later is It has the effect | action which crosslinks with resin which is (A) component, or polymerizes crosslinking agents. Examples of the photoacid generator include diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryl iodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, Oxime sulfonic acid ester, aromatic N-oxyimide sulfonate, aromatic sulfamide, haloalkyl group-containing hydrocarbon compound, haloalkyl group-containing heterocyclic compound, naphthoquinone diazide-4-sulfonic acid ester and the like. Such compounds may be used in combination of two or more as necessary or in combination with other sensitizers. Among the photoacid generators described above, aromatic oxime sulfonic acid esters and aromatic N-oxyimide sulfonates are more preferable in view of photosensitivity.

The compounding quantity of these photosensitizers is 1? With respect to 100 mass parts of (A) resin. 50 parts by mass, and from the viewpoint of light sensitivity characteristics, 2? 15 parts by mass is preferred. (C) It is excellent in light sensitivity by mix | blending 1 mass part or more with respect to 100 mass parts of (A) resin, and is excellent in thick film hardenability by mix | blending 50 mass parts or less.

In addition, as mentioned above, when (A) resin represented by General formula (11) is an ion bond type, in order to provide a photopolymerizable group via an ionic bond to the side chain of (A) resin, it has an amino group (meth ) Acrylic compounds are used. In this case, the (meth) acrylic compound having an amino group is used as the (C) photosensitive agent, for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate. , Dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, di Dialkyl aminoalkyl acrylates or methacrylates, such as ethylamino butyl methacrylate, are preferable, and the alkyl group on an amino group has C1-C? 10, alkyl chain having 1? Preference is given to 10 phosphorus dialkylaminoalkylacrylates or methacrylates.

The compounding quantity of the (meth) acryl compound which has these amino groups is 1? With respect to 100 mass parts of (A) resin. 20 parts by mass, and from the viewpoint of light sensitivity characteristics, 2? 15 parts by mass is preferred. (C) It is excellent in light sensitivity by mix | blending 1 mass part or more with respect to 100 mass parts of (A) resin, and mix | blending 20 mass parts or less with the (meth) acryl compound which has an amino group as a photosensitive agent, and is excellent in thick film hardenability.

Next, the case where a positive type is desired is demonstrated. In this case, a photoacid generator is used as the (C) photosensitive agent, and specifically, a diazoquinone compound, an onium salt, a halogen-containing compound, etc. can be used, but it has a diazoquinone structure from a solvent solubility and storage stability viewpoint. Compounds are preferred.

The diazoquinone compound is a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure, and is described in US Patent Nos. 2,772,972, 2,797,213, 3,669,658, and the like. By the substance already known. As an example of a preferable diazoquinone compound, the following general formula (30):

[Formula 44]

(30)

(30)

In Formula, Q is a hydrogen atom or following formula (31):

[Formula 45]

(31)

(31)

It is a naphthoquinone diazide sulfonic-acid ester group shown, and all Q is not the hydrogen atom at the same time. What is represented by Y is mentioned.

Among the naphthoquinone diazide sulfonic acid ester groups represented by the general formula (30), the following general formula (32):

[Formula 46]

(32)

(32)

In formula, Q is as defined in the said General formula (31).

It is especially preferable to represent.

Examples of the onium salts include iodonium salts, sulfonium salts, posiponium salts, phosphonium salts, ammonium salts and diazonium salts, and the like. Onium salts are preferred.

A haloalkyl group containing hydrocarbon compound etc. are mentioned as said halogen containing compound, and trichloromethyl triazine is preferable.

The compounding quantity of these photo-acid generators is 1-100 mass parts of (A) resin. 50 parts by mass and 5? 30 mass parts is preferable. (C) Patterning property by the photosensitive resin composition is favorable when the compounding quantity of the photo-acid generator as a photosensitive agent is 1 mass part or more, tensile elongation of the film | membrane after hardening of the photosensitive resin composition is favorable, and the image development residue of an exposure part is 50 mass parts or less. Less scum

You may make the photosensitive resin composition of this invention contain (D) crosslinking agent. When the crosslinking agent heat-cures the relief pattern formed using the photosensitive resin composition of this invention, (A) resin can be crosslinked, or the crosslinking agent itself can be a crosslinking agent which can form a crosslinking network. The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film formed of the photosensitive resin composition.

As a crosslinking agent, for example, having one thermally crosslinkable group, ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC (above, trade name, Honshu Chemical Industries, Ltd.) ), Pa type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), such as DM-BI25X-F, 46DMOC, 46DMOIPP, 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, 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, Honshu Chemical industry Co., Ltd., Nikarak MX-290 (brand name, Sanwa Chemical Co., Ltd.),

Ba type benzoxazine, Bm type benzoxazine (above, brand name, Shikoku Chemical Co., Ltd. product), 2, 6- dimethoxymethyl- 4-t- butylphenol, 2, 6- dimethoxymethyl- p- 4, such as cresol, 2, 6- diacetoxymethyl-p-cresol, etc. which have three, such as TriML-P, TriML-35XL, and TriML-TrisCR-HAP (above, brand names, Honshu Chemical Industries, Ltd. make) TM-BIP-A (trade name, manufactured by Asahi Organics Industry Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (above, trade name, Honshu Chemical Industry Co., Ltd.) ), Nicarac MX-280, Nicarac MX-270 (above, brand name, Sanwa Chemical Co., Ltd.), such as HML-TPPHBA, HML-TPHAP (above, brand name, Honshu Chemical Industry Co., Ltd.) (Manufactured), and Nicarak MW-390, and Nicarak MW-100LM (above, brand names, Sanwa Chemical Co., Ltd.).

Among these, in this invention, it is preferable to contain at least 2 thermal crosslinkable groups, Especially preferably, 46DMOC, 46DMOEP (above, a brand name, Asahi Organics Industry Co., Ltd. product), 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, trade name, Honshu Chemical Industry Co., Ltd., Nikarak MX-290 (brand name, Sanwa Chemical Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine (above, brand name, Shikoku Kasei Kogyo Co., Ltd.), 2 , 6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol and the like, TriML-P, TriML-35XL (or more, TM-BIP-A (trade name, manufactured by Asahi Organics Industry Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (Above, brand name, Honshu Chemical Industry Co., Ltd.), Nikarak MX-280, Nikarak MX-270 (above, brand name, San There may be mentioned Chemical Co.), etc., HML-TPPHBA, such as HML-TPHAP (or more, trade name, manufactured by Honshu Chemical Industry Co., Ltd.). Moreover, More preferably, Nikarak MX-290, Nikarak MX-280, Nikarak MX-270 (above, brand name, Sanwa Chemical Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine (or more) , Nikorak MW-390, Nikarak MW-100LM (above, brand names, Sanwa Chemical Co., Ltd.), etc. are mentioned.

In the balance with various performances other than heat resistance and chemical resistance, the compounding quantity when the photosensitive resin composition contains a crosslinking agent is 0.5 to 100 mass parts of (A) resin. It is preferable that it is 20 mass parts, More preferably, it is 2? 10 parts by mass. When the compounding quantity is 0.5 mass part or more, favorable heat resistance and chemical-resistance are expressed, and when it is 20 mass parts or less, it is excellent in storage stability.

(E) organic titanium compound

In the photosensitive resin composition of this invention, you may contain (E) organic titanium compound. By containing (E) organic titanium compound, even when hardened at about 250 degreeC low temperature, the photosensitive resin layer excellent in chemical-resistance can be formed. Moreover, especially when both (B) purine derivative and (E) organic titanium compound are contained in the photosensitive resin composition, the resin layer after curing shows the effect which is excellent in chemical-resistance in addition to board | substrate adhesiveness.

(E) As an organic titanium compound which can be used as an organic titanium compound, what the organic chemical substance couple | bonded with the titanium atom via the covalent bond or the ionic bond is mentioned.

(E) Specific examples of the organic titanium compound include the following I)? VII) is shown as follows:

I) Titanium chelate compound: Among them, a titanium chelate having two or more alkoxy groups is more preferable in that the storage stability and a good pattern of the negative photosensitive resin composition can be obtained, and specific examples thereof are titanium bis (triethanolamine) diisopro. Poxide, titanium di (n-butoxide) bis (2,4-pentanedionate), titanium diisopropoxide bis (2,4-pentanedionate), titanium diisopropoxide bis (tetramethylheptanedio Nate), titanium diisopropoxide bis (ethylacetoacetate), and the like.

II) Tetraalkoxy titanium compound: For example, titanium tetra (n-butoxide), titanium tetraethoxide, titanium tetra (2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium Tetramethoxyside, titanium tetramethoxypropoxide, titanium tetramethylphenoxyside, titanium tetra (n-nonyloxide), titanium tetra (n-propoxide), titanium tetrastearyl oxide, titanium tetrakis [bis {2,2- (aryloxymethyl) butoxide}] and the like.

III) Titanocene compound: For example, pentamethylcyclopentadienyl titanium trimethoxyside, bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluorophenyl) Titanium, bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, and the like.

IV) Monoalkoxy titanium compound: For example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide, etc.

V) Titanium oxide compound: For example, titanium oxide bis (pentane dionate), titanium oxide bis (tetramethylheptanedionate), a phthalocyanine titanium oxide, etc. are mentioned.

VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetonate.

VII) Titanate coupling agent: For example, isopropyl tridodecylbenzenesulfonyl titanate and the like.

Among them, the (E) organic titanium compound is at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxy titanium compound, and III) titanocene compound, which shows better chemical resistance. It is preferable from a viewpoint. In particular, titanium diisopropoxide bis (ethylacetoacetate), titanium tetra (n-butoxide), and bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluoro Rho-3- (1H-pyrrol-1-yl) phenyl) titanium is preferred.

(E) The compounding quantity at the time of mix | blending an organic titanium compound is 0.05 to 100 mass parts of (A) resin. It is preferable that it is 10 mass parts, More preferably, it is 0.1? 2 parts by mass. When the compounding quantity is 0.05 mass part or more, favorable heat resistance and chemical-resistance are expressed, and when it is 10 mass parts or less, it is excellent in storage stability.

(F) other ingredients

The photosensitive resin composition of this invention is the said (A)? You may further contain components other than (E) component. Since the photosensitive resin composition of this invention is typically used as the photosensitive resin composition which melt | dissolved each component and the arbitrary components used further as needed in the solvent, and made it into varnish shape, as (F) other components, it is a solvent Can be mentioned. As a solvent, it is preferable to use a polar organic solvent from a solubility with respect to (A) resin. Specifically, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, Cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, and the like. These can be used individually or in combination of 2 or more types.

According to the desired coating film thickness and viscosity of the photosensitive resin composition, the said solvent is 30-30 mass% with respect to 100 mass parts of (A) resins, for example. 1500 parts by mass, preferably 100? It can be used in the range of 1000 parts by mass.

Moreover, the solvent containing alcohol is preferable from a viewpoint of improving the storage stability of the photosensitive resin composition. The alcohols which can be preferably used are typically alcohols which have an alcoholic hydroxyl group in the molecule and do not have an olefinic double bond, and specific examples thereof include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, alkyl alcohols such as n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, lactic acid esters such as ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether Propylene glycol monoalkyl ethers such as propylene glycol-2-ethyl ether, propylene glycol-1- (n-propyl) ether and propylene glycol-2- (n-propyl) ether, ethylene glycol methyl ether and ethylene glycol ethyl ether , Dial alcohols such as monoalcohols such as ethylene glycol-n-propyl ether, 2-hydroxyisobutyric acid esters, ethylene glycol and propylene glycol It may be a flow. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters and ethyl alcohol are preferable, and ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and Propylene glycol-1- (n-propyl) ether is more preferred.

When the solvent contains an alcohol having no olefinic double bond, the content of alcohol having no olefinic double bond in the total solvent is 5? It is preferable that it is 50 mass%, More preferably, it is 10? 30 mass%. When the said content of the alcohol which does not have an olefinic double bond is 5 mass% or more, the storage stability of the photosensitive resin composition becomes favorable, and when it is 50 mass% or less, the solubility of (A) resin becomes favorable.

Moreover, when forming a cured film on the board | substrate which consists of copper or a copper alloy using the photosensitive resin composition of this invention, for example, an azole compound can be mix | blended arbitrarily in order to suppress discoloration on a copper phase.

As the azole compound, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4- t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) tria Sol, 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-t-butyl-5-methyl-2-hydroxyphenyl) -benzotriazole, 2- (3,5-di-t-amyl-2- Hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-car Dipoxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. are mentioned.

Especially preferably, tolyltriazole, 5-methyl- 1H- benzotriazole, and 4-methyl- 1H- benzotriazole are mentioned. Moreover, these azole compounds may be used by 1 type, and may be used by 2 or more types of mixtures.

The compounding quantity when the photosensitive resin composition contains the said azole compound is 0.1? With respect to 100 mass parts of (A) resin. It is preferable that it is 20 mass parts, and it is 0.5-from a viewpoint of photosensitivity characteristic. 5 mass parts is more preferable. When the compounding quantity of the azole compound with respect to 100 mass parts of (A) resin is discolored on the surface of copper or a copper alloy, when the photosensitive resin composition of this invention is formed on copper or a copper alloy, When it is 20 mass parts or less, it is excellent in photosensitivity.

Moreover, in order to suppress discoloration on a copper surface, a hindered phenol compound can be mix | blended arbitrarily. As a hindered phenol compound, 2, 6- di- t- butyl- 4-methyl phenol, 2, 5- di- t- butyl- hydroquinone, octadecyl-3- (3, 5- di-t- butyl 4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis (2,6-di -t-butylphenol), 4,4'-thio-bis (3-methyl-6-t-butylphenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol) , Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2, 2'-methylene-bis (4-ethyl-6-t-butylphenol),

Pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-t-butyl-4-hydroxybenzyl)- Isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3-hydroxy Roxy-2,6-dimethyl-4-isopropylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4 -t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5- Tris (4-s-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3 , 5-tris [4- (1-ethylpropyl) -3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H)- Trion,

1,3,5-tris [4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H)- Trione, 1,3,5-tris (3-hydroxy-2,6-dimethyl-4-phenylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -Trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl) -1,3,5-triazine-2,4,6- (1H , 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2 , 4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5 -Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl ) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5,6-diethyl-3 -Hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione,

1,3,5-tris (4-t-butyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione , 1,3,5-tris (4-t-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-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 Although, 3H, 5H) -trione etc. are mentioned, It is not limited to this. Among these, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione and the like are particularly preferred.

The compounding quantity of a hindered phenol compound is 0.1 to 100 mass parts of (A) resin. It is preferable that it is 20 mass parts, and it is 0.5-from a viewpoint of photosensitivity characteristic. It is more preferable that it is 10 mass parts. When the compounding quantity of the hindered phenol compound with respect to 100 mass parts of (A) resin is 0.1 mass part or more, for example, when the photosensitive resin composition of this invention is formed on copper or a copper alloy, discoloration of copper or a copper alloy Corrosion is prevented, and when it is 20 mass parts or less, it is excellent in photosensitivity.

The photosensitive resin composition of this invention may contain components other than the said component. Preferred examples of the component differ depending on whether the resin is negative type using a polyimide precursor or the like as the resin (A) or positive type using a polyoxazole precursor or the like.

(A) In the case of the negative type which uses a polyimide precursor etc. as resin, a sensitizer can be mix | blended arbitrarily in order to improve light sensitivity. As the sensitizer, for example, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, 2,6-bis (4 '-Diethylaminobenzal) cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'- Bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethyl Aminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-di Ethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyl Oxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3- Oxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyl diethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, Dimethylaminobenzoic acid isoamyl, diethylaminobenzoic acid isoamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminosty Reyl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl Styrene, etc. may be mentioned. These alone or for example 2? It can be used in combination of five kinds.

The compounding quantity when the photosensitive resin composition contains the sensitizer for improving photosensitivity is 0.1 to 100 mass parts of (A) resin. It is preferable that it is 25 mass parts.

Moreover, in order to improve the resolution of a relief pattern, the monomer which has a photopolymerizable unsaturated bond can be mix | blended arbitrarily. As such a monomer, the (meth) acryl compound which carries out radical polymerization reaction with a photoinitiator is preferable, Although it does not specifically limit to the following, Ethylene, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, is preferable. Mono or diacrylate and methacrylate of glycol or polyethylene glycol, mono or diacrylate and methacrylate of propylene glycol or polypropylene glycol, mono, di or triacrylate and methacrylate of glycerol, cyclohexanediacryl Late and dimethacrylate, diacrylate and dimethacrylate of 1,4-butanediol, diacrylate and dimethacrylate of 1,6-hexanediol, diacrylate and dimethacrylate of neopentylglycol , Bisphenol A mono or diacrylates and methacrylates, benzene Trimethacrylate, isobornylacrylate and methacrylate, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, trimethylolpropanetriacrylate and methacrylate, di or triacrylate and methacrylate of glycerol And di, tri, or tetraacrylates and methacrylates of pentaerythritol, and compounds such as ethylene oxide and propylene oxide adducts of these compounds.

When the photosensitive resin composition contains the monomer which has the said photopolymerizable unsaturated bond for improving the resolution of a relief pattern, the compounding quantity of the monomer which has a photopolymerizable unsaturated bond is 1-100 mass parts with respect to (A) resin. It is preferable that it is 50 mass parts.

Moreover, an adhesion | attachment adjuvant can be mix | blended arbitrarily for the adhesive improvement of the film | membrane and base material formed using the photosensitive resin composition of this invention. Examples of the adhesion aid include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-mercaptopropylmethyldimethoxy Silane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide, N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3'-bis (N- [3-triethoxysilyl] Propylamide) -4,4'-dicarboxylic acid, benzene-1,4-bis (N- [3-triethoxysilyl] propylamide) -2,5-dicarboxylic acid, 3- (trie Methoxysilyl) propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3- (trialkoxysilyl) propylsuccinate There may be mentioned anhydrides, such as silane coupling agents, and aluminum tris (ethylacetoacetate), aluminum tris (acetyl acetonate), ethylacetoacetate aluminum di-isopropylate, such as aluminum-based adjuvant, such as adhesive.

In these adhesion | attachment adjuvant, it is more preferable to use a silane coupling agent from an adhesive force viewpoint. When the photosensitive resin composition contains an adhesion | attachment adjuvant, the compounding quantity of an adhesion | attachment adjuvant is 0.5 to 100 mass parts of (A) resin. The range of 25 mass parts is preferable.

Moreover, especially a thermal polymerization inhibitor can be mix | blended arbitrarily in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition at the time of storage in the solution state containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, Glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-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, etc. This is used.

As a compounding quantity of the thermal-polymerization inhibitor in the case of mix | blending with the photosensitive resin composition, it is 0.005-about 100 mass parts of (A) resin. The range of 12 mass parts is preferable.

On the other hand, in the photosensitive resin composition of this invention, in the case of the positive type which uses a polyoxazole precursor etc. as (A) resin, it is conventionally used as an additive of the photosensitive resin composition, surfactant, and a base material. An adhesion | attachment adjuvant etc. for improving adhesiveness can be added.

More specifically, the additives include methyl violet, crystal violet, malachite green and the like as the dye. Moreover, as surfactant, For example, Nonionic surfactant which consists of polyglycols, such as polypropylene glycol or polyoxyethylene lauryl ether, or its derivatives, For example, Florade (brand name, the Sumitomo 3M company make), Fluorine-based surfactants such as Megapak (trade name, manufactured by Dainippon Ink and Chemicals Co., Ltd.) or Lumipron (trade name, manufactured by Asahi Glass Co., Ltd.), for example, KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisoh Corporation) And organic siloxane surfactants such as granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). As an adhesion | attachment adjuvant, alkylimidazoline, butyric acid, alkyl acid, polyhydroxy styrene, polyvinyl methyl ether, t-butyl novolak, an epoxy silane, an epoxy polymer, etc., and various silane coupling agents are mentioned, for example. .

Specific preferred examples of the silane coupling agent include, for example, N-phenyl-3-aminopropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 2- (trialkoxysilylethyl) pyridine, 3-methacryloxypropyltri Alkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3-aminopropyltrialkoxysilane and 3-aminopropyl dialkoxyalkyl And a reaction product of a silane and an acid anhydride and an acid dianhydride, and an amino group of 3-aminopropyltrialkoxysilane or 3-aminopropyldialkoxyalkylsilane is converted to a urethane group or a urea group. At this time, the alkyl group is methyl group, ethyl group, butyl group and the like, maleic anhydride and phthalic anhydride as acid anhydride, pyromellitic dianhydride as acid 2 anhydride, 3,3 ', 4,4' -Benzophenone tetracarboxylic dianhydride, 4,4'- oxydiphthalic acid dianhydride, a t-butoxycarbonylamino group etc. are mentioned as a urethane group, A phenylaminocarbonylamino group etc. are mentioned as a urea group.

<Manufacturing method and semiconductor device of hardening relief pattern>

Moreover, this invention is the process of (1) forming the resin layer on the board | substrate by apply | coating the photosensitive resin composition of this invention mentioned above on a board | substrate, (2) exposing the resin layer, (3) The manufacturing method of the cured relief pattern is provided including the process of developing the resin layer after the exposure, and forming a relief pattern, and (4) forming the cured relief pattern by heat-processing the relief pattern. Hereinafter, the typical aspect of each process is demonstrated.

(1) Process of forming a resin layer on the board | substrate by apply | coating the photosensitive resin composition on a board | substrate.

In this process, the photosensitive resin composition of this invention is apply | coated on a base material, it is made to dry after that, and a resin layer is formed as needed. As a coating method, the method used conventionally for the application of the photosensitive resin composition, for example, the method of apply | coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, etc., the method of spray application with a spray coater, etc. can be used. Can be.

As needed, the coating film which consists of a photosensitive resin composition can be dried. As a drying method, methods, such as air drying, oven drying with a hotplate, or vacuum drying, are used. Specifically, when air drying or heat drying is performed, it is 20 degreeC? 1 minute at 140 ℃? It can dry on conditions of 1 hour. As described above, the resin layer can be formed on the substrate.

(2) Process of exposing resin layer

In this process, the resin layer formed above is exposed using a photomask or a reticle having a pattern or directly by an ultraviolet light source or the like using an exposure apparatus such as a contact aligner, a mirror projection, or a stepper.

Thereafter, for the purpose of improving the photosensitivity, after exposure bake (PEB) and / or predevelopment bake by a combination of arbitrary temperatures and times may be performed as necessary. The baking conditions range from 40 ° C. 120 ℃, and the time is 10 seconds? Although it is preferable that it is 240 second, it is not limited to this range unless the various characteristics of the photosensitive resin composition of this invention are impaired.

(3) Process of developing resin layer after exposure and forming relief pattern

In this process, image development removes the exposed part or unexposed part of the photosensitive resin layer after exposure. When using a negative photosensitive resin composition (For example, when using a polyimide precursor as (A) resin), an unexposed part develops and removes, and uses a positive photosensitive resin composition (For example, For example, in the case of using a polyoxazole precursor as the resin (A), the exposed portion is removed. As a developing method, arbitrary methods can be selected and used among the conventionally well-known photoresist image development methods, for example, a rotary spray method, a paddle method, and the immersion method with an ultrasonic treatment. Moreover, after image development, you may bake after image development by the combination of arbitrary temperature and time as needed in order to adjust the shape of a relief pattern.

As a developing solution used for image development, the good solvent with respect to the photosensitive resin composition, or the combination of this good solvent and a poor solvent is preferable. For example, in the case of the photosensitive resin composition which does not melt | dissolve in aqueous alkali solution, as a good solvent, N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N- dimethylacetamide, cyclopentanone, Cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like are preferred, and the poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate and Water and the like are preferred. When mixing and using a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent with respect to a good solvent by the solubility of the polymer in the photosensitive resin composition. Moreover, you may use each solvent in combination of 2 or more types, for example.

On the other hand, in the case of the photosensitive resin composition which melt | dissolves in aqueous alkali solution, the developing solution used for image development dissolves and removes the aqueous alkali solution soluble polymer, and is typically the alkaline aqueous solution which melt | dissolved the alkali compound. The alkali compound dissolved in the developer may be either an inorganic alkali compound or an organic alkali compound.

As the inorganic alkali compound, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate And lithium borate, sodium borate, potassium borate and ammonia.

Moreover, as this organic alkali compound, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethyl Amine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine, and the like.

If necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol or ethylene glycol, a surfactant, a storage stabilizer, and a dissolution inhibiting agent of resin can be added to the alkaline aqueous solution. The relief pattern can be formed as mentioned above.

(4) Process of forming hardening relief pattern by heat-processing relief pattern

In this process, it converts into a hardening relief pattern by heating the relief pattern obtained by the said image development. As a method of heat hardening, various methods, such as using a hotplate, using an oven, and using the temperature rising oven which can set a temperature program, can be selected. Heating is for example 180 ℃? 30 minutes at 400 ℃? It can carry out on condition of 5 hours. As an atmospheric gas at the time of heat-hardening, air may be used and inert gas, such as nitrogen and argon, can also be used.

<Semiconductor device>

This invention also provides the semiconductor device containing the hardening relief pattern obtained by the manufacturing method of the hardening relief pattern of this invention mentioned above. This invention also provides the semiconductor device containing the base material which is a semiconductor element, and the hardening relief pattern of resin formed by the hardening relief pattern manufacturing method mentioned above on the said base material. Moreover, this invention is applicable also to the manufacturing method of the semiconductor device which uses the semiconductor element as a base material, and includes the manufacturing method of the hardening relief pattern mentioned above as a part of process. In the semiconductor device of the present invention, the hardening relief pattern formed by the hardening relief pattern manufacturing method is formed as a surface protective film, an interlayer insulating film, a redistribution insulating film, a protective film for a flip chip device, or a protective film of a semiconductor device having a bump structure. And it can manufacture by combining with a manufacturing method of a semiconductor device already known.

The photosensitive resin composition of this invention is useful also in uses, such as an interlayer insulation of a multilayer circuit, the cover coat of a flexible copper clad board, a soldering resist film, and a liquid crystal aligning film, in addition to the application to the above-mentioned semiconductor device.

Example

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this. In Examples, Comparative Examples, and Production Examples, physical properties of the photosensitive resin composition were measured and evaluated according to the following methods.

(1) weight average molecular weight

The weight average molecular weight (Mw) of each resin was measured by the gel permeation chromatography method (standard polystyrene conversion). The column used for the measurement is Showa Electric Co., Ltd. brand name "Shodex 805M / 806M series", and standard monodisperse polystyrene selects the Showa Electric Co., Ltd. brand name "Shodex STANDARD SM-105", and is a developing solvent. Is N-methyl-2-pyrrolidone, and the detector used the brand name "Shodex RI-930" manufactured by Showa Denko Co., Ltd.

(2) copper discoloration test

The photosensitive resin composition was spin-coated on a copper substrate, and it dried and formed the coating film of 30 micrometers thickness as a resin layer. Subsequently, in the case of the photosensitive resin composition which does not melt | dissolve in aqueous alkali solution, the coating film formed on the wafer is spray-developed by the developing machine (D-SPIN636 type | mold, Japan, the Dainippon Screen manufacturer) using cyclopentanone, and propylene glycol The coating film was completely dissolved by rinsing with methyl ether acetate. In the case of the photosensitive resin composition which melt | dissolves in aqueous alkali solution, after a 500-mJ / cm <2> energy is irradiated to the whole surface by parallel light mask aligner (PLA-501FA, Japan, Canon company), Paddle development was carried out with the developer using the alkaline developer (AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide aqueous solution), and the coating film was fully dissolved by rinsing with pure water. The copper substrate after melting was evaluated based on the following criteria:

"The best": The discoloration of a copper board | substrate is not observed even when visually observed with a 200 times optical microscope;

"Good": The discoloration of a copper substrate is not observed by the naked eye, but the discoloration of a copper substrate is slightly observed when observed with a 200 times optical microscope;

"Slightly good": Discoloration of the copper substrate is not observed by the naked eye, and discoloration of the copper substrate is observed when observed with a 200 times optical microscope;

"Poor": Discoloration of copper board is observed severely with naked eye.

(3) Copper adhesion test (substrate adhesion lattice number)

After spin-coating the photosensitive resin composition on a copper substrate, and drying and forming a 17-micrometer-thick coating film as a photosensitive resin layer, the temperature rising program type Cure (VF-2000 type | mold, Japan, Koyo Lindberg company make) It used and heat-processed (cure) at 200 degreeC for 1 hour and then at 250 degreeC in nitrogen atmosphere for 2 hours, the cured resin coating film of 10 micrometers thickness was obtained. The adhesion property between the copper substrate / cured resin coating film was evaluated based on the following criteria to the film after curing according to the cross-cut method of JISK5600-5-6 standard.

"Best": The lattice number of the cured resin coating film adhered to a board | substrate is 100.

"Good": Number of lattice of cured resin coating film adhered to substrate 80? Being 99.

"Slightly good": 50 or less lattice number of the cured resin coating film adhered to the substrate. Being one.

"Slightly bad": 20? Lattice number of the cured resin coating film adhered to the substrate. Being 49.

"Poor": The lattice number of the cured resin coating film in close contact with the substrate is less than 20.

(4) chemical resistance test

(Formation of Relief Pattern by Negative Photosensitive Resin)

The photosensitive resin composition was spin-coated on the silicon wafer (made by Kyoto International Co., Ltd.) in which the 6-inch nitride film was formed, and it dried and formed the 17-micrometer-thick coating film as a photosensitive resin layer. Energy was irradiated at 200 mJ / cm <2> and exposed by ghi stepper (Prisma-ghi, Ultratech Co., Ltd.) using the reticle in which the test pattern was formed in this coating film. Subsequently, the coating film formed on the wafer was spray-developed with a developing device (D-SPIN636 type, manufactured by Dainippon Screen Co., Ltd.) using cyclopentanone, rinsed with propylene glycol methyl ether acetate, and the unexposed part was developed and removed. , The relief pattern of the resin was obtained. The wafer on which the relief pattern was formed was heat-treated at 200 ° C. for 1 hour and then 250 ° C. for 2 hours under a nitrogen atmosphere using a temperature-programmed cure (VF-2000, manufactured by Koyo Lindberg, Japan), The hardening relief pattern of 10 micrometer thickness resin was obtained on the silicon wafer in which the nitride film was formed.

(Formation of Relief Pattern by Positive Photosensitive Resin)

The photosensitive resin composition was spin-coated on the silicon wafer (made by Tokyo International Corporation) with a 6-inch nitride film, and the coating film was formed as a photosensitive resin layer. Energy was irradiated at 300 mJ / cm <2> and exposed by i-line stepper (NSR2005i8A, Nikon Corporation make) using the reticle in which the test pattern was formed in this coating film. Subsequently, the coating film formed on the wafer was spray-developed with a developer (D-SPIN636 type, manufactured by Dainippon Screen, Japan) using a 2.38 mass% tetramethylammonium hydroxide aqueous solution, rinsed with pure water, and the exposed portion was developed and removed. , The relief pattern of the resin was obtained. The wafer on which the relief pattern was formed was heat-treated at 320 ° C. for 1 hour in a nitrogen atmosphere using a temperature-programmed cure (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd., Japan) to obtain a resin having a thickness of 10 μm. The hardening relief pattern was obtained on the silicon wafer in which the nitride film was formed.

(Chemical Resistance Evaluation of Curing Relief Pattern by Negative Photosensitive Resin)

The obtained hardening relief pattern was immersed at 100 degreeC for 1 hour in the solution which consists of 1 mass% of potassium hydroxide, 39 mass% of 3-methoxy-3-methyl-1- butanol, and 60 mass% of dimethyl sulfoxide. After water washing and air drying, the resin coating film was evaluated based on the following criteria by film thickness measurement and observation under an optical microscope:

"Best": When the film thickness variation of the coating film after immersion to the coating film before immersion is within ± 1% and no crack occurs.

"Good": When the film thickness variation of a coating film is within ± 3%, and a crack does not generate | occur | produce.

"Poor": When the thickness variation exceeds ± 3% or a crack occurs.

(Chemical resistance evaluation of hardening relief pattern by positive type photosensitive resin)

The obtained hardening relief pattern was immersed in ST-44 (brand name, ATMI company) solution at 80 degreeC for 5 minutes. After water washing and air drying, the resin coating film was evaluated based on the following criteria by film thickness measurement and observation under an optical microscope:

"Best": When the film thickness variation of the coating film after immersion to the coating film before immersion is within ± 1% and no crack occurs.

"Good": When the film thickness variation of a coating film is within ± 3%, and a crack does not generate | occur | produce.

"Poor": When the thickness variation exceeds ± 3% or a crack occurs.

<Production Example 1> (Synthesis of Polymer A as (A) Polyimide Precursor)

155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) was added to a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added to room temperature. It stirred under, and 81.5 g of pyridine was added stirring, and the reaction mixture was obtained. After completion | finish of exotherm by reaction, it was left to stand to room temperature and left to stand for 16 hours.

Next, under ice cooling, a solution in which 206.3 g of dicyclohexylcarbodiimide (DCC) was dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-dia The suspension of 93.0 g of minodiphenylether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After stirring again at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate composed of a crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration, followed by vacuum drying to obtain a powdery polymer (polymer A). The weight average molecular weight (Mw) was 20,000 as a result of measuring the molecular weight of polymer A by gel permeation chromatography (standard polystyrene conversion).

<Production Example 2> (Synthesis of Polymer B as (A) Polyimide Precursor)

Instead of using 155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) of Production Example 1, except that 147.1 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used, The reaction was carried out in the same manner as in the above-described Production Example 1 to obtain a polymer B. The weight average molecular weight (Mw) was 22,000 when the molecular weight of polymer B was measured by the gel permeation chromatography (standard polystyrene conversion).

<Production Example 3> (Synthesis of Polymer C as (A) Polyimide Precursor)

155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) was added to a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added to room temperature. It stirred under, and 81.5 g of pyridine was added stirring, and the reaction mixture was obtained. After completion | finish of exotherm by reaction, it was left to stand to room temperature and left to stand for 16 hours.

Next, under ice cooling, a solution in which 206.3 g of dicyclohexylcarbodiimide (DCC) was dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-dia The suspension of 93.0 g of minodiphenylether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After stirring at room temperature again for 2 hours, 13.6 g of 8-azadenine was added, followed by stirring for 2 hours. Next, 400 ml of γ-butyrolactone were added. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate composed of a crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration, followed by vacuum drying to obtain a powdery polymer (Polymer C). The weight average molecular weight (Mw) was 22,000 when the molecular weight of polymer C was measured by the gel permeation chromatography (standard polystyrene conversion).

<Production Example 4> (Synthesis of Polymer D as (A) Polyimide Precursor)

Instead of using 155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) of Production Example 3, except that 147.1 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used, The polymer D was obtained by reacting in the same manner as the method described in Production Example 3 described above. The weight average molecular weight (Mw) was 24,000 when the molecular weight of the polymer D was measured by the gel permeation chromatography (standard polystyrene conversion).

Production Example 5 (Synthesis of Polymer E as (A) Polyamide)

(Synthesis of Phthalic Acid Compound Seal AIPA-MO)

In a separable flask with a capacity of 5 L, 5-aminoisophthalic acid or less is abbreviated as AIPA.｝ 543.5 g and 1,700 g of N-methyl-2-pyrrolidone are charged and mixed, and the mixture is stirred to 50 ° C with a water bath. Warmed. The thing which diluted 512.0 g (3.3 mol) of 2-methacryloyl oxyethyl isocyanate to 500 g of (gamma) -butyrolactone was dripped at this with the dropping funnel, and it stirred at 50 degreeC for 2 hours as it is.

The completion of the reaction (dissipation of 5-aminoisophthalic acid) is described as low molecular weight gel permeation chromatography ｛, hereinafter referred to as low molecular weight GPC. After confirming with｝, the reaction solution is added to 15 L of ion-exchanged water, stirred, The mixture was stopped and waited for crystallization precipitation of the reaction product, and the resultant was separated by filtration. After appropriate washing with water, the resultant was dried under vacuum at 40 ° C. for 48 hours, whereby the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate worked. AIPA-MO was obtained. The low molecular weight GPC purity of the obtained AIPA-MO was about 100%.

(Synthesis of Polymer E)

Into a 2 L separable flask, 100.89 g (0.3 mol) of obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine and 400 g of GBL were charged and mixed, and cooled to 5 ° C by an ice bath. The dicyclohexylcarbodiimide (DCC) 125.0 g (0.606 mol) was melt | dissolved and diluted in 125 g of GBL over this, it dripped at about 20 minutes under ice-cooling, and then 4,4'-bis (4- Aminophenoxy) biphenyl ｛Hereinafter, it is described as BAPB.｝ 103.16 g (0.28 mol) dissolved in NMP 168 g was added dropwise over about 20 minutes, and then kept in an ice bath for 3 hours, followed by an ice bath. Was removed and stirred at room temperature for 5 hours. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

A mixture of 840 g of water and 560 g of isopropanol was added dropwise to the obtained reaction solution, the precipitated polymer was separated, and redissolved in 650 g of NMP. The obtained crude polymer solution was added dropwise to 5 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration, followed by vacuum drying to obtain a powdery polymer (polymer E). The weight average molecular weight (Mw) was 34,700 as a result of measuring the molecular weight of polymer E by gel permeation chromatography (standard polystyrene conversion).

Production Example 6 (Synthesis of Polymer F as (A) Polyoxazole Precursor)

In a separable flask with a volume of 3 L, 183.1 g of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 640.9 g of N, N-dimethylacetamide (DMAc), 63.3 g of pyridine It stirred and mixed at room temperature (25 degreeC), and set it as the homogeneous solution. What dissolve | melted 118.0 g of 4,4'- diphenyl ether dicarbonyl chlorides in 354 g of diethylene glycol dimethyl ether (DMDG) was dripped at this dropping funnel. At this time, the separable flask is 15? It cooled by the 20 degreeC water bath. The time required for dripping was 40 minutes, and reaction liquid temperature was 30 degreeC at the maximum.

After 3 hours from the end of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction solution, and the mixture was left to stand at room temperature for 15 hours to carboxylate 99% of all the amine end groups of the polymer chain. Sealed with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the residual amount of the 1,2-cyclohexyldicarboxylic acid anhydride added by high performance liquid chromatography (HPLC). Thereafter, the reaction solution was added dropwise to 2 liters of water under high speed stirring to disperse and precipitate the polymer. The polymer was recovered, washed with water and dehydrated appropriately, dried in vacuo, and measured by gel permeation chromatography (GPC). A crude polybenzoxazole precursor of 9,000 (polystyrene equivalent) was obtained.

After re-dissolving the crude polybenzoxazole precursor obtained above in γ-butyrolactone (GBL), it was treated with a cation exchange resin and an anion exchange resin, and the solution thus obtained was introduced into ion exchange water and then precipitated. The purified polybenzoxazole precursor F (polymer F) was obtained by filtering a polymer, washing with water, and vacuum drying.

<Production Example 7> (Synthesis of Polymer G as (A) Polyimide)

A glass-separable four-necked flask equipped with a Teflon® anchor type stirrer was equipped with a cooling tube with a Deanstock trap. The flask was immersed in a silicon oil bath while stirring with nitrogen gas.

2,2-bis (3-amino-4-hydroxyphenyl) propane (manufactured by Clariant Japan) (hereinafter referred to as BAP) 72.28 g (280 mmol), 5- (2,5-dioxotetrahydro-3 -Furanyl) -3-methyl-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC) 70.29 g (266 mmol), γ-butyrolactone 254.6 g And 60 g of toluene were added, after stirring for 4 hours at 100 rpm at room temperature, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic anhydride (made by Tokyo Chemical Industry Co., Ltd.) was added, The mixture was heated and stirred at 100 rpm at a silicon bath temperature of 50 ° C. for 8 hours while passing nitrogen gas. Then, it heated up at 180 degreeC of silicone bath temperature, and stirred by heating at 100 rpm for 2 hours. During the reaction, toluene and water were removed. After completion | finish of imidation reaction, it returned to room temperature.

Thereafter, the reaction solution was added dropwise to 3 liters of water under high speed stirring to disperse and precipitate the polymer. The polymer was recovered, washed with water and dehydrated appropriately, dried in vacuo, and measured by gel permeation chromatography (GPC). Crude polyimide of 23,000 (polystyrene equivalent) was obtained.

<Example 1>

The negative photosensitive resin composition was prepared by the following method using polymer A and B, and the prepared photosensitive resin composition was evaluated. 50 g of polymer A and 50 g of B which are polyimide precursors (corresponding to (A) resin), 0.2 g of 8-azadenine (corresponding to (B) purine derivative), 1-phenyl-1,2-propanedione-2 -(o-ethoxycarbonyl) -oxime (refer to "PDO" in Table 1) (corresponds to (C) sensitizer) 4 g, 1,3,5-tris (4-t-butyl-3-hydro Roxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione 1.5 g, N-phenyldiethanolamine 10 g, methoxymethylated Urea resin (MX-290) (corresponding to (D) crosslinking agent) 4 g, tetraethylene glycol dimethacrylate 8 g, N- [3- (triethoxysilyl) propyl] phthalamic acid, and 2- Together with 0.05 g of nitroso-1-naphthol, it was dissolved in a mixed solvent consisting of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the said mixed solvent, and it was set as the negative photosensitive resin composition.

When the said negative photosensitive resin composition was evaluated in accordance with the method mentioned above, evaluation of copper discoloration was "best", evaluation of copper adhesion was "best", and evaluation of chemical-resistance was "good".

<Examples 2 and 3>

The compounding quantity of 8-azadenine as (B) purine derivative in this invention of Example 1 was changed into the compositional content shown in Table 1, the negative photosensitive resin composition was prepared, and each evaluation similar to Example 1 is performed. It was. In any case, it evaluated by the method similar to Example 1, and the evaluation result was the same as that of Example 1.

<Example 4>

The compounding quantity of 8-azadenine as (B) purine derivative in this invention of Example 1 was changed to the composition content shown in Table 1, the negative photosensitive resin composition was prepared, and the same evaluation as Example 1 was performed. . The result of evaluating copper discoloration was "good", and the result of evaluating copper adhesion was "good". The evaluation result of chemical resistance was the same as that of Example 1.

<Example 5>

The compounding quantity of 8-azadenine as (B) purine derivative in this invention of Example 1 was changed to the composition content shown in Table 1, the negative photosensitive resin composition was prepared, and the same evaluation as Example 1 was performed. . Evaluation results were the same as in Example 1.

<Example 6>

Instead of 8-azadenine as (B) purine derivative of Example 1 of this invention, the negative photosensitive resin composition was prepared using 8-azaguanine as the composition content shown in Table 1, and Example 1 and The same evaluation was performed. Evaluation results were the same as in Example 1.

<Example 7>

Instead of 8-azadenine as (B) purine derivative in Example 1 of Example 1, adenine was used for the compositional content shown in Table 1, the negative photosensitive resin composition was prepared, and the same evaluation as Example 1 was performed. Was carried out. The result of evaluating copper discoloration was "good", and the result of evaluating copper adhesion was "good". The evaluation result of chemical resistance was the same as that of Example 1.

<Example 8>

Instead of 8-azadenine as the (B) purine derivative in Example 1 of Example 1, a negative photosensitive resin composition was prepared using N, N-dimethyl adenine as the composition content shown in Table 1, and Example Evaluation similar to 1 was performed. The result of evaluating copper discoloration was "good", and the result of evaluating copper adhesion was "slightly good." The evaluation result of chemical resistance was the same as that of Example 1.

<Example 9>

Instead of 8-azadenine as (B) purine derivative in Example 1 of this invention, hypoxanthine was used for the compositional content shown in Table 1, the negative photosensitive resin composition was prepared, and evaluation similar to Example 1 was performed. Was carried out. The result of evaluating copper discoloration was "slightly good", and the result of evaluating copper adhesion was "slightly good". The evaluation result of chemical resistance was the same as that of Example 1.

<Example 10>

A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that 0.1 g of titanium diisopropoxide bis (ethylacetoacetate) (E1) was further added to the composition of Example 1 (E) as an organic titanium compound. Was prepared. As a result of performing chemical-resistance evaluation, the film thickness fluctuation of a film | membrane variation was within +/- 1%, and no crack was observed and it was "best." Other evaluation results were the same as in Example 1.

<Example 11>

A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that 0.1 g of titanium tetra (n-butoxide) (E2) as the organic titanium compound (E) was further added to the composition of Example 1. As a result of performing chemical-resistance evaluation, the film thickness fluctuation of a film | membrane variation was within +/- 1%, and no crack was observed and it was "best." Other evaluation results were the same as in Example 1.

<Example 12>

In addition to the composition of Example 1, (E) bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1) as an organic titanium compound A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that 0.1 g of -yl) phenyl) titanium (E3) was added. As a result of performing chemical-resistance evaluation, the film thickness fluctuation of a film | membrane variation was within +/- 1%, and no crack was observed and it was "best." Other evaluation results were the same as in Example 1.

<Example 13>

As a resin (A) in the present invention, a negative photosensitive resin composition was prepared in the same manner as in Example 10 except that Polymer A 100 g was used instead of Polymer A 50 g and Polymer B 50 g, and Example 1 The same evaluation was performed. The evaluation result was the same as in Example 10.

<Example 14>

As a resin (A) in the present invention, a negative photosensitive resin composition was prepared in the same manner as in Example 1, except that Polymer E 100 g was used instead of Polymer A 50 g and Polymer B 50 g. The same evaluation was performed. Evaluation results were the same as in Example 1.

<Example 15>

Positive polymer photosensitive resin composition was prepared using the polymer F by the following method, and the prepared photosensitive resin composition was evaluated. Polymer F 100 g (corresponding to (A) resin) which is a polyoxazole precursor was represented by the following formula (33):

[Formula 47]

(33)

(33)

20 g of photosensitive diazoquinone compounds obtained by naphthoquinone diazide-4-sulfonic acid esterification of 77% of phenolic hydroxyl groups (corresponding to Toyo Synthetic Co., Ltd. (C) photosensitive agent) , 0.2 g of 8-azadenine (corresponding to (B) purine derivative) and 6 g of 3-t-butoxycarbonylaminopropyltriethoxysilane were dissolved in 100 g of γ-butyrolactone (as a solvent). . The viscosity of the obtained solution was adjusted to about 20 poise by adding a small amount of (gamma) -butyrolactone further, and it was set as positive type photosensitive resin composition.

When the said positive photosensitive resin composition was evaluated in accordance with the above-mentioned method, evaluation of copper discoloration was "best", evaluation of copper adhesion was "best", and evaluation of chemical-resistance was "good".

<Example 16>

A positive photosensitive resin composition was prepared in the same manner as in Example 15 except that Polymer G 100 g was used instead of Polymer F 100 g as the resin (A) in the present invention, and the same evaluation as in Example 15 was performed. It was. The evaluation result was the same as in Example 15.

<Comparative Example 1>

Except having added benzotriazole in the compounding quantity shown in Table 1 from the composition of Example 1 except having added benzotriazole, it carried out similarly to Example 1, and prepared the negative photosensitive resin composition, and the evaluation similar to Example 1 Was carried out. Although the polyimide coating film obtained by the application | coating, drying, exposure, image development, and heat processing to the silicon wafer and the copper substrate which were mentioned above was evaluated as "good", it contains the (B) purine derivative of this invention. Since it did not, evaluation of copper discoloration was "defect", and evaluation of copper adhesion was "slightly defective."

<Comparative Example 2>

Without blending benzotriazole in the composition of Comparative Example 1, and as the (A) polyimide precursor in the present invention, 50 g of polymer A and 50 g of polymer D were used instead of 50 g of polymer A and 50 g of polymer B. In the same manner as in Comparative Example 1, a negative photosensitive resin composition was prepared, and the same evaluation as in Example 1 was performed. The polyimide coating film obtained by coating, drying, exposing, developing, and heating the silicon wafer and the copper substrate according to the above-described method was evaluated as "good" in chemical resistance, but evaluation of copper discoloration was "bad", Evaluation of copper adhesion was "slightly favorable."

Industrial availability

The photosensitive resin composition of this invention can be preferably used in the field of the photosensitive material useful for manufacture of electrical and electronic materials, such as a semiconductor device and a multilayer wiring board, for example.

Claims (11)

(A) polyhydroxyamides, polyaminoamides, polyamides, polyamideimides, polyimides, polybenzoxazoles, polybenzoes, which may be polyamide acids, polyamic acid esters, and polyoxazole precursors which are polyimide precursors At least one resin selected from the group consisting of imidazole and polybenzthiazole: 100 parts by mass,
(B) Purine derivative: 0.01? Based on 100 parts by mass of the (A) resin. 10 parts by mass, and
(C) Photosensitive agent: 1? 50 parts by mass
Photosensitive resin composition containing. The method of claim 1,
The said (A) resin is following General formula (1):
[Formula 1]

(One)
In formula, X <_1> is a tetravalent organic group, Y <_1> is a divalent organic group, n <_1> is 2? An integer of 150, and R ₁ and R ₂ are each independently a hydrogen atom or the following general formula (2):
(2)

(2)
(In formula, R <_3> , R <_4> and R <_5> are respectively independently a hydrogen atom or a C1-C3 organic group, and m <_1> is an integer of 2-10.) Monovalent organic group represented by C1 or C1-C1 ? It is a saturated aliphatic group of 4. The polyimide precursor which has a structure represented by X, General formula (3) shown below:
(3)

(3)
In formula, X <_2> has 6? It is a trivalent organic group of 15, Y <_2> is C6? It is a 35-valent divalent organic group, may have the same structure, or may have multiple structure, and R <_6> is C3-C? It is an organic group which has at least 1 radically polymerizable unsaturated bond group of 20, and n <_2> is 1? An integer of 1000.
Polyamide having a structure represented by the following general formula (4):
[Chemical Formula 4]

(4)
In formula, Y <_3> is a tetravalent organic group which has a carbon atom, Y <_4> , X <_3> and X <_4> are each independently a divalent organic group which has 2 or more carbon atoms, and n <_3> is 1? Is an integer of 1000 and n ₄ is 0? An integer of 500, n ₃ / (n ₃ + n ₄ )> 0.5, and n ₃ dihydroxydiamide units comprising X ₃ and Y ₃ and n ₄ dia comprising X ₄ and Y ₄ The order of the mid units does not matter.
Polyoxazole precursor which has a structure represented by following, and following General formula (5):
[Chemical Formula 5]

(5)
In the formula, X ₅ is 4? 14 valence organic group, Y ₅ is 2? The divalent organic group, R ₇ and R ₈ each independently represent an organic group having at least one group selected from phenolic hydroxyl group, sulfonic acid group or thiol group, and n ₅ is 3? Is an integer of 200, and m <_2> and m <_3> are 0? Represents an integer of 10.
The photosensitive resin composition which is at least 1 sort (s) of resin chosen from the group which consists of polyimide which has a structure shown by the following. The method according to claim 1 or 2,
The (B) purine derivative is represented by the following general formula (6):
[Formula 6]

(6)
In formula, R <_9> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? An alkyl group or aromatic group of ₁₀ , and R ₁₀ represents a hydrogen atom, a halogen atom, or a carbon atom; 6 alkoxy group, hydroxyl group, hydroxyalkyl group or C1-C? It is an amino group which may be substituted by the alkyl group or aromatic group of 10. The compound represented by v, following general formula (7):
[Formula 7]
(7)
In formula, R <_11> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? An alkyl group or an aromatic group of 10, and R ₁₂ and R ₁₃ each independently represent a hydrogen atom, a hydroxyl group, a hydroxyalkyl group or a carbon atom; It is an alkyl group or aromatic group of 10. The compound represented by i, the following general formula (8):
[Chemical Formula 8]

(8)
In formula, R <_14> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? An alkyl group or an aromatic group of 10, and R ₁₅ represents a hydrogen atom, a halogen atom or C 1? 6 alkoxy group, hydroxyl group, hydroxyalkyl group or C1-C? It is an amino group which may be substituted by the alkyl group or aromatic group of 10. The compound represented by X and following General formula (9):
[Formula 9]

(9)
In formula, R <_16> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? An alkyl group or an aromatic group of 10, and R ₁₇ and R ₁₈ each independently represent a hydrogen atom, a hydroxyl group, a hydroxyalkyl group or a carbon atom; It is an alkyl group or an aromatic group of 10. The photosensitive resin composition which is at least 1 sort (s) of purine derivatives chosen from the group which consists of a compound shown by v. The method according to any one of claims 1 to 3,
The (B) purine derivative is represented by the following general formula (10):
[Formula 10]

10
In formula, R <_19> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? It is an alkyl group or aromatic group of 10. The compound represented by v, following general formula (11):
(11)

(11)
In formula, R <_20> is a hydrogen atom, a hydroxyalkyl group, or C1-C? It is an alkyl group of 10. The compound represented by X, following General formula (12):
[Formula 12]

(12)
In formula, R <_21> is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or C1-C? It is an alkyl group or aromatic group of 10. The compound represented by X and following General formula (13):
[Formula 13]

(13)
In formula, R <_22> represents a hydrogen atom, a hydroxyalkyl group, or C1-C? It is an alkyl group of 10. The photosensitive resin composition which is at least 1 sort (s) of purine derivatives chosen from the group which consists of a compound shown by v. The method according to any one of claims 1 to 3,
The photosensitive resin composition whose said (B) purine derivative is at least 1 sort (s) of compound chosen from the group which consists of a compound represented by the said General formula (12), and the compound represented by the said General formula (13). 6. The method according to any one of claims 1 to 5,
(D) Crosslinking agent: 0.5-based on 100 mass parts of said (A) resins. The photosensitive resin composition which further contains 20 mass parts. The method according to any one of claims 1 to 6,
(E) Organic titanium compound: 0.05? On the basis of 100 parts by mass of the above (A) resin. The photosensitive resin composition containing 10 mass parts further. The method of claim 7, wherein
The said (E) organic titanium compound is the photosensitive resin composition which is at least 1 sort (s) of compound chosen from the group which consists of a titanium chelate compound, a tetraalkoxy titanium compound, and a titanocene compound. (1) Process of forming the photosensitive resin layer on the board | substrate by apply | coating the photosensitive resin composition of any one of Claims 1-8 on a board | substrate,
(2) exposing the photosensitive resin layer,
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) Process of forming hardening relief pattern by heat-processing the relief pattern
Method of producing a cured relief pattern comprising a. The method of claim 9,
The substrate is formed of copper or a copper alloy. The semiconductor device containing the hardening relief pattern obtained by the manufacturing method of Claim 9 or 10.