KR101249605B1 - Photosensitive resin composition, process for producing cured relief pattern, and semiconductor device - Google Patents

Abstract

The present invention has a photosensitive resin composition having a high residual film ratio at the time of curing when forming a cyclized resin, having a high sensitivity and positive lithography performance, a method of producing a cured relief pattern using the photosensitive resin composition, and a cured relief pattern thereof. A semiconductor device is provided. The photosensitive resin composition of this invention is a hydroxyl group in the alpha position of (A) 100 mass parts of aqueous alkali aqueous solution soluble polymers which have a specific precursor structure, (B) 1-50 mass parts of photoacid generators, and (C) carboxyl group, It contains 5-20 mass parts of monocarboxylic acid compounds with 8 or more carbon atoms which have at least 1 functional group chosen from the group which consists of an ether group and an ester group.

Description

PHOTOSENSITIVE RESIN COMPOSITION, PROCESS FOR PRODUCING CURED RELIEF PATTERN, AND SEMICONDUCTOR DEVICE}

A semiconductor device having a photosensitive resin composition which is a precursor of a heat resistant resin that can be used as a surface protective film and an interlayer insulating film of a semiconductor device, a method of producing a cured relief pattern having heat resistance using the photosensitive resin composition, and a cured relief pattern It is about.

BACKGROUND OF THE INVENTION Polyimide resins having excellent heat resistance, electrical properties, mechanical properties, and the like are widely used for surface protective films and interlayer insulating films of semiconductor devices. This polyimide resin is often provided in the form of the photosensitive polyimide precursor composition now generally. In the process of manufacturing a semiconductor device, the precursor composition is applied to a substrate such as a silicon wafer to form a precursor layer, the precursor layer is patterned using active light, the precursor layer is developed, and the precursor layer By heat-imidizing, a polyimide resin film can be easily formed as a surface protection film, an interlayer insulation film, etc. which are a part of the semiconductor device. Therefore, the manufacturing process of the semiconductor device using the photosensitive polyimide precursor composition is large compared with the manufacturing process using the conventional nonphotosensitive polyimide precursor composition which needed to pattern these by the lithographic method after forming surface protection film etc. It has the characteristic that process shortening becomes possible.

By the way, in the image development process of this photosensitive polyimide precursor composition, it is necessary to use organic solvents, such as N-methyl- 2-pyrrolidone, as a developing solution. Therefore, there has been a demand for an anti-organic solvent countermeasure due to the recent increase in environmental problems. For this reason, in recent years, various proposals of the heat resistant photosensitive resin material which can be developed with alkaline aqueous solution like the photoresist are made | formed.

Especially, the alkaline aqueous solution soluble hydroxy polyamide which becomes a heat resistant resin after hardening, for example, a polybenzoxazole (henceforth "PBO") precursor, is made into photoacid generators, such as a naphthoquinone diazide compound; Patent Literatures 1 and 2 disclose a method of using a mixed PBO precursor composition as a photosensitive resin composition, which has attracted attention in recent years.

The developing mechanism of this photosensitive resin composition, which is a PBO precursor composition, has a slow dissolution rate for the naphthoquinone diazide compound of the unexposed portion and the alkaline aqueous solution of the PBO precursor, while the naphthoquinone diazide compound (i. The quinquinone compound) is chemically changed to an indencarboxylic acid compound to increase the dissolution rate in the alkaline aqueous solution of the exposed part. By using the difference of the dissolution rate with respect to the developing solution between this exposure part and an unexposed part, the relief pattern which consists of an unexposed part can be manufactured.

A positive relief pattern can be formed by developing the above-mentioned PBO precursor composition by exposure and alkaline aqueous solution. In addition, when the PBO precursor composition is heated, an oxazole ring is formed, and the PBO film after curing has thermosetting film properties equivalent to that of the polyimide film, so that the PBO precursor composition is a promising substitute material for the organic solvent developing polyimide precursor composition. It is attracting attention as.

In patent document 3, the photosensitive resin composition which consists of a phenolic hydroxyl group containing solvent soluble polyimide (henceforth "soluble PI"), and a naphthoquinone diazide compound is proposed.

In patent document 4, the composition which can be negative-type patterned by adding a naphthoquinone diazide compound and a specific organic acid to PBO precursor or PI precursor is proposed.

In patent document 5, the highly sensitive photosensitive resin composition obtained by combining organic acid, such as m-toluic acid and m-anisic acid, as an essential component with a PBO precursor as an essential component is proposed.

Japanese Patent Publication No. 01-046862 Japanese Laid-Open Patent Publication No. 63-096162 International Publication No. 07/029614 Pamphlet Japanese Patent Application Laid-Open No. 04-186247 International Publication No. 08/020573

However, the PBO precursor composition and soluble PI composition proposed in the above-mentioned patent document have a problem that a sensitivity is low compared with the photosensitive polyimide precursor composition, and there exists a demand for a more sensitive composition.

In the negative photosensitive system proposed by Patent Document 4, it is difficult to produce a high resolution which is a characteristic of a positive type. Moreover, in the technique of patent document 5, since a PBO precursor volatilizes at the time of cyclization resin formation, the improvement of the residual film rate at the time of hardening at the time of cyclization resin formation was calculated | required.

The present invention has a photosensitive resin composition having a high residual film ratio at the time of curing when forming a cyclized resin, having a high sensitivity and positive lithography performance, a method of producing a cured relief pattern using the photosensitive resin composition, and a cured relief pattern thereof. It is an object to provide a semiconductor device.

MEANS TO SOLVE THE PROBLEM This inventor solved the said subject by combining the photoacid generator and specific monocarboxylic acid with the heat resistant alkali aqueous solution soluble polymer which has a specific structure, and the residual film rate at the time of hardening at the time of forming a cyclization resin is high, The photosensitive resin composition which has a positive lithography performance was discovered, and the present invention was achieved. That is, the present invention is as follows.

 [1] (A) The following general formula (1):

(Wherein, X ₁ and Y ₁ each independently represent a divalent tetravalent organic group having at least two carbon atoms, and R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). , n ₁ , n ₂ , n ₃ and n ₄ are each independently an integer of 0 to 2, n ₁ + n ₂ + n ₃ + n ₄ > 0, and m ₁ is an integer of 1 to 1000)

Structure represented by following General formula (2):

(Wherein, X ₂ and Y ₂ each independently represent a tetravalent organic group having at least two carbon atoms, and m ₂ is an integer of 1 to 1000)

100 parts by mass of an aqueous alkali solution soluble polymer (hereinafter, also referred to as "(A) alkali aqueous solution soluble polymer") having at least one kind of structure selected from the group consisting of structures represented by

(B) 1-50 mass parts of photoacid generators, and

(C) Monocarboxylic acid compound of 8 or more carbon atoms which has at least 1 functional group chosen from the group which consists of a hydroxyl group, an ether group, and ester group in the (alpha) position of a carboxyl group (Hereinafter, "(C) monocarboxylic acid compound Photosensitive resin composition containing 5-20 mass parts.

[2] The photosensitive resin composition according to the above [1], wherein the photoacid generator (B) is a compound having a naphthoquinone diazide structure.

[3] The (C) monocarboxylic acid compound of the following general formula (3):

Wherein R ₁ represents an organic group, R ₂ represents a group having at least one structure selected from the group consisting of a hydrogen atom and an alkyl group, and Z ₁ is selected from the group consisting of a hydroxyl group, an ether group and an ester group Group having at least one functional group)

The photosensitive resin composition as described in said [1] or [2] which is an at least 1 sort (s) of compound represented by the group which consists of a compound with 8-30 carbon atoms.

[4] The (C) monocarboxylic acid compound of the following general formula (4):

(Wherein R ₃ represents a group having at least one structure selected from the group consisting of a hydrogen atom and an alkyl group, R ₄ represents a group having at least one structure selected from the group consisting of a hydrogen atom, an alkyl group and a carbonyl group, Z ₂ represents a hydroxyl group or an organic group, n ₅ is an integer of 0 to 5, and in the case where a plurality of Z ₂ are present, they may be the same as or different from each other)

The photosensitive resin composition in any one of said [1]-[3] which is an at least 1 sort (s) of compound chosen from the group which consists of a compound with 8-30 carbon atoms.

[5] The structure represented by the general formula (1) in the aqueous alkali-soluble polymer (A) has the following general formula (5):

(In formula, X <_1> represents the bivalent tetravalent organic group which has at least 2 carbon atom, R <_1> represents a hydrogen atom or a C1-C10 hydrocarbon group, n <_1> and n <_3> are respectively independently 0- is an integer of _{2, n 1 + n 3>} 0 and, m ₁ is an integer of _{1 ~ 1000, L 1, L} 2 and L ₃ each independently represents a hydrogen atom or a methyl group, and L ₄ represents a hydrogen atom, Methyl group or hydroxyl group)

The photosensitive resin composition in any one of said [1]-[4] which has a structure shown by these.

[6] The structure represented by the general formula (1) in the aqueous alkali-soluble polymer (A) is the following general formula (6):

(Wherein X ₃ is a single bond and the following formula (7):

At least 1 type of structure chosen from the group which consists of a structure shown by these, L <_1> , L <_2> and L <_3> respectively independently represent a hydrogen atom or a methyl group, L <_4> represents a hydrogen atom, a methyl group, or a hydroxyl group, and m ₁ is an integer of 1 to 1000)

The photosensitive resin composition in any one of said [1]-[5] which has a structure shown by these.

[7] The structure represented by the above general formula (2) in the aqueous alkali-soluble polymer (A) is a structure represented by the following general formula (8) and a structure represented by the following general formula (9):

(Wherein X ₄ is a single bond and the following formula (7):

At least 1 type of structure chosen from the group which consists of a structure shown by these, and m <_2> is an integer of 1-1000)

The photosensitive resin composition in any one of said [1]-[6] which has at least 1 sort (s) of polyimide structure chosen from the group which consists of in a molecule | numerator.

[8] The terminal of the aqueous alkali-soluble polymer (A) is the following General Formula (10):

(Wherein L ₅ represents —CH ₂ —, —O— or —S—, and L ₆ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 1 to 6 carbon atoms)

The photosensitive resin composition in any one of said [1]-[7] containing at least 1 sort (s) of terminal group chosen from the group which consists of terminal groups shown by these.

[9] The above-mentioned [1]-further containing (D) a compound having three or more organic groups capable of crosslinking in a molecule, in an amount of 1 to 40 parts by mass based on 100 parts by mass of the aqueous alkali solution-soluble polymer (A). The photosensitive resin composition in any one of [8].

[10] The compound having three or more organic groups capable of crosslinking (D) in a molecule thereof is trimethylolpropanetrimethacrylate, trimellitic acid triallyl, and the following general formula (11):

In the formula, D ₁ represents a group having at least one structure selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and an organic group that can be crosslinked, M ₁ represents -CH _2- , -O- or -S-, Z ₃ represents a divalent organic group, n ₆ is an integer of 0 to 4, and a plurality of D ₁ are the same as each other. May be different)

The photosensitive resin composition as described in said [9] which is at least 1 sort (s) of compound chosen from the group which consists of a compound shown by these.

[11] The compound having three or more organic groups in the molecule (D) capable of crosslinking is represented by the following formula (12):

The photosensitive resin composition as described in said [9] or [10] which is at least 1 sort (s) of compound chosen from the group which consists of a compound shown by these.

[12] (1) Process of forming photosensitive resin layer which consists of photosensitive resin composition in any one of said [1]-[11] on board | substrate,

(2) forming an exposed portion by exposing the photosensitive resin layer with a chemical ray through a mask, or directly irradiating a part of the photosensitive resin layer with a light beam, an electron beam or an ion ray,

(3) A developing step of forming a relief pattern by eluting and removing the exposed portion or the irradiated portion of the photosensitive resin layer, and

(4) The manufacturing method of the hardening relief pattern containing the heating process of heat-processing the obtained relief pattern and forming a hardening relief pattern.

[13] A semiconductor device having a cured relief pattern obtained by the production method described in [12] above.

According to the present invention, a photosensitive resin composition having a high sensitivity and having a positive lithography performance having a high residual film ratio at the time of curing when forming a cyclized resin, a method for producing a cured relief pattern using the photosensitive resin composition, and a cured relief pattern thereof The semiconductor device which has a can be provided.

<Photosensitive resin composition>

The photosensitive resin composition which concerns on this invention,

(A) the following general formula (1):

(Wherein, X ₁ and Y ₁ each independently represent a divalent tetravalent organic group having at least two carbon atoms, and R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). , n ₁ , n ₂ , n ₃ and n ₄ are each independently an integer of 0 to 2, n ₁ + n ₂ + n ₃ + n ₄ > 0, and m ₁ is an integer of 1 to 1000)

Structure represented by following General formula (2):

(Wherein, X ₂ and Y ₂ each independently represent a tetravalent organic group having at least two carbon atoms, and m ₂ is an integer of 1 to 1000)

100 parts by mass of an aqueous alkali solution soluble polymer (hereinafter, also referred to as "(A) alkali aqueous solution soluble polymer") having at least one kind of structure selected from the group consisting of structures represented by

(B) 1-50 mass parts of photoacid generators, and

(C) Monocarboxylic acid compound of 8 or more carbon atoms which has at least 1 functional group chosen from the group which consists of a hydroxyl group, an ether group, and ester group in the (alpha) position of a carboxyl group (Hereinafter, "(C) monocarboxylic acid compound And 5 to 20 parts by mass. Each component which comprises the photosensitive resin composition of this invention is demonstrated concretely below. In addition, the structure shown using the same code | symbol in each general formula through this specification may mutually be same or different, unless there is particular notice.

(A) Alkali aqueous solution soluble polymer

(A) Alkali aqueous solution soluble polymer which is a base polymer of the photosensitive resin composition of this invention is following General formula (1):

(Wherein, X ₁ and Y ₁ each independently represent a divalent tetravalent organic group having at least two carbon atoms, and R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). , n ₁ , n ₂ , n ₃ and n ₄ are each independently an integer of 0 to 2, n ₁ + n ₂ + n ₃ + n ₄ > 0, and m ₁ is an integer of 1 to 1000)

Structure represented by following General formula (2):

(Wherein, X ₂ and Y ₂ each independently represent a tetravalent organic group having at least two carbon atoms, and m ₂ is an integer of 1 to 1000)

It has at least 1 sort (s) of structure chosen from the group which consists of a structure shown by these.

(A) Alkali aqueous solution soluble polymer is polyhydride which is derived from alkali aqueous solution soluble polymer which is PBO precursor, aqueous alkali solution soluble polyimide which has phenolic hydroxyl group, tetracarboxylic acid and diamine, and has a carboxyl group in the ortho position of an amide bond. The polyamic acid ester which sealed the polyamic acid which is a precursor, and a part of this carboxyl group is mentioned.

(A) Alkaline aqueous solution soluble polymer may consist of the structure represented by the said General formula (1) and / or (2), but is represented by the said General formula (1) or (2) in order to control alkali solubility of resin. You may also include the repeating unit structure which substituted a part of repeating unit structure.

Specifically, (A) alkali aqueous solution soluble polymer is a structure related to the said General formula (1), and following General formula (13):

(Wherein, X ₁ and Y ₁ each independently represent a divalent tetravalent organic group having at least two carbon atoms, and R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). , n ₁ , n ₂ , n ₃ and n ₄ are each independently an integer of 0 to 2, n ₁ + n ₂ + n ₃ + n ₄ > 0 and X ₅ and Y ₃ are each independently at least two A divalent organic group having a carbon atom, m ₁ is an integer from 1 to 1000, m ₃ is an integer from 1 to 500, m ₁ / (m ₁ + m ₃ )> 0.5, and X ₁ and Y _{The order} of m ₁ units containing ₁ and m ₃ units containing X ₅ and Y ₃ does not matter)

You may have a structure shown by. Examples of the polymer having a structure represented by General Formula (13) include a structure derived from X ₁ (NH ₂ ) ₂ (OH) ₂ (for example, bisaminophenol) and a structure of X ₅ (NH ₂ ) ₂ . The polymer which has a structure derived from diamine is mentioned.

Moreover, (A) alkali aqueous solution soluble polymer is a structure related to the said General formula (2), and following General formula (14):

(Wherein X ₂ , Y ₂ and Y ₄ each independently represent a tetravalent organic group having at least two carbon atoms, X ₆ represents a divalent and trivalent organic group having at least two carbon atoms, n ₇ Is 0 or 1, m ₂ is an integer from 1 to 1000, m ₄ is an integer from 1 to 500, and m ₂ units including X ₂ and Y ₂ , and X ₆ and Y ₄ are included. arrangement order of ₄ m of unit is irrelevant)

You may have a structure shown by. Examples of the polymer having a structure represented by General Formula (14) include a structure derived from X ₂ (NH ₂ ) ₂ (OH) ₂ (for example, bisaminophenol), and X ₆ (NH ₂ ) ₂ (OH) ( for example, there may be mentioned a polymer having a structure derived from a diamine having the structure of amino-phenol), or X ₆ (NH _{2) 2.}

It is preferable that X <_1> is a tetravalent organic group which has 2 or more and 30 or less carbon atoms from the point which the solubility with respect to alkaline developing solution and the heat resistance of the resin film obtained are favorable. Y ₁ is preferably soluble and the resulting heat-resistant resin film is preferred in that, a divalent organic group having 30 or fewer carbon atoms in two or more in an alkali developing solution. m ₁ is the preferred solubility and the resin film, the mechanical properties obtained in an alkali developing solution that, of 1 to 1000 integer, two or more preferably an integer of not, and, and it is an integer of 2 to 100 and more preferably of from 200 3 to 60 of the Most preferably, it is an integer.

(A) an alkaline aqueous solution having soluble polymer is desired, the formula m ₃ of diamide units in the 13, X ₅ (NH ₂₎ of a diamine, and Y ₃ (COOH) ₂ having a structure of _two It has a structure which polycondensed the dicarboxylic acid which has a structure. X ₅ is preferably soluble and the resulting heat-resistant resin film is preferred in that, a divalent organic group having 30 or fewer carbon atoms in two or more in an alkali developing solution. Y ₃ is preferably soluble and the resulting heat-resistant resin film is preferred in that, a divalent organic group having 30 or fewer carbon atoms in two or more in an alkali developing solution. m <_3> is an integer of 1-500 and it is more preferable that it is an integer of 1-10 from the point which the solubility with respect to alkaline developing solution and the mechanical property of the resin film obtained are favorable.

(A) Alkaline aqueous solution solubility with respect to the alkaline aqueous solution used as a developing solution, so that the ratio of the unit (for example, dihydroxydiamide unit) containing X <_1> and Y <_1> is high in the structure represented by the said General formula (13). since the increase in the solubility of the _{polymer, m 1 / (m 1 +} m 2) value is the most preferably not less than than 0.5 and, preferably, 0.8, and more preferably not less than 0.7.

In the structure represented by the said General formula (1) and the said General formula (13), when the unit containing X <_1> and Y <_1> is a dihydroxydiamide unit (that is, (A) alkali aqueous solution soluble polymer contains a PBO precursor) Will be described).

In the PBO precursor, the dihydroxydiamide unit is obtained by polycondensing a dicarboxylic acid having a structure of Y ₁ (COOH) ₂ and a bisaminophenol having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ . Has a structure. Two sets of amino groups and hydroxyl groups of the bisaminophenol are each at ortho positions. Dihydroxydiamide (hydroxypolyamide) is closed by heating to about 250-400 degreeC, and it turns into polybenzoxazole which is a heat resistant resin.

Examples of the bisaminophenol having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-di Hydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-dia Mino-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'-dihydroxy Cidiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene , 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, and the like. These bisaminophenols can be used individually or in mixture of 2 or more types.

Particularly preferred among bisaminophenols having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ is bisaminophenol, wherein X ₁ is an aromatic group selected from the following.

In addition, as a compound having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ , a diamine having two sets of amide bonds and phenolic hydroxyl groups in the ortho position of each other (hereinafter, "diamine having a PBO precursor structure in a molecule"). Can be used). For example, there may be mentioned to the diamine represented by the general formula obtained by reacting two molecules of nitrobenzoic acid of the bisaminophenol having a structure of X ₁ (NH ₂₎ of the ₂ (OH) ₂ by reduction.

(Wherein X ₇ represents a tetravalent organic group having at least two carbon atoms)

X ₇ is preferably an organic group represented by X ₁ and is preferably at least one organic group selected from the group consisting of the aforementioned organic groups.

As another method for obtaining a diamine having a PBO precursor structure in a molecule, two molecules of nitroaminophenols are reacted with a dicarboxylic acid dichloride having a structure of Y ₅ (COCl) ₂ , and reduced to give a diamine represented by the following general formula. There is also a way to get.

(Wherein Y ₅ is a divalent organic group having at least two carbon atoms)

It is preferable that Y <_5> is at least 1 sort (s) of organic group chosen from the group which consists of organic groups mentioned later as a preferable thing of the organic group represented by Y <_1> .

Examples of the diamine having a structure of X ₅ (NH ₂ ) ₂ include aromatic diamine, silicone diamine, and the like.

Among these, as aromatic diamine, for example, m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodi Phenylether, 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'-diaminodi Phenyl ketone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 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-diami Naphthalene, 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-aminophenoxy) 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'-diamino Benzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, o-toluidinesulfone, 2,2 Bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-ami Nophenoxyphenyl) sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-di- (3-aminophenoxy) diphenylsulfone, 4,4'-diaminobenzanilide and the like, and hydrogen atoms of aromatic nuclei of these aromatic diamines, chlorine atoms, fluorine atoms, bromine atoms, The compound substituted by the at least 1 group or atom chosen from the group which consists of a methyl group, a methoxy group, a cyano group, and a phenyl group is mentioned.

Further, in order to increase the adhesion of the photosensitive resin composition and the base material of the present invention, it is possible to select a silicon-diamine as a part or all of the diamine having the structure of X ₅ (NH _{2) 2.} 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.

As the dicarboxylic acid having Y ₁ (COOH) ₂ and Y ₃ (COOH) ₂ structures, Y ₁ and Y ₃ are the followings:

Wherein A ₁ is selected from the group consisting of -CH _2- , -O-, -S-, -SO _2- , -CO-, -NHCO-, -C (CF ₃ ) _2- , and a single bond; Represents a divalent group, L ₇ represents a hydrogen atom, a halogen atom, an alkyl group or an unsaturated group, and k is an integer of 0 to 4)

And

(In formula, L <_8> , L <_9> and L <_10> respectively independently represent a hydrogen atom or a methyl group, and L <_11> represents a hydrogen atom, a methyl group, or a hydroxyl group.)

The dicarboxylic acid which is an aromatic group or aliphatic group chosen from the group which consists of these is mentioned. From the viewpoint of good mechanical properties of the resulting resin film, L ₈ , L ₉ , L ₁₀ and L ₁₁ are most preferably hydrogen atoms.

The structure of the unit represented by the said General formula (1) and the unit containing X <_1> and Y <_1> in the structure represented by the said General formula (13) is a viewpoint of transparency in i line | wire area | region, and the solubility with respect to the alkaline developing solution of an exposure part. In which the alicyclic structure has the following general formula (5):

In the formula, X ₁ represents a divalent tetravalent organic group having at least two carbon atoms, R ₁ represents a hydrogen atom or a hydrocarbon group of 1 to 10 carbon atoms, and L ₁ , L _2, and L ₃ are each independently Represents a hydrogen atom or a methyl group, L ₄ represents a hydrogen atom, a methyl group or a hydroxyl group, n ₁ and n ₃ each independently represent an integer of 0 to 2, and m ₁ represents an integer of 1 to 1000)

It is preferable to include the structure shown by.

The structure of the unit represented by the said General formula (1) and the unit containing X <_1> and Y <_1> in the structure represented by the said General formula (13) is a viewpoint of transparency in i line | wire area | region, and the solubility with respect to the alkaline developing solution of an exposure part. In which the alicyclic structure has the following general formula (6):

(Wherein X ₃ is a single bond and the following formula (7):

At least 1 type of structure chosen from the group which consists of a structure shown by these, L <_1> , L <_2> and L <_3> represent a hydrogen atom or a methyl group each independently, L <_4> represents a hydrogen atom, a methyl group, or a hydroxyl group, and m ₁ is an integer of 1 to 1000)

It is preferable to include the structure shown by.

Moreover, the tricyclodecane moiety in the structure of the said General formula (6) further has following formula (15):

It is preferable that it is at least 1 sort (s) chosen from the structural group shown by these. Especially, especially following formula (16):

The structure represented by is preferable.

As a typical compound as a dicarboxylic acid which has a tricyclodecane skeleton, bis (carboxy) tricyclo [5, 2, 1, 0 2, ⁶ ] decane is mentioned. The compound is the synthesis method according to Production Example A of JP-A-58-110538, the synthesis method according to Example 1 of JP-A-2002-504891, or Synthesis Example 2 of JP-A 09-15846. It can obtain according to the synthesis method by. However, in these methods, since a heavy metal is used as an oxidizing agent, the following manufacturing method is more preferable at the point which does not use a heavy metal. That is, tricyclo (5,2,1,0) decanedimethanol (catalog No. T0850 manufactured by Tokyo Chemical Industries, Ltd.) is dissolved in acetonitrile or the like and 2,2,6,6-tetramethylpiperidine-1- By adding a catalyst such as oxyl (hereinafter also referred to as "TEMPO") and adjusting pH using sodium dihydrogen phosphate, sodium dihydrogen phosphate, etc., sodium chlorite and sodium dichlorite are oxidized and purified, , Bis (carboxy) tricyclo [5,2,1,0 ^2,6 ] decane, which is a target compound, can be produced.

Moreover, the dicarboxylic acid compound which has a structure represented by the structural group of said Formula (15) other than the compound mentioned above can be obtained, for example by the following method. That is, methylcyclopentadiene dimer (catalog No.M0920 by the Tokyo Chemical Industry Co., Ltd.), 1-methyldicyclopentadiene (catalog No.M0910 by the Tokyo Chemical Industry Co., Ltd.) or 1-hydroxydicyclopentadiene (Tokyo Chemical Industry Co., Ltd.) Production catalog No. H0684) as a raw material, J. Org. Chem., 45,3527 (1980), followed by addition of hydrogen bromide or hydrogen chloride to the unsaturated bond site of the raw material, followed by J. Am. Chem. According to a method known from Soc., 95,249 (1973), two hydroxymethyl groups can be introduced into the backbone of tricyclo [5,2,1,0 ^2,6 ] decane by addition of carbon monoxide and water. . As a method for synthesizing the dihydroxymethyl body, J. Am. Chem. Soc., 91,2150 (1969), by the addition of 9-borabicyclo (3,3,1) nonane to the unsaturated bond site of the raw material to form an intermediate, and further reacted with carbon monoxide The dihydroxymethyl body can also be manufactured by reducing with LiAlH (OCH ₃ ) ₃ . The dihydroxymethyl group of the dihydroxymethyl body thus obtained is oxidized in the same manner according to the method described when obtaining bis (carboxy) tricyclo [5,2,1,0 ^2,6 ] decane. Dicarboxylic acid can be obtained.

Moreover, derivatives of 5-aminoisophthalic acid may be used as part or all of the dicarboxylic acids having the above Y ₁ (COOH) ₂ and Y ₃ (COOH) ₂ structures. Specific compounds to be reacted with 5-aminoisophthalic acid to obtain the derivatives include 5-norbornene-2,3-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6 Tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic anhydride, 4-ethynyl-1,2-phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 1-cyclo Hexene-1,2-dicarboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydro phthalic anhydride, allylsuccinic anhydride, Isocyanate ethyl methacrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 3-cyclohexene-1-carboxylic acid chloride, 2-furancarboxylic acid chloride, crotonic acid chloride, cinnamic acid chloride, methacrylic acid Chloride, acrylic acid chloride, Propionic acid chloride, tetratrol chloride, thiophene 2-acetylchloride, p-styrenesulfonyl chloride, glycidyl methacrylate, allyl glycidyl ether, chloroformate methyl ester, chloroformate ethyl ester, chloroformic acid n-propyl Ester, chloroformic acid isopropyl ester, chloroformic acid isobutyl ester, chloroformic acid 2-ethoxy ester, chloroformic acid-sec-butyl ester, chloroformic acid benzyl ester, chloroformic acid 2-ethylhexyl ester, chloroformic acid allyl ester, chloroformic acid Phenyl ester, chloroformic acid 2,2,2-trichloroethyl ester, chloroformic acid-2-butoxyethyl ester, chloroformic acid -p-nitrobenzyl ester, chloroformic acid -p-methoxybenzyl ester, chloroformic acid isobornyl Benzyl ester, chloroformic acid-p-biphenylisopropylbenzyl ester, 2-t-butyl Cycarbonyl-oxyimino-2-phenylacetonitrile, St-butyloxycarbonyl-4,6-dimethyl-thiopyrimidine, di-t-butyldicarbonate, N-ethoxycarbonylphthalimide, ethyl Dithiocarbonyl chloride, formic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, methanesulfonic acid chloride, acetyl chloride, trityl chloride, trimethylchlorosilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide , Bis (trimethylsilyl) trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane, trimethylsilyldiphenylurea, bis (trimethylsilyl) urea, phenyl isocyanate, isocyanate N-butyl ansan, n-octadecyl isocyanate, o-tolyl isocyanate, 1,2-phthalic anhydride, and cis-1,2-cyclohexanedicarboxylic anhydride, and glutaric anhydride have.

Furthermore, as dicarboxylic acids having Y ₁ (COOH) ₂ and Y ₃ (COOH) ₂ structures, dicarboxylic acids obtained by ring-opening tetracarboxylic dianhydride with, for example, monoalcohol or monoamine can be used. It may be. Examples of the monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, benzyl alcohol, and the like, and examples of the monoamine include butylamine and aniline. Examples of the tetracarboxylic dianhydride include the following chemical formulas:

Wherein A ₂ is a divalent group selected from the group consisting of -CH _2- , -O-, -S-, -SO _2- , -CO-, -NHCO- and -C (CF ₃ ) _2- Indicates)

And the like.

Alternatively, the tetracarboxylic dianhydride may be reacted with bisaminophenol or diamine, and the resulting carboxylic acid residue may be esterified or amidated with monoalcohol or monoamine.

Moreover, dicarboxylic acid obtained by reacting trimellitic acid chloride with bisaminophenol, producing tetracarboxylic dianhydride, and ring-opening it by the same method as said tetracarboxylic dianhydride can also be used. As tetracarboxylic dianhydride obtained here, the following general formula:

(In formula, X <_8> represents the divalent organic group represented by X <_1> (OH) ₂ (NH-) ₂ , X <_1> is the same meaning as the thing in the said General formula (1).

And the like.

As a polycondensation method of the above-mentioned dicarboxylic acid and bisaminophenol (diamine) for synthesizing the dihydroxydiamide which is hydroxy polyamide, after obtaining diacid chloride using dicarboxylic acid and thionyl chloride, The method of making bisaminophenol (diamine) act on this, the method of polycondensing dicarboxylic acid and bisaminophenol (diamine) with dicyclohexyl carbodiimide, etc. are mentioned. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can also be made to work simultaneously.

The precursor (for example, PBO precursor) which has a repeating unit represented by General Formula (1) and General Formula (13) mentioned above is used by sealing the terminal group with an organic group (hereinafter also referred to as "sealing group"). It is also preferable. For example, in polycondensation of hydroxypolyamides, when the dicarboxylic acid component is used in an excessive molar number compared to the sum of the bisaminophenol component and the diamine component, a compound having an amino group or a hydroxyl group as a sealing group is used. It is preferable to use. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, hydroxyethyl acrylate, and the like. Can be mentioned.

On the contrary, in the case where the sum of the bisaminophenol component and the diamine component is used in an excess molar number compared to the dicarboxylic acid component, the compound having an acidic anhydride, a carboxylic acid, an acid chloride, an isocyanate group or the like as a compound having a sealing group Preference is given to using. Examples of the compound include benzoyl chloride, norbornenedicarboxylic acid anhydride, norbornenecarboxylic acid, ethynylphthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic acid anhydride, Methyl cyclohexane dicarboxylic anhydride, cyclohexene dicarboxylic acid anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, tosylic acid chloride, etc. are mentioned. Among these, as a preferable terminal group, following General formula (10):

(Wherein L ₅ represents —CH ₂ —, —O— or —S—, and L ₆ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 1 to 6 carbon atoms)

The group represented by is mentioned.

Next, the case where (A) alkali aqueous solution soluble polymer has a structure represented by the said General formula (2) or the said General formula (14) is demonstrated. In General Formulas (2) and (14), a soluble PI structure is formed by a unit containing X ₂ and Y ₂ .

Formula (2) and the above-mentioned formula (14) when the synthesis of the soluble PI having a structure shown, respectively, a tetracarboxylic acid dianhydride, specifically, Y _2, or Y ₂ and tetravalent organic groups of Y ₄ The containing tetracarboxylic dianhydride is used. Among them, in terms of solubility in solvents and solubility in aqueous alkali solutions, aromatic tetracarboxylic dianhydrides having 8 to 36 carbon atoms and alicyclic tetracarboxylic dianhydrides having 6 to 34 carbon atoms are selected. Compounds are preferred. Specifically 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3, 4-benzenetetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride, 3, 3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -terphenyl phenyl tetracarboxylic dianhydride, 3,3''', 4, 4 '''-quater-phenyl tetracarboxylic dianhydride, 3,3'''',4,4''''-quinque-phenyl tetracarboxylic dianhydride, 2 , 2 ', 3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2 -Propylidene-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4,4'-diphthalic acid dianhydride, 1,3-trimethylene-4,4'-diphthalic acid dianhydride, 1,4 -Tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic acid dianhydride Water, bis (3,4-dicarboxyphenyl) ether dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis (3,4 -Dicarboxyphenyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3 -Bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, 2,2-bis [3- (3, 4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-dicarboxyphenoxy) dimethylsilane Dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1 , 4,5,8-naphthalenetetracarboxylic dianhydride, 1,2, 5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7 , 8-phenanthrene tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid Dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3, 3 ', 4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'- Bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethyl Liden-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) Dianhydride, oxy-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride , Sulfonyl-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo [2,2,2] octo-7-ene-2,3,5,6-tetra Carboxylic dianhydride, rel- [1S, 5R, 6R] -3-oxabicyclo [3,2,1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2' , 5'-dione), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, ethylene glycol- Bis (3, 4- dicarboxylic acid anhydride phenyl) ether, etc. are mentioned, Especially, 5- (2, 5- dioxotetrahydro-3-furanyl) -3-methyl-cyclohexene-1, 2-dicarboxylic acid anhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 4,4 '-(4,4'-isopropylidene Diphenoxy) bis (phthalic anhydride) is preferred, and among them, 5 -(2,5-dioxotetrahydro-3-furyl) -3-methyl-cyclohexene-1,2-dicarboxylic acid anhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, mercury lamp It is more preferable in terms of transparency to the i-line, solubility in aqueous alkali solution and light sensitivity.

Therefore, the soluble PI structures represented by the general formulas (2) and (14) each have a structure represented by the following general formula (8) from the viewpoint of transparency of the i-line region and solubility in the alkaline developer of the exposed portion; Structure represented by the following general formula (9):

(Wherein X ₄ is a single bond and the following formula (7):

At least one structure selected from the group consisting of m ₂ is an integer of 1 to 1000)

It is preferable to have at least 1 sort (s) of polyimide structure selected from the group which consists of in a molecule | numerator.

A general formula (2) and (14) to the imide with a diamine having available in the case of synthesizing unit, a phenolic hydroxyl group-containing monovalent organic group of X _2, the description having a phenolic hydroxyl group as the structure shown, respectively preferably selected from the group consisting of a phenolic diamine group, and among them 2,2-bis (3-amino-4-hydroxyphenyl) propane, more preferably comprises in the high light sensitivity of the resin composition point of view, and an organic group of X ₆ Examples of the diamines to be mentioned include nonphenolic diamines (when n ₁ = 0) and 2,4-diaminophenols (when n ₁ = 1).

The dehydration condensation reaction at the time of synthesizing the imide unit having a phenolic hydroxyl group is carried out using the tetracarboxylic dianhydride and the phenolic diamine according to the method described in, for example, International Publication No. 01/034679 pamphlet. In the presence of an acid catalyst or a base catalyst, it can carry out by heating to 30 to 220 degreeC, Preferably it is 170 to 200 degreeC. As the acid catalyst, an inorganic acid such as sulfuric acid or an organic acid such as p-toluenesulfonic acid, which is commonly used in the production of polyimide, can be used. γ-valerolactone and pyridine may be used. Examples of the base catalyst include pyridine, triethylamine, dimethylamino pyridine, 1,8-diazabicyclo (5,4,0) undecene-7,1,3,5,7-tetraazatricyclo (3,3 (1,1,3,7) decane, triethylenediamine, etc. may be used.

In addition, the reaction system is maintained at or above the temperature at which the imidization reaction occurs without adding a polycondensation catalyst and the like, and the water generated by the dehydration reaction is reacted with an azeotropic solvent with water such as toluene. The method may be removed to complete the imidized dehydration condensation reaction.

In the dehydration condensation reaction, it is preferable to use, as a reaction solvent, a polar organic solvent for dissolving an aqueous alkali aqueous solution soluble polymer in an aqueous alkali solution, in addition to toluene, which is a solvent for azeotropic water. Γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, tetramethylurea, sulfolane and the like are used as this polar solvent.

Moreover, when using two or more components of tetracarboxylic dianhydride, or two or more components of phenolic diamine or nonphenolic diamine, you may form a block copolymer using a sequential reaction. In addition, when inject | pouring a raw material of three or more components, a raw material may be injected simultaneously into a reaction system, and may be made a random copolymer.

The terminal of soluble PI may be modified by the following compound, for example. As a method of modifying a terminal, maleic anhydride, succinic anhydride, cinnamic anhydride, 4-ethynyl phthalic anhydride, phenylethynyl phthalic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, cyclohexane-1 , 2-dicarboxylic acid anhydride, 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, 4-aminostyrene, 4-ethynylaniline, 3-ethynylaniline and the like are suitable amounts in the synthesis of soluble PI The method of adding is mentioned. Moreover, you may leave dicarboxylic acid as a terminal.

The terminal group of the soluble PI is, in terms of sensitivity, the following general formula (10):

(Wherein L ₅ represents —CH ₂ —, —O— or —S—, and L ₆ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 1 to 6 carbon atoms)

It is preferable that it is at least 1 sort (s) of end group chosen from the group which consists of terminal groups represented by these.

(A) It is preferable that it is 3,000-70,000, and, as for the polystyrene conversion weight average molecular weight by gel permeation chromatography (henceforth "GPC") of aqueous alkali aqueous solution, it is more preferable that it is 6,000-50,000. As for the weight average molecular weight, 3,000 or more are preferable from a viewpoint of the physical property of a hardening relief pattern. Moreover, 70,000 or less are preferable from a viewpoint of resolution. As a developing solvent of GPC, tetrahydrofuran (henceforth "THF") and N-methyl- 2-pyrrolidone (henceforth "NMP") can be recommended. Moreover, molecular weight is calculated | required from the calibration curve manufactured using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko.

(A) Alkali aqueous solution soluble polymer may have both the structure represented by the said General formula (1) and the said General formula (13), and the structure represented by the said General formula (2) and the said General formula (14).

Both structures have a phenolic hydroxyl group obtained by cyclocondensing tetracarboxylic dianhydride and the aromatic diamine which has a phenolic hydroxyl group as a structure represented by General formula (2) or (14), for example. A polyimide skeleton can be obtained by copolymerizing with the above-mentioned polymerization component in formation of the structure represented by General formula (1) or (13). The copolymerization ratio at the time of copolymerization is arbitrarily selected, but the ratio of [structure represented by General formula (1) or (13)]: [structure represented by General formula (2) or (14)], for example, hydroxypolyamide: It is preferable from the viewpoint of light sensitivity that the ratio of soluble PI is in the range of 10:90 to 100: 0.

(B) photoacid generator

As the photoacid generator (B), a compound having a naphthoquinone diazide structure, an onium salt, a halogen-containing compound, and the like can be used. From the viewpoint of solvent solubility and storage stability, a compound having a naphthoquinone diazide structure ( Hereinafter, "also called a naphthoquinone diazide compound" is preferable.

As said onium salt, an iodonium salt, a sulfonium salt, a phosphonium salt, an ammonium salt, a diazonium salt, etc. are mentioned, Onion salt selected from the group which consists of a diaryl iodonium salt, a triarylsulfonium salt, and a trialkylsulfonium salt This is preferred.

Examples of the halogen-containing compound include a halo alkyl group-containing hydrocarbon compound, and trichloromethyltriazine is preferable.

The naphthoquinone diazide compound is typically a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure, and described in US Pat. No. 2,772,972, US Pat. No. 2,797,213. And US Pat. No. 3,669,658 and the like. The naphthoquinone diazide compound is typically 1,2-naphthoquinone diazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail later, and 1,2 of the polyhydroxy compound. It is at least 1 sort (s) of compound (henceforth "NQD compound") chosen from the group which consists of naphthoquinone diazide-5-sulfonic acid ester.

The NQD compound is a naphthoquinone diazide sulfonic acid compound as sulfonyl chloride with chlorsulfonic acid or thionyl chloride according to a conventional method, and condensation reaction of the obtained naphthoquinone diazide sulfonyl chloride and a polyhydroxy compound. It is obtained by making it. For example, a predetermined amount of the polyhydroxy compound and 1,2-naphthoquinone diazide-5-sulfonyl chloride or 1,2-naphthoquinone diazide-4-sulfonyl chloride can be added to dioxane, acetone, tetra In a solvent such as hydrofuran, an NQD compound can be obtained by reacting in the presence of a basic catalyst such as triethylamine to perform esterification and washing the product with water and drying.

As the NQD compound, those listed below are preferably used.

General formula (17) below:

(Wherein n ₈ , n ₉ , n ₁₀ and n ₁₁ are each independently 1 or 2 and R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ And R ₁₄ each independently represent a hydrogen atom or a halogen atom or at least one monovalent group selected from the group consisting of an alkyl group, an alkenyl group, an alkoxy group, an allyl group and an acyl group, and Y ₆ , Y ₇ and Y ₈ are Each independently a single bond, -O-, -S-, -SO-, -SO _2- , -CO-, -CO _2- , cyclopentylidene, cyclohexylidene, phenylene, and the following general formula:

(Wherein R ₁₅ and R ₁₆ each independently represent a hydrogen atom or at least one monovalent group selected from the group consisting of an alkyl group, an alkenyl group, an allyl group and a substituted allyl group)

(In formula, R <_17> , R <_18> , R <_19> and R <_20> respectively independently represent a hydrogen atom or an alkyl group, and m <_5> is an integer of 1-5.)

(Wherein, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ each independently represent a hydrogen atom or an alkyl group)

At least one divalent group selected from the group consisting of organic groups represented by the formula

NQD cargo of the polyhydroxy compound shown by.

As a specific compound, NQD cargo of the polyhydroxy compound of Unexamined-Japanese-Patent No. 2001-109149 (Formula 18)-(Formula 32) is mentioned.

Especially, NQD cargo of the following polyhydroxy compounds is preferable at the point which has high sensitivity and low precipitation property in the photosensitive resin composition.

General formula (18) below:

Wherein X ₉ is a chemical formula

At least one tetravalent group selected from the organic groups represented by the formula (R), R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ each independently represent a monovalent organic group, l is 0 or 1, and m ₆ , m ₇ , m ₈ and m ₉ are each independently an integer of 0 to 3, and n ₁₂ , n ₁₃ , n ₁₄ and n ₁₅ are each independently an integer of 0 to 2)

NQD cargo of the polyhydroxy compound shown by.

As a specific compound, the compound of Unexamined-Japanese-Patent No. 2001-092138 (23)-(28) is mentioned. Especially, NQD cargo of the following polyhydroxy compounds is preferable at the point which has high sensitivity and low precipitation property in the photosensitive resin composition.

General formula (19) below:

(Wherein, L ₁₂ and L ₁₃ each independently represent a hydrogen atom or a monovalent organic group, L ₁₄ represents a monovalent organic group having one or more carbon atoms, j is an integer of 1 to 5, and m ₁₀ Is an integer of 3 to 8)

NQD cargo of the polyhydroxy compound shown by.

As a specific preferable example, the compound of Unexamined-Japanese-Patent No. 2004-347902 (Formula 24) and (Formula 25) is mentioned. Especially, NQD cargo of the following polyhydroxy compounds is preferable at the point which has high sensitivity and low precipitation property in the photosensitive resin composition.

(Wherein p is an integer of 0 to 9)

General formula (20) below:

(In formula, M <_2> represents the divalent organic group containing aliphatic tertiary or quaternary carbon, and A <_3> is a following formula:

At least one divalent group selected from the group represented by

NQD cargo of the polyhydroxy compound represented by.

As a specific compound, the compound of Unexamined-Japanese-Patent No. 2003-131368-(Formula 22)-(Formula 28) is mentioned. Especially, NQD cargo of the following polyhydroxy compounds is preferable at the point which has high sensitivity and low precipitation property in the photosensitive resin composition.

(Wherein, L ₁₅ represents —CH ₂ —, —O— or —S—, and L ₁₆ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 1 to 6 carbon atoms)

(In the formulas, L ₁₇ is -CH ₂ -, represents a -O- or -S-, and L ₁₈ represents an alkenyl group of a hydrogen atom, a carbon atom number of 1 to 6 carbon atoms or alkyl of 1 to 6)

General formula (21) below:

{In formula, R ₂₉ , R ₃₀ and R ₃₁ are each independently the following general formula:

(In formula, R <_32> represents at least 1 sort (s) of monovalent organic group chosen from a hydrogen atom or an alkyl group and a cycloalkyl group, and m <_14> is an integer of 0-2.)

Represents a monovalent organic group represented by and m ₁₁ , m ₁₂ and m ₁₃ each independently represent an integer of 0 to 2}.

NQD cargo of the polyhydroxy compound shown by.

As a specific compound, NQD cargo of the polyhydroxy compound of Unexamined-Japanese-Patent No. 2004-109849-(Formula 17)-(Formula 22) is mentioned. Especially, NQD cargo of the following polyhydroxy compounds is preferable at the point which has high sensitivity and low precipitation property in the photosensitive resin composition.

General formula (22) below:

(In formula, R <_33> represents at least 1 sort (s) of monovalent organic group chosen from the group which consists of a hydrogen atom or an alkyl group, an alkoxy group, and a cycloalkyl group.)

NQD cargo of the polyhydroxy compound shown by.

As a specific compound, the compound of Unexamined-Japanese-Patent No. 2001-356475 (Formula 18)-(Formula 22) is mentioned. Especially, NQD cargo of the following polyhydroxy compounds is preferable at the point which has high sensitivity and low precipitation property in the photosensitive resin composition.

General formula (23) below:

(Wherein, R ₃₄ is the following general formula:

(Wherein, R ₃₈ represents an organic group with at least one kind of monovalent is selected from the group consisting of a hydrogen atom, or an alkyl group and a cycloalkyl group, and m ₁₈ is an integer from 0 to 2)

Represents a monovalent organic group represented by R ₃ , R ₃₆ and R ₃₇ each independently represent a hydrogen atom or at least one monovalent group selected from the group consisting of an alkyl group and a cycloalkyl group, and m ₁₅ , m ₁₆ And m ₁₇ are each independently an integer of 0 to 2}

NQD cargo of the polyhydroxy compound represented by.

As a specific compound, NQD cargo of the polyhydroxy compound of Unexamined-Japanese-Patent No. 2005-008626 (Formula 15) and (Formula 16) is mentioned. Especially, NQD cargo of the following polyhydroxy compounds is preferable at the point which has high sensitivity and low precipitation property in the photosensitive resin composition.

As another structure, the following are specifically preferable.

As a naphthoquinone diazide sulfonyl group in a NQD compound, both 5-naphthoquinone diazide sulfonyl group and 4-naphthoquinone diazide sulfonyl group are preferable. 4-naphthoquinone diazide sulfonyl ester compound has absorption in i line | wire area | region, such as a mercury lamp, and is suitable for i line | wire exposure. The 5-naphthoquinone diazide sulfonyl ester compound has absorption extended to the g line region of a mercury lamp, and is suitable for g line exposure. In this invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or 5-naphthoquinone diazide sulfonyl ester compound according to the wavelength used for exposure. Moreover, the naphthoquinone diazide sulfonyl ester compound which has both 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group in the same molecule can also be used, and 4-naphthoquinone diazide sulfonyl is used. You may use it by mixing an ester compound and 5-naphthoquinone diazide sulfonyl ester compound.

In the photosensitive resin composition of this invention, the compounding quantity of (B) photoacid generator is 1-50 mass parts with respect to 100 mass parts of (A) alkali aqueous solution soluble polymer, and 5-30 mass parts is preferable. (B) The patterning property of resin is favorable when the compounding quantity of a photo acid generator is 1 mass part or more, the tensile elongation rate of the film | membrane after hardening is favorable when there are 50 mass parts or less, and there is little development residue (scum) of an exposure part.

(C) monocarboxylic acid compound

The monocarboxylic acid compound (C) is a monocarboxylic acid compound having 8 or more carbon atoms having at least one functional group selected from the group consisting of a hydroxyl group, an ether group and an ester group at the α position of the carboxyl group.

As the (C) monocarboxylic acid compound, for example, 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3 -Methoxymandelic acid, 2-methoxy-2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, acetylmandelic acid, α-methoxyphenylacetic acid.

Among them, the following general formula (3):

Wherein R ₁ represents an organic group, R ₂ represents a group having at least one structure selected from the group consisting of a hydrogen atom and an alkyl group, and Z ₁ is selected from the group consisting of a hydroxyl group, an ether group and an ester group Group having at least one functional group)

At least 1 sort (s) of compound chosen from the group which consists of a compound represented by this is preferable from a viewpoint of the residual film rate improvement at the time of hardening. It is preferable that carbon number of the compound represented by the said General formula (3) is 8-30.

Specifically as a compound represented by General formula (3), 3-phenyl lactic acid, 4-hydroxyphenyl lactic acid, 4-hydroxy mandelic acid, 3, 4- dihydroxy mandelic acid, 4-hydroxy-3- Methoxymandelic acid, 2-methoxy-2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, O-acetylmandelic acid and α-methoxyphenylacetic acid.

In addition, the following general formula (4):

(Wherein R ₃ represents a group having at least one structure selected from the group consisting of a hydrogen atom and an alkyl group, R ₄ represents a group having at least one structure selected from the group consisting of a hydrogen atom, an alkyl group and a carbonyl group, Z ₂ represents a hydroxyl group or an organic group, n ₅ is an integer of 0 to 5, and in the case where a plurality of Z ₂ are present, they may be the same as or different from each other)

At least 1 sort (s) of compound chosen from the group which consists of a compound represented by is more preferable from a viewpoint of the residual film rate improvement at the time of hardening. It is preferable that carbon number of the compound represented by the said General formula (4) is 8-30. In addition, when Z ₂ is an organic group, Z ₂ is preferably an organic group having 1 to 6 carbon atoms.

Specifically as a compound represented by General formula (4), 4-hydroxy mandelic acid, 3, 4- dihydroxy mandelic acid, 4-hydroxy-3- methoxy mandelic acid, mandelic acid, atrolactic acid, O-acetyl mandelic acid, (alpha)-methoxyphenyl acetic acid, etc. are mentioned.

Especially, it is more preferable that R <_4> is group which has at least 1 structure chosen from the group which consists of an alkyl group and a carbonyl group as a substituent. As such a compound, O-acetyl mandelic acid, (alpha)-methoxyphenyl acetic acid, etc. are mentioned specifically ,.

(C) The monocarboxylic acid compound has 8 or more carbon atoms from the viewpoint of improving the residual film ratio during curing. Moreover, it is preferable that the carbon atom number is 30 or less from a viewpoint of the solubility to a solvent. Moreover, it is more preferable that it is 20 or less, and, as for the said carbon atom number, from a viewpoint that precipitation after time passes is small, it is further more preferable that it is 15 or less. Moreover, as a means for efficiently remaining carboxylic acid in the film | membrane formed using the photosensitive resin composition of this invention, (C) monocarboxylic acid compound consists of a hydroxyl group, an ether group, and ester group in the alpha position of a carboxyl group. It has at least 1 functional group chosen from a group. In particular, an ether group and an ester group are preferable from a viewpoint of the adhesiveness of the film | membrane and a board | substrate being favorable. Moreover, when forming a cured resin film from a photosensitive resin composition, the site | part of the said functional group is made into crosslinking groups, such as a methylol group and an alkoxy methyl group, so that the carboxylic acid compound remaining after prebaking may not volatilize a resin composition. Most preferred.

(C) A monocarboxylic acid compound may be used individually or in mixture of 2 or more types. (C) The effect of adding a monocarboxylic acid compound has a higher PBO precursor than a soluble PI in the difference in reactivity with respect to a polymer.

The compounding quantity with respect to the aqueous alkali solution soluble polymer of the said (C) monocarboxylic acid compound is 5-20 mass parts with respect to 100 mass parts of (A) alkali aqueous solution soluble polymers, and 5-10 mass parts is preferable. When the compounding quantity of (C) carboxylic acid compound is 5 mass parts or more, the image development residue of an exposed part will become small, and the adhesiveness of the film | membrane formed using the photosensitive resin composition and a silicon substrate is favorable. Moreover, when the said compounding quantity is 20 mass parts or less, the film reduction at the time of hardening is small, and the tensile elongation rate of the film | membrane after hardening is favorable.

(D) A compound having three or more organic groups which can be crosslinked in a molecule

It is preferable that the photosensitive resin composition of this invention contains the compound which has three or more organic groups which can be bridge | crosslinked (D) from a viewpoint of further residual film ratio improvement at the time of hardening, and the glass transition temperature improvement of resin after heat processing. In particular, by combining the above-mentioned (C) monocarboxylic acid compound and the compound which has three or more organic groups which can be bridge | crosslinked (D), the thermal crosslinkability at the time of curing of the photosensitive resin composition improves.

(D) It is preferable that the compound which has three or more organic groups which can be bridge | crosslinked is a compound with 16-40 carbon atoms.

(D) The crosslinkable organic group which the compound which has three or more crosslinkable organic groups has crosslinking reactivity includes the general organic group known to those skilled in the art, For example, (meth) acryl group, At least one selected from the group consisting of alkenyl, acetylene, thiol, disulfide, isocyanate, cyanate, methylol, alkoxymethyl, N-methylol, N-alkoxymethyl, silanol and epoxy groups The functional group is mentioned. Among them, from the viewpoint of crosslinking performance, a (meth) acryl group, an alkenyl group, a methylol group, an alkoxymethyl group, an N-methylol group and an N-alkoxymethyl group are preferable, and from the viewpoint of good reactivity at low temperatures of the crosslinking group, (Meth) acryl group and alkenyl group are preferable.

(D) As a compound which has three or more organic groups which can be bridge | crosslinked, a trimethylol propane trimethacrylate, 1,3,5- benzene tricarboxylic acid triallyl, trimellitic acid triallyl, pyromellitate tetraallyl Esters, pentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, and the following general formula (11):

In the formula, D ₁ represents a group having at least one structure selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and an organic group that can be crosslinked, M ₁ represents -CH _2- , -O- or -S-, Z ₃ represents a divalent organic group, n ₆ is an integer of 0 to 4, and a plurality of D ₁ are the same as each other. May be different)

And the like. Especially, from a viewpoint of a sensitivity, the compound represented by trimethylolpropane trimethacrylate, trimellitic acid triallyl, and the said General formula (11) is preferable. As a specific example of the compound represented by the said General formula (11), following formula (12):

Although the compound shown by these is mentioned, BANI-X (Maruzen Petrochemical Co., Ltd. make: brand name) which consists of a meta- xylylenediamine structure is the most preferable among these compounds from a viewpoint of a cure shape and a sensitivity.

(D) The compound which has three or more organic groups which can be bridge | crosslinked may be used independently, or may be used in mixture of 2 or more types.

(D) It is preferable that the compounding quantity at the time of containing the compound which has three or more organic groups which can be bridge | crosslinked is 1-40 mass parts with respect to 100 mass parts of (A) alkali aqueous solution soluble polymers, and it is 2-30 mass parts further It is preferable and it is especially preferable that it is 4-20 mass parts. When the said compounding quantity is 1 mass part or more, the residual film rate at the time of hardening improves, the tensile elongation rate of the film | membrane after hardening is favorable, and when it is 40 mass parts or less, there is no developing residue of an exposure part, and shows favorable lithographic performance.

(E) other additives

Adhesion of the film | membrane and silicon wafer formed to the photosensitive resin composition of this invention using the phenolic compound, dye, surfactant, stabilizer, and photosensitive resin composition which are known as an hydroxyl group containing compound and the additive of the photosensitive resin composition as needed. You may mix | blend 1 type, or 2 or more types of adhesion | attachment adjuvant etc. for improving the property. Hereinafter, the more detailed example of the additive which can be mix | blended is described concretely.

As the hydroxyl group-containing compound, a compound having 4 to 14 carbon atoms is preferable. It is preferable to add a hydroxyl group containing compound to the photosensitive resin composition of this invention from a viewpoint of a sensitivity and a resolution. Specific examples of the hydroxyl group-containing compound include cyclopropylcarbinol, 2-cyclohexen-1-ol, cyclohexanemethanol, 4-methyl-1-cyclohexanemethanol, 3,4-dimethylcyclohexanol, 4- Ethylcyclohexanol, 4-t-butycyclocyclohexanol, cyclohexaneethanol, 3-cyclohexyl-1-propanol, 1-cyclohexyl-1-pentanol, 3,3,5-trimethylcyclohexanol, nord Boran-2-methanol, cyclooctanol, 2,3,4-trimethyl-3-pentanol, 2,4-hexadien-1-ol, cis-2-hexen-1-ol, trans-2-heptene -1-ol, cis-4-hepten-1-ol, cis-3-octen-1-ol, 4-ethyl-1-octin-3-ol, 2,7-octadienol, 3,6-dimethyl -1-heptin-3-ol, 3-ethyl-2-methyl-3-pentanol, 2-ethyl-1-hexanol, 2,3-dimethyl-2-hexanol, 2,5-dimethyl-2- Hexanol, trans, cis-2,6-nonadien-1-ol, 1-nonene-3-ol, cis-2-butene-1,4-diol, 2,2-diethyl-1,3-propane Diol, 2,4-diethyl-1,5-pentanediol, 1,5-hexadiene-3,4-diol, 2,5-dimethyl-3-hexyl-2,5-diol, 2,4,7 , 9-tetra Methyl-5-decine-4,7-diol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanediol, trans-p-mentan-3,8-diol, 2, 4- dimethoxy benzyl alcohol, butyroin, etc. are mentioned.

Among them, 2,3,4-trimethyl-3-pentanol, 2,4-hexadiene-1-ol, cis-2-hexen-1-ol, trans-2-hepten-1-ol, cis-4 -Hepten-1-ol, cis-3-octen-1-ol, trans, cis-2,6-nonadien-1-ol, cis-2-butene-1,4-diol, 1,5-hexadiene Hydroxyl group-containing compounds having an unsaturated bond and / or branched structure, such as -3,4-diol, are preferable, and monoalcohol is more preferable than diol from the viewpoint of adhesion between the film and the substrate formed using the photosensitive resin composition. Do. Among them, 2,3,4-trimethyl-3-pentanol, 3-ethyl-2-methyl-3-pentanol, and glycerol-α, α'-diallyl ether are particularly preferable.

These hydroxyl group containing compounds may be used independently, or may mix and use 2 or more types.

As for the compounding quantity in the case of mix | blending the said hydroxyl group containing compound, 70 mass parts or less are preferable with respect to 100 mass parts of (A) alkali aqueous solution soluble polymers, 0.01-70 mass parts are more preferable, 0.1-50 mass parts is still more preferable 1-40 mass parts is more preferable, and 5-25 mass parts is especially preferable. When the said compounding quantity of a hydroxyl-group containing compound is 0.01 mass part or more, the image development residue of an exposed part decreases, and when it is 70 mass part or less, the tensile elongation rate of the film | membrane after hardening is favorable.

As said phenolic compound, the ballast agent used for the naphthoquinone diazide compound mentioned above, and linear phenolic compounds, such as paracumyl phenol, bisphenol, resorcinol, and Mtris PC, Mtetra PC (Honshu Chemical Industry Co., Ltd.) Production: Brand name), and also non-linear phenolic compounds (trade name: manufactured by Honshu Chemical Co., Ltd.) such as Tris P-HAP, Tris P-PHBA, and Tris P-PA, and hydrogen atoms of the phenyl group of diphenylmethane. The compound which substituted -5 with the hydroxyl group, the compound which substituted 1-5 hydrogen atoms of the phenyl group of 2, 2- diphenyl propane, with a hydroxyl group, etc. are mentioned. By addition of this phenolic compound, the adhesiveness of the relief pattern at the time of image development and a base material can be improved, and generation | occurrence | production of a residue can be suppressed. In addition, a ballast agent refers to the phenol compound used as a raw material of the above-mentioned naphthoquinone diazide compound (photosensitive diazoquinone compound) whose phenolic hydrogen atom is a part of naphthoquinone diazide sulfonic-acid esterified phenolic compound.

50 mass parts or less are preferable with respect to 100 mass parts of (A) alkali aqueous solution soluble polymer, and, as for the compounding quantity at the time of mix | blending the said phenolic compound, 1-30 mass parts is more preferable. When the compounding quantity is 50 mass parts or less, the heat resistance of the film | membrane after thermosetting is favorable.

As said dye, methyl violet, crystal violet, malachite green, etc. are mentioned, for example. As for the compounding quantity at the time of mix | blending dye, 0.1-10 mass parts is preferable with respect to 100 mass parts of (A) alkali aqueous solution soluble polymers. When the compounding quantity is 0.1 mass part or more, a coloring effect is favorable, and when it is 10 mass parts or less, the heat resistance of the film | membrane after thermosetting is favorable.

As said surfactant, nonionic surfactant which consists of polyglycols, such as polypropylene glycol and polyoxyethylene lauryl ether, and its derivative (s) is mentioned. Fluoride (registered trademark) (manufactured by Sumitomo 3M, trade name), MegaPak (registered trademark), manufactured by Dainippon Ink and Chemicals, Inc. (trade name), or Lumiflon (registered trademark) (manufactured by Asahi Glass Co., Ltd.) And fluorine-based surfactants. Moreover, organic siloxane surfactants, such as KP341 (made by Shin-Etsu Chemical Co., Ltd.), DBE (Made by Chisso Corp .: brand name), and glanol (made by Kyoeisha Chemical Company: brand name), are mentioned. By mix | blending this surfactant, the cratering of the coating film in the wafer edge at the time of application | coating of the photosensitive resin composition can be prevented from generating more easily.

10 mass parts or less are preferable with respect to 100 mass parts of (A) alkali aqueous solution soluble polymer, and, as for the compounding quantity when mix | blending the said surfactant, 0.01-1 mass part is more preferable. When the compounding quantity is 10 mass parts or less, the heat resistance of the film | membrane after thermosetting is favorable.

As said adhesion | attachment adjuvant, various silane coupling agents, such as alkyl imidazoline, butyric acid, alkyl acid, polyhydroxy styrene, polyvinyl methyl ether, t-butyl novolak, an epoxy polymer, and an epoxy silane, are mentioned.

As a specific preferable example of a silane coupling agent, 3-mercaptopropyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd. make: brand name KBM803, Chisso Corporation make: brand name Cyra Ace S810), 3-mercaptopropyl triethoxysilane (Az | Max Co., Ltd. make: brand name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd. make: brand name LS1375, Azmax Co., Ltd. make: brand name SIM6474.0), mercaptomethyltrimethoxysilane (Azmax Co., Ltd. make: brand name SIM6473.5C), mercaptomethylmethyldimethoxysilane (Azmax Co., Ltd. make: brand name SIM6473.0), 3-mercaptopropyl diethoxy methoxysilane, 3-mercaptopropyl ethoxy dimethoxysilane , 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimer Methoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2 Mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydiprop Foxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (Shin-Etsu Chemical Co., Ltd.) Preparation: Brand name LS3610, AZMAX Co., Ltd. Manufacture: Brand name SIU9055.0), N- (3-trimethoxysilylpropyl) urea (Azmax Co., Ltd. product name: SIU9058.0), N- (3-diethoxymethoxysilyl Propyl) urea, N- (3-ethoxydimethoxysilylpropyl) urea, N- (3-tripropoxy Sisylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea, N- (3-methoxydipropoxysilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) Urea, N- (3-tripropoxysilylethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydi Propoxysilylethyl) urea, N- (3-trimethoxysilylbutyl) urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m -Aminophenoxy) propyltrimethoxysilane (manufactured by AZMAX Corporation: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by AZMAX Corporation: trade name SLA0599.0), p-aminophenyltrimethoxysilane (Azmax (Product name: SLA0599.1) Aminophenyltrimethoxysilane (manufactured by Azmax, Inc .: Brand name SLA0599.2), 2- (trimethoxysilylethyl) pyridine (manufactured by Azmax, Inc., trade name: SIT8396.0), 2 -(Triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, (3-triethoxysilylpropyl) -t-butylcarbamate, ( 3-glycidoxy propyl) triethoxysilane etc. are mentioned. Moreover, although the following structure is mentioned as especially preferable thing, It is not limited to this.

As for the compounding quantity at the time of mix | blending the said adhesion | attachment adjuvant, 20 mass parts or less are preferable with respect to 100 mass parts of (A) alkali aqueous solution soluble polymers, 0.01-20 mass parts or less are more preferable, 0.05-10 mass parts is more preferable , 0.1-8 mass parts is more preferable, and 1-6 mass parts is especially preferable. When the said compounding quantity of an adhesion | attachment adjuvant (especially a silicone type coupling agent) is 0.01 mass part or more, there is no image development residue of an exposure part, When adhesiveness of the film | membrane formed using the photosensitive resin composition and a silicon substrate is favorable, and it is 20 mass parts or less, Time-lapse stability in the adhesiveness is favorable.

Moreover, you may use the following compound further as an additive. Specifically, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-part Methoxysilane, tetrakis (methoxyethoxysilane), tetrakis (methoxy-n-propoxysilane), tetrakis (ethoxyethoxysilane), tetrakis (methoxyethoxyethoxysilane), bis ( Trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, bis (triethoxysilyl) ethylene, bis (triethoxysilyl) Octane, bis (triethoxysilyl) octadiene, bis [3- (triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl] tetrasulfide, di-t-butoxydia Cetoxysilane, di-i-butoxy aluminoxetriethoxysilane, bis (pentadionate) titanium-O, O'-bis (oxyethyl) -aminopropyl triethoxysilane, etc. . Especially, tetramethoxysilane and tetraethoxysilane are especially preferable. As for the compounding quantity of the said compound, 0-10 mass parts is preferable with respect to 100 mass parts of (A) alkali aqueous solution soluble polymers, 0.1-6 mass parts is more preferable, 1-4 mass parts is especially preferable. When the said compounding quantity is 0.1 mass part or more, there is no image development residue of an exposure part, adhesiveness of the film | membrane formed using the photosensitive resin composition and a silicon substrate is favorable, and when it is 10 mass parts or less, time-lapse stability in the adhesiveness Is good.

(F) solvent

It is preferable to make the photosensitive resin composition of this invention melt | dissolve in a solvent, to make a varnish shape, and to use as a photosensitive resin composition solution. As such a solvent, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone (henceforth "GBL"), cyclopentanone, cyclohexanone, isophorone, N, N-dimethylacetamide ( Hereinafter, also referred to as "DMAc"), dimethylimidazolinone, tetramethylurea, dimethyl sulfoxide, diethylene glycol dimethyl ether (hereinafter also referred to as "DMDG"), diethylene glycol diethyl ether, diethylene glycol dibutyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1, 3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, etc. can be used individually or in mixture of 2 or more types. Of these solvents, non-amide solvents are preferred because they have little effect on photoresist and the like. Specific more preferable examples include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofurfuryl alcohol, and the like. These organic solvents may be used independently, or may mix and use 2 or more types.

It is preferable that it is 100-2000 mass parts with respect to 100 mass parts of (A) alkali aqueous solution soluble polymers, and, as for the addition amount of (F) solvent, it is more preferable that it is 100-1000 mass parts. By changing the addition amount of the solvent, the viscosity can be controlled. It is preferable to set the addition amount of a solvent so that it may become a viscosity suitable for an application | coating device and application | coating thickness within the said range from the point which can facilitate manufacture of a hardening relief pattern.

<Method for Manufacturing Cured Relief Pattern and Semiconductor Device>

This invention also provides the manufacturing method of the hardening relief pattern using the photosensitive resin composition of this invention mentioned above, The manufacturing method is

(1) Process of forming photosensitive resin layer which consists of photosensitive resin composition of this invention mentioned above on board | substrate,

(2) forming an exposed portion by exposing the photosensitive resin layer with a chemical ray through a mask, or directly irradiating a part of the photosensitive resin layer with a light beam, an electron beam or an ion ray,

(3) A developing step of forming a relief pattern by eluting and removing the exposed portion or the irradiated portion of the photosensitive resin layer, and

(4) The heating process of forming the hardening relief pattern by heat-processing the obtained relief pattern is included. The manufacturing method of the hardening relief pattern which concerns on this invention is demonstrated concretely below.

(1) The process (1st process) of forming the photosensitive resin layer which consists of the photosensitive resin composition of this invention mentioned above on a board | substrate.

In this step, the photosensitive resin composition is typically in the form of a photosensitive resin composition solution, for example, spin coating using a spin coater on a substrate such as a silicon wafer, a ceramic substrate, an aluminum substrate, or a die coater or roll coater. Apply by coater. Alternatively, the photosensitive resin composition solution may be applied to a predetermined place by using an inkjet nozzle or a dispenser. Thus, the board | substrate with which the photosensitive resin composition solution was apply | coated was heated to 50-140 degreeC, Preferably it is 100-140 degreeC using oven or a hotplate, and a solvent is dried and removed (hereinafter "soft baking" or "free". Bake ”), and a photosensitive resin layer is formed on a board | substrate.

(2) Process of exposing photosensitive resin layer with actinic ray through a mask and forming an exposure part, or irradiating a light ray, an electron beam, or an ion beam directly to a part of photosensitive resin layer to form an irradiation part (2nd process).

Subsequently, the photosensitive resin layer is exposed using a chemical ray through a mask to form an exposed portion, or a light irradiation portion is formed by directly irradiating a part of the photosensitive resin layer with a light beam, an electron beam or an ion beam. Specifically, exposure is performed by actinic rays using a contact aligner or stepper, or a light beam, an electron beam or an ion beam is directly irradiated to a predetermined portion of the photosensitive resin layer. As actinic rays which are active rays, g rays, h rays, i rays and KrF lasers can be used, for example.

(3) The developing process (third process) which forms a relief pattern by eluting and removing the exposure part or irradiation part of the photosensitive resin layer.

Subsequently, the exposed part or the irradiated part of the photosensitive resin layer is eluted (dissolved) and removed by a developing solution, and preferably, the desired relief pattern is obtained by continuing and rinsing with a rinse liquid. As the developing method, spray, puddle, dip, ultrasonic wave, or the like can be used. Distilled water, deionized water, etc. can be used as a rinse liquid.

The developing solution used for developing the photosensitive resin layer dissolves and removes (A) alkali aqueous solution soluble polymer, and needs to be 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.

Examples of the inorganic alkali compounds include 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, and carbonic acid. Potassium, lithium borate, sodium borate, potassium borate, ammonia, and the like.

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

In addition, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, ethylene glycol, a surfactant, a storage stabilizer, a resin dissolution inhibitor, and the like can be added to the alkaline aqueous solution as necessary.

(4) The heating process (fourth process) which heat-processes the obtained relief pattern and forms a hardening relief pattern.

Finally, the obtained relief pattern is heat-processed (hereinafter, this process is called "cure"). By curing, for example, when (A) alkali aqueous solution soluble polymer has a PBO precursor structure, the heat resistant hardening relief pattern which consists of resin which has a polybenzoxazole structure can be formed. As a heating apparatus, an oven, a hot plate, a vertical furnace, a belt conveyor, a pressure oven, etc. can be used, As a heating method, heating by hot air, infrared rays, electromagnetic induction, etc. is recommended. 200-450 degreeC is preferable and 250-400 degreeC of heating temperature is more preferable. Moreover, 15 minutes-8 hours are preferable, and, as for a heat time, 1 hour-4 hours are more preferable. Moreover, as for the atmosphere at the time of heating, inert gas, such as nitrogen and argon, is preferable.

A hardening relief pattern can be formed by the above method.

This invention also provides the semiconductor device which has a hardening relief pattern obtained by the manufacturing method of this invention mentioned above. The semiconductor device which concerns on this invention forms the above-mentioned hardening relief pattern in at least any one of a surface protective film, an interlayer insulation film, an insulating film for redistribution, a protective film for flip chip devices, and a protective film of the device which has a bump structure, and is a well-known semiconductor It can manufacture by combining the manufacturing method of an apparatus.

Example

The present invention is further described based on the reference examples and examples.

<Production of bis (carboxy) tricyclo [5,2,1,0 ^2,6 ] decane>

[Referential Example 1]

71.9 g (0.366 mol) of tricyclo [5,2,1,0 ^2,6 ] decanedimethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) in a glass-separable three-necked flask equipped with an anchor stirrer made of Teflon (registered trademark) ) Dissolved in 1 L of acetonitrile, and further, a solution of 256.7 g (1.808 mol) of sodium dihydrogen phosphate and 217.1 g (1.809 mol) of sodium dihydrogen phosphate in 1.4 L of ion-exchanged water was added. . To this, 2.8 g (0.0179 mol) of 2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Tokyo Kasei Kogyo Co., hereinafter, also referred to as "TEMPO") was added, stirred, and dissolved.

The dilution of 143.2 g (1.267 mol) of 80% sodium chlorite with 850 ml of ion-exchange water was dripped at the solution obtained above. Subsequently, 3.7 ml of 5% sodium dichlorate aqueous solution was diluted with 7 ml of ion-exchanged water, and it was dripped in the solution. This solution was kept at 35-38 degreeC by the thermostat, and it stirred for 20 hours and made it react.

After the reaction, the obtained reaction solution was cooled to 12 ° C, an aqueous solution in which 75 g of sodium sulfite was dissolved in 300 ml of ion-exchanged water was added dropwise to the reaction mixture, and the excess sodium chlorite was deactivated, followed by 500 ml of ethyl acetate. The reaction solution was washed with. Thereafter, 115 ml of 10% hydrochloric acid was added dropwise to adjust the pH of the reaction solution to 3-4 to recover the precipitate by decantation. This precipitate was dissolved in 200 ml of tetrahydrofuran. The aqueous layer was extracted twice with 500 ml of ethyl acetate, washed with brine, and the precipitate was dissolved in tetrahydrofuran in the same manner. 58.4 g of bis (carboxy) tricyclo [5,2,1,0 ^2,6 ] decane were mixed by mixing the above tetrahydrofuran solution, drying it with anhydrous sodium sulfate, and further concentrating and drying with an evaporator. Yield 71.1%) of white crystals was obtained.

<Preparation of bis (chlorocarbonyl) tricyclo [5,2,1,0 ^2,6 ] decane>

[Reference Example 2]

62.5 g (278 mmol) of bis (carboxy) tricyclo [5,2,1,0 ^2,6 ] decane obtained in Reference Example 1, 97 ml (1.33 mol) of thionyl chloride, and 0.4 ml (5.0 mmol) of pyridine ) Was injected into the reaction vessel, and the mixture was stirred at 25 to 50 ° C for 18 hours to react. After completion of the reaction, toluene was added to the reaction product, and the reaction product was concentrated by azeotropic excess thionyl chloride with toluene under reduced pressure, thereby obtaining an oily bis (chlorocarbonyl) tricyclo [5,2,1,0 ^{2. , 6} ] 73.3 g (yield 100%) of decane was obtained.

<(A) Synthesis of aqueous alkali solution soluble polymer>

[Reference Example 3]

In a 2 L separable flask, 197.8 g (0.54 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 75.9 g (0.96 mol) of pyridine, and 692 g of DMAc were room temperature It stirred by mixing and stirring at (25 degreeC). The thing which melt | dissolved 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic acid anhydrides (made by Tokyo Chemical Co., Ltd.) in 88 g of DMDG was dripped at this separately from the dropping funnel. The time required for dripping was 40 minutes, and reaction liquid temperature was 28 degreeC at maximum.

It was confirmed that the absorption properties of already deugi ^one shown ^- after the addition was completed, the reaction mixture was heated to 50 ℃ and 1385 ㎝ ^-1 and 1772 ㎝ then stirred for 18 hours by measuring the IR spectrum of the reaction solution by tangyok.

Next, this was cooled to 8 degreeC by the water bath, and what melt | dissolved 142.3 g (0.48 mol) of 4,4'- diphenyl ether dicarboxylic acid dichlorides in 398 g of DMDG was dripped at this by the dropping funnel. The time required for dripping was 80 minutes, and reaction liquid temperature was 12 degreeC at maximum. After 3 hours from the end of the dropwise addition, the obtained reaction solution was added dropwise to 12 liters of water under high speed stirring to disperse and precipitate the polymer, and this was recovered, vacuum-dried after washing with water and dewatering as appropriate, and as an aqueous alkali aqueous solution soluble polymer (P-1). PBO precursor was obtained. Thus, the weight average molecular weight (Mw) by GPC (high speed liquid chromatography) of the aqueous alkali solution soluble polymer synthesize | combined was confirmed that a single composition was obtained as a single sharp curve which is 14000 in polystyrene conversion. The analysis conditions of GPC are described below.

Column: Showa Denko Corporation Brand Name Shodex 805/804/803 Serial

Eluent: tetrahydrofuran 40 ℃

Flow rate: 1.0 ml / min

Detector: Showa Denko brand name Shodex RI SE-61

[Reference Example 4]

Bis (3-amino-4-hydroxyphenyl) propane (manufactured by Clarity Japan Co., Ltd.) (hereinafter referred to as "BAP") in a glass-separable three-necked flask equipped with an anchor stirrer made of Teflon (registered trademark) 69.17 g (268 mmol), 276 g of NMP, and 12.7 g (160 mmol) of pyridine were added, the nitrogen inlet tube was attached, and it stirred under the state which made nitrogen gas flow, and dissolved BAP. After BAP was dissolved, the reaction vessel was cooled by dipping into a vessel in which dry ice was added to methanol. 69.99 g (268 mmol) of bis (chlorocarbonyl) tricyclo [5,2,1,0 ^2,6 ] decane prepared in Reference Example 2 was dissolved in 280 g of -butyrolactone, and -10 to-. It was dripped at the reaction vessel over 30 minutes, maintaining at 19 degreeC. After completion of the dropwise addition, the reaction vessel was immersed in an ice bath, kept at 0 to 10 ° C, and stirred for 2 hours. Further 29.65 g (375 mmol) of pyridine was added to the reaction vessel.

Ethanol was added to the reaction solution obtained above, the polymer was precipitated, and this was recovered and dissolved in 350 ml of NMP. Subsequently, the obtained solution was ion-exchanged with 78 g of cation exchange resin (organo company make, Amberlyst A21) and 75 g of anion exchange resin (organo company make, Amberlyst 15). The solution was added dropwise to 3 L of ion-exchanged water under high-speed stirring, the polymer was dispersed and precipitated, recovered, washed with water and dehydrated appropriately, and dried in vacuo to form a PBO precursor as an alkali aqueous solution-soluble polymer (P-2) composed of a PBO precursor unit. Got it. The weight average molecular weight by GPC of the alkali aqueous solution soluble polymer synthesize | combined in this way confirmed that a single composition was obtained as a single sharp curve which is 36800 in polystyrene conversion. The analysis conditions of GPC are described below.

Column: Showa Denko Corporation Brand Name Shodex 805M / 806M Serial

Eluent: N-methylpyrrolidone 40 ℃

Flow rate: 1.0 ml / min

Detector: Nippon spectrometer brand name RI-930

[Reference Example 5]

A glass-separable four-necked flask equipped with an anchor stirrer manufactured by Teflon (registered trademark) was equipped with a cooling tube with a Dean Stark trap. 5- (2,5-dioxotetrahydro-3-furyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 35.14 g (133 mmol), 41.26 g (133 mmol) of bis (3,4-dicarboxyphenyl) ether dianhydride, 72.28 g (280 mmol) of BAP, 254.6 g of γ-butyrolactone and 60 g of toluene were added, and at 100 rpm at room temperature. After stirring for 4 hours, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic anhydride is added and heated at 100 rpm at a silicon bath temperature of 50 ° C. for 8 hours while allowing nitrogen gas to pass through. Stirred. Then, it heated up at 180 degreeC of silicone bath temperature, and stirred by heating at 100 rpm for 2 hours. During the reaction, the outflow of toluene and water was removed. After completion | finish of imidation reaction, it returned to room temperature.

The reaction liquid obtained above was dripped at 3 L of water under high speed stirring, and the polymer was dispersed and precipitated, this was collect | recovered, and it washed suitably, and it vacuum-dried after dehydration, and obtained soluble PI as alkali aqueous solution soluble polymer (P-3). The weight average molecular weight by GPC of the alkali aqueous solution soluble polymer synthesize | combined in this way was the single sharp curve which is 23000 in polystyrene conversion. The analysis conditions of GPC are described below.

Column: Showa Denko Corporation Brand Name Shodex 805M / 806M Serial

Eluent: N-methylpyrrolidone 40 ℃

Flow rate: 1.0 ml / min

Detector: Nippon spectrometer brand name RI-930

[Reference Example 6]

In a 2 L separable flask, 105.7 g (0.4 mol) of 5- (2,5-dioxotetrahydro-3-furyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride , 59.3 g (0.8 mol) of isobutyl alcohol and 320 g of GBL were dissolved by mixing and stirring at room temperature (25 ° C.), 63.3 g (0.8 mol) of pyridine was added while stirring under ice cooling, and allowed to cool to room temperature after the end of exotherm, It was left for 16 hours.

To this, a solution obtained by dissolving 165 g (0.8 mol) of dicyclohexylcarbodiimide in 120 g of GBL was added for 40 minutes while stirring under ice cooling, followed by 74.5 g (0.37 mol) of 4,4'-diaminodiphenyl ether. Suspended in 150 g of GBL was added in the same manner for 60 minutes while stirring under ice cooling. After stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added, followed by stirring for 1 hour. Further, 250 ml of DMAc and 400 ml of THF were added. Then, the precipitate was removed by suction filtration and the reaction solution was obtained with 15 L of ethyl. The resultant precipitate was added to alcohol, and the resulting precipitate was filtered off and dried in vacuo to obtain a PI precursor as polyamic acid ester (P-4). The weight average molecular weight by GPC of the alkali aqueous solution soluble polymer synthesize | combined in this way was a single sharp curve which is 33000 in polystyrene conversion. The analysis conditions of GPC are described below.

Column: Showa Denko Corporation Brand Name Shodex 805M / 806M Serial

Eluent: N-methylpyrrolidone 40 ℃

Flow rate: 1.0 ml / min

Detector: Nippon spectrometer brand name RI-930

<B Synthesis of Naphthoquinonediazide Compound>

[Reference Example 7]

In a 1 L separable flask, 109.9 g (0.3 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 330 g of tetrahydrofuran (THF), 47.5 g of pyridine ( 0.6 mol), and 98.5 g (0.6 mol) of 5-norbornene-2,3-dicarboxylic anhydrides were added to this at room temperature at room temperature. After carrying out the stirring reaction for 3 days at room temperature in that state, when the reaction was confirmed by HPLC, the raw material was not detected at all, and the product was detected by purity 99% as a single peak. The reaction solution was added dropwise to 1 L of ion-exchanged water under stirring, the precipitate was filtered off, and then, 500 mL of THF was added to the precipitate, followed by stirring to dissolve it. The resultant homogeneous solution was added to a cation exchange resin: Amberlyst 15 (Organo company make) It passed through the glass column filled with 100 g, and the residual pyridine was removed. Next, this solution was dripped in 3 L of ion-exchanged water under high speed stirring, and the product was precipitated, This was filtered off and dried in vacuo.

The product is the imidization, the IR spectrum 1394 cm ^-1 and 1774 cm ^{- 1} already has the characteristic absorption of deugi appears that there is no characteristic absorption of amide group in the vicinity of 1540 cm ^-1 and 1650 cm ^-1, and NMR spectra confirmed that there were no peaks of protons of amides and carboxylic acids.

Next, 65.9 g (0.1 mol) of this product, 53.7 g (0.2 mol) of 1, 2- naphthoquinone diazide-4-sulfonyl chlorides, and 560 g of acetone were added to the reaction container, and it stirred and melted at 20 degreeC. . What diluted 21.2 g (0.21 mol) of triethylamine with 106.2 g of acetone to this was dripped at the fixed speed over 30 minutes. At this time, the reaction liquid was temperature-controlled in 20-30 degreeC using the ice-water bath.

After completion of the dropwise addition, the mixture was left to stir at 20 ° C for 30 minutes, and then 5.6 g of 36 mass% hydrochloric acid aqueous solution was added at a time, the reaction solution was then cooled in an ice water bath, and the precipitated solid was separated by suction filtration. The filtrate obtained at this time was dripped at 5 L of 0.5 mass% hydrochloric acid aqueous solution over 1 hour under the stirring, the target substance was precipitated, and it collected by suction filtration and collect | recovered. The obtained cake-like recovered product was further dispersed in 5 L of ion-exchanged water, stirred, washed, and separated by filtration, and this washing operation was repeated three times. The cake shape finally obtained was vacuum-dried at 40 degreeC for 24 hours, and the photosensitive diazoquinone compound (naphthoquinone diazide compound) (Q-1) was obtained.

[Reference Example 8]

4,4 '-(1- (2- (4-hydroxyphenyl) -2-propyl) phenyl) ethylidene) bisphenol (manufactured by Honshu Chemical Industries, Ltd.) as a polyhydroxy compound : 30 g (0.0707 mol) of the compound of Tris-PA) was added, and 47.49 g (0.177 mol) of 1,2-naphthoquinone diazide-4-sulfonic acid chloride in an amount corresponding to 83.3 mol% of the OH group was added. After adding what was stirred and dissolved in 300 g of acetone, the flask was adjusted to 30 degreeC in the thermostat. Next, 17.9 g of triethylamine was dissolved in 18 g of acetone and injected into a dropping funnel, and this was added dropwise into the flask over 30 minutes. After completion of the dropwise addition, stirring was further continued for 30 minutes, and then hydrochloric acid was added dropwise, followed by stirring for 30 minutes again to terminate the reaction. It filtered after that and removed triethylamine hydrochloride. The filtrate obtained here was dripped at the 3 L beaker which mixed and stirred 1640 g of pure waters and 30 g of hydrochloric acid, stirring, and obtained the precipitate. The precipitate was washed with water and filtered, and then dried at 40 ° C. under reduced pressure for 48 hours to obtain a photosensitive diazoquinone compound (naphthoquinone diazide compound) (Q-2).

[Reference Example 9]

<Preparation of Adhesion Aids>

As the reaction vessel, a glass-separable three-necked flask equipped with an anchor stirrer made of Teflon (registered trademark) was used. 131.0 g of di-t-butyl dicarbonate and 780 g of γ-butyrolactone were injected into the reaction vessel, and a solution obtained by mixing 132.8 g of 3-aminopropyltriethoxysilane and 270 g of γ-butyrolactone was slowly added at room temperature. It was dripped under room temperature. As it dripped, the reaction liquid heated up to about 40 degreeC. Moreover, generation | occurrence | production of the carbon dioxide gas was confirmed with reaction. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and then the reaction solution was confirmed by high performance liquid chromatography (HPLC). As a result, no raw materials were detected. The mate was detected with a purity of 98% as a single peak. In this way, an adhesion aid solution was obtained.

<Production of Photosensitive Resin Composition>

Examples 1 to 21 and Comparative Examples 1 to 11

The heat-resistant (A) alkali aqueous solution soluble polymer (P-1-P-4) 100 obtained in Examples 1-21 and Table 1 which are shown in Table 1, and Comparative Examples 1-11 is obtained in the said Reference Examples 3-6. (B) Naphthoquinone diazide compound (Q-1 and Q-2) obtained by the said Reference Examples 7 and 8 with respect to a mass part, (C of following C-1 to C-11) ) A monocarboxylic acid compound and a compound having three or more organic groups capable of crosslinking (D) in the following D-1 to D-3 in a molecule thereof are suitably dissolved in 170 to 220 parts by mass of GBL, and then, in Reference Example 9 30 mass parts of obtained adhesion | attachment adjuvant was added, and it filtered and prepared with a 0.2 micrometer filter.

(C-1) 3-phenyllactic acid

(C-2) hydroxymandelic acid

(C-3) 4-hydroxy-3-methoxymandelic acid

(C-4) mandelic acid

(C-5) atrolactic acid

(C-6) O-acetylmandelic acid

(C-7) α-methoxyphenylacetic acid

(C-8) 2-phenylbutyric acid

(C-9) 3- (4-hydroxyphenyl) propionic acid

(C-10) trough acid

(C-11) m-toluic acid

(D-1) BANI-X (Maruzen Petrochemical: Product Name)

(D-2) trimethylolpropane trimethacrylate

(D-3) trimellitic acid triallyl

<Evaluation of the photosensitive resin composition>

(1) patterning characteristics evaluation

Preparation of prebaked film and measurement of film thickness

The photosensitive resin composition of the said Example and the comparative example was spin-coated to a 6 inch silicon wafer with the spin coater (Clean Track Mark8 by Tokyo Electron, Inc.), and it prebaked for 125 degreeC and 180 second on a hotplate, and obtained the film for evaluation. The initial film thickness of each composition was adjusted so that P-1 and P-2 may be 7 micrometers, and P-3 may be 5 micrometers by the resin film thickness after hardening when cured at 320 degreeC for 1 hour. The film thickness was measured by a film thickness measuring device (Lamuda Ace manufactured by Dainippon Screen Manufacturer).

Exposure

The film for evaluation was exposed through the reticle in which the test pattern was formed, using the stepper (NSR2005i8A by Nikon Corporation) which has an exposure wavelength of i line | wire (365 nm), changing exposure amount in steps.

·phenomenon

The developing time was set so that the film after the exposure was subjected to an alkali developer (AZAZMIMI developer manufactured by AZ Electronics, AZ300MIF developer, 2.38% by mass of tetramethylammonium hydroxide solution) so that the film thickness after development under conditions of 23 ° C was 85% of the initial film thickness. It developed by adjusting and rinsing with pure water, and formed the positive relief pattern.

Preparation of cure film

Subsequently, the film after image development was cured at 320 degreeC for 1 hour using the temperature rising oven (VF200B by Koyo Thermo Systems, Inc.), and the cured film which has a hardening relief pattern was manufactured.

In addition, the sensitivity of the photosensitive resin composition and the residual film ratio at the time of hardening were evaluated as follows. The results are shown in Table 2 below.

[Sensitivity (mJ / cm 2)]

The sensitivity (mJ / cm 2) was defined as the minimum exposure amount that can completely dissolve and remove the exposed portion of the coating film in the film thickness after the prescribed development.

[Residual Film Rate at Curing (%)]

Residual film rate (%) at the time of hardening was prescribed | regulated as (film thickness of the hardening relief pattern after curing) / (film thickness of the relief pattern after development) x100.

Industrial availability

The photosensitive resin composition of the present invention is a surface protective film, an interlayer insulating film, a redistribution insulating film, a protective film for a flip chip device, a protective film of a device having a bump structure, an interlayer insulating film of a multilayer circuit, and a flexible copper plate of a semiconductor device. It can use suitably as a cover coat, a soldering resist film, a liquid crystal aligning film, etc.

Claims (13)

(A) the following general formula (1):
[Formula 1]

(In formula, X <_1> represents the bivalent tetravalent organic group which has at least 2 carbon atoms, Y <_1> represents the 2-6 valent organic group which has at least 2 carbon atoms, and R <_1> and R <_2> are respectively independently hydrogen A hydrocarbon group having 1 to 10 carbon atoms or atoms, n ₁ , n ₂ and n ₄ are each independently an integer of 0 to 2, n ₃ is 0, and n ₁ + n ₂ + n ₃ + n ₄ > 0, and m ₁ is an integer of 1 to 1000)
Structure represented by following General formula (2):
(2)

(Wherein, X ₂ and Y ₂ each independently represent a tetravalent organic group having at least two carbon atoms, and m ₂ is an integer of 1 to 1000)
100 parts by mass of an aqueous alkali solution soluble polymer having at least one kind of structure selected from the group consisting of structures represented by
(B) 1-50 mass parts of photoacid generators, and
(C) Photosensitive resin composition containing 5-20 mass parts of monocarboxylic acid compounds which are represented by following General formula (4) and are at least 1 sort (s) of compound chosen from the group which consists of a compound with 8-30 carbon atoms.
[Chemical Formula 4]

(Wherein R ₃ represents a group having at least one structure selected from the group consisting of a hydrogen atom and an alkyl group, R ₄ represents a group having at least one structure selected from the group consisting of a hydrogen atom, an alkyl group and a carbonyl group, Z ₂ represents a hydroxyl group or an organic group, n ₅ is an integer of 0 to 5, and in the case where a plurality of Z ₂ are present, they may be the same as or different from each other) The method of claim 1,
The photosensitive resin composition whose said (B) photoacid generator is a compound which has a naphthoquinone diazide structure. The method of claim 1,
The structure represented by the said General formula (1) in the said (A) alkali aqueous solution soluble polymer has the following general formula (5):
[Chemical Formula 5]

(In formula, X <_1> represents the bivalent tetravalent organic group which has at least 2 carbon atom, R <_1> represents a hydrogen atom or a C1-C10 hydrocarbon group, n <_1> is an integer of 0-2, n ₃ is 0, m ₁ is an integer of 1 to 1000, L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or a methyl group, and L ₄ represents a hydrogen atom, a methyl group or a hydroxyl group)
Photosensitive resin composition which has a structure shown by. The method of claim 1,
The structure represented by the said General formula (1) in the said (A) alkali aqueous solution soluble polymer has the following general formula (6):
[Chemical Formula 6]

(Wherein X ₃ is a single bond and the following formula (7):
(7)

At least 1 type of structure chosen from the group which consists of a structure shown by these, L <_1> , L <_2> and L <_3> represent a hydrogen atom or a methyl group each independently, L <_4> represents a hydrogen atom, a methyl group, or a hydroxyl group, and m ₁ is an integer of 1 to 1000)
The photosensitive resin composition which has a structure shown by these. The method of claim 1,
The structure represented by the said General formula (2) in the said (A) alkali aqueous solution soluble polymer is a structure represented by following General formula (8), and the structure shown by following General formula (9):
[Chemical Formula 8]

(Wherein X ₄ is a single bond and the following formula (7):
[Chemical Formula 9]

At least 1 type of structure chosen from the group which consists of a structure shown by these, and m <_2> is an integer of 1-1000)
The photosensitive resin composition which has in a molecule the at least 1 sort (s) of polyimide structure chosen from the group which consists of. The method of claim 1,
The terminal of the said (A) alkali aqueous solution soluble polymer has the following general formula (10):
[Formula 10]

(Wherein L ₅ represents —CH ₂ —, —O— or —S—, and L ₆ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 1 to 6 carbon atoms)
The photosensitive resin composition containing at least 1 sort (s) of end group chosen from the group which consists of terminal groups represented by these. The method of claim 1,
(D) The photosensitive resin composition which further contains the compound which has three or more organic groups which can be bridge | crosslinked in a molecule | numerator in the quantity of 1-40 mass parts with respect to 100 mass parts of said (A) alkali aqueous solution soluble polymers. The method of claim 7, wherein
The compound which has 3 or more of said (D) crosslinkable organic groups in a molecule | numerator is trimethylol propane trimethacrylate, trimellitic acid triallyl, and following General formula (11):
(11)

In the formula, D ₁ represents a group having at least one structure selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and an organic group that can be crosslinked, M ₁ represents -CH _2- , -O- or -S-, Z ₃ represents a divalent organic group, n ₆ is an integer of 0 to 4, and a plurality of D ₁ are the same as each other. May be different)
The photosensitive resin composition which is at least 1 sort (s) of compound chosen from the group which consists of a compound shown by these. The method of claim 7, wherein
The compound which has 3 or more of said organic groups which can bridge | crosslink (D) in a molecule | numerator is a following formula (12):
[Chemical Formula 12]

The photosensitive resin composition which is at least 1 sort (s) of compound chosen from the group which consists of a compound shown by these. (1) Process of forming on the board | substrate the photosensitive resin layer which consists of the photosensitive resin composition of any one of Claims 1-9,
(2) exposing the photosensitive resin layer with a chemical ray through a mask to form an exposed portion, or directly irradiating a portion of the photosensitive resin layer with a light beam, an electron beam or an ion ray to form an irradiation portion;
(3) A developing step of forming a relief pattern by eluting and removing the exposed portion or the irradiated portion of the photosensitive resin layer, and
(4) The manufacturing method of the hardening relief pattern containing the heating process of heat-processing the obtained relief pattern and forming a hardening relief pattern. The semiconductor device which has a hardening relief pattern obtained by the manufacturing method of Claim 10. delete delete