KR20100133495A - Photosensitive resin composition - Google Patents

Abstract

{식 중, X¹, X², Y¹, Y², l, m 은 청구항에 정의하는 것이다.} 로 나타내는 구조를 함유하는 하이드록시폴리아미드 100 질량부, (B) 하기 일반식 (2) :

{식 중, k, X, R¹, R², n, p, q 는 청구항에 정의하는 것이다.} 로 나타내는 알콕시알킬기 함유 화합물 0.01 ∼ 30 질량부, 및 (C) 디아조퀴논 화합물 1 ∼ 100 질량부를 함유하는 것을 특징으로 한다.INDUSTRIAL APPLICABILITY The present invention provides a novel photosensitive resin composition having a positive type lithography performance excellent in storage stability, high sensitivity and excellent over time stability of sensitivity after exposure, a method of producing a cured relief pattern using the composition, and a cured relief thereof A semiconductor device having a pattern is provided. The photosensitive resin composition which concerns on this invention is (A) following General formula (1):

{In formula, X <^1> , X <^2> , Y <^1> , Y <^2> , l and m are what is defined in a claim.} 100 mass parts of hydroxypolyamide containing the structure shown by (B) following General formula (2) :

{In formula, k, X, R <^1> , R <^2> , n, p, q are what is defined in a claim.} 0.01-30 mass parts of alkoxyalkyl group containing compounds and (C) diazoquinone compound 1-100 It is characterized by containing a mass part.

Description

Photosensitive resin composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a method for producing a cured relief pattern having heat resistance using the photosensitive resin composition used as a surface protective film of a semiconductor device, an interlayer insulating film, and the photosensitive resin composition, and a semiconductor device having the cured relief pattern.

DESCRIPTION OF RELATED ART Conventionally, the polyimide resin which combines the outstanding heat resistance, an electrical characteristic, a mechanical characteristic, etc. is used for the surface protection film and interlayer insulation film of a semiconductor device. This polyimide resin is currently generally provided in the form of a photosensitive polyimide precursor composition, and is applied to a substrate, patterned by actinic light, development, thermal imidization treatment, and the like, thereby providing a surface protective film and an interlayer on the semiconductor device. It is possible to easily form an insulating film and the like, and has a feature that a significant process shortening can be made as compared with a conventional non-photosensitive polyimide precursor composition.

By the way, the photosensitive polyimide precursor composition needs to use a large amount of organic solvents, such as N-methyl- 2-pyrrolidone, as a developing solution in the image development process, and deorganic-solvent solvent is due to the heightening of recent environmental problems, etc. Measures are required. Thereby, various proposals of the heat resistant photosensitive resin material which can be developed with alkaline aqueous solution are made | formed in recent years like a photoresist.

Among them, a positive photosensitive resin is a PBO precursor composition obtained by mixing an alkaline aqueous solution-soluble hydroxypolyamide, for example, a polybenzoxazole (hereinafter also referred to as "PBO") precursor with a photoactive component such as a diazoquinone compound. The method of using as a composition attracts attention recently (for example, refer the following patent document 1).

The developing mechanism of this positive photosensitive resin is that the diazoquinone compound of the unexposed part is insoluble in the alkaline aqueous solution, whereas the diazoquinone compound causes chemical change by exposure, thereby making it an indencarboxylic acid compound and soluble in the alkaline aqueous solution. It is used. 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 of only an unexposed part can be produced.

The PBO precursor composition mentioned above can form a positive type relief pattern by exposure and image development by alkaline aqueous solution. In addition, an oxazole ring is formed by heating (hereinafter also referred to as "cure"), and the PBO film after curing has a thermosetting film characteristic equivalent to that of a polyimide film, and thus is a promising alternative material for the organic solvent developing type polyimide precursor. It is attracting attention as.

When manufacturing a semiconductor using such a photosensitive resin composition, what is especially important is the photosensitivity of the photosensitive resin composition. In the exposure process at the time of manufacture of a semiconductor device, the reduced-projection exposure machine called i line stepper (henceforth simply a "stepper") using the i line of a mercury lamp is mainly used. Since this stepper is a very expensive machine, when the photosensitive resin composition is low, the exposure time required for forming a relief pattern becomes long, and the number of necessary steppers increases, leading to high cost of the exposure process.

As a method of improving the photosensitivity of a positive photosensitive resin composition, the technique of adding the compound which has a thermal crosslinkable group to a composition is known. When the compound having a thermally crosslinkable group is added to the photosensitive resin composition, it causes an addition reaction between the aromatic ring of the polymer during curing, suppresses shrinkage due to decomposition of the polymer and thermal relaxation, and shrinkage of the film during curing. There is a function to suppress. When shrinkage of cures is suppressed, a thicker final film thickness can be obtained even with an initial coating film thickness of the same composition, in other words, a thin initial coating film thickness is sufficient to obtain the same final film thickness. The thinner the initial application film thickness, the easier the light energy in the exposure step is to reach the bottom of the film, and the higher sensitivity can be realized as the positive photosensitive resin composition in which the exposed part is opened.

As a technique for adding a known thermally crosslinkable group to a composition, for example, a compound having a methylol-based thermally crosslinkable urea-based organic group is added to an alkali-soluble resin (see, for example, claim 2 of Patent Document 1), or The thing which added the compound which has an epoxy group to alkali-soluble resin (for example, following patent document 2), and the thing which added the compound which has a benzoxazine group to alkali-soluble resin (for example, following patent document 2) Proposed.

Japanese Unexamined Patent Publication No. 2002-328472 Japanese Laid-Open Patent Publication 2004-093816 Japanese Laid-Open Patent Publication 2000-305268 Japanese Laid-Open Patent Publication No. 2006-178437 Japanese Laid-Open Patent Publication 2005-037925 Japanese Unexamined Patent Publication No. 2007-016214 Japanese Patent Application Laid-Open No. 06-27654

The thermal crosslinking agent reacts with the polymer with high efficiency and exhibits a high crosslinking effect.Because of its high reactivity, the thermal crosslinking agent is applied by heating in a process of forming a photosensitive resin layer by applying the composition on a substrate (hereinafter also referred to as "prebaking"). The unexposed portion may also be crosslinked to hinder the resolution, the heat crosslinking agent may react with the acid generated by the exposure in the exposed portion, and the sensitivity may be impaired, or the storage stability of the composition may be impaired. . Moreover, what added the methylol thermal crosslinking compound which has a phenolic hydroxyl group to alkali-soluble resin (for example, Claim 1 of patent document 1, patent document 3, patent document 4) was developed and known, These compounds are known. Silver contains a phenolic hydroxyl group, so that the alkali solubility of the composition is increased, and if the amount added is increased to an amount sufficient to suppress the shrinkage during curing, the difference in the dissolution rate (contrast) of the exposed portion and the unexposed portion is inhibited, and conversely, the reduction is reduced. It becomes. It is also known to add a compound containing a methylol group to an alkali-soluble resin without containing a phenolic hydroxyl group (see Patent Document 5, for example), but the compound having a methylol group reacts slowly in the composition (cancer) ) Reaction) and the storage stability (viscosity stability) of the photosensitive resin composition were bad. Moreover, the composition which adds the thermal crosslinking | crosslinked compound which has alkoxy methyl group more stable than methylol group to alkali-soluble resin is disclosed (refer patent document 2, patent document 6), and it is described that the compound which does not contain a phenolic hydroxyl group can also be used. Although, in fact, the example by the alkoxy methyl group containing compound which does not have a phenolic hydroxyl group is not described.

In view of the problems of the prior art, the problem to be solved by the present invention is to provide a novel photosensitive resin composition having a positive lithography performance excellent in storage stability, high sensitivity, and excellent over time stability of sensitivity after exposure. It is providing the manufacturing method of the used hardening relief pattern, and the semiconductor device which has this hardening relief pattern.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, as a result, it combines the thermal crosslinkable low molecular compound which has a specific structure with the polybenzoxazole resin precursor, and does not inhibit storage stability (viscosity stability), It was found that a photosensitive resin composition having positive lithography characteristics was obtained. Furthermore, by combining with the thermally crosslinkable low molecular weight compound having a specific structure, it has been found that the photosensitive resin composition having a small time-lapse change after exposure of high-sensitivity lithography characteristics and excellent in the time-lapse stability of sensitivity is obtained, thus completing the present invention. It came to the following.

That is, this invention is as follows.

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

[Formula 1]

{Wherein, X ¹ is a tetravalent organic group having carbon atoms, X ² , Y ¹ and Y ² are each independently a divalent organic group having two or more carbon atoms, and l is an integer of 2 to 1000; m is an integer from 0 to 500, l / (l + m)> 0.5, l dihydroxydiamide units containing X ¹ and Y ¹ and m dia containing X ² and Y ² The order of arrangement of the mid units does not matter} 100 parts by mass of hydroxypolyamide containing the structure represented by (B) the following general formula (2):

[Formula 2]

{Wherein k is an integer of 1 to 4, when (i) k = 1, X is C _n H _2n OR ¹ or R ² , and R ¹ is a methyl group, an ethyl group, an n-propyl group and an isopropyl group It is a monovalent organic group chosen from the group which consists of R <^2> , A group which consists of a hydrogen atom, a C1-C4 alkyl group, a C2-C10 ester group, a C2-C10 urethane group, and a C1-C10 alkoxy group It is a monovalent organic group chosen from, n is an integer of 1-3, p is an integer of 1-5, q is an integer of 0-4, and (p + q) = 5, (ii) k When = 2 to 4, X is a single bond or a 2 to 4 valent organic group, R ¹ is a monovalent organic group selected from the group consisting of methyl group, ethyl group, n-propyl group and isopropyl group, and R ² is hydrogen Selected from the group consisting of atoms, alkyl groups of 1 to 4 carbon atoms, ester groups of 2 to 10 carbon atoms, and urethane groups of 2 to 10 carbon atoms It is a monovalent organic group, n is an integer of 1-3, p is an integer of 1-5, q is an integer of 0-4, and (p + q) = 5. However, when two or more C _n H _2n OR ¹ and R ² are present, 0.01 to 30 parts by mass of an alkoxyalkyl group-containing compound represented by n, p, q, R ¹ and R ² may be the same as or different from each other; and (C) 1-100 mass parts of diazoquinone compounds, The photosensitive resin composition characterized by the above-mentioned.

[2] The (B) alkoxyalkyl group-containing compound is represented by the following general formula (3):

(3)

{Wherein k is 1 or 2, (i) when k = 1, X is C _n H _2n OR ¹ or R ² , and R ¹ is a group consisting of a methyl group, an ethyl group, an n-propyl group and an isopropyl group It is a monovalent organic group chosen from R <^2> is chosen from the group which consists of a hydrogen atom, a C1-C4 alkyl group, a C2-C10 ester group, a C2-C10 urethane group, and a C1-C10 alkoxy group N is an integer of 1 to 3, and when (ii) k = 2, X is a single bond or the following general formula (4):

[Formula 4]

Is a divalent tetravalent organic group selected from the group represented by R <^1> , R <^1> is the monovalent organic group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and isopropyl group, and R <^2> is a hydrogen atom and C1-C4 Is a monovalent organic group selected from the group consisting of an alkyl group, a C 2-10 ester group, and a C 2-10 urethane group, n is an integer of 1 to 3, p is an integer of 1 to 5, and q is It is an integer of 0-4 and (p + q) = 5. However, when two or more C _n H _2n OR ¹ and R ² are present, n, p, q, R ¹ and R ² may be the same as or different from each other}

The photosensitive resin composition of the said [1] shown by the above.

[3] The (B) alkoxyalkyl group-containing compound is represented by the following general formula (5):

[Chemical Formula 5]

{In formula, R <^1> is monovalent organic group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and isopropyl group, n is an integer of 1-3, p is an integer of 1-5, k is 1 or 2, (i) when k = 1, X is a hydrogen atom or C _n H _2n OR ¹ , (ii) when k = 2, X is a single bond or the following general formula (6):

[Formula 6]

It is a bivalent tetravalent organic group chosen from group represented by it. ^{_{However, (C n H 2n OR 1}} ) are present if a plurality, n and R ¹ are may be the same or different from each other even if the} shown in (1) or a photosensitive resin composition described in [2].

[4] (B) Alkoxyalkyl group-containing compound is bis (methoxymethyl) benzene, tris (methoxymethyl) benzene, tetrakis (methoxymethyl) benzene, pentakis (methoxymethyl) benzene, hexakis (methoxy Methyl) benzene, tris (methoxymethyl) trimethoxybenzene, methoxymethylbiphenyl, bis (methoxymethyl) biphenyl, bis (methoxymethyl) diphenylether, and bis (methoxymethyl) diphenylmethane The photosensitive resin composition in any one of said [1]-[3] chosen from the group which consists of these.

[5] The (B) alkoxyalkyl group-containing compound is represented by the following general formula (7):

[Formula 7]

{Wherein Z ¹ is the following general formula (8):

[Formula 8]

(In formula, R <^3> -R <^5> is a C1-C9 organic group each independently, R <^6> is monovalent organic group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and isopropyl group, and R ⁷ to R ¹⁰ are each independently a substituent selected from a group represented by an organic group having 1 to 12 carbon atoms, k is an integer of 1 to 4, and when (i) k = 1, Z ² is C _n H _2n OR ¹ or R ² , R are each independently a methyl group or an ethyl group, R ¹ is a monovalent organic group selected from the group consisting of methyl group, ethyl group, n-propyl group and isopropyl group, R ² is a hydrogen atom, And a monovalent organic group selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, n is an integer of 1 to 3, and (ii) when k = 2 to 4, Z ² is a single bond or a 2 to 4 valent oil. device is, Z ¹ in this case the presence of a plurality, Z ¹ is represented by may be the same or different} The photosensitive resin composition according to group (1).

[6] The (B) alkoxyalkyl group-containing compound is represented by the following general formula (9):

[Formula 9]

{In formula, R is a methyl group or an ethyl group each independently, Z <^1> is each independently following General formula (10):

[Formula 10]

(In formula, R <^3> -R <^5> is a C1-C9 organic group each independently, R <^6> is monovalent organic group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and isopropyl group, and R ⁷ to R ¹⁰ each independently represent an organic group having 1 to 12 carbon atoms), and Z ³ is a single bond or the following General Formula (11):

[Formula 11]

Photosensitive resin composition as described in said [5] shown by the above.

[7] In the formula (9), Z ³ is a single bond, and Z ¹ is each independently the following formula (12):

[Formula 12]

The photosensitive property as described in said [6] which is a substituent chosen from group represented by {In formula, R <^3> and R <^5> is respectively independently a C1-C9 organic group, and R <^7> is a C1-C12 organic group. Resin composition.

[8] In the general formula (9), Z ³ is a single bond, and Z ¹ is each independently the following general formula (13):

[Formula 13]

The photosensitive resin composition as described in said [6] which is a substituent chosen from the group represented by the following.

[9] A step of forming a photosensitive resin layer composed of the photosensitive resin composition according to any one of the above [1] to [8] on a substrate, or exposure to active light through a mask, or a light beam, an electron beam or an ion beam directly The manufacturing method of the hardening relief pattern containing the process of irradiating, the process of developing, and the process of heating the obtained relief pattern.

[10] A semiconductor device having a cured relief pattern layer obtained by the method described in the above [9].

According to the present invention, there is provided a novel photosensitive resin composition having excellent storage stability and having high sensitivity and positive lithography performance, a method for producing a cured relief pattern using the composition, and a semiconductor device having the cured relief pattern.

<Photosensitive resin composition>

Each component which comprises the photosensitive resin composition of this invention is demonstrated concretely below.

(A) hydroxypolyamide

The hydroxypolyamide which is a base polymer of the photosensitive resin composition of this invention contains the structure represented by following General formula (1).

[Formula 14]

{Wherein, X ¹ is a tetravalent organic group having carbon atoms, X ² , Y ¹ and Y ² are each independently a divalent organic group having two or more carbon atoms, and l is an integer of 2 to 1000; m is an integer from 0 to 500, l / (l + m)> 0.5, l dihydroxydiamide units containing X ¹ and Y ¹ and m dia containing X ² and Y ² The order of the mid units does not matter}.

In General Formula (1), X ¹ is preferably a tetravalent organic group having 2 or more and 30 or less carbon atoms, and X ² , Y ¹ , and Y ² are each independently 2 or more and 30 or less It is preferable that it is a divalent organic group which has a carbon atom.

The dihydroxydiamide unit of the hydroxypolyamide is polycondensed with dicarboxylic acid having a structure of Y ¹ (COOH) ₂ and bisaminophenol having a structure of X ¹ (NH ₂ ) ₂ (OH) ₂ . Has a structure. Here, two sets of amino groups and hydroxy groups of the bisaminophenol are each at ortho-position, and the dihydroxydiamide unit is closed by heating the hydroxypolyamide at about 280 to 400 ° C. And a benzoxazole unit which is a heat resistant resin. l is in the range of 2 to 1000, preferably 2 to 200, more preferably 3 to 50, and still more preferably 3 to 20.

In the hydroxypolyamide, m diamide units of the general formula (1) may be condensed, if necessary. The diamide unit has a structure in which diamine having a structure of X ² (NH ₂ ) ₂ and dicarboxylic acid having a structure of Y ² (COOH) ₂ are polycondensed. m is the range of 0-500, and the range of 0-10 is preferable. The higher the ratio of the hydroxypolyamide units in the hydroxypolyamide, the higher the solubility in the alkaline aqueous solution used as the developing solution, and the shorter the time required for the development can be shortened. Therefore, l / (l + m) The value of is 0.5 or more, preferably 0.7 or more, and more preferably 0.8 or more.

^{_{X 1 (NH 2) 2 (}} OH) to the bisaminophenol having the structure of ₂ is, for example, 3,3'-dihydroxy-benzidine, 3,3'-diamino-4,4'-dihydroxydiphenyl Roxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino -3,3'-dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2 -Bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3- Hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-dia Mino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenylether, 3,3'-diamino-4,4'-dihydroxydi Phenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3- And the like amino-2,4-dihydroxy-benzene, 1,3-diamino-4,6-dihydroxy-benzene. You may use these bisaminophenol individually or in mixture.

Particularly preferred among these bisaminophenols, X ¹ is:

[Formula 15]

Aromatic group selected from.

A diamine having a structure of X ^₂ (NH ^{2) 2} there may be mentioned aromatic diamine, and silicon diamines as desired.

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 Phenoxyphenyl) sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4 The hydrogen atoms of 4,4'-di- (3-aminophenoxy) diphenylsulfone and 4,4'-diaminobenzanilide, and the aromatic nuclei of these aromatic diamines are chlorine atom, fluorine atom, bromine atom, methyl group, methoxy The compound substituted by the at least 1 sort (s) of group or atom chosen from the group which consists of time period, a cyano group, and a phenyl group is mentioned.

Moreover, in order to improve adhesiveness with a base material, silicone diamine can be selected and this example includes bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, and bis (4-aminophenyl) tetra. Methyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) Tetraphenyl disiloxane, and the like.

Examples of the dicarboxylic acid having a structure of Y ¹ (COOH) ₂ or Y ² (COOH) ₂ include those in which Y ¹ and Y ² are an aliphatic or aromatic group having a linear, branched, or cyclic structure. . If one, Y ^1, Y ² is an aromatic group, for example, can be cited as preferable examples below:

[Formula 16]

{Wherein A is -CH _2- , -O-, -S-, -SO _2- , -CO-, -NHCO-, -C (CF ₃ ) ₂ -and 2 selected from the group consisting of a single bond Represents an optional group, each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group and a halogen atom, and k represents an integer of 0 to 4}.

In addition, some or all of the dicarboxylic acid having the above-mentioned Y ¹ (COOH) ₂ or Y _² (COOH) ² structure, it is also preferable to use a derivative of 5-amino-isophthalic acid.

Specific compounds to be reacted with 5-aminoisophthalic acid to obtain derivatives thereof include 5-norbornene-2,3-dicarboxylic acid anhydride and 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 acid anhydride, 1-cyclo Hexene-1,2-dicarboxylic acid anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic 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, acrylate, pro Olic acid chloride, tetralic acid chloride, thiophene-2-acetyl chloride, p-styrenesulfonyl chloride, glycidyl methacrylate, allyl glycidyl ether, chloroformate methyl ester, chloroformate ethyl ester, chloroformate 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, isochloroformic acid Borylbenzyl ester, chloroformic acid-p-biphenylisopropylbenzyl ester, 2-t-butyloxy Carbonyl-oxyimino-2-phenylacetonitrile, St-butyloxycarbonyl-4,6-dimethyl-thiopyrimidine, di-t-butyldicarbonate, N-ethoxycarbonylphthalimide, ethyldithi Ocarbonyl 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, isocyanic acid n-butyl, isocyanate n-octadecyl, isocyanate o-tolyl, 1,2-phthalic anhydride, cis-1,2-cyclohexanedicarboxylic acid anhydride, glutaric anhydride.

Furthermore, as the dicarboxylic acid having Y ¹ (COOH) ₂ or Y _² (COOH) ² structure, it is also possible to use a more bright compound with the tetracarboxylic dianhydride, a monoalcohol, monoamine and the like. Examples of the monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, benzyl alcohol, and the like. Examples of the monoamine include butylamine and aniline. Examples of the tetracarboxylic dianhydride include the following ones:

[Formula 17]

Wherein B represents a divalent group selected from the group consisting of -CH _2- , -O-, -S-, -SO _2- , -CO-, -NHCO- and -C (CF ₃ ) _2- do}.

Furthermore, trimellitic acid chloride is made to react with said bisaminophenol, tetracarboxylic dianhydride is produced, and it ring-opens by the same method, and dicar having a Y ¹ (COOH) ₂ or Y ² (COOH) ₂ structure. It can also be used as an acid. The following are mentioned as tetracarboxylic dianhydride obtained here:

[Formula 18]

{In formula, X <^3> represents X <^1> (OH) ₂ (NH-) <_2> and X <^1> is the same as what was defined by the said General formula (1)}.

Alternatively, the above-mentioned tetracarboxylic dianhydride and the above-mentioned bisaminophenol can be reacted to produce esterified or amidated carboxylic acid residues with monoalcohol or monoamine.

When Y <^1> , Y <^2> is an aliphatic group, substituents, such as an alkyl chain, a cyclobutyl ring, a cyclopentyl ring, a cyclohexyl ring, a bicyclo ring, are mentioned. As the dicarboxylic acid having a Y ¹ (COOH) ₂ or Y ² (COOH) ₂ structure having an aliphatic group, for example, malonic acid, methylmalonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, Itaconic acid, maleic acid, diglycolic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedica Carboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, octa Hydro-1H-4,7-methanoindenedicarboxylic acid, and the like, and the like. When octahydro-1H-4,7-methanoindenedicarboxylic acid is used as the dicarboxylic acid having an aliphatic group, It is preferable because high transparency and high solubility in a solvent are compatible.

As a method for polycondensing dicarboxylic acid having a structure of Y ¹ (COOH) ₂ and bisaminophenol having a structure of X ¹ (NH ₂ ) ₂ (OH) ₂ to form a dihydroxydiamide unit, Dithionate is produced from dicarboxylic acid, and then bisaminophenol is produced after the formation of diacid chloride; dicarboxylic acid and bisaminophenol are polycondensed with dicyclohexylcarbodiimide. have. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can also be made to work simultaneously. In the above-mentioned (A) hydroxypolyamide, it is also preferable to seal the terminal group with an organic group (henceforth a "sealing group"), and to use it.

In polycondensation of hydroxypolyamides, when the dicarboxylic acid component is used in an excessive molar number relative to the sum of the bisaminophenol component and the diamine component, it is preferable to use a compound having an amino group or a hydroxyl group as the sealing group. Do. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, hydroxyethyl acrylate, and the like. have.

On the contrary, in the case where the sum of the bisaminophenol component and the diamine component is used in an excessive molar number compared to the dicarboxylic acid component, it is preferable to use a compound having an acid anhydride, a carboxylic acid, an acid chloride, an isocyanate group, or the like as the sealing group. desirable. Examples of the compound include benzoyl chloride, norbornenedicarboxylic acid anhydride, norbornenecarboxylic acid, ethynylphthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic acid anhydride, Methylcyclohexane dicarboxylic acid anhydride, cyclohexene dicarboxylic acid anhydride, methacroyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, tosylic acid chloride, etc. are mentioned.

(A) It is preferable that it is 3,000-50,000, and, as for the polystyrene conversion weight average molecular weight by gel permeation chromatography (henceforth "GPC") of hydroxy polyamide, it is more preferable that it is 6,000-30,000. As for a weight average molecular weight, 3,000 or more are preferable from a physical property viewpoint of a hardening relief pattern. Moreover, 50,000 or less are preferable from a resolution viewpoint. 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 analytical curve created using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the standard solvent grade standard STANDARD SM-105 manufactured by Showa Denko.

(B) Alkoxyalkyl group containing compound

The photosensitive resin composition contains at least 1 sort (s) of alkoxyalkyl group containing compound chosen from the group which consists of a compound represented by (B) following General formula (2):

[Formula 19]

{Wherein k is an integer of 1 to 4, when (i) k = 1, X is C _n H _2n OR ¹ or R ² , and R ¹ is a methyl group, an ethyl group, an n-propyl group and an isopropyl group It is a monovalent organic group chosen from the group which consists of R <^2> , A group which consists of a hydrogen atom, a C1-C4 alkyl group, a C1-C10 alkoxy group, a C2-C10 ester group, and a C2-C10 urethane group It is a monovalent organic group chosen from, n is an integer of 1-3, p is an integer of 1-5, q is an integer of 0-4, and (p + q) = 5, (ii) k When = 2 to 4, X is a single bond or a 2 to 4 valent organic group, R ¹ is a monovalent organic group selected from the group consisting of methyl group, ethyl group, n-propyl group and isopropyl group, and R ² is hydrogen Selected from the group consisting of atoms, alkyl groups of 1 to 4 carbon atoms, ester groups of 2 to 10 carbon atoms, and urethane groups of 2 to 10 carbon atoms It is a monovalent organic group, n is an integer of 1-3, R <^1> is monovalent organic group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and isopropyl group, R <^2> is a hydrogen atom and C1-C1- It is a monovalent organic group chosen from the group which consists of an alkyl group of 4, a C2-C10 ester group, and a C2-C10 urethane group, and n is an integer of 1-3. However, when two or more C _n H _2n OR ¹ and R ² are present, n, p, q, R ¹ , and R ² may be the same as or different from each other}.

MEANS TO SOLVE THE PROBLEM This inventor adds the (B) alkoxyalkyl group containing compound to the photosensitive resin composition containing the (A) hydroxy polyamide, not only shows high lithography performance, but also shows the high sensitivity lithography performance, and is the time of the sensitivity after exposure. It was found that the change over time was small and the sensitivity stability was also excellent. That is, by adding the compound (B) to the photosensitive resin composition, it is crosslinked to the aromatic ring of hydroxypolyamide during curing, thereby suppressing shrinkage due to thermal decomposition or thermal relaxation of hydroxypolyamide, Shrinkage can be suppressed. Therefore, the photosensitive resin composition to which the (B) compound is added can make thin the application film thickness, and can efficiently reach the optical energy of an exposure process, and becomes high sensitivity. By having an alkoxyalkyl group as a crosslinkable group, it is excellent in the storage stability of a varnish, and does not have a phenolic hydroxyl group, and since it does not lower the dissolution rate difference (contrast) of an exposure part and an unexposed part, it becomes high sensitivity. The detailed reason why the time-dependent change in sensitivity after exposure is small is not clear, and it is not desired to be bound by a specific theory. Even when carboxylic acid generate | occur | produces and becomes acidic condition, it can be considered that it does not produce the chemical reaction which lowers a sensitivity.

The (B) alkoxyalkyl group-containing compound of the present invention is synthesized by a known method, for example, a method of obtaining an alkoxyalkyl group-containing compound by adding a halogenated alkyl group to a compound having an aromatic ring and then reacting with an alcohol, And a method of obtaining an alcohol by reacting an aromatic alkyl alcohol compound obtained by reducing an aromatic compound having a carboxyl group, or a method of acylating an alkoxyalkyl group-containing phenol obtained by adding an halogenated alkyl group to a phenol compound and then reacting the alcohol. .

Preferable examples of the alkoxyalkyl group-containing compound represented by the general formula (2) include one having an alkoxyalkyl group, methoxymethylbenzene, ethoxymethylbenzene, methoxyethylbenzene, ethoxymethylbenzene, 2-methoxymethyl Toluene, 3-methoxymethyltoluene, 4-methoxymethyltoluene, 2-methoxymethylbiphenyl, 3-methoxymethylbiphenyl, 4-methoxymethylbiphenyl, etc. Bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 1,4-bis (methoxymethyl) benzene, 1,2-bis (ethoxymethyl) benzene, 1,3-bis ( Ethoxymethyl) benzene, 1,4-bis (ethoxymethyl) benzene, 2,4'-bis (methoxymethyl) biphenyl, 3,4'-bis (methoxymethyl) biphenyl, 4,4 ' -Bis (methoxymethyl) biphenyl, 2,4'-bis (methoxymethyl) diphenyl ether, 3,4'-bis (methoxymethyl) diphenyl ether, 4,4'-bis (methoxymethyl ) Diphenyl ether, 2,4'-bis (methoxymethyl) diphenylmethane, 3,4'-bis (methoxymethyl) diphenylmethane , 4,4'-bis (methoxymethyl) diphenylmethane, 2,4'-bis (methoxymethyl) diphenylsulfone, 3,4'-bis (methoxymethyl) diphenylsulfone, 4,4 ' -Bis (methoxymethyl) diphenylsulfone, 2,4'-bis (methoxymethyl) diphenylpropane, 3,4'-bis (methoxymethyl) diphenylpropane, 4,4'-bis (methoxy Methyl) diphenylpropane, 2,4'-bis (methoxymethyl) diphenylhexafluoropropane, 3,4'-bis (methoxymethyl) diphenylhexafluoropropane, 4,4'-bis (meth Methoxymethyl) diphenylhexafluoropropane, etc. are mentioned, As an example of what has 3 or more, the following compounds are mentioned:

[Formula 20]

{In formula, L may mutually be same or different, and represents a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group, or a methoxyisopropyl group}.

Moreover, from the viewpoint of the dissolution time (development time) at the time of alkali image development, as a (B) alkoxyalkyl group containing compound of this invention, at least 1 sort (s) of alkoxy chosen from the group which consists of a compound represented by following General formula (3) Alkyl group-containing compounds are preferred:

[Formula 21]

{In formula, R <^1> is monovalent organic group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and an isopropyl group, R <^2> is a hydrogen atom, a C1-C4 alkyl group, and a C2-C10 ester group , And a monovalent organic group selected from the group consisting of urethane groups of 2 to 10 carbon atoms, n is an integer of 1 to 3, p is an integer of 1 to 5, q is an integer of 0 to 4, (p + q) = 5, k is 1 or 2, (i) when k = 1, X is C _n H _2n OR ¹ or R ² , and (ii) when k = 2, X is a single bond or General formula (4):

[Formula 22]

The divalent to tetravalent organic group chosen from the group represented by is shown. However, when two or more C _n H _2n OR ¹ and R ² are present, n, p, q, R ¹ , and R ² may be the same as or different from each other}.

Specific examples include methoxymethylbenzene, ethoxymethylbenzene, methoxyethylbenzene, ethoxymethylbenzene, 2-methoxymethyltoluene, 3-methoxymethyltoluene, 4-methoxymethyltoluene, 2-methoxymethyl Biphenyl, 3-methoxymethylbiphenyl, 4-methoxymethylbiphenyl, 1,2-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 1,4-bis (methoxy Methoxymethyl) benzene, 1,2-bis (ethoxymethyl) benzene, 1,3-bis (ethoxymethyl) benzene, 1,4-bis (ethoxymethyl) benzene, 2,4'-bis (methoxy Methyl) biphenyl, 3,4'-bis (methoxymethyl) biphenyl, 4,4'-bis (methoxymethyl) biphenyl, 2,4'-bis (methoxymethyl) diphenylether, 3, 4'-bis (methoxymethyl) diphenylether, 4,4'-bis (methoxymethyl) diphenylether, 2,4'-bis (methoxymethyl) diphenylmethane, 3,4'-bis ( Methoxymethyl) diphenylmethane, 4,4'-bis (methoxymethyl) diphenylmethane, 2,4'-bis (methoxymethyl) diphenylsulfone, 3,4'-bis (methoxymethyl) di Phenylsulfone, 4,4'-bis (methoxymethyl) Diphenylsulfone, 2,4'-bis (methoxymethyl) diphenylpropane, 3,4'-bis (methoxymethyl) diphenylpropane, 4,4'-bis (methoxymethyl) diphenylpropane, 2 , 4'-bis (methoxymethyl) diphenylhexafluoropropane, 3,4'-bis (methoxymethyl) diphenylhexafluoropropane, 4,4'-bis (methoxymethyl) diphenylhexafluoro Ropropan, etc., and the following compounds:

(23)

{In formula, L may mutually be same or different and shows a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group, or a methoxyisopropyl group}

Can be mentioned.

Moreover, from the heat resistant viewpoint of the crosslinked structure by Cure, as (B) alkoxyalkyl group containing compound of this invention, at least 1 sort (s) of alkoxyalkyl group containing compound chosen from the group which consists of a compound represented by following General formula (5) is preferable. Do :

[Formula 24]

{In formula, R <^1> is monovalent organic group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and isopropyl group, n is an integer of 1-3, p is an integer of 1-5, k is 1 or 2, (i) when k = 1, X is a hydrogen atom or C _n H _2n OR ¹ , (ii) when k = 2, X is a single bond or the following general formula (6):

[Formula 25]

The divalent tetravalent organic group chosen from the group represented by this is shown. However, when two or more (C _n H _2n OR ¹ ) are present, n and R ¹ may be the same as or different from each other}.

Specific examples include methoxymethylbenzene, ethoxymethylbenzene, methoxyethylbenzene, ethoxymethylbenzene, 2-methoxymethyltoluene, 3-methoxymethyltoluene, 4-methoxymethyltoluene, 2-methoxymethyl Biphenyl, 3-methoxymethylbiphenyl, 4-methoxymethylbiphenyl, 1,2-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 1,4-bis (methoxy Methoxymethyl) benzene, 1,2-bis (ethoxymethyl) benzene, 1,3-bis (ethoxymethyl) benzene, 1,4-bis (ethoxymethyl) benzene, 2,4'-bis (methoxy Methyl) biphenyl, 3,4'-bis (methoxymethyl) biphenyl, 4,4'-bis (methoxymethyl) biphenyl, 2,4'-bis (methoxymethyl) diphenylether, 3, 4'-bis (methoxymethyl) diphenylether, 4,4'-bis (methoxymethyl) diphenylether, 2,4'-bis (methoxymethyl) diphenylmethane, 3,4'-bis ( Methoxymethyl) diphenylmethane, 4,4'-bis (methoxymethyl) diphenylmethane, 2,4'-bis (methoxymethyl) diphenylsulfone, 3,4'-bis (methoxymethyl) di Phenylsulfone, 4,4'-bis (methoxymethyl) Diphenylsulfone, 2,4'-bis (methoxymethyl) diphenylpropane, 3,4'-bis (methoxymethyl) diphenylpropane, 4,4'-bis (methoxymethyl) diphenylpropane, 2 , 4'-bis (methoxymethyl) diphenylhexafluoropropane, 3,4'-bis (methoxymethyl) diphenylhexafluoropropane, 4,4'-bis (methoxymethyl) diphenylhexafluoro Ropropan, etc., and the following compounds:

[Formula 26]

{In formula, L may mutually be same or different, and a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group, or a methoxyisopropyl group are mentioned}.

In addition, from the viewpoint of the effect of suppressing shrinkage of the film thickness by Cure, as the (B) alkoxyalkyl group-containing compound of the present invention, methoxymethylbiphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) biphenyl At least 1 type of compound chosen from the group which consists of bis (methoxymethyl) diphenyl ether, and bis (methoxymethyl) diphenylmethane is especially preferable.

In addition, from the viewpoint of chemical resistance of the cured film, tris (methoxymethyl) benzene, tetrakis (methoxymethyl) benzene, pentakis (methoxymethyl) benzene, hexakis (methoxymethyl) benzene, tris (methoxymethyl At least one compound selected from the group consisting of trimethoxybenzene and tetrakis (methoxymethyl) dimethoxybenzene is particularly preferred.

The photosensitive resin composition of this invention is a (B) following General formula (7): from a viewpoint of the residual film ratio improvement at the time of hardening at the time of setting it as cyclization resin, and a high sensitivity.

[Formula 27]

{Wherein Z ₁ is the following general formula (8):

[Formula 28]

(In formula, R <^3> -R <^5> is a C1-C9 organic group each independently, R <^6> is monovalent organic group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and isopropyl group, and R ⁷ to R ¹⁰ are each independently a substituent selected from a group represented by an organic group having 1 to 12 carbon atoms, k is an integer of 1 to 4, and when (i) k = 1, Z ² is C _n H _2n OR ¹ or R ² , R are each independently a methyl group or an ethyl group, R ¹ is a monovalent organic group selected from the group consisting of methyl group, ethyl group, n-propyl group and isopropyl group, R ² is a hydrogen atom, And a monovalent organic group selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, n is an integer of 1 to 3, and (ii) when k = 2 to 4, Z ² is a single bond or a 2 to 4 valent oil. device is, Z ¹ in this case the presence of a plurality, Z ¹ is represented by may be the same or different} That the alkyl group contains at least one kind of alkoxy compound selected from the group consisting of the compounds is preferred. The alkoxyalkyl group-containing compound corresponds to the following general formula (14):

[Formula 29]

{Wherein, k is an integer of 1 ~ 4, (i) when k = 1 il, Z ² is a C _n H _2n OR ¹ or R ^2, R ¹ is methyl, ethyl, n- propyl and isopropyl Monovalent organic group chosen from the group which consists of groups, R <^2> is monovalent organic group chosen from the group which consists of a hydrogen atom and a C1-C4 hydrocarbon group, n is an integer of 1-3, (ii) k = 2 to 4, Z ² represents a single bond or a divalent tetravalent organic group}, an alkoxyalkyl group-containing phenol, an isocyanate compound, a carboxylic acid chloride, a sulfonic anhydride, a sulfonyl chloride, a silyl chloride, and the like. It can obtain by making it react in a suitable solvent.

As one of the alkoxyalkyl group containing phenol compounds represented by General formula (8), following General formula (15):

[Formula 30]

{In formula, R is a methyl group or an ethyl group each independently, Z <^3> is a single bond or following General formula (16):

[Formula 31]

The alkoxyalkyl group containing phenol compound represented by} is shown.

Among them, from the viewpoint of the sensitivity of the resin composition, the following general formula (17):

[Formula 32]

It is preferable to use the alkoxyalkyl group containing phenol represented by {In formula, R may mutually be same or different, and represents a methyl group or an ethyl group. Moreover, Especially, from a heat resistant viewpoint, the following general formula (18):

[Formula 33]

It is most preferable to use the alkoxyalkyl group containing phenolic compound represented by {in formula, R may mutually be same or different and represents a methyl group or an ethyl group}.

As a compound made to react with an alkoxyalkyl group containing phenol, following General formula (19):

[Formula 34]

{In formula, R <^3> -R <^5> is a C1-C9 organic group each independently, R <^6> is monovalent organic group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and isopropyl group, and R ⁷ to R ¹⁰ are each independently an organic group having 1 to 12 carbon atoms.

Examples of the compound represented by the general formula (19) include acetyl chloride, cyclopropane carbonyl chloride, monoethyl succinate, tert-butylacetyl chloride, 3-cyclohexene-1-carboxylic acid chloride and 2-furancarboxylic acid. Chloride, crotonic acid chloride, cinnamic acid chloride, methacrylic acid chloride, acrylic acid chloride, propiolic acid chloride, tetralic acid chloride, thiophene-2-acetyl chloride, 2-ethoxybenzoyl chloride, 2-methoxybenzoyl chloride, 4 -Methoxybenzoyl chloride, trimellitic acid chloride, 3,5,5-trimethylhexanoyl chloride, 2,4,6-trimethylbenzoyl chloride, chloroformate-4-nitrophenyl, 9-fluorenylmethylchloroformate, Di-tert-butyl dicarbonate, dibenzyl bicarbonate, 4-ethylbenzenesulfonyl chloride, p-toluenesulfonyl chloride, benzenesulfonyl chloride, p-shaped Ethylene-2-sulfonylchloride, 2-mesitylenesulfonylchloride, 4-propylbenzenesulfonylchloride, 4-methoxybenzenesulfonylchloride, 4-tert-butylbenzenesulfonylchloride, 4-biphenylsulfonylchloride , 2,4,6-triisopropylbenzenesulfonyl chloride, methanesulfonyl chloride, phenyl isocyanate, isocyanate ethyl methacrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, isocyanate-2-tri Fluoromethylphenyl, n-butyl isocyanate, n-octadecyl isocyanate, o-tolyl isocyanate, chlorodimethylsilane, trimethylchlorosilane, chlorotriethylsilane, chlorodiisopropylsilane, diethylisopropylsilyl Chloride, tert-butyldimethylchlorosilane, dimethylethylchlorosilane, dimethylisopropylchlorosilane, triisopropylsilyl chloride, chlorodimethylpropylsilane, allylchlorodimethylsilane, n-part Dimethylchlorosilane, chlorodimethylvinylsilane, dimethyl-n-octylchlorosilane, chloro (decyl) dimethylsilane, chloro (dodecyl) dimethylsilane, (3-cyanopropyl) dimethylchlorosilane, (chloromethyl) dimethylchlorosilane And (bromomethyl) chlorodimethylsilane. Among these, trimethylchlorosilane, p-toluenesulfonyl chloride, methacrylic acid chloride, crotonic acid chloride and the like can be cited as preferred examples. Among these, methacrylic acid chloride is the most preferable from the viewpoint of the solubility to an organic solvent.

As a solvent used when synthesize | combining the compound represented by General formula (7), acetone, tetrahydrofuran (THF), (gamma) -butyrolactone (GBL), N-methyl- 2-pyrrolidone (NMP), N , N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) and the like.

In order to accelerate the reaction when synthesizing the present compound, basic compounds such as pyridine, picoline, collidine, lutidine, triethylamine and 4-dimethylaminopyridine are preferably coexisted. The basic catalyst may be used alone or in combination of two or more thereof. The usage-amount of a basic catalyst can be adjusted according to the kind of basic catalyst, It can select in the range of 0.01-10 equivalent (mol equivalent) with respect to 1 mol of alkoxyalkyl-group containing phenol compounds which are raw materials, Usually 0.1-5 equivalent, More preferably, it is preferable Preferably it is about 1-3 equivalents.

It is preferable to control reaction temperature between 10 degreeC-50 degreeC, and in high reactive compounds, such as carboxylic acid chloride and a sulfonyl chloride, 10 degreeC-30 degreeC is preferable. The reaction time varies depending on the amount of the compound or the catalyst to be reacted and the type of the reaction. The reaction time is preferably 1 hour to 48 hours, and in a highly reactive compound such as carboxylic acid chloride or sulfonyl chloride, about 1 hour to 5 hours is required. desirable.

As a method for removing the basic compound contained in the alkoxyalkyl group-containing compound thus synthesized, reprecipitation in a poor solvent such as water, redissolved in a solvent such as THF, and treatment with a cation exchange resin It is mentioned as a method. When synthesizing the present compound, in the case of using a halide such as carboxylic acid chloride, the salt may be precipitated out of the reaction system by selecting the solvent of the catalyst, and the salt may be recovered by filtration, and the filtrate is cation exchanged. It is preferable to use not only resin but also anion exchange resin together and to process. The treated solution can be concentrated by evaporation, dissolved in a good solvent such as ethyl acetate, recrystallized in a poor solvent such as hexane, and vacuum dried to isolate the target product.

The alkoxyalkyl group containing compound obtained by the said method is the following general formula (9):

[Formula 35]

{In formula, R is a methyl group or an ethyl group each independently, Z <^1> is each independently following General formula (10):

[Formula 36]

(In formula, R <^3> -R <^5> is a C1-C9 organic group each independently, R <^6> is monovalent organic group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and isopropyl group, and R ⁷ to R ¹⁰ each independently represent an organic group having 1 to 12 carbon atoms), and Z ³ is a single bond or the following General Formula (11):

[Formula 37]

It is a substituent selected from the group represented by the following}. It is an alkoxyalkyl group containing compound represented by. Especially, in General formula (9), Z <^3> is a single bond, Z <^1> is respectively independently following General formula (12):

[Formula 38]

The alkoxyalkyl group containing compound represented by {in formula, R <^3> and R <^5> is respectively independently a C1-C9 organic group, and R <^7> is a C1-C12 organic group}. In addition, in General formula (9), Z <^3> is a single bond, Z <^1> is respectively independently following General formula (13):

[Formula 39]

The alkoxyalkyl group containing compound which is a substituent chosen from the group represented by is preferable from a heat resistant viewpoint.

The alkoxyalkyl group-containing compound (B) may be used alone or in combination of two or more thereof.

The compounding quantity of the (B) alkoxyalkyl group containing compound is 0.01-30 mass parts with respect to 100 mass parts of (A) hydroxy polyamides, and 1-20 mass parts is preferable. (B) When the compounding quantity of the alkoxyalkyl group containing compound is 1 mass part or more, the remaining film rate after curing ((film thickness of relief pattern after cure) / (film thickness of relief pattern after development) x 100) is high, and is 30 mass parts or less Sensitivity is good.

(C) Diazoquinone Compound

Diazoquinone compounds used in the photosensitive resin composition are compounds having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure, and are described in US Patent Specification Nos. 2,772,972, 2,797,213, 3,669,658, and the like. It is a substance known by the. Preferred examples include, for example, the following:

[Formula 40]

Wherein Q is a hydrogen atom or

[Formula 41]

It is a naphthoquinone diazide sulfonic acid ester group shown by the following, and all Q is not a hydrogen atom at the same time}.

Particularly preferred among these are the followings:

[Formula 42]

(Q is a hydrogen atom or

And at the same time there is no hydrogen atom).

The compounding quantity of (C) diazoquinone compound is 1-100 mass parts with respect to 100 mass parts of (A) hydroxy polyamide, and 10-30 mass parts is preferable.

(C) The patterning property of resin is favorable in the compounding quantity of a diazoquinone compound at 1 mass part or more, On the other hand, in 100 mass parts or less, the tensile elongation of a film | membrane after hardening is favorable, and the image development residue (scum) of an exposure part is few.

You may add a thermal radical generating agent with respect to the photosensitive resin composition. As a radical generating agent used here, it is preferable to generate | occur | produce a radical in heat processing conditions, As a preferable example, an organic peroxide, for example, dicumyl peroxide, an organic non-peroxide, for example, dimethyl diphenyl butane is mentioned.

0-20 mass parts is preferable with respect to 100 mass parts of (A) hydroxy polyamides, and, as for the addition amount at the time of adding a thermal radical generating agent, 0.1-10 mass parts is more preferable. When the amount added is within 20 parts by mass, storage stability is good.

As needed, you may add the phenolic compound, dye, surfactant, the adhesion | attachment adjuvant for improving adhesiveness with a board | substrate, a stabilizer, etc. which are conventionally used as an additive of the photosensitive resin composition to a photosensitive resin composition.

More specifically, the phenolic compound may include a ballast agent, paracumylphenol, bisaminophenol, resorcinol and the like. In addition, a ballast agent means the phenol compound used as a raw material for the above-mentioned diazoquinone compound whose phenolic hydrogen atom is a part of naphthoquinone diazide sulfonic-acid esterified phenolic compound. As dye, methyl violet, crystal violet, malachite green, etc. are mentioned, for example.

As for the addition amount at the time of adding a phenol compound, 0-50 mass parts is preferable with respect to 100 mass parts of (A) hydroxy polyamide, and 1-30 mass parts is preferable. When the amount added is within 50 parts by mass, the tensile elongation of the film after thermal curing is good.

Moreover, as surfactant, For example, nonionic surfactant which consists of polyglycols, such as polypropylene glycol or polyoxyethylene lauryl ether, or its derivatives, for example, Furodo (registered trademark, brand name, Sumitomo 3M company) Fluorine-based surfactants such as MegaPak (registered trademark, trade name, manufactured by Dainippon Ink and Chemicals, Inc.) or Lumifuron (registered trademark, trade name, manufactured by Asahi Glass, Inc.), for example, KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) And organic siloxane surfactants such as DBE (trade name, manufactured by Tosoh Corporation) and gurnor (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

0-10 mass parts is preferable with respect to 100 mass parts of (A) hydroxy polyamides, and, as for the addition amount when adding surfactant, 0.01-1 mass part is more preferable. When the amount added is within 10 parts by mass, the tensile elongation of the film after thermal curing is good. By the addition of the surfactant, it is possible to prevent the cratering of the coating film at the wafer edge at the time of coating from occurring better.

Moreover, as an adhesion | attachment adjuvant, alkylimidazoline, butyric acid, an alkyl acid, polyhydroxy styrene, polyvinyl methyl ether, t-butyl novolak, an epoxy silane, an epoxy polymer, etc., and various silane coupling agents are mentioned, for example. Can be mentioned.

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

0-30 mass parts is preferable with respect to 100 mass parts of (A) hydroxy polyamides, and, as for the addition amount when adding an adhesion | attachment adjuvant, 0.1-10 mass parts is more preferable. When the amount added is within 30 parts by mass, the tensile elongation of the film after thermal curing is good.

The photosensitive resin composition mentioned above is melt | dissolved in a solvent, it is set as varnish shape, and can be used as a photosensitive resin composition solution.

Examples of such a solvent include N-methyl-2-pyrrolidone, γ-butyrolactone (hereinafter also referred to as "GBL"), 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-mono Methyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, etc. can be used individually or in mixture. Of these solvents, non-amide solvents are preferable in that they have little influence on photoresist and the like, and specifically, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl Ether acetate, and the like.

As for the addition amount of a solvent, 50-1000 mass parts is preferable with respect to 100 mass parts of hydroxy polyamides. The amount of the solvent added is preferably set to a viscosity suitable for the coating device and the coating thickness within the above-described range, which facilitates the manufacture of the cured relief pattern.

<The hardening relief pattern and the manufacturing method of a semiconductor device>

Hereinafter, the method of apply | coating the photosensitive resin composition of this invention to a board | substrate and producing a hardening relief pattern is demonstrated concretely.

(1) Process of forming the photosensitive resin layer which consists of photosensitive resin composition on a board | substrate (1st process).

The photosensitive resin composition solution is apply | coated to the board | substrates, such as a silicon wafer, a ceramic substrate, and an aluminum substrate, for example by rotation coating using a spin coater, or a coater, such as a die coater or a roll coater. Alternatively, it may be applied to a predetermined point by using an inkjet nozzle or a dispenser. This is dried at 50-140 degreeC using an oven or a hotplate, and a solvent is removed ("prebaking").

(2) Process of exposing with actinic light through a mask or irradiating a light ray, an electron beam, or an ion beam directly (2nd process).

Then, the photosensitive resin layer is exposed by actinic light through a mask, ie, by actinic rays using a contact aligner or a stepper. Or it exposes by directly irradiating a light ray, an electron beam, or an ion beam. As an actinic light, g line | wire, h line | wire, i line | wire, KrF laser can also be used.

(3) developing step (third step)

As a 3rd process, an exposure part or an irradiation part is eluted or removed with a developing solution. Subsequently, a desired relief pattern is preferably obtained by rinsing with a rinse liquid. The developing method may be spray, paddle, dip, ultrasonic wave, or the like. Distilled water, deionized water, etc. can be used for a rinse liquid.

The developing solution used for developing the photosensitive resin layer which consists of a photosensitive resin composition dissolves and removes an alkali-soluble polymer, and needs to be an alkaline aqueous solution which melt | dissolved the alkali compound. The alkali compound dissolved in the alkaline aqueous solution may be either an inorganic alkali compound or an organic alkali compound.

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

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

If necessary, 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, or the like can be added to the alkaline aqueous solution.

(4) Process of heating the obtained relief pattern (4th process)

Finally, the obtained relief pattern is heat-processed and the heat resistant hardening relief pattern which consists of resin which has a polybenzoxazole structure is formed. As a heating apparatus, an oven furnace, a hot plate, a vertical furnace, a belt conveyor, a pressure oven, etc. can be used, and as a heating method, hot air, infrared rays, heating by electromagnetic induction, etc. can be recommended. 200-450 degreeC is preferable and 250-400 degreeC of temperature is more preferable.

15 minutes-8 hours are preferable, and, as for a heat time, 1 hour-4 hours are more preferable.

The atmosphere is preferably in an inert gas such as nitrogen or argon. A semiconductor device can be manufactured by combining a hardening relief pattern with the manufacturing method of a semiconductor device known as a protective film of a surface protective film, an interlayer insulating film, a redistribution insulating film, a protective film for flip chip devices, or a device having a bump structure.

Moreover, the photosensitive resin composition of this invention is useful also in uses, such as the interlayer insulation of a multilayer circuit, the cover coat of a flexible copper clad board, a soldering resist film, or a liquid crystal aligning film.

Example

The present invention will be described based on reference examples and examples. Evaluation of the photosensitive resin composition in the Example followed the following method.

<Evaluation of the photosensitive resin composition>

(1) patterning characteristics evaluation

The photosensitive resin composition was spin-coated onto a 5-inch silicon wafer by a spin coater (Dspin SW-636, manufactured by Dainippon Screen Co., Ltd.), prebaked at 125 ° C. for 180 seconds on a hot plate, and coated with a film thickness of 9.0 μm. A film was formed. The cured film was heat-processed (cure) at 320 degreeC for 1 hour in nitrogen atmosphere using the temperature rising program cure (VF-2000 type | mold, manufactured by Koyo Lindberg Co., Ltd.), and the cured film was obtained on the silicon wafer. The film thickness was measured with an optical film thickness measuring device (Lamuda Ace VM-1200, manufactured by Dainippon Screen Co., Ltd.) at a refractive index of 1.65. The cure shrinkage percentage (%) was calculated from the film thicknesses before and after the cure.

Next, the photosensitive resin composition was spin-coated on a 5-inch wafer by the method mentioned above, and the coating film was formed. A test pattern formation reticle was passed through this coating film, and it exposed by changing the exposure amount in steps using the Nikon stepper (NSR2005i8A) which has an exposure wavelength of i-line (365 nm). Using an alkaline developer (AZ300MIF developer, a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution) manufactured by AZ Electric Materials Co., Ltd., the developing time was adjusted so that the developing residual film ratio of the unexposed part was 85%, and under 23 ° C conditions. The paddle was developed and rinsed with pure water to form a positive relief pattern. Thereafter, curing was performed at 320 ° C. for 1 hour. At this time, the coating film thickness of the coating film was set inverted from the curing shrinkage ratio so that the final film thickness of the relief pattern obtained by performing a curing treatment of 320 ° C. for 1 hour was 7.0 μm.

In addition, the time-lapse stability of the sensitivity, the resolution, the sensitivity after exposure, and the storage stability of the photosensitive resin composition were evaluated as follows.

[Sensitivity (mJ / cm 2)]

The minimum exposure amount which can completely melt | dissolve and remove the exposure part of a coating film in the said developing time.

[Resolution (μm)]

Minimum resolution pattern dimensions at the exposure dose.

[Time-lapse Stability of Sensitivity After Exposure]

The photosensitive resin composition was spin-coated on a 5-inch wafer by the method mentioned above, the coating film was formed, and it exposed to this coating film by the method mentioned above, and was left to stand in the clean room for 24 hours. Then, it developed by the method mentioned above and formed the relief pattern. It was made favorable that the time-dependent change of the sensitivity after exposure at this time is less than +/- 50 (mJ / cm <2>), and made into defect being more than +/- 50 (mJ / cm <2>).

[Storage Stability Evaluation]

After measuring the viscosity at 23 degreeC using the E-type viscosity meter (RE-80E, Touki Industries Co., Ltd.) for the said photosensitive resin composition, after leaving at room temperature for 2 weeks, the viscosity was measured again and the change rate (Thickness percentage) was calculated. The thing whose viscosity change is less than +/- 5% was made good, and what made + -5% or more was considered bad.

<Synthesis of hydroxypolyamide>

[Reference Example 1]

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 in 88 g of DMDGs separately was dripped at this from the dropping funnel. The time required for dripping was 40 minutes, and reaction liquid temperature was 28 degreeC at the maximum.

After completion of the dropwise addition, the mixture was warmed to 50 ° C by a bath and stirred for 18 hours, and then the IR spectrum of the reaction solution was measured to confirm that the characteristic absorption of the imide groups of 1385 cm ^-1 and 1772 cm ^-1 appeared.

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 chlorides in 398 g of DMDG was dripped at this by the dripping funnel. The time required for dripping was 80 minutes, and reaction liquid temperature was 12 degreeC at the maximum. After 3 hours from the end of the dropwise addition, the reaction solution was added dropwise to 12 L of water under high-speed stirring to precipitate and disperse the polymer, which was recovered, washed with water and dehydrated appropriately, and dried in vacuo to obtain hydroxypolyamide (P-1). . The weight average molecular weight by GPC of the hydroxy polyamide synthesize | combined in this way was 14,000 in polystyrene conversion. The analysis conditions of GPC are described below.

Column: Showa Denko Co., Ltd. trade name Shodex 805/804/803 serial

Eluent: tetrahydrofuran 40 ℃

Flow rate: 1.0 ml / min

Detector: Showa Major Manufactured Shotrade RI SE-61

[Reference Example 2]

125.35 g (0.48 mol) of octahydro-1H-4,7-methanoindene dicarboxylic acid dichloride instead of 142.3 g (0.48 mol) of 4,4'- diphenyl ether dicarboxylic acid dichlorides in the reference example 1 2,2-bis (3-amino-4-hydroxyphenyl) -propane 139.45 instead of 197.8 g (0.54 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane Except having used g (0.54 mol), it carried out similarly to the reference example 1, and obtained the polybenzoxazole resin precursor (P-2). The polystyrene reduced weight average molecular weight of this resin was 22000 (Mw).

[Reference Example 3]

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 acid anhydrides were added to this at room temperature at room temperature. After stirring at room temperature for 3 days, the reaction was confirmed by HPLC. As a result, no raw materials were detected, and the product was detected with a purity of 99% as a single peak. The reaction solution was added dropwise while stirring into 1 L of ion-exchanged water as it was, the precipitate was filtered off, and then, 500 ml of THF was added thereto, followed by stirring and dissolving. The homogeneous solution was passed through a glass column filled with a cation exchange resin. To remove the remaining pyridine. Next, this solution was dripped in 3 L of ion-exchange water under high speed stirring, and the product was precipitated, This was filtrated off, and it dried under vacuum.

The imidized product shows characteristic absorption of imide groups of 1394 cm ^-1 and 1774 cm ^{-1 in} the IR spectrum, and there is no characteristic absorption of amide groups around 1540 cm ^-1 and 1650 cm ^-1 . In addition, it confirmed by the absence of the peak of the proton of amide and carboxylic acid in an NMR spectrum.

Next, 53.7 g (0.2 mol) and 560 g of acetone were added, and 65.9 g (0.1 mol) of this product and 1,2- naphthoquinone diazide- 4-sulfonyl chloride were stirred and dissolved at 20 degreeC. The thing which diluted 21.2 g (0.21 mol) of triethylamines with 106.2 g of acetone was dripped at this at the constant 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% by weight aqueous hydrochloric acid solution was added at once, the reaction solution was then cooled with 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 weight% hydrochloric acid aqueous solution over 1 hour under the stirring, and the target object was precipitated, and it collected by suction filtration. 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 diazoquinone compound (Q-1) was obtained.

[Reference Example 4]

In a separable flask with a capacity of 1 L, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (trade name Tris-P-PA- MF, manufactured by Honshu Chemical Industries, Ltd.) 30.6 g (0.1 mol), 1,2-naphthoquinone diazide-4-sulfonyl chloride, 67.1 g (0.25 mol) and acetone 560 g are added and stirred at 20 ° C. Dissolved. What diluted 26.2 g (0.26 mol) of triethylamines with 131.1 g of acetone to this was dripped at the constant 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% by weight aqueous hydrochloric acid solution was added at once, the reaction solution was then cooled with 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 weight% hydrochloric acid aqueous solution over 1 hour under the stirring, and the target object was precipitated, and it collected by suction filtration. 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 diazoquinone compound (Q-2) was obtained.

[Reference Example 5]

235 g (1.4 mol) of 1,3,5-trimethoxybenzene, 156 g (5.19 mol) of acetaldehyde, and 532 g of glacial acetic acid were added to a 5 L separable flask equipped with a stirring bar, a drying tube, and a thermometer, It stirred at 20 degreeC-25 degreeC in slurry shape for 2 hours. When 2000 g of the solution which mixed 7.41 mol equivalent 30-% hydrogen bromide aqueous solution and acetic acid was dripped, it heated up to 56 degreeC. The color of the solution changed from white to yellow and purple upon dropping. After completion of the dropwise addition, the solution was completely dissolved by stirring at 70 ° C. for 50 minutes, and the reaction solution changed to brown after stirring for 3 hours. Thereafter, the mixture was cooled to 20 ° C and a reaction solution was added to 7860 g of water. Chloroform 9000g was added to this, and the reaction material was extracted. 4080 g of 5% sodium bicarbonate water 600g was added to this, and it wash | cleaned. Then, 4080 g of 20% saline solution is added, 600 g of magnesium sulfate is further added to dehydrate, the chloroform layer is filtered and washed, and the solvent is distilled off by vacuum drying at 8 mmHg while heating the solvent to 50 ° C. , 456 g of a brown liquid, 1,3,5-trimethoxy-2,4,6-tribromomethylbenzene was obtained.

Next, 108.28 g (0.2435 mol) of 1,3,5-tris (bromomethyl) -2,4,6-trimethoxymethylbenzene in a 1 L four-necked flask equipped with a stirring bar, a nitrogen introduction tube, and a thermometer. ) Was dissolved in 435 g of toluene. 235.05 g (1.217 mol) of 28% sodium methoxide solution was dripped at 8 degreeC inside and around 23 degreeC to this. After stirring at 35 ° C. for 27 hours, 46.97 g (1.0 mol) of 28% sodium methoxide solution was further added, followed by stirring for 25 hours. The reaction solution was poured into 2176 g of cold water at 5 ° C, 1741 g of toluene was further added, and the solution was separated into an organic solvent layer and an aqueous layer. 1306 g of 20% saline solution was added, the aqueous layer was discarded, and this was repeated three times. After adding 200 g of magnesium sulfate to the toluene layer and adding 300 ml of toluene, the magnesium sulfate was filtered and washed, and the toluene solvent was distilled off by vacuum drying at 10 mmHg while heating the solvent to 50 ° C. to obtain 81.9 g of the desired substance. By obtaining a crude substance, column chromatography was purified by 3 kg of silica gel using a developing solvent in which hexane and ethanol were mixed at 4: 1, and the main chromatogram was collected and vacuum dried at 50 ° C. for 40 hours. 56 g of 1,3,5-tris (methoxymethyl) -2,4,6-trimethoxybenzene was obtained. When the reaction was confirmed by HPLC, no raw material was detected at all, and the product was detected with a purity of 99% as a single peak.

[Reference Example 6]

101.7 g (0.226 mol) of 1,2,4,5-tetrakis (bromomethyl) benzene (made by Aldrich) and 1.5 L of methanol in a 2.0 L four-necked flask equipped with a thermometer, a drying tube and a stirrer Was injected and stirred at room temperature. When 80.9 g (1.49 mol) of sodium methoxides were added to this, the temperature rose about 20 degreeC. It was immersed in an oil bath of 65 degreeC, it stirred at 65 degreeC for 4 hours, and after stirring was complete, 500 ml of methanol was distilled off using the rotary evaporator and the concentration operation was performed. This concentrated reaction solution was poured into 2 L of ice water. After adding 2 L of toluene to this, it moved to the separating funnel and performed extraction operation, and extracted the target object with the toluene layer. 50 g of magnesium sulfate was added thereto, dehydration operation was carried out, and magnesium sulfate was filtered off, and then toluene was distilled off using a rotary evaporator to obtain a crude product of the desired product. Toluene and ethyl acetate were used for this as a developing solvent, and column chromatography of 600 g of silica gel was performed. The main part was recovered and the solvent was distilled off again using a rotary evaporator to obtain 20 g of purified product of 1,2,4,5-tetrakis (trimethoxymethyl) benzene. As a result of confirming the target product by HPLC, no raw material was detected at all, and the product was detected with a purity of 99% as a single peak.

[Reference Example 7]

3,3 ', 5,5'-tetrakis (methoxymethyl) -4,4'-dihydroxybiphenyl (trade name TMOM-BP, manufactured by Honshu Chemical Industries, Ltd.) in a 500 ml separable flask; The structural formula is shown below) 36.2 g (0.1 mol), GBL 110g, 19.0 g (0.24 mol) of pyridine were added, and 28.1 g (0.2 mol) of benzoic acid chlorides were dripped. At this time, the reaction liquid was temperature-controlled in the range of 10-30 degreeC using an ice-water bath, and after making it react for 2 hours, after confirming reaction by HPLC, a raw material was not detected at all and a product is a single peak. It was detected with 99% purity. The reaction solution was added dropwise while stirring in 1 L of ion-exchanged water as it was, the precipitate was filtered off, and then, 500 mL of GBL was added thereto, followed by stirring and dissolving. The homogeneous solution was filled with a cation exchange resin and an anion exchange resin. The glass column was passed through to remove residual chlorine ions and pyridine. Next, this solution was dripped in 3 L of ion-exchange water under high speed stirring, and the product was precipitated, This was filtrated and vacuum-dried, and the alkoxyalkyl group containing compound was obtained (C-1, structural formula is shown below).

[Reference Example 8]

In Reference Example 7, except that 21.0 g (0.2 mol) of methacrylic acid chloride was used instead of 28.1 g (0.2 mol) of benzoic acid chloride, all were the same as in Reference Example 7 to obtain an alkoxyalkyl group-containing compound (C-2, Structural formula is shown below). When the reaction was confirmed by HPLC, no raw material was detected at all, and the product was detected with a purity of 99% as a single peak.

[Reference Example 9]

In the reference example 7, except having used 38.2 g (0.2 mol) of p-toluenesulfonic acid chlorides instead of 28.1 g (0.2 mol) of benzoic acid chlorides, it carried out similarly to the reference example 7, and obtained the alkoxyalkyl group containing compound (C-3). And structural formulas below). When the reaction was confirmed by HPLC, no raw material was detected at all, and the product was detected with a purity of 97.7% as a single peak.

[Reference Example 10]

In Reference Example 7, 3,3 ', 5,5 instead of 36.2 g (0.1 mol) of 3,3', 5,5'-tetrakis (methoxymethyl) -4,4'-dihydroxybiphenyl Except for using 30.6 g (0.1 mol) of '-tetrakis (hydroxymethyl) -4,4'-dihydroxybiphenyl (trade name TML-BP, manufactured by Honshu Chemical Industries, Ltd., structural formula below) In the same manner as in Reference Example 7 to obtain a methylol group-containing compound (C-4, structural formulas below). When the reaction was confirmed by HPLC, no raw material was detected at all, and the product was detected with a purity of 99% as a single peak.

[Formula 43]

EXAMPLE 1

4,4 'as 20 mass parts of the diazoquinone compound (Q-1) obtained by the said Reference Example 3, and the alkoxyalkyl group containing compound with respect to 100 mass parts of hydroxy polyamide (P-1) obtained by the said Reference Example 1 After dissolving 2 mass parts of -bis (methoxymethyl) biphenyl in 170 mass parts of (gamma) -butyrolactone, it filtered with the 0.2 micrometer filter and prepared the photosensitive resin composition A. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

EXAMPLE 2

4,4 'as 20 mass parts of the diazoquinone compound (Q-1) obtained by the said Reference Example 3, and the alkoxyalkyl group containing compound with respect to 100 mass parts of hydroxy polyamide (P-1) obtained by the said Reference Example 1 After dissolving 8 mass parts of -bis (methoxymethyl) biphenyl in 170 mass parts of (gamma) -butyrolactone, it filtered with the 0.2 micrometer filter and prepared the photosensitive resin composition B. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

EXAMPLE 3

4,4 'as 20 mass parts of the diazoquinone compound (Q-1) obtained by the said Reference Example 3, and the alkoxyalkyl group containing compound with respect to 100 mass parts of hydroxy polyamide (P-1) obtained by the said Reference Example 1 After dissolving 20 mass parts of -bis (methoxymethyl) biphenyl in 170 mass parts of (gamma) -butyrolactone, it filtered with the 0.2 micrometer filter and prepared the photosensitive resin composition C. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

EXAMPLE 4

Photosensitive resin composition D was prepared like Example 2 except having used the alkoxy alkyl-group containing compound as 1, 4-bis (methoxymethyl) benzene. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

[Example 5]

Photosensitive resin composition E was prepared like Example 2 except having used the alkoxy alkyl-group containing compound as 4,4'-bis (methoxymethyl) diphenyl ether. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

EXAMPLE 6

Photosensitive resin composition F was prepared like Example 2 except having set the alkoxyalkyl-group containing compound to 4,4'-bis (methoxymethyl) diphenylmethane. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

EXAMPLE 7

Photosensitive resin composition G was prepared like Example 2 except having used the alkoxy alkyl-group containing compound as 4-methoxymethyl biphenyl. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

[Example 8]

Photosensitive resin composition H was prepared like Example 2 except having used the alkoxyalkyl group containing compound as the alkoxyalkyl group containing compound (C-1) obtained by the reference example 7 mentioned above. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

EXAMPLE 9

Diaside obtained in Reference Example 4 using the hydroxypolyamide (P-2) obtained in Reference Example 2 instead of hydroxypolyamide (P-1) and replacing 20 parts by mass of the diazoquinone compound (Q-1). The photosensitive resin composition I was prepared like Example 2 except having used 14 mass parts of a quinquinone compound (Q-2). Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

EXAMPLE 10

Diaside obtained in Reference Example 4 using the hydroxypolyamide (P-2) obtained in Reference Example 2 instead of hydroxypolyamide (P-1) and replacing 20 parts by mass of the diazoquinone compound (Q-1). Photosensitive resin composition J was prepared in the same manner as in Example 4, except that 14 parts by mass of the crude quinone compound (Q-2) were used. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

EXAMPLE 11

Instead of hydroxypolyamide (P-1), hydroxypolyamide (P-2) obtained in Reference Example 2 was used, and the alkoxyalkyl group-containing compound was 1,3,5-tris (methoxymethyl) -2,4 Photosensitive resin composition K was prepared in the same manner as in Example 2, except that the residue was changed to 6-trimethoxybenzene. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

[Example 12]

Photosensitive resin composition L was prepared like Example 11 except having set the alkoxyalkyl-group containing compound into 1,2,4,5- tetrakis (methoxymethyl) benzene. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

EXAMPLE 13

Photosensitive resin composition M was prepared like Example 11 except having used the alkoxyalkyl group containing compound as the alkoxyalkyl group containing compound (C-2) obtained by the reference example 8 mentioned above. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

EXAMPLE 14

Photosensitive resin composition N was prepared like Example 11 except having used the alkoxyalkyl group containing compound as the alkoxyalkyl group containing compound (C-3) obtained by the reference example 9 mentioned above. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

[Comparative Example 1]

A photosensitive resin composition O was prepared in the same manner as in Example 1, except that 8 parts by mass of a methylol group-containing compound DML-PTBP (manufactured by Honshu Chemical Industry Co., Ltd .: structural formula is shown below) instead of an alkoxyalkyl group-containing compound. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

[Comparative Example 2]

A photosensitive resin composition P was prepared in the same manner as in Example 1, except that 8 parts by mass of DMOM-PTBP (manufactured by Honshu Chemical Industry Co., Ltd .: structural formula is shown below) as the alkoxyalkyl group-containing compound. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

(Comparative Example 3)

A photosensitive resin composition Q was prepared in the same manner as in Example 1 except that 8 parts by mass of 2,6-dimethylol-p-cresol was used instead of the alkoxyalkyl group-containing compound. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

(Comparative Example 4)

Photosensitive resin composition R was prepared like Example 1 except having used 8 mass parts of 1, 4- dibenzyl alcohol instead of the alkoxyalkyl group containing compound. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

[Formula 44]

(Comparative Example 5)

A photosensitive resin composition S was prepared in the same manner as in Example 1, except that 8 parts by mass of the methylol group-containing compound TML-BP (manufactured by Honshu Chemical Industry Co., Ltd .: Structural Formula described above) was used instead of the alkoxyalkyl group-containing compound. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

(Comparative Example 6)

A photosensitive resin composition T was prepared in the same manner as in Example 1 except that the alkoxyalkyl group-containing compound was 8 parts by mass of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd .: structural formula described above). Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

(Comparative Example 7)

A photosensitive resin composition U was prepared in the same manner as in Example 1 except that 8 parts by mass of the methylol group-containing compound (C-4) obtained in Reference Example 10 was used instead of the alkoxyalkyl group-containing compound. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

(Comparative Example 8)

A photosensitive resin composition V was prepared in the same manner as in Example 1 except that 8 parts by mass of dimethoxymethylurea (trade name MX-290, manufactured by Mitsui Scitech Co., Ltd.) was used as the alkoxyalkyl group-containing compound. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

(Comparative Example 9)

Photosensitive resin in the same manner as in Example 1, except that 8 parts by mass of hydrogenated bisphenol A diglycidyl ether (trade name Eporaito 4000, manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of the alkoxyalkyl group-containing compound. Composition W was prepared. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

(Comparative Example 10)

A photosensitive resin composition X was prepared in the same manner as in Example 1, except that 8 parts by mass of a benzoxazine compound (trade name B-a type benzoxazine, manufactured by Shikoku Chemical Industries, Ltd.) was used instead of the alkoxyalkyl group-containing compound. Using the obtained photosensitive resin composition, the relief pattern was produced on the silicon wafer by the method mentioned above, and the cure shrinkage rate, the sensitivity of a composition, and the resolution were evaluated. Moreover, the time-lapse stability of the sensitivity after exposure was evaluated by the method mentioned above. Moreover, the viscosity of the composition was measured by the method mentioned above and storage stability was evaluated.

Examples 1-14 and the list of compositions of the photosensitive resin composition of Comparative Examples 1-10 are shown in following Table 1, and an evaluation result is shown in the following Table 2.

From Table 2, it can be seen that the photosensitive resin composition of the present invention has good storage stability, can form a high sensitivity and a high resolution relief pattern, and is excellent in time-lapse stability of sensitivity after exposure. On the other hand, it turns out that the composition of Comparative Examples 1-10 which does not contain the alkoxyalkyl group containing compound which satisfy | fills the requirements of this invention has a problem that a favorable sensitivity and a resolution are not obtained, or the stability of a composition is inferior.

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 flip chip devices, a protective film of a device having a bump structure, an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper plate, and a solder resist of a semiconductor device. It can use preferably as a film and a liquid crystal aligning film.

Claims (10)

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

{Wherein, X ¹ is a tetravalent organic group having carbon atoms, X ² , Y ¹ and Y ² are each independently a divalent organic group having two or more carbon atoms, and l is an integer of 2 to 1000; m is an integer from 0 to 500, l / (l + m)> 0.5, and ^one dihydroxydiamide unit containing X ¹ and Y ¹ and m dia containing X ² and Y ² The order of arrangement of the mid units does not matter} 100 parts by mass of hydroxypolyamide containing the structure represented by (B) the following general formula (2):
(2)

{Wherein k is an integer of 1 to 4, when (i) k = 1, X is C _n H _2n OR ¹ or R ² , and R ¹ is a methyl group, an ethyl group, an n-propyl group and an isopropyl group It is a monovalent organic group chosen from the group which consists of R <^2> , A group which consists of a hydrogen atom, a C1-C4 alkyl group, a C2-C10 ester group, a C2-C10 urethane group, and a C1-C10 alkoxy group It is a monovalent organic group chosen from, n is an integer of 1-3, p is an integer of 1-5, q is an integer of 0-4, and (p + q) = 5, (ii) k When = 2 to 4, X is a single bond or a 2 to 4 valent organic group, R ¹ is a monovalent organic group selected from the group consisting of methyl group, ethyl group, n-propyl group and isopropyl group, and R ² is hydrogen Selected from the group consisting of atoms, alkyl groups of 1 to 4 carbon atoms, ester groups of 2 to 10 carbon atoms, and urethane groups of 2 to 10 carbon atoms It is a monovalent organic group, n is an integer of 1-3, p is an integer of 1-5, q is an integer of 0-4, and (p + q) = 5. However, when two or more C _n H _2n OR ¹ and R ² are present, 0.01 to 30 parts by mass of an alkoxyalkyl group-containing compound represented by n, p, q, R ¹ and R ² may be the same as or different from each other; and (C) 1-100 mass parts of diazoquinone compounds, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
(B) an alkoxyalkyl group-containing compound is represented by the following general formula (3):
(3)

{Wherein k is 1 or 2, (i) when k = 1, X is C _n H _2n OR ¹ or R ² , and R ¹ is a group consisting of a methyl group, an ethyl group, an n-propyl group and an isopropyl group It is a monovalent organic group chosen from R <^2> is chosen from the group which consists of a hydrogen atom, a C1-C4 alkyl group, a C2-C10 ester group, a C2-C10 urethane group, and a C1-C10 alkoxy group N is an integer of 1 to 3, and when (ii) k = 2, X is a single bond or the following general formula (4):
[Chemical Formula 4]

Is a divalent tetravalent organic group selected from the group represented by R <^1> , R <^1> is the monovalent organic group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and isopropyl group, and R <^2> is a hydrogen atom and C1-C4 Is a monovalent organic group selected from the group consisting of an alkyl group, a C 2-10 ester group, and a C 2-10 urethane group, n is an integer of 1 to 3, p is an integer of 1 to 5, and q is It is an integer of 0-4 and (p + q) = 5. However, when two or more C _n H _2n OR ¹ and R ² are present, n, p, q, R ¹ and R ² may be the same as or different from each other}
Photosensitive resin composition represented by. The method of claim 1,
(B) an alkoxyalkyl group-containing compound is represented by the following general formula (5):
[Chemical Formula 5]

{In formula, R <^1> is monovalent organic group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and isopropyl group, n is an integer of 1-3, p is an integer of 1-5, k is 1 or 2, (i) when k = 1, X is a hydrogen atom or C _n H _2n OR ¹ , (ii) when k = 2, X is a single bond or the following general formula (6):
[Formula 6]

It is a bivalent tetravalent organic group chosen from group represented by it. However, when two or more (C _n H _2n OR ¹ ) exist, n and R <^1> may mutually be same or different. The method of claim 1,
(B) Alkoxyalkyl group containing compound is bis (methoxymethyl) benzene, tris (methoxymethyl) benzene, tetrakis (methoxymethyl) benzene, pentakis (methoxymethyl) benzene, hexakis (methoxymethyl) benzene , Tris (methoxymethyl) trimethoxybenzene, methoxymethylbiphenyl, bis (methoxymethyl) biphenyl, bis (methoxymethyl) diphenylether, and bis (methoxymethyl) diphenylmethane Photosensitive resin composition selected from. The method of claim 1,
(B) an alkoxyalkyl group-containing compound is represented by the following general formula (7):
[Formula 7]

{Wherein Z ¹ is the following general formula (8):
[Chemical Formula 8]

(In formula, R <^3> -R <^5> is a C1-C9 organic group each independently, R <^6> is monovalent organic group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and isopropyl group, and R ⁷ to R ¹⁰ are each independently a substituent selected from a group represented by an organic group having 1 to 12 carbon atoms, k is an integer of 1 to 4, and when (i) k = 1, Z ² is C _n H _2n OR ¹ or R ² , R are each independently a methyl group or an ethyl group, R ¹ is a monovalent organic group selected from the group consisting of methyl group, ethyl group, n-propyl group and isopropyl group, R ² is a hydrogen atom, And a monovalent organic group selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, n is an integer of 1 to 3, and (ii) when k = 2 to 4, Z ² is a single bond or a 2 to 4 valent oil. device is, Z ¹ in this case the presence of a plurality, Z ¹ is represented by may be the same or different} Light blocking resin composition. The method of claim 5, wherein
(B) an alkoxyalkyl group-containing compound is represented by the following general formula (9):
[Formula 9]

{In formula, R is a methyl group or an ethyl group each independently, Z <^1> is each independently following General formula (10):
[Formula 10]

(In formula, R <^3> -R <^5> is a C1-C9 organic group each independently, R <^6> is monovalent organic group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and isopropyl group, and R ⁷ to R ¹⁰ each independently represent an organic group having 1 to 12 carbon atoms), and Z ³ is a single bond or the following General Formula (11):
(11)

It is a substituent selected from the group shown by the following. The method according to claim 6,
In General Formula (9), Z ³ is a single bond, and Z ¹ is each independently the following General Formula (12):
[Formula 12]

The photosensitive resin composition which is a substituent chosen from group represented by {in formula, R <^3> and R <^5> is respectively independently a C1-C9 organic group, and R <^7> is a C1-C12 organic group. The method according to claim 6,
In General formula (9), Z <^3> is a single bond, Z <^1> is respectively independently following General formula (13):
[Formula 13]

The photosensitive resin composition which is a substituent chosen from the group represented by the. The process of forming the photosensitive resin layer which consists of a photosensitive resin composition in any one of Claims 1-8 on a board | substrate, and exposing with actinic light through a mask, or directly irradiating a light beam, an electron beam, or an ion beam. The manufacturing method of the hardening relief pattern containing the process of developing, and the process of heating the obtained relief pattern. The semiconductor device which has a hardening relief pattern layer obtained by the method of Claim 9.