KR20120022712A - Photosensitive resin composition - Google Patents

Abstract

{식 중, Z₁, Z₂ 및 Z₃ 은 각각 독립적으로 2 가의 유기기이고, Z₁, Z₂ 및 Z₃ 중 적어도 1 개는 지환식 구조 또는 지방족 구조를 갖고, 그리고 m₁ 은 0 또는 1 의 정수이다.} 로 나타내는 구조 및 하기 일반식 (2) :

{식 중, Z₁, Z₂ 및 Z₃ 은 각각 독립적으로 2 가의 유기기이고, Z₁, Z₂ 및 Z₃ 중 적어도 1 개는 지환식 구조 또는 지방족 구조를 갖고, 그리고 m₁ 은 0 또는 1 의 정수이다.} 로 나타내는 구조로 이루어지는 군에서 선택되는 적어도 1 종의 구조를 갖는 하이드록시폴리아미드 수지 (A), 및 광산 발생제 (B) 를 함유한다.Provided is a photosensitive resin composition having a high residual film ratio, high sensitivity, and high elongation and high storage stability. The photosensitive resin composition which concerns on this invention is following General formula (1):

{Wherein Z ₁ , Z ₂ and Z ₃ are each independently a divalent organic group, at least one of Z ₁ , Z ₂ and Z ₃ has an alicyclic structure or an aliphatic structure, and m ₁ is 0 or It is an integer of 1.} and the following general formula (2):

{Wherein Z ₁ , Z ₂ and Z ₃ are each independently a divalent organic group, at least one of Z ₁ , Z ₂ and Z ₃ has an alicyclic structure or an aliphatic structure, and m ₁ is 0 or Hydroxypolyamide resin (A) and a photoacid generator (B) which have at least 1 sort (s) of structure chosen from the group which consists of a structure shown by the following.

Description

Photosensitive resin composition {PHOTOSENSITIVE RESIN COMPOSITION}

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

BACKGROUND OF THE INVENTION Polyimide resins having excellent heat resistance, electrical characteristics, mechanical properties, and the like are widely used for surface protection films and interlayer insulating films of semiconductor devices. This polyimide resin is often provided today in the form of a photosensitive polyimide precursor composition.

By the way, this photosensitive polyimide precursor composition needs to use organic solvents, such as N-methyl- 2-pyrrolidone, as a developing solution in the image development process, and the countermeasures for an organic solvent are deteriorated because of the recent increase of environmental problems. It has been demanded. In recent years, the proposal of the heat resistant photosensitive resin material which can develop in alkaline aqueous solution similarly to a photoresist is made | formed in recent years.

Among them, a photoacid generator such as a naphthoquinone diazide compound is used as a hydroxypolyamide resin of an aqueous alkaline solution soluble to be a heat resistant resin after curing, for example, a polybenzoxazole (hereinafter also referred to as "PBO") precursor. The method of using the PBO precursor composition mixed with the photosensitive resin composition is disclosed by the following patent documents 1 and 2.

The developing mechanism of the photosensitive resin composition is that the photosensitive diazoquinone compound is chemically converted into an indencarboxylic acid compound by exposing the naphthoquinone diazide compound and the PBO precursor of the unexposed part to a low dissolution rate in an alkaline aqueous solution. It changes and the dissolution rate with respect to the alkaline aqueous solution of an exposure part is used. The relief pattern which consists of an unexposed part is attained using the difference of the dissolution rate with respect to the developing solution between this exposure part and the unexposed part.

The PBO precursor composition mentioned above can form a positive type relief pattern by exposure and image development by alkaline aqueous solution. Moreover, an oxazole ring is produced | generated by heat, and the PBO film | membrane after hardening will have the thermosetting film characteristic equivalent to a polyimide film | membrane.

Similarly, the photosensitive resin composition which consists of a polyamic acid which can develop alkali, and a polyamic acid ester and a naphthoquinone diazide compound is disclosed by the following patent documents 3, 4, and 5.

Moreover, the following photosensitive resin composition which consists of a phenolic hydroxyl group containing solvent soluble polyimide (henceforth "soluble PI") and a naphthoquinone diazide compound which can develop alkali is proposed.

Moreover, the photosensitive resin composition which consists of a PBO precursor polymer and an naphthoquinone diazide compound containing an ester bond is proposed by the following patent documents 7, and consists of a PI precursor polymer and a naphthoquinone diazide compound containing an ester bond The photosensitive resin composition is proposed by patent document 8, 9, 10.

Japanese Patent Publication No. 01-046862 Japanese Laid-Open Patent Publication No. 63-096162 Japanese Patent Laid-Open No. 52-013315 Japanese Patent Application Laid-Open No. 02-181149 Japanese Unexamined Patent Publication No. 2004-334089 International Publication No. 07/029614 Brochure Japanese Unexamined Patent Publication No. 2007-171945 Japanese Unexamined Patent Publication No. 2007-140319 Japanese Unexamined Patent Publication No. 2007-314583 Japanese Unexamined Patent Publication No. 2007-314614

Said patent document 1? The prior art described in 10 has room for improvement because of the following problems.

Since the surface protection film and the interlayer insulation film of the semiconductor element using the heat resistant photosensitive resin material which can develop with conventional alkaline aqueous solution have low sensitivity regarding the i-line (365 nm) permeability of a polymer skeleton, industrial productivity will fall.

Patent Document 1? In the invention described in 4 and Patent Document 6, the developing residual film ratio is 80? By setting it as low as 85%, it is a practical sensitivity in industrial production. However, at the present time when micromachining is progressing, the space | interval of a pattern and a pattern becomes short, and the developing residual film rate is 80? When it is made low as 85%, in the unexposed part adjacent to the open exposure part, even if the dissolution rate of the unexposed part is small, it is developed not only from the upper side of the film but also from the side at the time of development, so that the pattern shape becomes too thin and the semiconductor It lowers the reliability of a semiconductor package in the manufacturing process of an apparatus.

Patent Literature 5 proposes a method of increasing the development residual film ratio by making the alkali solubility of the polyimide precursor itself very low, but the sensitivity is low.

Patent Document 7 proposes a polyamide resin incorporating an ester group. However, since all divalent linking organic groups in the resin have an aromatic structure, i-line (365 nm) permeability is low, and sensitivity evaluation is similar to that in the prior art. Value.

Polyimide precursor resin which introduce | transduced ester group in patent documents 8, 9, 10 is proposed.

In patent document 8, since all divalent connection organic groups in resin have aromatic structure similarly to patent document 7, i line | wire (365 nm) permeability is low and sensitivity is low.

In Patent Document 9, the transparency of the resin itself is increased by introducing an alicyclic structure into a divalent linking organic group in the resin, and the alkali solubility of the polyimide precursor is controlled by using a specific bulky structure and an ester group. Data is not disclosed. Moreover, when the carboxyl group of a polyimide precursor and diazonaptoquinone interact with the interaction of the phenolic group and diazonaphthoquinone of a hydroxy polyamide resin, alkali dissolution inhibiting effect is low because of the difference of pKa, and high transparency This does not necessarily mean high sensitivity. Moreover, when a carboxyl group is not sealed by a protecting group, a polyimide precursor also has the problem that imidation advances easily even at room temperature, and the storage stability of a varnish worsens.

In patent document 10, similarly to patent document 7, since all divalent connection organic groups in resin have an aromatic structure, i line | wire (365 nm) permeability is low and elongation is low. When elongation is low, problems, such as a crack generate | occur | produce in a buffer layer, generate | occur | produce a problem by test which repeats temperature-falling temperature, such as a thermal cycle test (TCT), and fall reliability.

As described above, the photosensitive resin composition of the prior art almost does not dissolve the unexposed portion as in the photoresist (this development is referred to as having a high development residual film ratio, and in the present invention, the development residual film ratio is 95 to 100% as a high development residual film ratio). It is difficult to develop, and even if it is possible to develop by adjusting the composition, a very high exposure dose is required (this is called a low degree), so that the photosensitive resin material has the necessary thermomechanical properties and storage stability, and is developed. A resin composition having a high residual film ratio and high sensitivity is still not provided.

The problem to be solved by the present invention under such a situation is that by using a hydroxypolyamide resin containing both an alicyclic structure or an aliphatic structure and an ester bond, the development residual film ratio is high, high sensitivity, high elongation and high storage It is providing the photosensitive resin composition which has stability, the manufacturing method of the hardening relief pattern using this composition, and the semiconductor device and light emitting device which have this hardening relief pattern.

MEANS TO SOLVE THE PROBLEM This inventor earnestly examined in view of the above-mentioned problem of the prior art, and found that the polymer which solves the said subject, and the photosensitive resin composition are obtained by setting it as the hydroxy polyamide resin which has a specific structure as a result of repeating experiment. The present invention has been completed.

That is, this invention is as follows.

[1] the following general formula (1):

[Formula 1]

{Wherein Z ₁ , Z ₂ and Z ₃ are each independently a divalent organic group, at least one of Z ₁ , Z ₂ and Z ₃ has an alicyclic structure or an aliphatic structure, and m ₁ is 0 or It is an integer of 1.} and the following general formula (2):

[Formula 2]

{Wherein Z ₁ , Z ₂ and Z ₃ are each independently a divalent organic group, at least one of Z ₁ , Z ₂ and Z ₃ has an alicyclic structure or an aliphatic structure, and m ₁ is 0 or It is an integer of 1.} The photosensitive resin composition containing the hydroxy polyamide resin (A) which has at least 1 sort (s) of structure chosen from the group which consists of a structure shown by this, and a photo-acid generator (B).

[2] The hydroxypolyamide resin (A) is represented by the following general formula (3):

(3)

{In formula, X <_1> and Y <_1> are 2? It is a tetravalent organic group, R <_1> ? Each R ₃ independently represents a hydrogen atom or 1? 10 is a hydrocarbon group, m ₂ is 1? N ₁ is an integer of 1 or 2, n ₂ ? n ₄ are each independently 0? At least one of the structures represented by Y ₁ (OR ₁ ) _{n 2} (COOR ₃ ) _n 4 in the formula is the general formula (1) or the following general formula (4):

[Formula 4]

(Wherein, Y ₂ is a divalent tetravalent organic group having at least two carbon atoms, Z ₁ is a divalent organic group, Y ₂ And at least _one of Z ₁ has an alicyclic structure or an aliphatic structure, and R ₄ and R ₅ each independently represent a hydrogen atom or a carbon number of 1? It is a hydrocarbon group of 10, and m <_3> is 1? Is an integer of 100, and n ₅ and n ₆ are each independently 0? Or an above general formula (2) or the following general formula (5):

[Chemical Formula 5]

(Wherein, Y ₂ is a divalent tetravalent organic group having at least two carbon atoms, Z ₁ is a divalent organic group, at least one of Y ₂ and Z ₁ has an alicyclic structure or an aliphatic structure, R ₄ and R ₅ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, m ₃ is an integer of 1 to 100, and n ₅ and n ₆ are each independently an integer of 0 to 2. The photosensitive resin composition as described in said [1] which has a structure shown by}.

[3] The photoacid generator (B) is a naphthoquinone diazide compound, and the content of the naphthoquinone diazide compound is 1? To 100 parts by mass of the hydroxypolyamide resin (A). It is 50 mass parts, and the said photosensitive resin composition is a compound (C) 1-? Which promotes the solubility to aqueous alkali solution with respect to 100 mass parts of said hydroxy polyamide resins (A). The photosensitive resin composition as described in said [1] or [2] which further contains 100 mass parts.

[4] The above-mentioned [1], wherein the compound (C) for promoting solubility in the aqueous alkali solution contains a compound containing at least one group selected from the group consisting of phenolic hydroxyl groups, carboxyl groups and sulfonyl groups. The photosensitive resin composition in any one of [3].

[5] A compound (D) 1 to generate a crosslinking reaction with heat based on 100 parts by mass of the hydroxypolyamide resin (A). The above-mentioned [1] which further contains 50 mass parts. The photosensitive resin composition in any one of [4].

[6] The compound (D) which causes a crosslinking reaction by the heat is an epoxy compound, an oxetane compound, a melamine compound, an alkenyl compound, and the following general formula (6)

[Formula 6]

{In formula, R <_6> is a hydrogen atom or the monovalent group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and isopropyl group, and R <_7> is a hydrogen atom, a hydroxyl group, and carbon number 1? At least one monovalent organic group selected from the group consisting of 10 alkyl groups, alkoxy groups, ester groups and urethane groups, n ₇ is 1? Is an integer of 5 and n ₈ is 0? Is an integer of 4, where n ₇ + n ₈ = 5 and m ₄ is 1? Is an integer of 4 and Z ₄ is CH ₂ OR ₆ when m ₄ = 1 Or R ₇ And m ₄ = 2? When 4, single bond or 2? Tetravalent organic group, wherein CH ₂ OR ₆ and R ₇ When there are a plurality of R ₆ and R ₇ May be the same as or different from each other.} A compound having a structure represented by Formula (7):

[Formula 7]

{In formula, R <_8> and R <_9> is respectively independently a hydrogen atom or a carbon number of 1? A compound selected from the group consisting of a hydrocarbon group of ₁₀ and R ₁₀ CO-, wherein R ₁₀ is a hydrocarbon group of 1 to ₁₀ carbon atoms. 8) :

[Formula 8]

{Wherein, D ₁ is the number of carbon atoms 1? 6 is a functional group selected from the group consisting of an alkyl group, an alkenyl group, and a crosslinkable organic group, M ₁ is a group selected from the group consisting of -CH _2- , -O-, and -S-, and Z ₅ is 2 Is an organic group, and n ₉ is 0? Is an integer of 4, D ₁ is the case that a plurality, may be a plurality of D ₁ may be the same or different.} Is at least one compound selected from the group consisting of compounds having the structure represented by the above-mentioned [1]? The photosensitive resin composition in any one of [5].

[7] A compound (E) which generates an acid by heat with respect to 100 parts by weight of the hydroxypolyamide resin (A) 0.1? The above-mentioned [1] which further contains 30 mass parts. The photosensitive resin composition in any one of [6].

[8] the following process:

(1) above [1]? Forming a photosensitive resin layer made of the photosensitive resin composition according to any one of [7] on a substrate;

(2) exposing step;

(3) developing process,

(4) heat-processing the obtained relief pattern,

Method of producing a cured relief pattern comprising a.

[9] A cured relief pattern produced by the method described in [8] above.

[10] A semiconductor device comprising a semiconductor element and a cured film formed on the semiconductor element, wherein the cured film is a cured relief pattern according to the above [9].

[11] A display device comprising a display element and a cured film formed over the semiconductor element, wherein the cured film is a cured relief pattern according to the above [9].

[12] at least one alkali-soluble polymer and naphthoquinonediazide compound selected from the group consisting of a polybenzoxazole precursor having a (thio) ester structure, a polyimide precursor, and a phenol group-containing polyimide in the main chain; As a photosensitive resin composition to contain,

(i) the following steps (a), (b) and (c):

(a) The alkali-soluble polymer is dissolved in γ-butyrolactone at a concentration of 35% by mass of resin solids to prepare a solution of the alkali-soluble polymer:

(b) The film thickness at the time of apply | coating the solution of the alkali-soluble polymer produced by said (a) on a 6-inch silicon wafer, prebaking for 125 degreeC 180 second, and using a contact film thickness meter, and measuring it A film having a thickness of 10 µm ± 0.2 µm; And

(c) The film thickness obtained by measuring the film after prebaking by arbitrary refractive index (n _f1 ) using a non-contact film thickness meter was made into T _f1 , and obtained by measuring by the contact film thickness meter in (b). The true refractive index (n _r1 ) obtained when the film thickness is T _r1 is expressed by the following equation:

n _r1 = n _f1 × T _f1 / T _r1

Obtained by;

The refractive index (n _r1 ) of the alkali-soluble polymer obtained by performing the procedure in order was 1.570? Is in the range of 1.650,

(ii) the following (a '), (b') and (c '):

(a ') 100 mass parts of the said alkali-soluble polymer is melt | dissolved in (gamma) -butyrolactone at the density | concentration of 35 mass% of resin solid content, 15 mass parts of said naphthoquinone diazide compounds are further dissolved, and the solution of the photosensitive resin composition is produced. ;

(b ') When the solution of the photosensitive resin composition produced by said (a') was apply | coated on a 6 inch silicon wafer, it prebaked for 125 degreeC 180 second, and measured using a contact film thickness meter. To form a film having a film thickness of 10 µm ± 0.2 µm; And

(c ') non-contact to the film using a thickness meter, a film after pre-baking at any of the refractive index the film thickness obtained by measuring a (n _f2) to T _f2, and the (b' contact film measured by the thickness meter in) The true refractive index (n _r2 ), which is obtained when the film thickness obtained by making T _r2 is expressed by the following equation:

n _r2 = n _f2 × T _f2 / T _r2

Obtained by;

The refractive index (n _r2 ) of the said photosensitive resin composition obtained by carrying out in order, and the refractive index (n _r1 ) of the said alkali-soluble polymer are the following conditions:

{Refractive index (n _r1 ) / refractive index (n _r2 ) of the photosensitive resin composition} of an alkali-soluble polymer} × 100 = 1.0? 3.0 (%)

The photosensitive resin composition satisfying the.

According to the present invention, it has a photoresist composition having a high residual film ratio, high sensitivity, high elongation and high storage stability, a method for producing a cured relief pattern using the positive photosensitive resin composition, and a cured relief pattern. A semiconductor device or a light emitting device is provided.

1 is a ¹³ C-NMR diagram of a hydroxypolyamide resin (A) P-1.
Fig. 2 is a ¹³ C-NMR diagram of the hydroxypolyamide resin (A) P-2.
3 is a ¹³ C-NMR diagram of the hydroxypolyamide resin (A) P-3.
4 is a ¹³ C-NMR diagram of the hydroxypolyamide resin (A) P-4.
5 is a ¹³ C-NMR diagram of the hydroxypolyamide resin (A) P-5.

<Photosensitive resin composition>

Hereinafter, each component which comprises the hydroxy polyamide resin which concerns on this invention, and the photosensitive resin composition containing it is demonstrated in detail.

Hydroxypolyamide Resin (A)

The hydroxypolyamide resin (A) used for the photosensitive resin composition of this invention is following General formula (1):

[Formula 9]

{Wherein Z ₁ , Z ₂ and Z ₃ are each independently a divalent organic group, at least one of Z ₁ , Z ₂ and Z ₃ has an alicyclic structure or an aliphatic structure, and m ₁ is 0 or It is an integer of 1.} and the following general formula (2):

[Formula 10]

{Wherein Z ₁ , Z ₂ and Z ₃ are each independently a divalent organic group, at least one of Z ₁ , Z ₂ and Z ₃ has an alicyclic structure or an aliphatic structure, and m ₁ is 0 or It is an integer of 1.} It has at least 1 sort (s) of structure chosen from the group which consists of a structure shown.

In this specification, the structure represented by the said General formula (1) is called "ester group containing structure", The structure represented by the said General formula (2) is also called "thioester group containing structure", These are collectively called "(thio) ester" Group-containing structure ”. Z ₁ , Z ₂ and Z ₃ At least one of the structures is an alicyclic structure or an aliphatic structure.

Hydroxypolyamide resin (A) is a structure synthesize | combined with at least 1 type of carboxylic acid compound and polyvalent amino compound chosen from the group which consists of polyhydric carboxylic acid and its derivatives in addition to the said (thio) ester group containing structure. Has

Here, as polyhydric carboxylic acid and its derivative (s), dicarboxylic acid, tricarboxylic acid, these acid chloride compounds, an acid anhydride compound, etc. are mentioned. Moreover, as a polyvalent amino compound, the compound which has at least two amino groups, specifically, diamine, such as diamino benzoic acid, diamino phenol, bis (amino phenol), is mentioned. These compounds may be substituted.

That is, the hydroxypolyamide resin (A) is a polyamide which is derived from dicarboxylic acid, tricarboxylic acid and derivatives thereof and bis (aminophenol), and is a PBO precursor having a phenol group at the ortho position of the amide bond, and dica A structure selected from polyamides having a phenol group derived from carboxylic acid, tricarboxylic acid, derivatives thereof and diaminophenol; It is preferable to have said (thio) ester group containing structure.

First, the (thio) ester group containing structure is demonstrated.

By having an alicyclic or aliphatic structure in the resin skeleton, the hydroxypolyamide resin (A) realizes high transparency to i-rays (365 nm), which leads to an improvement in sensitivity and further lowers the elastic modulus ( In the case of the wholly aromatic structure, the polymer skeleton can be rigid and the elastic modulus can be increased. In addition, by having a (thio) ester group-containing structure, the proportion of the amide bonds is relatively reduced, and the aggregation of the hydroxypolyamide resin (A) by the hydrogen bonds derived from the amide bonds is suppressed. This becomes high (it becomes easy to melt | dissolve in a solvent, and gelatinization is suppressed).

The hydroxypolyamide resin (A) according to the present invention exhibits an effect of high development residual film ratio. Although this reason is not clear, the present inventor estimates the reason as follows. By having both an alicyclic structure or an aliphatic structure and a (thio) ester group-containing structure, the interaction between the resins is moderately reduced (in the case of the aromatic structure, it is considered that there is a π-π stacking effect between the aromatics, Since it is relatively low compared with the case, it becomes moderate alkali solubility with respect to the alkaline developing solution (2.38 mass% tetramethylammonium hydroxide aqueous solution) used for general alkali image development. On the other hand, when using the photosensitive resin composition {hydroxypolyamide (A) and a photo-acid generator (B)}, the hydrophobicity of the (thio) ester group containing structure is exhibited, and as a result, an alkali developing solution itself becomes difficult to permeate a composition, It becomes an environment in which the dissolution inhibiting force of the oxypolyamide (A) and the photoacid generator (B) is easy to be maintained, and the alkali solubility with respect to the alkaline developer is greatly reduced.

It is needless to say that when the polyhydroxyamide having only an aromatic structure instead of an alicyclic structure or aliphatic structure is used as the resin skeleton of the hydroxypolyamide resin, i-ray permeability of the resin itself is low. There is also an effect, and alkali solubility to the alkaline developer disappears.

Moreover, the said hydroxy polyamide resin (A) has the following general formula (3):

[Formula 11]

{In formula, X <_1> and Y <_1> are 2? It is a tetravalent organic group, R <_1> ? Each R ₃ independently represents a hydrogen atom or 1? 10 is a hydrocarbon group, m ₂ is 1? N ₁ is an integer of 1 or 2, n ₂ ? n ₄ are each independently 0? At least one of the structures represented by Y ₁ (OR ₁ ) _{n 2} (COOR ₃ ) _n 4 in the formula is the general formula (1) or the following general formula (4):

[Chemical Formula 12]

(Wherein, Y ₂ is a divalent tetravalent organic group having at least two carbon atoms, Z ₁ is a divalent organic group, Y ₂ And at least _one of Z ₁ has an alicyclic structure or an aliphatic structure, and R ₄ and R ₅ each independently represent a hydrogen atom or a carbon number of 1? It is a hydrocarbon group of 10, and m <_3> is 1? Is an integer of 100, and n ₅ and n ₆ are each independently 0? Or an above general formula (2) or the following general formula (5):

[Formula 13]

(Wherein, Y ₂ is a divalent tetravalent organic group having at least two carbon atoms, Z ₁ is a divalent organic group, at least one of Y ₂ and Z ₁ has an alicyclic structure or an aliphatic structure, R ₄ and R ₅ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, m ₃ is an integer of 1 to 100, and n ₅ and n ₆ are each independently an integer of 0 to 2. It is preferable to have a structure represented by}.

The (thio) ester group-containing structure specifically comprises (1) a hydroxyl group-containing compound or thiol compound having a structure of Z ₁ , and (2) a polyvalent carboxylic acid having a structure of Z ₂ and Z ₃ and a derivative thereof. It can obtain by making at least 1 sort (s) of carboxylic compound selected from the group react.

Or less, (1) Z ₁ The hydroxyl group containing compound or thiol compound which has a structure is demonstrated.

A phenol compound and an alcohol compound are mentioned as a hydroxyl group containing compound.

As a specific example of a phenol compound, hydroquinone, resorcinol, 4,4'- dihydroxy biphenyl, 2,2'- dihydroxy biphenyl, 4,4'- dihydroxy diphenylmethane, 4 , 4'-methylenebis (2-methylphenol), 4,4'-methylenebis (2,6-dimethylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 4 , 4'-ethylidenebisphenol, 4,4'-dihydroxydiphenylpropane, TM124 (Degusa Japan: brand name), 2,2-bis (4-hydroxyphenyl) butane, 4,4 '-(1 , 3-dimethylbutylidene) diphenol, 4,4 '-(2-ethylhexylidene) diphenol, hexestrol, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2, 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 1,3-bis [2- (4-hydroxy Phenyl) -2-propyl] benzene, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 4,4 ' -Butylidenebis (6-tert-butyl-m-cresol), 1,1-bis (4-lower Hydroxyphenyl) cyclohexane, 4,4 '-(α-methylbenzylidene) bisphenol, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 9,9-bis (4 -Hydroxyphenyl) fluorene, 4,4'-dihydroxytetraphenylmethane, 4,4'-dihydroxydiphenylhexafluoropropane, 4,4'-dihydroxybenzophenone, 4,4 ' Dihydroxydiphenyl ether, 1,3-bis (4-hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, diphenolic acid and the like Can be mentioned.

Moreover, as a phenol compound, the phenol compound containing a functional group can also be used. Examples of the functional group include amide groups, imide groups, urea groups, urethane groups and the like.

As a method of synthesize | combining the phenol compound containing these functional groups, the method of making the phenol compound which has an amino group as a starting material, and making the amino group react is mentioned.

Specifically, the phenol compound containing an amide group is obtained by making the amino group of the phenol compound which is a raw material react with carboxylic acid or its acid chloride. Similarly, a phenol compound containing an imide group is obtained by reacting an amino group with a carboxylic anhydride, a phenol compound containing a urea group is obtained by reacting an amino group with an isocyanate compound, and the phenol compound containing a urethane group is an amino group and a bicarbonate. It is obtained by making carbonic acid compounds, such as di-t-butyl, react.

Specific examples of the alcohol compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1, 9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1, 2-nonanediol, 1,2-decanediol, 1,2-dodecanediol, 2,5-hexanediol, cis-2butene-1,4-diol, 2,2-diethyl-1,3-propane Diol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,5-hexadiene-3,4-diol, 2,5-dimethyl- 3-hexyl-2,5-diol, 2,4,7,9-tetramethyl-5-decine-4,7-diol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1 , 2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, trans-p-mentan-3,8-diol, 2,4-dimethoxy Benzyl alcohol, 1,3-bis (4-hydroxybutyl) tetramethyldisiloxane, X-22-160AS (Shin-Etsu Chemical Co., Ltd.), FM-4411 (Chiso: Trade Name), butyroin, etc. Can be mentioned.

Similarly to the phenol compound, an alcohol compound containing a functional group can also be used. Examples of the functional group include amide groups, imide groups, urea groups, urethane groups and the like.

The method of introducing these functional groups into the alcohol compound is the same as the method of introducing the functional groups into the phenol compound.

Specific examples of the thiol compound include 1,4-benzenedithiol, 4,4'-biphenyldithiol, 4,4'-thiobisbenzenethiol, 3,7-dithia-1,9-nonanedithiol , 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, Karenz BD1 (Showa Denko), and the like.

Similarly to the phenol compound, a thiol compound containing a functional group can also be used. Examples of the functional group include amide groups, imide groups, urea groups, urethane groups and the like.

The method of introducing these functional groups into the thiol compound is the same as the method of introducing the functional groups into the phenol compound.

Hereinafter, a carboxylic acid compound of at least one polyhydric having the structure wherein Z ₂ and Z ₃ selected from the group consisting of carboxylic acids and their derivatives.

Z polyvalent carboxylic acid having in the structure of ₂ and Z ₃ may be mentioned a dicarboxylic acid having a structure of Z ₂ or Z ₃ which is selected from, respectively:

[Formula 14]

{Wherein A ₁ is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ — and a single bond; A divalent group, L ₁ is at least one group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, an amide group, a urea group, an imide group, and a urethane group, and k = 4, and a plurality of L ₁ May be the same or different.},

[Formula 15]

{N ₁₀ is 1? Is an integer of 12}, or

[Formula 16]

{In formula, L <_2> , L <_3> and L <_4> are respectively independently a hydrogen atom or a methyl group, and L <_5> is a hydrogen atom, a methyl group, or a hydroxyl group.}.

Further, in the in the structure represented by the following formula _{(3), Y 1 (COOH} ) 2 (OR 1) n2 (COOR 3) carboxylic polyhydric having _n4 structure acid is a carboxylic polyhydric having the structure above Z ₂ and Z ₃ acid It may be the same as the mountain group.

Further, the general formula 4 and the structure shown by the general formula (5), Y ₂ (OR _{4) n5} (COOR ₅₎ wherein the carboxylic acid is a polyvalent Z ₂ and Z ₃ having the structure _n6 It may be the same as the group of the polyvalent carboxylic acid corresponding to.

From the viewpoint of i-ray permeability of the hydroxypolyamide resin (A), the general formula (1), the general formula (2), the general formula (4), or the general formula ( Z ₁ in the structure represented by 5) Is aromatic, and Z ₂ and Z ₃ are both preferably an alicyclic structure or an aliphatic structure. From the viewpoint of solubility in solvents, Z ₁ has ₁ to 3 carbon atoms. 30 and Z ₂ and Z ₃ have 1? It is preferable that it is 15. Z ₁ , Z ₂ and Z ₃ It is preferable to include at least 1 type of group chosen from the group which consists of a silver hydrocarbon group, an ether group, an amide group, an imide group, a urea group, a urethane group, a sulfonyl group, and a fluorine-containing group.

Moreover, it is more preferable that the hydroxypolyamide resin (A) has a structure represented by General formula (9) or (10) from a viewpoint of i line | wire permeability and lithographic performance improvement. Specifically, Z ₁ is the following General Formula (9):

[Formula 17]

{In formula, R <_10> is a carbon number of 1? It is a hydrocarbon group of 18, and R <_11> is respectively independently a hydrogen atom and C1-C atoms. At least one group selected from the group consisting of a hydrocarbon group, an ether group, an amide group, an imide group, a urea group and a urethane group of 17.}, and Z ₂ and Z ₃ are the following General Formula (10) :

[Formula 18]

{Wherein A ₁ is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ — and a single bond; Represents a divalent group, and L ₁ represents a hydrogen atom or a carbon atom having 1? A hydrocarbon group of 6 is represented, k = 4, a plurality of L ₁ may be the same or different, and L ₂ ? L ₄ Are each independently a hydrogen atom or a methyl group, L ₅ is a hydrogen atom, a methyl group or a hydroxyl group, and n ₁₀ is 1? It is an integer of 12.} It is preferable that it is a structure shown.

On the other hand, from the viewpoint of thermal properties and mechanical properties of the hydroxypolyamide resin (A), in particular from the viewpoint of mechanical properties, the above general formula (1), the general formula (2), and the above-mentioned (thio) ester group-containing structure Z _{1 in the} structure represented by the general formula (4) or the general formula (5). Is an alicyclic structure or an aliphatic structure, and Z ₂ and Z ₃ are preferably aromatic. Moreover, from the viewpoint of solubility to a solvent, the number of carbon atoms of Z ₁ , Z ₂ and Z ₃ is 1? It is preferable that it is an organic group of 15. Z ₁ , Z ₂ And Z ₃ preferably includes at least one group selected from the group consisting of a hydrocarbon group, an ether group, an amide group, an imide group, a urea group, a urethane group, a sulfonyl group and a fluorine-containing group.

Moreover, from a mechanical viewpoint, it is preferable that hydroxy polyamide resin (A) has a structure represented by following General formula (11). Specifically, Z ₁ is the following General Formula (11):

[Formula 19]

{Wherein A ₁ is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ — and a single bond; Represents a divalent group, and L ₁ represents a hydrogen atom or a carbon atom having 1? A hydrocarbon group of 6 is represented, k = 4, a plurality of L ₁ may be the same or different, and L ₂ ? L ₄ Are each independently a hydrogen atom or a methyl group, L ₅ is a hydrogen atom, a methyl group or a hydroxyl group, and n ₁₀ is 1? It is an integer of 8.}, and Z ₂ or Z ₃ is the following general formula (12):

[Formula 20]

{Wherein L ₁ is at least one group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, an amide group, a urea group, an imide group and a urethane group, k = 4, and a plurality of L ₁ are the same May be different, or R ₁₂ Has 1 carbon atom? It is preferable that it is a structure shown.

As a manufacturing method of a hydroxy polyamide resin (A), the method of polycondensing the said hydroxyl group containing compound or thiol compound, and polyhydric carboxylic acid, and then polycondensing a polyvalent amino compound is mentioned.

The hydroxypolyamide resin (A) is -25 deg. C to an excess of dicarboxylic acid, hydroxyl group-containing compound or thiol compound in the presence of a base catalyst such as pyridine, triethylamine and benzyltriethylamine. It reacts in 40 degreeC, and synthesize | combines the (thio) ester group containing structure whose both ends are carboxylic acid or its derivative (s), and then contains the (thio) ester group whose both ends obtained are carboxylic acid or its derivative (s). The structure and polyhydric amino compounds, such as bis (aminophenol), are -25 degreeC? It can synthesize | combine by polycondensing in the range of 10 degreeC. Here, "the derivative" means carboxylic acid chloride.

Dicarboxylic acid can also be used in the acid chloride state using thionyl chloride. As the synthesis method of the acid chloride, specifically dicarboxylic acid and an excess of thionyl chloride are reacted in the presence of a catalyst such as N, N-dimethylformamide, pyridine, benzyltriethylamine, and excess thionyl chloride. The method of distilling off by heating and pressure reduction can be mentioned, The residue of this reaction liquid can be obtained by recrystallization with solvents, such as hexane and toluene, and can also be used for superposition | polymerization of resin, without refine | purifying. Moreover, the catalyst which used dicarboxylic acid and N-hydroxy benzotriazole (henceforth "HOBT") as a HOBT active ester body using dehydrating condensing agents, such as dicyclohexyl carbodiimide, can also be used.

In the (thio) ester group-containing structure, m ₃ in the general formula (4) or the general formula (5) is 1 ?, since the solubility in the alkali developer and the mechanical properties of the resin film obtained are good. It is preferable that it is an integer of 100, and 2? It is more preferable that it is an integer of 50, and it is 3? It is more preferable that it is an integer of 30. Moreover, said General formula (1), said about the structure represented by the said General formula (3) synthesize | combined with at least 1 sort (s) of carboxylic compound and polyvalent amino compound chosen from the group which consists of polyhydric carboxylic acid and its derivative (s). The ratio of the (thio) ester group-containing structure represented by the general formula (2), the general formula (4) or the general formula (5) is 0.05? In terms of the solubility in the alkaline developer and the mechanical properties of the resulting resin film. It is preferable that it is 0.80.

The photosensitive resin composition of this invention can be used also as a positive type or a negative type.

When the ratio of the above-mentioned (thio) ester group containing structure is made into a positive composition, it is 0.10? It is more preferable that it is 0.50, and 0.15? It is more preferable that it is 0.40, and when it is set as a negative composition, it is 0.20? It is preferable that it is 0.80, and 0.30? It is more preferable that it is 0.60. Moreover, from a heat resistant viewpoint, the hydroxy polyamide resin (A) containing an ester group is superior to the hydroxy polyamide resin (A) containing a thioester group.

Next, in the structure shown by the said General formula (3), it is a hydroxy polyamide structure which is a structure other than the (thio) ester group containing structure.

The hydroxy polyamide structure of _{X 1 (NH 2) 2 (} OH) n1 (COOR 2) the amino compound consisting of _n3 and _{Y 1 (COOH) 2 (OR} 1) n2 (COOR 3) carboxylic polyhydric consisting _n4 material It is formed by the condensation reaction of acids.

Polyhydric represented by the above general formula (3), a carboxylic acid, that is Y ₁ (COOH) ₂ (OR _{1) n2} (COOR _{3) n4} are carboxylic polyhydric represented by the general formulas (4) and the formula (5) acid Y ₂ (COOH) ₂ (OR ₄ ) _n5 (COOR ₅ ) _n6 Y ₂ in General Formula (4) or (5) may have the same meaning as Y ₁ in General Formula (3), including a preferable range, and preferably in the group consisting of organic groups described later. in that at least one organic group is selected, the general formula (3) formula to the value indicated by the in n ₂ (4) or general formula (5) is a value represented by n ₅ represent the same range, the formula (3) of the value represented by n ₄ and formula (4) or general formula (5) also applies to the value represented by n _6.

First, the "PBO precursor" is demonstrated.

As the specification, the portion other than the (thio) ester structure, wherein X ₁ in the structure represented by the following formula _{(3) (NH 2) 2} (OH) n1 (COOR 2) n3, Y 1 (COOH) 2 (OR 1 ) is defined as _n2 (COOR ₃₎ according to _{n4, n 1 = 2, n} 2 = 0, n 3 = 0 and n ₄ = 0 indicates that the general formula (3) in the case of "PBO precursor".

The PBO precursor is a hydroxypolyamide having a structure obtained by polycondensing a dicarboxylic acid having a structure of bis (aminophenol) and Y ₁ (COOH) ₂ having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ . It corresponds to resin. The two sets of amino groups and the hydroxyl groups of the bis (aminophenol) are each at ortho positions. Dihydroxydiamide (hydroxypolyamide resin) is about 250? It is ring-closed by heating at 400 degreeC, and it changes into PBO which is a heat resistant resin. X ₁ is preferably a tetravalent organic group having 2 or more and 30 or less carbon atoms in terms of good solubility in alkaline developing solution and heat resistance of the resulting resin film. Further, Y ₁ is preferably soluble and the resulting heat-resistant resin layer is preferably a divalent organic group in the point, having 30 or less carbon atoms that two or more in an alkali developing solution. m ₂ is 1? in that the solubility in an alkaline developer and the mechanical properties of the resulting resin film are good. Is an integer of 1000 and 2? It is more preferable that it is an integer of 200, and it is 2? It is more preferable that it is an integer of 100, and 3? Most preferably, it is an integer of 60.

Examples of the bis (aminophenol) having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-di Hydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-da Amino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2, 2-bis- (3-amino-4-hydroxy-5-methylphenyl) propane, 1,1-bis- (3-amino-4-hydroxyphenyl) -1-phenylethane, 3,3'-diamino -4,4'-dihydroxytetraphenylmethane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-amino-3-hydroxy Phenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-diamino-3 , 3'-dihydroxybenzophenone, 3,3'-diamino-4,4'- Hydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenylether, 3,3'-diamino-4,4'-dihydroxydiphenylether, 1,4- Amino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene, bis (3-amino- 4-hydroxyphenyl) sulfide etc. are mentioned. These bis (aminophenol) can be used individually or in mixture of 2 or more types.

Among these bis (aminophenol) s having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ , X ₁ is preferably the following:

[Formula 21]

Bis (aminophenol) which is an aromatic group selected from. The bis (aminophenol) may be any of an amino group in the meta position, a hydroxyl group in the para position, a hydroxyl group in the meta position, or a hydroxyl group in the meta position and an amino group in the para position. It is more preferable that a meta position is an amino group and a para position is a hydroxyl group from a solubility viewpoint with respect to.

Examples of the dicarboxylic acid having a Y ₁ (COOH) ₂ structure include dicarboxylic acids selected from the group consisting of an aromatic group, an aliphatic group, and an alicyclic structure, wherein Y ₁ is each selected from:

[Formula 22]

{Wherein A ₁ is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ — and a single bond; A divalent group, L ₁ is at least one group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, an amide group, a urea group, an imide group, and a urethane group, and k = 4, and a plurality of L ₁ May be the same or different.}

(23)

{N ₁₀ is 1? Is an integer of 12}

[Formula 24]

{In formula, L <_2> , L <_3> and L <_4> are respectively independently a hydrogen atom or a methyl group, and L <_5> is a hydrogen atom, a methyl group, or a hydroxyl group.}.

As a typical compound as a dicarboxylic acid which has the said tricyclodecane skeleton, bis (carboxy) tricyclo [5, 2, 1, 0 2, ⁶ ] decane is mentioned. Examples of preparation of the compound can be obtained according to the synthesis examples of international publication WO2009 / 081950.

In addition, as part or all of the dicarboxylic acid having the Y ₁ (COOH) ₂ structure, a derivative of 5-aminoisophthalic acid may be used. Specific compounds to be reacted with 5-aminoisophthalic acid to obtain the derivatives include 5-norbornene-2,3-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6 Tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic anhydride, 4-ethynyl-1,2-phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 1-cyclo Hexene-1,2-dicarboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydro phthalic anhydride, allylsuccinic anhydride, Isocyanate ethyl methacrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 3-cyclohexene-1-carboxylic acid chloride, 2-furancarboxylic acid chloride, crotonic acid chloride, cinnamic acid chloride, methacryl Acid chloride, acrylic acid chloride, Propionic acid chloride, tetratrol 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, chloroformic acid isobornyl Benzyl ester, chloroformic acid-p-biphenylisopropylbenzyl ester, 2-t-butyloxy Carbonyl-oxyimino-2-phenylacetonitrile, St-butyloxycarbonyl-4,6-dimethyl-thiopyrimidine, di-t-butyl-dicarbonate, N-ethoxycarbonylphthalimide, ethyl Dithiocarbonyl chloride, formic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, methanesulfonic acid chloride, acetyl chloride, trityl chloride, trimethylchlorosilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide , Bis (trimethylsilyl) trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane, trimethylsilyldiphenylurea, bis (trimethylsilyl) urea, phenyl isocyanate, isocyanate N-butyl ansulfate, n-octadecyl isocyanate, o-tolyl isocyanate, 1,2-phthalic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, glutaric anhydride.

Next, the "structure which has a PBO precursor" is demonstrated. Resin represented by the above general formula (3) is a gatneunde the portion derived from the raw material diamine, the raw material diamine, diethylene addition to hydroxy-diamine _{(X 1 (NH 2) 2} (OH) 2), X 2 , as needed (NH ₂₎ may be used in the diamine having the structure of _FIG. Here, X <_2> is synonymous including the preferable range with X <_1> in the said General formula (3).

Because of the structure shown by the general formula (3), the higher the proportion of the dihydroxy-diamide units increase the solubility in an alkaline aqueous solution used as a _{developer, [X 1 (NH 2)} 2 (OH) 2] The value of / [X ₁ (NH ₂ ) ₂ (OH) ₂ + X ₂ (NH ₂ )] is preferably 0.5 or more, more preferably 0.7 or more, and most preferably 0.8 or more.

Also referred to as X ₂ (NH ₂₎ by the structure of the _two compounds, "diamine having a PBO precursor structure in the molecule" diamine (hereinafter referred to as having an amide bond and the phenolic hydroxyl group in the ortho position to each other of the second set in the molecule You can also use.) For example, the following general formula (13) obtained by reacting bis (aminophenol) having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ with 2 molecules of nitrobenzoic acid to reduce it:

[Formula 25]

{Wherein, X ₃ represents a tetravalent organic group having at least two carbon atoms.}

The diamine shown by is mentioned.

X ₃ is X ₁ in the general formula (3) It is synonymous with including a preferable range.

As another method for obtaining a diamine having a PBO precursor structure in a molecule, dicarboxylic acid dichloride having a structure of Y ₃ (COCl) ₂ is reduced by reacting two molecules of nitroaminophenols, thereby reducing the general formula (14)

[Formula 26]

{Wherein Y ₃ is a divalent organic group having at least two carbon atoms.}

There is also a method of obtaining a diamine. Where Y ₃ Is the same meaning including the preferable range with Y <_1> in the said General formula (3).

A diamine having a structure of X ₂ (NH _{2) 2} there may be mentioned aromatic diamine, a silicon diamine.

Among these, as aromatic diamine, for example, m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl Ether, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3 ' -Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylketone , 4,4'-diaminodiphenylketone, 3,4'-diaminodiphenylketone, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (4-aminophenyl) hexa Fluoropropane, 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-diamino 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-amino Oxyphenyl) sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4 Hydrogen atoms of the aromatic nucleus of '-di- (3-aminophenoxy) diphenylsulfone and 4,4'-diaminobenzanilide, and these aromatic diamines are chlorine atom, fluorine atom, bromine atom, methyl group, methoxy group, The compound substituted by the at least 1 group or atom chosen from the group which consists of a cyano group and a phenyl group is mentioned.

To increase the adhesion to the substrate, a silicon diamine may be selected as part or all of the diamine having a structure of X ₂ (NH _{2) 2.} Examples of the silicone diamine include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane And 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane and the like.

Digital camera to the dicarboxylic acid having Y ₁ (COOH) ₂ structure, there may be mentioned the above-mentioned aromatic group or aliphatic group that is used in the PBO precursor dicarboxylic acid. Moreover, dicarboxylic acid which has an amide bond and phenolic hydroxyl group of two sets mutually ortho-position in a molecule | numerator can also be used. For example, bis (aminophenol) having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ or diaminophenol having a structure of X ₁ (NH ₂ ) ₂ (OH) has two molecules of trimellitic acid The following general formula (15) obtained by reacting a chloride and further reacting an acid anhydride with an alcohol:

[Formula 27]

{In formula, X ₅ Represents a trivalent or tetravalent organic group having at least two carbon atoms, and R ₁₃ represents 1? And a hydrocarbon group of 10, and n ₁₁ represents an integer of 1 or 2.} includes a structure having two sets of amide bonds and phenolic hydroxyl groups located at each other in the ortho position. X <_5> is synonymous including the preferable range with X <_1> in the said General formula (3).

The hydroxypolyamide resin (A) has the following general formula (16) from the viewpoint of lithography characteristics:

[Formula 28]

{In formula, X <_6> represents the tetravalent organic group which has at least 2 carbon atom, Z <_1> is at least 1 sort (s) of structure chosen from the group which consists of said general formula (9), and L <_6> , L <_7> and L <_8>. Each independently represents a hydrogen atom or a methyl group, L ₉ represents a hydrogen atom, a methyl group or a hydroxyl group, and m ₂ and m ₃ each independently represent 1? It is an integer of 1000.} It is preferable to include the structure shown by. X <_6> is synonymous including the preferable range with X <_1> in the said General formula (3).

The tricyclodecane moiety in the structure represented by the general formula (16) is represented by the following general formula (17):

[Formula 29]

It is preferable that at least 1 is chosen from the structural group shown by these.

Especially the tricyclodecane site | part is the following general formula (18) from the point that the mechanical property of the resin film obtained is favorable.

[Formula 30]

It is more preferable that is.

Moreover, a hydroxy polyamide resin (A) is a following general formula (19) from a viewpoint of a thermosystem property.

[Formula 31]

{Wherein, X ₆ represents a tetravalent organic group having at least two carbon atoms, and Y ₄ represents the following general formula (20):

[Formula 32]

(Wherein L ₁ is at least one group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, an amide group, a urea group, an imide group and a urethane group, and k = 4, and a plurality of L ₁ are May be the same or different.), Z ₁ is at least one kind of structure selected from the group consisting of the general formula (9), and m ₂ and m ₃ are each independently 1 ? An integer of 1000. Two or more Y <_4> may be same or different. It is preferable to include the structure shown by the following. Here, X <_6> has the same meaning as X <_1> in the said General formula (3).

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

Moreover, it is also preferable to use the hydroxy polyamide which has a repeating unit represented by General formula (3) mentioned above by sealing the terminal group with an organic group (henceforth a "sealing group"). For example, in the polycondensation of hydroxypolyamide resins, when the dicarboxylic acid component is used in an excess molar number compared to the sum of the bisaminophenol component and the diamine component, a compound having an amino group or a hydroxyl group as a sealing group is used. It is preferable to use. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, ethanol, propargyl alcohol, And nitrogen-containing cyclic compounds such as benzyl alcohol, hydroxyethyl methacrylate, hydroxyethyl acrylate, 2-aminobenzotriazole, benzothiadiazole and tetrazole.

On the contrary, in the case where the sum of the bisaminophenol component and the diamine component is used as an excess mole number compared to the dicarboxylic acid component, a compound having an acid anhydride, a carboxylic acid, an acid chloride, an isocyanate group or the like is used as the compound having a sealing group. It is preferable. Examples of the compound include benzoyl chloride, norbornenedicarboxylic acid anhydride, norbornenecarboxylic acid, 5-benzimidazole carboxylic acid, ethynylphthalic anhydride, glutaric anhydride, maleic anhydride and phthalic anhydride. And cyclohexanedicarboxylic acid anhydride, methylcyclohexanedicarboxylic acid anhydride, cyclohexenedicarboxylic acid anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, tosylic acid chloride and the like. . Moreover, it can also be set as an oxetane terminal by making it react with the compound containing an amino group and a hydroxyl group using trimellitic acid chloride.

Preferable end groups include nitrogen-containing cyclic compounds such as benzotriazole, tetrazole and 5-benzimidazole carboxylic acid, methylol group, alkoxymethyl group, oxetane group and the following general formula (21):

[Formula 33]

{Wherein, L ₁₀ is -CH ₂ -, -O-, or represents a -S-, and L ₁₁ is a hydrogen atom or a carbon atom 1? And at least one end group selected from the group consisting of end groups represented by. As a methylol group, the alkoxy methyl group, and an oxetane group, following General formula (22):

[Formula 34]

{In formula, R <_14> and R <_15> is a hydrogen atom or a carbon number of 1? It is a hydrocarbon group of 10, R <_16> is a hydrogen atom or C1-C atom? At least one monovalent organic group selected from the group consisting of 10 hydrocarbon groups, alkoxy groups, ester groups and urethane groups, n ₁₂ is 1? Is an integer of 5 and n ₁₃ is 0? An integer of 4, where n ₁₂ + n ₁₃ = 5, and in the case where a plurality of CH ₂ OR ₁₅ and R ₁₆ are present, R ₁₅ and R ₁₆ may be the same as or different from each other. It is preferable that it is a structure.

Polystyrene conversion weight average molecular weight by gel permeation chromatography (henceforth "GPC") of the hydroxy polyamide resin which has a structure represented by the said General formula (3) is 3,000? It is preferable that it is 70,000, and 6,000? It is more preferable that it is 50,000. 3,000 or more are preferable from a viewpoint of the physical property of a hardening relief pattern, and, as for a weight average molecular weight, 70,000 or less are preferable from a viewpoint of resolution. As a developing solvent of GPC, tetrahydrofuran (henceforth "THF") and N-methyl- 2-pyrrolidone (henceforth "NMP") are 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 organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko.

Mine Generator (B)

A photoacid generator (B) is a compound which generates an acid by actinic light irradiation, and as such a compound, for example, a compound having a halogen-containing compound, an onium salt and a naphthoquinone diazide structure (hereinafter referred to as "naphtho And quinonediazide compounds. "

By using a naphthoquinone diazide compound as a photo-acid generator (B), it can be set as the positive photosensitive resin composition. In addition, the hydroxy polyamide resin of this invention can also be made into negative type by a suitable combination of a photo-acid generator (B) and an additive.

Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound, and trichloromethyltriazines are preferable.

Specific examples of trichloromethyl-s-triazines include tris (2,4,6-trichloromethyl) -s-triazine and 2-phenyl-bis (4,6-trichloromethyl) -s-tri Azine, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-chlorophenyl) -bis (4,6-trichloromethyl) -s-tri Azine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methoxyphenyl) -bis (4,6-trichloromethyl) -s -Triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) bis (4,6-trichloromethyl-s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis (4,6- Trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3,4,5-trimeth Oxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s -Triazine, 2- (3-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methylthio-β-styryl) -bis ( 4,6-trichloromethyl) -s-triazine etc. are mentioned.

Examples of the onium salts include iodonium salts, sulfonium salts, phosphonium salts, ammonium salts, diazonium salts, and the like. Onium salts selected from the group consisting of diaryl iodonium salts, triarylsulfonium salts, and trialkylsulfonium salts are preferable. Do.

As a specific example of diallyl iodoniums, diphenyl iodonium tetrafluoroborate, diphenyl iodonium tetrafluoro phosphate, diphenyl iodonium tetrafluoro arsenate, diphenyl iodonium trifluoromethanesulfonate, Diphenyl iodonium trifluoroacetate, diphenyl iodonium-p-toluenesulfonate, 4-methoxyphenylphenyl iodonium tetrafluoroborate, 4-methoxyphenylphenyl iodonium hexafluorophosphonate, 4- Methoxyphenylphenyl iodonium hexafluoroarsenate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluoroacetate, 4-methoxyphenylphenyl iodonium p-toluenesulfonate, bis (4-ter-butylphenyl) iodoniumtetrafluoroborate, bis (4-ter-butylphenyl) iodonium hexafluoroarsenate, bis (4-ter-butylphenyl) iodine Nium trifluoromethanesulfonate, bis (4-ter- butylphenyl) iodonium trifluoro acetate, bis (4-ter- butylphenyl) iodonium-p-toluenesulfonate, etc. are mentioned.

Specific examples of the triarylsulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, Triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfoniumtetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenyl Sulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4 -Phenylthiophenyl Phenyltrimethoxysilane and the like can be mentioned fluoro-methane-sulfonate, 4-thiophenyl-diphenyl-trifluoroacetate, 4-thiophenyl-diphenyl -p- toluenesulfonate.

Among these compounds, trichloromethyl-S-triazines include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -S-triazine and 2- (4-chlorophenyl) -bis ( 4,6-trichloromethyl) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-methoxy-β- Styryl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -S-triazine and the like Examples of the ryl iodonium salts include diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, and 4-methoxyphenylphenyl iodonium tri. Examples of the fluoroacetates include triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, and 4-methoxyphenyldiphenyl. Sulfonium trifluoro Three lactate, there may be mentioned 4-thiophenyl-diphenyl-trifluoromethane sulfonate a carbonate, such as 4-thiophenyl-diphenyl-trifluoroacetate as desired.

In addition, the compound shown below can also be used.

(1) sulfone compounds

As a sulfone compound, the (beta) -keto sulfone compound, the (beta) -sulfonyl sulfone compound, and the (alpha)-diazo compound of these compounds are mentioned, for example, 4-trisfenacyl sulfone, mesityl phenacyl sulfone, Bis (phenacylsulfonyl) methane etc. are mentioned.

(2) sulfonic acid compounds

Examples of the sulfonic acid compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates, and the like, and preferred examples thereof include benzointosylate and pyrogallol tristrifluoro. Methanesulfonate, o-nitrobenzyltrifluoromethanesulfonate, o-nitrobenzyl p-toluenesulfonate, and the like.

(3) sulfonimide compounds

As specific examples of the sulfonimide compound, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsul Ponyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy ) Naphthyl imide, and the like.

(4) oxime ester compound

2- [2- (4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophen-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals, Inc., brand name "irga Cure PAG121 "), [2- (propylsulfonyloxyimino) -2,3-dihydrothiophen-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals, Inc., brand name" irga Cure PAG103 ") etc. are mentioned.

(5) diazomethane compounds

As a specific example of a diazomethane compound, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, etc. are mentioned, for example. have.

(6) diazoketone compounds

As a diazo ketone compound, a 1, 3- diketone 2- diazo compound, a diazo benzoquinone compound, a diazonaphthoquinone compound, etc. are mentioned, for example, The 1,2-naph of phenols is mentioned as a specific example. A toquinone diazide-4- sulfonic acid ester compound is mentioned.

When it is set as positive type photosensitive resin composition, the said (6) diazo ketone compound is preferable from a solvent solubility and storage stability viewpoint, and the compound which has a naphthoquinone diazide structure especially from a viewpoint of a sensitivity (hereinafter, Also called "naphthoquinone diazide compound."

Moreover, when it is set as a negative photosensitive resin composition, the said (4) oxime ester compound is especially preferable from a viewpoint of a sensitivity.

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

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

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

NQD cargo of the polyhydroxy compound represented by the following general formula (23)

[Formula 35]

Wherein X ₇ is a chemical formula

[Formula 36]

Represents at least one tetravalent group selected from organic groups represented by R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ each independently represent a monovalent organic group, l is 0 or 1, m ₅ , m ₆ , m ₇ and m ₈ are 0? Represents an integer of 3 and n ₁₄ , n ₁₅ , n ₁₆ And n ₁₇ Is 0? Is an integer of 2}

As a specific compound, Unexamined-Japanese-Patent No. 2001-092138? The compound described in Formula 28 is mentioned.

Among these, NQD products of the following polyhydroxy compounds are preferable in that they have high sensitivity and low precipitation in the positive photosensitive resin composition:

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

NQD cargo of the polyhydroxy compound represented by the following general formula (24)

[Formula 41]

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

[Formula 42]

At least one divalent group selected from the group represented by.

As a specific compound, Unexamined-Japanese-Patent No. 2003-131368? The compound described in Formula 28 is mentioned.

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

[Formula 43]

[Formula 44]

{Wherein, L ₁₂ is -CH ₂ -, -O-, or represents a -S-, and L ₁₃ is a hydrogen atom or a carbon atom 1? And a hydrocarbon group of 6}.

NQD cargo of the polyhydroxy compound represented by the following general formula (25)

[Formula 45]

{Wherein R ₂₁ , R ₂₂ and R ₂₃ Are each independently of the following general formula:

[Formula 46]

In the formula, each R ₂₄ independently represents a hydrogen atom or at least one monovalent organic group selected from an alkyl group and a cycloalkyl group, and m ₁₂ represents an integer of 0 to 2. And m ₉ , m ₁₀ and m ₁₁ are each independently 0? Is an integer of 2}.

As a specific compound, Unexamined-Japanese-Patent No. 2004-109849? NQD cargo of the polyhydroxy compound described in Formula 22 is mentioned.

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

[Formula 47]

[Formula 48]

NQD cargo of the polyhydroxy compound represented by the following general formula (26)

[Formula 49]

{Wherein R ₂₅ is a general formula of

[Formula 50]

(Wherein, R ₂₉ each independently represent a hydrogen atom, or an alkyl group and represents an organic group with at least one monovalent is selected from the group consisting of a cycloalkyl group, and m ₁₆ is 0,? Is an integer of 2.) Monovalent organic represented by Group and R ₂₆ , R ₂₇ and R ₂₈ Represents a hydrogen atom or at least one monovalent organic group selected from the group consisting of an alkyl group and a cycloalkyl group, and m ₁₃ , m ₁₄ and m ₁₅ represent 0? Is an integer of 2}.

As a specific compound, NQD cargo of the polyhydroxy compound described in Unexamined-Japanese-Patent No. 2005-008626, and [Formula 16] is mentioned.

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

[Formula 51]

[Formula 52]

Other structures include the following:

[Formula 53]

This is preferred.

As a naphthoquinone diazide sulfonyl group in NQD compound, both 5-naphthoquinone diazide sulfonyl group or 4-naphthoquinone diazide sulfonyl group is preferable.

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

In the photosensitive resin composition of this invention, the compounding quantity of a photo-acid generator (B) is 1-1 with respect to 100 mass parts of hydroxy polyamide resins (A). It is preferable that it is 50 mass parts, and it is 2? From a viewpoint of solubility to a solvent. 40 mass parts is more preferable, and from the viewpoint of sensitivity, 5? 25 mass parts is more preferable. The patterning property of resin is favorable that the compounding quantity of a photo-acid generator (B) is 1 mass part or more, On the other hand, when it is 50 mass parts or less, the tensile elongation of a film | membrane after hardening is favorable, and there is little development residue (scum) of an exposure part.

Compound (C) promoting solubility in aqueous alkali solution

It is preferable to mix | blend the compound (C) which promotes the solubility to aqueous alkali solution further from the viewpoint of improving the solubility to the alkali of an exposure part and making it highly sensitive to the photosensitive resin composition which concerns on this invention.

The compound (C) which promotes the solubility in aqueous alkali solution represents the compound containing the functional group soluble in aqueous alkali solution, ie, the compound containing at least 1 group chosen from the group which consists of a phenolic hydroxyl group, a carboxyl group, and a sulfonyl group.

As a compound containing a phenolic hydroxyl group (henceforth a "phenol compound"), the compound which has the compound which has superposed | polymerized the compound and the compound which has at least one phenol group is mentioned.

A compound having at least one phenol group having 6 to 6 carbon atoms; As the compound of 40, specifically, a linear phenol compound such as a ballast agent, paracumylphenol, bisphenol, resorcinol, MtrisPC, MtetraPC, etc., which is used in the photosensitive diazoquinone compound, Non-chain phenolic compounds (Honshu Chemical Co., Ltd. make: brand name), such as Honshu Chemical Co., Ltd. make, brand name), TrisP-HAP, TrisP-PHBA, and TrisP-PA, and hydrogen atom of the phenyl group of diphenylmethane 2? Hydrogen atom 1 of the compound which substituted five with the hydroxyl group, and the phenyl group of 2, 2- diphenyl propane; The compound etc. which substituted five by the hydroxyl group are mentioned. In addition, a ballast agent means the phenol compound used as a raw material for the photosensitive diazoquinone compound mentioned above whose one part of a phenolic hydrogen atom is a phenol compound naphthoquinone diazide sulfonic-acid esterified.

Among the compounds having at least one phenolic group, from the standpoint of promoting alkali dissolution, a phenol compound having two or more phenol groups is preferable, and resorcinol is more preferable from the viewpoint of suppressing the occurrence of residue. As resorcinol, resorcinol, 2-methyl resorcinol, 4-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, 4-ethyl resorcinol, 4-hexyl Resorcinol and the like.

As a polymer which superposed | polymerized the compound, a phenol resin, its derivative (s), polyhydroxy styrene, its derivative (s), etc. are mentioned.

As a phenol resin and its derivative, a novolak-type resin is mentioned specifically ,. As a novolak-type resin, what is widely used by the technical field of a resist can be used. This novolak-type resin can be obtained by, for example, reacting phenols with aldehydes or ketones in the presence of an acidic catalyst.

As the phenols, in addition to the above-mentioned compounds, for example, phenol, orthocresol, metacresol, paracresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol , 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-t -Butylphenol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 2-methoxy-5-methylphenol, 2-t-butyl-5-methylphenol, thymol, isothymol, etc. are mentioned. These can be used individually or in combination of 2 types or more, respectively.

Examples of the aldehydes include formaldehyde, formalin, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, and o-hydroxybenzaldehyde. m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butyl Benzaldehyde, terephthalaldehyde and the like. Acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone, etc. are mentioned as ketones. These can be used individually or in combination of 2 types or more, respectively.

Among these, novolak-type resin which used metacresol and paracresol together and condensed these and formaldehyde, formalin, or paraformaldehyde is especially preferable from a viewpoint of sensitivity controllability. The injection weight ratio of metacresol and paracresol is usually 20:80? 80: 20, preferably 50: 50? 70: 30.

The molecular weight is usually a weight average molecular weight of 1,000? 20,000, preferably 1,000? 15,000, more preferably 1,000? In the range of 10,000. The weight average molecular weight of the said resin can be controlled in a desired range by adjusting synthetic | combination conditions. In addition, the narrower the molecular weight distribution, the higher the optical sensitivity, so that the resin obtained by the synthesis is solid-liquid extracted with an organic solvent having a suitable solubility, or the resin is dissolved in a good solvent and added dropwise into a poor solvent. Alternatively, the poor solvent may be added dropwise to extract solid-liquid or liquid-liquid to control the molecular weight distribution. As a specific example of this phenol resin, EP4000B (Asahi organic materials industry: brand name), EP4020G (Asahi organic materials industry: brand name), EP4050G (Asahi organic materials industry: brand name), EP4080G (Asahi organic materials industry: brand name), etc. are mentioned.

As specific examples of polyhydroxystyrene or derivatives thereof, for example, poly-o-hydroxystyrene, poly-m-hydroxystyrene, poly-p-hydroxystyrene, poly-α-methyl-o-hydroxy Styrene, poly-α-methyl-m-hydroxystyrene, poly-α-methyl-p-hydroxystyrene, partial acetylides thereof, silylates and the like. The weight average molecular weight of these polyhydroxy styrene or its derivative (s) 3,000? 100,000, particularly preferably 4,000? It is in the range of 20,000.

The compounding quantity at the time of mix | blending a phenol compound is 1? With respect to 100 mass parts of hydroxypolyamide resins (A). 100 mass parts is preferable, and it is 1? 70 mass parts is preferable. If the said compounding quantity is less than 70 mass parts, the heat resistance of the film | membrane after thermosetting will be favorable. These can be used individually or in combination of 2 types or more, respectively.

A compound containing a carboxyl group (hereinafter also referred to as a "carboxylic acid compound") has at least one carboxyl group in the molecule, and has 6 to 6 carbon atoms. As a 30 phosphorus compound, a monocarboxylic acid compound, a dicarboxylic acid compound, a tricarboxylic acid compound, etc. are mentioned.

Moreover, it is preferable that a carboxylic acid compound is a monocarboxylic acid compound from a viewpoint of adhesiveness, and it is preferable that it is a compound which has a branched structure, a ring structure, or an unsaturated double bond from a viewpoint of a sensitivity. Specifically, 2-nonenoic acid, isononanoic acid, 2-decenoic acid, 10-undecenoic acid, 3-cyclohexene-1-carboxylic acid compound, 4- (3-butenyloxy) benzoic acid, m-anisic acid , 4-biphenylacetic acid, 2-phenylbutyric acid, 4-propylbenzoic acid, diphenylacetic acid, m-toluic acid, m-tolylacetic acid, o-anisic acid, o-toluic acid, o-tolylacetic acid, p-anisic acid , p-toluic acid, p-tolylacetic acid, 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxyman Delic acid, 2-methoxy-2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, acetylmandelic acid, α-methoxyphenylacetic acid, and the like.

Since the effect is expressed by remaining in the film | membrane at the time of prebaking, the carboxylic acid compound of 8 or more carbon atoms is preferable from a viewpoint of remainder to a prebaking film, From a viewpoint of solubility to a solvent The number of carbon atoms is preferably 30 or less, from the viewpoint of precipitation after elapse of time, the number of carbon atoms is 20 or less, more preferably 15 or less. Moreover, as a means for efficiently remaining a carboxylic acid compound in a film | membrane, it is preferable that there exists a functional group selected from a hydroxyl group, an ether group, and an ester group in the (alpha) position of a carboxyl group, Especially, an ether group and an ester group are especially a board | substrate. It is preferable from the viewpoint of adhesiveness, and from the viewpoint of sensitivity, the crosslinking group such as a methylol group or an alkoxymethyl group is used to prevent the carboxylic acid compound remaining after the prebaking from evaporating the resin composition when the cured resin film is obtained. It is especially preferable.

The said carboxylic acid compound may be used independently and may be used in mixture of 2 or more types.

The compounding quantity at the time of mix | blending the said carboxylic acid compound is 1? With respect to 100 mass parts of hydroxypolyamide resin (A). 100 mass parts is preferable, and it is 1? 40 mass parts is more preferable, and from the viewpoint of sensitivity, 5? 20 mass parts is more preferable.

When the compounding quantity of a carboxylic acid compound is 1 mass part or more, the image development residue of an exposed part will become small, and adhesiveness of the film | membrane formed using the photosensitive resin composition and a silicon substrate is favorable, and if the said compounding quantity is 40 mass parts or less, after hardening The tensile elongation of the membrane is good.

A compound containing a sulfonyl group (hereinafter also referred to as a "sulfonic acid compound") means that the number of carbon atoms having at least one sulfonyl group in the molecule is 1? 20 phosphorus compound. Specifically, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, p-xylene-2-sulfonic acid, mesitylenesulfonic acid, 2-naphthalenesulfonic acid, pyridine-2-sulfonic acid, pyridine-3-sulfonic acid, (± ) -10-camphorsulfonic acid, and the like.

The sulfonic acid compounds may be used alone or in combination of two or more thereof.

The compounding quantity at the time of mix | blending the said sulfonic acid compound is 0.1? With respect to 100 mass parts of hydroxypolyamide resin (A). 15 mass parts is preferable, and from a viewpoint of adhesiveness, it is 0.5? 10 mass parts is more preferable, and it is 1? From the viewpoint of sensitivity. 5 mass parts is more preferable.

When the compounding amount of the sulfonic acid compound is 1 part by mass or more, the developing residue of the exposed part decreases, and the adhesion between the film formed using the photosensitive resin composition and the silicon substrate is good, while when the compounding amount is 15 parts by mass or less, the tension of the film after curing Elongation is good.

Among the compounds having these functional groups, phenol compounds and carboxylic acid compounds may be mentioned as preferred compounds for achieving good lithography performance and appropriate alkali solubility for 2.38 mass% TMAH.

Compound (D) causing crosslinking reaction by heat

In the photosensitive resin composition which concerns on this invention, since the residual film rate at the time of hardening after performing the heat processing (Hereinafter, this process is called "cure") is performed for the relief pattern obtained by developing, it is possible to make an initial film thickness thin. It is preferable to further mix | blend the compound (D) which produces a crosslinking reaction by heat from a viewpoint of expressing better lithographic performance.

Compound (D) which causes crosslinking reaction by heat The compound which causes crosslinking reaction with hydroxypolyamide resin (A) by heat is used. Here, as the temperature causing the crosslinking reaction, 150? 350 ° C. is preferred. Crosslinking reaction occurs at the time of heat processing after pattern formation by image development.

As a specific example of the compound (D) which causes a crosslinking reaction by heat, the compound which has a structure represented by an epoxy compound, an oxetane compound, a melamine compound, and an alkenyl compound, and following General formula (6), following General formula (7) Although the compound which has a structure represented by these, and the compound which has a structure represented by following General formula (8) are mentioned, It is not limited to these.

Here, an alkenyl compound shows the compound containing unsaturated double bond groups, such as a (meth) acrylate group, an allyl group, and a vinyl group.

Specific examples of the epoxy compound include bisphenol A type epoxy resins, cresol novolac type epoxy resins, phenol novolac type epoxy resins, glycidylamine type epoxy resins, polysulfide type epoxy resins, and the like. It doesn't work.

An oxetane compound is a compound which has a 4-membered cyclic ether structure, and is capable of cationic ring-opening polymerization reaction or addition reaction with carboxylic acid, thiol, and phenol. Specific examples of the oxetane compound include 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis [1-ethyl (3-oxetanyl)] methyl ether, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4'-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis ( 3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenoate, trimethylol Propane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritoltetrakis (3-ethyl-3-oxetanylmethyl) ether, poly [[3-[(3-ethyl-3-oxeta Yl) methoxy] propyl] silsesquioxane] derivatives, oxetanyl silicate, phenol novolak type oxetane, 1,3-bis [(3-ethyloxetan-3-yl) methoxy] benzene, OXT121 ( Toa synthesis: brand name), OXT221 (Toa synthesis: brand name), etc. are mentioned, It is not limited to these.

From the viewpoint of heat resistance, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4'-bis (3-ethyl-3-oxetanylmethoxy) biphenyl , OXT121 (Toa synthesis: brand name) is preferable.

Specific examples of the melamine compound include trimethylolmelamine, hexamethylolmelamine, trimethoxymethylmelamine, hexamethoxymethylmelamine and the like. From the viewpoint of storage stability, trimethoxymethylmelamine and hexamethoxymethylmelamine This is preferred.

Specific examples of the allyl compound include allyl alcohol, allyl anisole, benzoic acid allyl ester, cinnamic acid allyl ester, N-aryloxyphthalimide, allyl phenol, allyl phenyl sulfone, allyl urea, diallyl phthalate and diallyl isophthalic acid. , Diallyl terephthalic acid, diallyl maleic acid, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl, cyanuric acid triallyl, triallylamine, 1,3,5-benzenetricarboxylic acid triallyl, Trimellitic acid triallyl (manufactured by Wako Junyaku Co., Ltd., TRIAM705), pyromellitic acid triallyl (manufactured by Wako Junyaku Co., Ltd., TRIAM805), triallyl oxydiphthalate, triallyl phosphate, triallyl phosphite, triallyl citrate It may be, but is not limited to these. From the viewpoint of sensitivity, trimellitic acid triallyl (manufactured by Wako Junyaku Co., Ltd., TRIAM705) and pyromellitic acid triallyl (manufactured by Wako Junyaku Co., Ltd., TRIAM805) are preferable.

The (meth) acrylate compound refers to a compound selected from the group consisting of acrylic acid esters, methacrylic acid esters, acrylamides and methacrylamides.

As a specific example of a preferable thing, NK-ester series, M-20G, M-40G, M-90G, M-230G, CB-1, SA, S, AMP-10G, AMP-20G, the product made by Shin-Nakamura Chemical Industries, Ltd., AMP-60G, AM-90G, A-SA, LA, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, HD, NPG, 9PG, 701, BPE-100, BPE-200, BPE-500, BPE-1300, A-200, A-400, A-600, A-HD, A-NPG, APG-200, APG-400, APG-700, A-BPE-4, 701A, TMPT, A-TMPT, A-TMM-3, A-TMM-3L, A-TMMT and 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, 1,3-bis (acryloyloxy) Although 2-propanol etc. are mentioned, It is not limited to these. It is preferable that a (meth) acrylate compound is 9 or more carbon atoms, and 30 or less are preferable from a viewpoint of the solubility to a solvent.

Moreover, it is preferable from a viewpoint of alkali solubility that a (meth) acrylate compound contains polar groups, such as a hydroxyl group, a carbonyl group, an amino group, and a thiol group, and from a viewpoint of adhesiveness, it is preferable that a polar group is a hydroxyl group. . Specific examples of the compound include NK-701, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, 1,3-bis (acryloyloxy) -2-propanol, and the like. Can be. In addition, in this specification, a (meth) acrylate refers to both an acrylate and a methacrylate.

The following general formula (6):

[Formula 54]

{In formula, R <_6> is a hydrogen atom or the monovalent group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and an isopropyl group, and R <_7> Is a hydrogen atom, a hydroxyl group, carbon number 1? At least one monovalent organic group selected from the group consisting of 10 alkyl groups, alkoxy groups, ester groups and urethane groups, n ₇ is 1? Is an integer of 5 and n ₈ is 0? Is an integer of 4, where n ₇ + n ₈ = 5 and m ₄ is 1? Is an integer of 4 and Z ₄ is CH ₂ OR ₆ when m ₄ = 1 Or R ₇ And m ₄ = 2? When 4, single bond or 2? Is a tetravalent organic group, in which, CH ₂ OR ₆ and R ₇ in this case the plurality present, R ₆ and R ₇ is a compound having a structure represented by be the same or different.} Are to each other, methylol compounds, Alkoxymethyl compound is mentioned.

 As a specific example of the compound represented by General formula (6), it is following General formula (27) from a viewpoint of a sensitivity:

(55)

And the following general formula (28)

(56)

The compound selected from the group which consists of these is more preferable.

General formula (7)

(57)

{In formula, R <_8> and R <_9> is respectively independently a hydrogen atom or a carbon number of 1? A compound having a structure represented by a hydrocarbon group of ₁₀ and R ₁₀ CO- (wherein R ₁₀ is a hydrocarbon group having 1 to ₁₀ carbon atoms) is represented by. Ole compound and an N-alkoxy methyl compound are mentioned.

Specifically, the compound represented by General formula (7) has the following general formula (29) from a viewpoint of a sensitivity:

(58)

The compound selected from the group which consists of these is more preferable.

The following general formula (8):

[Chemical Formula 59]

{Wherein, D ₁ is the number of carbon atoms 1? 6 is a functional group selected from the group consisting of an alkyl group, an alkenyl group, and a crosslinkable organic group, M ₁ is a group selected from the group consisting of -CH _2- , -O-, and -S-, and Z ₅ is 2 Is an organic group, and n ₉ is 0? It is an integer of 4, and when there are two or more D <_1> , some D <_1> may be same or different.} As a compound which has a structure shown by these, a bisallynalideimide compound, a bisnorbornene imide compound, etc. are mentioned. Can be.

 The compound represented by General formula (8) specifically has the following General formula (30) from a viewpoint of a sensitivity:

(60)

The compound selected from the group which consists of this is more preferable.

The compound (D) which causes a crosslinking reaction by the above heat may be used alone or in combination of two or more thereof.

The compounding quantity at the time of mix | blending the compound (D) which causes a crosslinking reaction by the said heat is 1? With respect to 100 mass parts of hydroxypolyamide resin (A). 50 mass parts is preferable, and 2? 30 mass parts is more preferable, and 4? 20 mass parts is more preferable. When the compounding quantity of this compound is 1 mass part or more, the cured shape at the time of hardening becomes favorable, and when it is 50 mass parts or less, the tensile elongation of the film | membrane after hardening is favorable, and shows favorable adhesiveness and lithographic performance.

Compound generating acid by heat (E)

It is preferable to further mix | blend the compound (E) which generate | occur | produces an acid by heat from the viewpoint of expressing better adhesiveness with a board | substrate after curing to the photosensitive resin composition which concerns on this invention.

The compound (E) which generates an acid by heat is a compound which promotes the reaction of the compound (D) which causes a crosslinking reaction by the heat, and the acid is generated at 150? 350 ° C. is preferred.

Specific compounds include ethyl acetate, methyl acetate, t-butyl acetate, t-butyl acetoacetate, t-butyl acrylate, allyl chloroacetate, chloroacetate n-butyl, t-butyl chloroacetate, ethyl chloroacetate, methyl chloroacetate, Chloroacetic acid benzyl, isopropyl chloroacetate, chloroacetic acid 2-methoxyethyl, methyl dichloroacetic acid, methyl trichloroacetic acid, trichloroacetic acid, trichloroacetic acid 2-ethoxyethyl, cyanoacetic acid t-butyl, methacrylic acid t-butyl, ethyl trifluoroacetic acid, methyl trifluoroacetic acid, phenyl trifluoroacetic acid, vinyl trifluoroacetic acid, isopropyl trifluoroacetic acid, allyl trifluoroacetic acid, ethyl benzoate, methyl benzoate, benzoic acid t- Butyl, methyl 2-chlorobenzoate, ethyl 2-chlorobenzoate, ethyl 4-chlorobenzoate, 2,5-dichlorobenzo Ethyl acid, methyl 2,4-dichlorobenzoate, ethyl p-fluorobenzoate, methyl p-fluorobenzoate, t-butyl pentachlorophenylcarboxylic acid, methyl pentafluoropropionate, ethyl pentafluoropropionate, crotonic acid t -Carboxylic acid esters, such as butyl, Cyclic carboxylic acid esters, such as a phenolphthalein and thymolphthalein, Methanesulfonic acid ethyl, Methanesulfonic acid methyl, Methanesulfonic acid 2-methoxyethyl, Methanesulfonic acid 2-isopropoxyethyl, p-toluenesulfonic acid phenyl, p-toluenesulfonic acid ethyl, p-toluenesulfonic acid methyl, p-toluenesulfonic acid 2-phenylethyl, p-toluenesulfonic acid n-propyl, p-toluenesulfonic acid n-butyl, p-toluenesulfonic acid t-butyl , p-toluenesulfonic acid n-hexyl, p-toluenesulfonic acid n-heptyl, p-toluenesulfonic acid n-octyl, p-toluenesulfonic acid 2-methoxyethyl, p-toluenesulfonic acid propargyl, p-toluenesulfonic acid 3-buty Neyl, ethyl trifluoromethanesulfonic acid, n-butyl trifluoromethanesulfonic acid, Sulfonic acid esters such as ethyl perfluorobutane sulfonate, methyl perfluorobutane sulfonate and ethyl perfluorooctane sulfonate, 1,4-butanesultone, 2,4-butanesultone, 1,3-propanesultone, phenol red, Cyclic sulfonic acid esters such as bromocresol green and bromocresol purple, 2-sulfobenzoic anhydride, p-toluenesulfonic anhydride, phthalic anhydride and the like.

Among these acid derivative compounds, ethyl methanesulfonic acid, methyl methanesulfonic acid, 2-methoxyethyl methanesulfonic acid, 2-isopropoxyethyl methanesulfonic acid, phenyl p-toluenesulfonic acid, ethyl p-toluenesulfonic acid, and p-toluenesulfonic acid Methyl, p-toluenesulfonic acid 2-methoxyethyl, ethyl trifluoromethanesulfonic acid, n-butyl trifluoromethanesulfonic acid, ethyl perfluorobutanesulfonic acid, methyl perfluorobutanesulfonic acid, methyl perfluorooctane sulfonate, 1 Sulfonic acid esters such as, 4-butanesultone and 2,4-butanesultone, 2-sulfobenzoic anhydride and p-toluenesulfonic anhydride.

Moreover, from a viewpoint of adhesiveness with a board | substrate, more preferable compounds are ethyl methanesulfonic acid, methyl methanesulfonic acid, 2-methoxyethyl methanesulfonic acid, ethyl p-toluenesulfonic acid, methyl p-toluenesulfonic acid, and p-toluenesulfonic acid 2-meth Oxyethyl, ethyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, 1,4-butanesultone, 2,4-butanesultone, 2-sulfobenzoic anhydride, p-toluenesulfonic anhydride and the like. Moreover, these compounds may be used independently and may be used in mixture of 2 or more.

The compounding quantity at the time of mix | blending the compound (E) which generate | occur | produces an acid by the said heat is 0.1? With respect to 100 mass parts of hydroxypolyamide resin (A). 30 mass parts is preferable and 0.5? 10 mass parts is more preferable, and 1? It is more preferable that it is 5 mass parts. If the addition amount is 0.1 parts by mass or more, there is an effect of maintaining the pattern after thermal curing. On the other hand, if the addition amount is 30 parts by mass or less, there is no adverse effect on the lyso performance and the stability of the composition is good.

Organic Solvents (F)

In the present invention, it is preferable to dissolve the above-described various components in an organic solvent (F) to form a varnish and use it as a solution of the photosensitive resin composition. As such an organic solvent (F), N-methyl- 2-pyrrolidone, (gamma) -butyrolactone (henceforth "GBL"), cyclopentanone, cyclohexanone, isophorone, N, N- Dimethylacetamide (hereinafter also referred to as "DMAc"), dimethylimidazolinone, tetramethylurea, dimethyl sulfoxide, diethylene glycol dimethyl ether (hereinafter also referred to as "DMDG"), diethylene glycol diethyl ether , Diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butyl Lenglycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, etc. can be used individually or in mixture.

Of these solvents, non-amide solvents are preferred because they have little effect on photoresist and the like. As a more preferable example, (gamma) -butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofurfuryl alcohol, etc. are mentioned. These organic solvents may be used alone or in combination of two or more thereof.

The compounding quantity at the time of mix | blending an organic solvent (F) becomes like this. Preferably it is 100? With respect to 100 mass parts of hydroxypolyamide resin (A). It is 2,000 mass parts, The viscosity can be controlled by changing the addition amount of an organic solvent, More preferably, it is 100? 1,000 parts by mass. By adjusting the addition amount of an organic solvent, it becomes a viscosity suitable for an application | coating device and application | coating thickness, and manufacture of a hardening relief pattern can be made easy.

Other additives (G)

The photosensitive resin composition which concerns on this invention contains alcohol, a dye, a fragrance | flavor, surfactant for improving the in-plane uniformity of a coating film, adhesive adjuvant for improving adhesiveness with a silicon substrate or a copper substrate, a composition solution at the time of necessity. In order to improve the stability of the viscosity and light sensitivity, a polymerization inhibitor or the like may be added.

In more detail, the alcohol has 4 to 4 carbon atoms. It is preferable that it is 14, specifically, cyclopropyl carbinol, 2-cyclohexen-1-ol, cyclohexane methanol, 4-methyl-1- cyclohexane methanol, 3, 4- dimethyl cyclohexanol, 4-ethylcyclo Hexanol, 4-t-butycyclocyclohexanol, cyclohexaneethanol, 3-cyclohexyl-1-propanol, 1-cyclohexyl-1-pentanol, 3,3,5-trimethylcyclohexanol, norbornane 2-methanol, cyclooctanol, 2,3,4-trimethyl-3-pentanol, 2,4-hexadien-1-ol, cis-2-hexen-1-ol, trans-2-hepten-1 -Ol, cis-4-hepten-1-ol, cis-3-octen-1-ol, 4-ethyl-1-octin-3-ol, 2,7-octadienol, 3,6-dimethyl-1 -Heptin-3-ol, 3-ethyl-2-methyl-3-pentanol, 2-ethyl-1-hexanol, 2,3-dimethyl-2-hexanol, 2,5-dimethyl-2-hexanol , trans, cis-2,6-nonadien-1-ol, 1-nonen-3-ol, cis-2-butene-1,4-diol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,5-hexadiene-3,4-diol, 2,5-dimethyl-3-hexine-2,5-diol, 2,4,7,9 Tetramethyl-5-de -4,7-diol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanediol, trans-p-mentan-3,8-diol, 2,4-dime Oxybenzyl alcohol, butyroin and the like.

Among these, 2,3,4-trimethyl-3-pentanol, 2,4-hexadien-1-ol, cis-2-hexen-1-ol, trans-2-hepten-1-ol, cis-4 -Hepten-1-ol, cis-3-octen-1-ol, trans, cis-2,6-nonadien-1-ol, cis-2-butene-1,4-diol, 1,5-hexadiene A hydroxyl group-containing compound having an unsaturated bond or a branched structure, such as -3,4-diol, is preferable, and monoalcohol is preferable to diol from the viewpoint of adhesion to the substrate, and in particular, 2,3,4-trimethyl-3 Particular preference is given to -pentanol, 3-ethyl-2-methyl-3-pentanol, glycerol-α, α'-diallylether.

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

The compounding quantity at the time of mix | blending the said alcohol is 0.01 to 100 mass parts of hydroxypolyamide resin (A). 70 mass parts is preferable and 0.1? 50 mass parts is more preferable, and 1? 40 mass parts is more preferable, and 5? 25 is particularly preferred. If the compounding quantity of a hydroxyl group containing compound is 0.01 mass part or more, the image development residue of an exposed part will become small, and if it is 70 mass parts or less, the tensile elongation of the film after hardening will be favorable.

As dye, methyl violet, crystal violet, malachite green, etc. are mentioned, for example. The compounding quantity at the time of mix | blending dye is 0.1? With respect to 100 mass parts of hydroxypolyamide resin (A). 10 mass parts is preferable. If the addition amount is 10 parts by mass or less, the heat resistance of the film after thermosetting is good.

A terpene compound is mentioned as a fragrance | flavor, A monoterpene compound and a sesquiterpene compound are preferable from a solubility to a solvent.

Specifically, linalool, isopitol, dihydrolinalool, linalyl acetate, linalool oxide, geranilinolol, rabendulol, tetrahydrolabendulol, rabendulol acetate, nerol, nerrol acetate, gerani All, citral, geranyl acetate, geranyl acetone, geranic acid, citral dimethyl acetal, citronellol, citronellal, hydroxycitronellal, dimethyloctanal, citronellic acid, citronelyl acetate, tagetone , Artemisia ketone, pulleol, isofulegol, menthol, menthol acetate, isomenthol, neomenthol, mentanol, mentantriol, mentantetraol, carbomenthol, menthoxyacetic acid, peryl alcohol, perylaldehyde, Caberols, Piperitol, Terpen-4-ol, Terpineol, Terpineol, Dihydroterpineol, Sobreol, Timol, Borneol, Boryl Acetate, Isobornaneol, Isobornyl Acetate, Cineol , Pinol, pinoccarveol, Myrtenol, Myrtenal, Verbenol, Pinocampolol, Camphorsulfonic acid, Nerolidol, Terpinene, Ionone, Pinene, Campen, Campolenaldehyde, Camphoronic acid, Isocamporonic acid, Camphoric acid, Avieteic acid, Glyciletin And acid. These terpene compounds may be used independently or may be used in mixture of 2 or more.

The compounding quantity at the time of mix | blending a fragrance | flavor is 0.1 to 100 mass parts of hydroxy polyamide resin (A). 70 mass parts is preferable, and 1? 50 mass parts is more preferable. If the addition amount is 70 parts by mass or less, the heat resistance of the film after thermal curing is good.

As surfactant, nonionic surfactant which consists of polyglycols, such as polypropylene glycol and polyoxyethylene lauryl ether, and derivatives thereof is mentioned. Moreover, fluorine-type surfactant, such as Florade (made by Sumitomo 3M company: brand name), Megapak (made by Dainippon Ink Chemical Co., Ltd. brand name), and Lumipron (made by Asahi Glass Company: brand name), are mentioned. Moreover, organic siloxane surfactant, such as KP341 (made by Shin-Etsu Chemical Co., Ltd.), DBE (made by Chisso Co., Ltd .: brand name), and granol (made by Kyoeisha Chemical Co., Ltd .: brand name), is mentioned. By the addition of the surfactant, it is possible to make the cratering of the coating film at the wafer edge at the time of coating more difficult to occur.

The compounding quantity at the time of mix | blending surfactant is 0 to 100 mass parts of hydroxypolyamide resins (A). 10 mass parts is preferable, and 0.01? 1 mass part is more preferable. If the addition amount is within 10 parts by mass, the heat resistance of the film after thermal curing is good.

As an adhesion | attachment adjuvant which improves adhesiveness with a silicon substrate or a copper substrate, Alkyl imidazoline, polyhydroxy styrene, polyvinyl methyl ether, t-butyl novolak, an epoxy polymer, an organosilicon compound, a triazole, tetrazole, Heterocyclic structure compounds, such as oxazole, thiazole, and imidazole, are mentioned.

An organosilicon compound is a compound containing one or more functional alkoxyl groups, and a silanol group, and becomes an adhesion | attachment adjuvant for improving adhesiveness with a silicon wafer. The number of carbon atoms of the organosilicon compound is 4? From the viewpoint of solubility to a solvent. It is preferable that it is 30, and 4? It is more preferable that it is 18.

Specific examples of the compound include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM803, manufactured by Chisso Corporation, trade name: Cyra Ace S810), and 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd. make: brand name LS1375, Azmax Co., Ltd. make: brand name SIM6474.0), mercaptomethyltrimethoxysilane (Azmax Co., Ltd. make: SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Inc .: trade name SIM6473.0), 3-mercaptopropyl diethoxymethoxysilane, 3-mercaptopropyl ethoxydimethoxysilane, 3-mer Captopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3- Lecaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxy Silane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercapto Butyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, azmax Co., Ltd. make: brand name SIU9055.0), N- (3-trimethoxysilylpropyl) urea (Azmax Co., Ltd. make: brand name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- ( 3-ethoxydimethoxysilylpropyl) urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea, N- (3-methoxydipro Foxysilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3 -Tripropoxysilylethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea , N- (3-trimethoxysilylbutyl) urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyl Trimethoxysilane (manufactured by Azmax Co., Ltd .: brand name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Inc .: brand name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.): product name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0599.2), 2- (trimethoxysilylethyl) pyridine (manufactured by Azmax Corporation: trade name SIT8396.0), 2- (trier Methoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, (3-triethoxysilylpropyl) -t-butylcarbamate, (3-glycid Doxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, Tetra-t-butoxysilane, tetrakis (methoxyethoxysilane), tetrakis (methoxy-n-propoxysilane), tetrakis (ethoxyethoxysilane), tetrakis (methoxyethoxyethoxy Silane), bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, bis ( Liethoxysilyl) ethylene, bis (triethoxysilyl) octane, bis (triethoxysilyl) octadiene, bis [3- (triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl ] Tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminooxytriethoxysilane, bis (pentadionate) titanium-O, O'-bis (oxyethyl) -aminopropyltri Ethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butyldiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilane Diol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenyl Silanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylfe Silanol, ethyl isopropylphenyl silanol, n-butyl ethyl phenyl silanol, isobutyl ethyl phenyl silanol, tert-butyl ethyl phenyl silanol, methyl diphenyl silanol, ethyl diphenyl silanol, n-propyl diphenyl Although silanol, isopropyl diphenyl silanol, n-butyl diphenyl silanol, isobutyl diphenyl silanol, tert- butyl diphenyl silanol, triphenyl silanol, etc. are mentioned, It is not limited to these. These may be used alone or in combination of two or more.

As an organosilicon compound, it is the following general formula (31) from a viewpoint of storage stability among the organosilicon compounds mentioned above:

(61)

{Wherein Z ₆ represents 1? It is the aromatic ring or heterocyclic structure which may be substituted of 14, and R <_30> is a C1-C atom. It is a hydrocarbon group of 20, and R <_31> is a hydrogen atom or C1-C atom? 5 is a hydrocarbon group, n ₁₈ is 1? Is an integer of 3 and n ₁₉ is 0? Is an integer of 2 and n ₂₀ is 1? Is an integer of 3, wherein n ₂₂ + n ₂₃ + n ₂₄ = 4}, or the following general formula (32):

[Formula 62]

It is preferable that it is an organosilicon compound shown by.

The organosilicon compound represented by the general formula (31) has the following general formula (33) in terms of heat resistance:

(63)

{In formula, R <_32> and R <_33> may represent a hydrogen atom or a carbon number of 1? A hydrocarbon group of 5, m ₁₇ = 5, n ₂₁ and n ₂₂ Is 1? 3 is an integer from, here, an n ₂₁ + n ₂₂ = 4. It is more preferred that the compound represented by}.

Specific examples of these compounds include phenylsilane triol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, Triphenyl silanol etc. are mentioned.

The organosilicon compounds may be used alone or in combination of two or more thereof. The compounding quantity at the time of mix | blending an organosilicon compound is 1? With respect to 100 mass parts of hydroxypolyamide resins (A). 40 parts by mass and 2? 30 mass parts is preferable, and 4? 20 mass parts is more preferable. If the compounding quantity of the compound is 1 part by mass or more, there is no developing residue of the exposed part, and the adhesion with the silicon substrate is good, while if it is 40 parts by mass or less, the tensile elongation of the film after curing is good, showing good adhesion and lithographic performance.

As a specific compound of the heterocyclic structure compound, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 1,3-dimethyl-5-pyrazolone, 3,5-dimethylpyrazole, 5,5-dimethyl Hydantoin, 3-methyl-5-pyrazolone, 3-methyl-1-phenyl-5-pyrazolone, 2-methylimidazole, 1,10-phenanthroline, phenothiazine, phenoxazine, phenoxatin, Mercaptobenzothiazole, mercaptobenzoxazole, methylthiobenzothiazole, dibenzothiazyldisulfide, methylthiobenzimidazole, benzimidazole, phenylmercaptothiazoline, mercaptophenyltetrazole and mercaptomethyltetra Sol and the like. Moreover, as an example of benzotriazoles, following General formula (34):

&Lt; EMI ID =

{In formula, Z <_7> is a hydrogen atom or a carbon number of 1? It is at least 1 group chosen from the group which consists of a hydrocarbon group of 5, and a carboxyl group, Z <_8> is a hydrogen atom, or a hydroxyl group, C1-C? It is at least 1 group chosen from the group which consists of a hydrocarbon group of 5, and an aminoalkyl group.} Is mentioned.

Among the heterocyclic-containing compounds, 5-mercapto-1-phenyltetrazole, 1,2,3-benzotriazole, benzothiazole, benzoxazole, and benzimidazole from the viewpoint of sensitivity on a copper substrate. And 2-mercaptobenzoxazole are more preferable.

These heterocyclic compounds may be used alone or in combination of two or more thereof.

The compounding quantity at the time of mix | blending a heterocyclic containing compound is 0.1? With respect to 100 mass parts of hydroxypolyamide resin (A). 30 mass parts is preferable and 0.5? 10 mass parts is more preferable. If the compounding quantity of a heterocyclic containing compound is 0.1 mass part or more, the adhesiveness to the copper substrate of the film | membrane after thermosetting will become favorable, and if it is 30 mass parts or less, stability of a composition will be favorable.

Examples of the polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid and 1,2-cyclohexanediamine 4 Acetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1- Naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamineammonium salt, N-nitroso-N-phenylhydroxylamineammonium salt, N- Nitroso-N- (1-naphthyl) hydroxylamineammonium salt, bis (4-hydroxy-3,5-ditert-butyl) phenylmethane and the like can be used.

The compounding quantity at the time of mix | blending a polymerization inhibitor is 0.01? With respect to 100 mass parts of hydroxypolyamide resin (A). It is preferable that it is 5 mass parts, and it is 0.05? It is more preferable that it is 1 mass part. If the addition amount is within 5 parts by mass, the heat resistance of the film after thermal curing is good.

Photosensitivity containing at least one alkali-soluble polymer and naphthoquinone diazide compound selected from the group consisting of a polybenzoxazole precursor having a (thio) ester structure, a polyimide precursor, and a phenol group-containing polyimide in the main chain As the resin composition,

(i) the following steps (a), (b) and (c):

(a) The alkali-soluble polymer is dissolved in γ-butyrolactone at a concentration of 35% by mass of a resin solid content to prepare a solution of an alkali-soluble polymer;

(b) The film thickness at the time of apply | coating the solution of the alkali-soluble polymer produced by said (a) on a 6-inch silicon wafer, prebaking for 125 degreeC 180 second, and using a contact film thickness meter, and measuring it A film having a thickness of 10 µm ± 0.2 µm; And

(c) The film thickness obtained by measuring the film after prebaking by arbitrary refractive index (n _f1 ) using a non-contact film thickness meter was made into T _f1 , and obtained by measuring by the contact film thickness meter in (b). The refractive index (n _r1 ) obtained when the film thickness is T _r1 is expressed by the following equation:

n _r1 = n _f1 × T _f1 / T _r1

Obtained by;

The refractive index (n _r1 ) of the alkali-soluble polymer obtained by performing the procedure in order was 1.570? Is in the range of 1.650,

(ii) the following (a '), (b') and (c '):

(a ') 100 mass parts of the said alkali-soluble polymer is melt | dissolved in (gamma) -butyrolactone at the density | concentration of 35 mass% of resin solid content, 15 mass parts of said naphthoquinone diazide compounds are further dissolved, and the solution of the photosensitive resin composition is produced. ;

(b ') When the solution of the photosensitive resin composition produced by said (a') was apply | coated on a 6 inch silicon wafer, it prebaked for 125 degreeC 180 second, and measured using a contact film thickness meter. To form a film having a film thickness of 10 µm ± 0.2 µm; And

(c ') non-contact to the film using a thickness meter, a film after pre-baking at any of the refractive index the film thickness obtained by measuring a (n _f2) to T _f2, and the (b' contact film measured by the thickness meter in) The true refractive index (n _r2 ), which is obtained when the film thickness obtained by making T _r2 is expressed by the following equation:

n _r2 = n _f2 × T _f2 / T _r2

Obtained by;

The refractive index (n _r2 ) of the said photosensitive resin composition obtained by carrying out in order, and the refractive index (n _r1 ) of the said alkali-soluble polymer are the following conditions:

{Refractive index (n _r1 ) / refractive index (n _r2 ) of the photosensitive resin composition} of an alkali-soluble polymer} × 100 = 1.0? 3.0 (%)

The said photosensitive resin composition which satisfy | fills is also in the scope of this invention.

By satisfy | filling the conditions regarding the said refractive index, it becomes a photosensitive resin composition which is high in developing residual film rate, high sensitivity, and has high elongation and high storage stability.

Although the mechanism is not clear, the inventor guesses as follows. By using the alkali-soluble polymer which has a (thio) ester structure for a principal chain, the hydrophobicity of a (thio) ester group containing structure is exhibited and it becomes an environment in which alkali developing solution itself becomes difficult to permeate a composition. It is more preferable that it is an ester structure. And it is inferred that the refractive index (n _r ) of an alkali-soluble polymer is 1.570-1.650 which shows that it is the distance which an naphthoquinone diazide compound is easy to intercalate as an intermolecular distance of alkali-soluble polymers, and a more preferable range The furnace is 1.570-1.630 (the lower the value, the wider the intermolecular distance).

Although the refractive index of the photosensitive resin composition depends on the ratio of the naphthoquinone diazide compound in the photosensitive resin composition, it becomes saturated at some extent or more. The refractive index of a saturated state can be measured by making the measurement conditions of the refractive index of the photosensitive resin composition into 15 mass parts of naphthoquinone diazide compounds with respect to 100 mass parts of alkali-soluble polymers. It is inferred that the refractive index (n _r2 ) of the photosensitive resin composition is higher than the refractive index (n _r1 ) of the alkali-soluble polymer, indicating that the naphthoquinone diazide compound is appropriately intercalated in the free volume between the molecules of the alkali-soluble polymer. . {Refractive index (n _r1 ) / refractive index (n _r2 ) of the photosensitive resin composition} of an alkali-soluble polymer} × 100 = 1.0? By satisfy | filling 3.0 (%), the mechanism of the said interlayer insertion acts effectively, and it becomes the photosensitive resin composition which shows the said effect. This range is 1.5%? 3.0% is more preferable.

When measuring the refractive index of the alkali-soluble polymer or the photosensitive resin composition, the solution is dissolved using γ-butyrolactone, but when not dissolved in γ-butyrolactone, dilution is performed using any solvent in which the alkali-soluble polymer is dissolved. You can also do it.

As a contact film thickness measuring apparatus, P-15 by a KLA TENCOR company is mentioned, for example, As a non-contact film thickness measuring apparatus, the lambda ace manufactured by Dainippon Screen Manufacturer is mentioned.

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

Hereinafter, the manufacturing method of the hardening relief pattern of this invention is demonstrated.

Using the photosensitive resin composition which concerns on this invention, a hardening relief pattern can be manufactured by the following method.

The following process:

(1) process of forming the photosensitive resin layer obtained by apply | coating the solution of said photosensitive resin composition or photosensitive resin composition on a board | substrate,

(2) exposing step;

(3) developing process,

(4) heat-processing the obtained relief pattern,

Method of producing a cured relief pattern comprising a.

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

The photosensitive resin composition or its solution is applied to a substrate such as a silicon wafer, a ceramic substrate, an aluminum substrate, or the like using a spinner or a coater such as a die coater or a roll coater. This can be done using an oven or hotplate. 140 ° C, preferably 100? The organic solvent is removed by drying by applying heat at 140 ° C (hereinafter also referred to as "soft bake" or "prebaking").

(2) Process of exposing by actinic ray through mask or by directly irradiating light, electron beam or ion beam (second process)

Subsequently, the photosensitive resin layer is exposed by actinic rays using a contact aligner or stepper through a mask, or directly exposed to light, an electron beam or an ion beam. As the active light, g-ray, h-ray, i-ray, KrF laser can be used.

(3) Process of eluting or removing the exposed part with developing solution in case of positive photosensitive composition (3rd process)

Next, in the case of a positive photosensitive composition, the exposed portion is dissolved in the negative photosensitive composition, and in the case of a negative photosensitive composition, the unexposed portion is dissolved and removed, followed by rinsing with a rinse liquid to obtain a desired relief pattern. The developing method may be spray, paddle, dip, ultrasonic wave, or the like. Distilled water, deionized water, etc. can be used as a rinse liquid.

The developing solution used for developing the film | membrane formed by the photosensitive resin composition is what melt | dissolves and removes the hydroxypolyamide resin (A), and needs to be the alkaline aqueous solution which melt | dissolved the alkali compound. The alkali compound dissolved in the developer may be either an inorganic alkali compound or an organic alkali compound.

Examples of the inorganic alkali compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, Lithium borate, sodium borate, potassium borate, ammonia and the like.

Moreover, as an organic alkali compound, For example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine And 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 inhibiting agent, or the like can be appropriately added to the alkaline aqueous solution.

(4) Process of heat-processing the obtained relief pattern (4th process)

Finally, the obtained relief pattern is cured to form a heat resistant cured relief pattern made of a resin having a polybenzoxazole structure. As a heating apparatus, an oven furnace, a hotplate, 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. are recommended. The temperature is 200? 450 degreeC is preferable and 250? 400 degreeC is more preferable. Heating time is 15 minutes 8 hours is preferred, 1 hour? 4 hours is more preferable. As an atmosphere, inside of inert gas, such as nitrogen and argon, is preferable.

The semiconductor device produced using the photosensitive resin composition of this invention is combined with the manufacturing method of a well-known semiconductor device, and is used as a protective film of the device which has a surface protective film, an interlayer insulation film, an insulation film for redistribution, a protective film for flip chip devices, and a bump structure. It can manufacture as having a hardening relief pattern which consists of a photosensitive resin composition.

As an example of a semiconductor device use, what has a cured film formed in the upper part of a semiconductor element, and the cured film is a cured relief pattern which consists of a cured film of the photosensitive resin composition mentioned above. As the cured film, a passivation film on a semiconductor element, a protective film such as a buffer coat film formed by forming a cured film of the photosensitive resin composition described above on a passivation film, and the positive photosensitive resin composition described above on a circuit formed on a semiconductor element. Insulating films such as an interlayer insulating film formed by forming a cured film of the same, an α-ray blocking film, a planarizing film, a projection (resin post), a partition wall, and the like.

Moreover, the photosensitive resin composition of this invention is useful also for uses, such as the interlayer insulation of a multilayer circuit, the cover coat of a flexible copper clad board, a soldering resist film, the liquid crystal aligning film of a display apparatus, and the use of a light emitting element.

As an example of a display apparatus use, what has a display element and the cured film formed in the upper part of this display element, and the cured film is a cured relief pattern which consists of a cured film of the photosensitive resin composition mentioned above. A protective film formed by forming the cured film of the photosensitive resin composition mentioned above on a display element, insulating films, such as TFT elements and color filters, or planarization films, projections, such as for MVA-type liquid crystal display devices, partition walls, such as for organic electroluminescent element cathodes Etc. can be mentioned. The use method is based on forming the photosensitive resin composition layer patterned on the board | substrate in which the display element and the color filter were formed according to the semiconductor device use by the said method. Although high transparency is required for display device applications, in particular for insulating films and planarization films, a resin layer excellent in transparency may be obtained by introducing a post-exposure step before curing of the photosensitive resin composition layer, which is more preferable in practical use. .

Example

Hereinafter, the present invention will be described based on reference examples, examples and comparative examples.

[Reference Example 1: Preparation of bis (carboxy) tricyclo [5,2,1,0 ^2,6 ] decane]

71.9 g (0.366 mol) of tricyclo [5,2,1,0 ^2,6 ] decanedimethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) in a glass separable three-necked flask equipped with a Teflon (registered trademark) anchor type stirrer What dissolve | melted in 1 L of nitriles, the thing which melt | dissolved 256.7 g (1.808 mol) of sodium dihydrogen phosphates and 217.1 g (1.809 mol) of sodium dihydrogen phosphates in 1.4 L of ion-exchange water was added. 2.8 g (0.0179 mol) of 2,2,6,6- tetramethyl piperidine-1-oxyl (made by Tokyo Chemical Co., Ltd. hereafter, also called "TEMPO") was added, it stirred, and it melt | dissolved.

143.2 g (1.267 mol) of 80% sodium chlorite was diluted with 850 ml of ion-exchanged water, and this was dripped at the reaction liquid. Subsequently, what diluted 3.7 ml of 5 mass% sodium dichlorate aqueous solution with 7 ml of ion-exchange water was dripped at the reaction liquid. The reaction solution was heated to 35? It maintained at 38 degreeC, and stirred for 20 hours and made it react.

After reaction, the reaction liquid was cooled to 12 degreeC, the aqueous solution which melt | dissolved 75 g of sodium sulfite in 300 ml of ion-exchange water was dripped at the reaction liquid, and excess sodium chlorite was deactivated, and it wash | cleaned with 500 ml of ethyl acetate. . After that, 115 ml of 10% hydrochloric acid was added dropwise to adjust the pH of the reaction solution to 3? Adjust to 4 and recover the precipitate by decantation. This precipitate was dissolved in 200 ml of tetrahydrofuran. The aqueous layer was extracted twice with 500 ml of ethyl acetate, washed with brine, and the precipitate was dissolved in a solution of tetrahydrofuran in the same manner. These tetrahydrofuran solutions were mixed and dried over anhydrous sodium sulfate. This solution was concentrated and dried in an evaporator to obtain 58.4 g (yield 71.1%) of bis (carboxy) tricyclo [5,2,1,0 ^2,6 ] decane.

[Reference Example 2: Preparation of bis (chlorocarbonyl) tricyclo [5,2,1,0 ^2,6 ] decane]

62.5 g (278 mmol) of bis (carboxy) tricyclo [5,2,1,0 ^2,6 ] decane obtained in Reference Example 1, 97 ml (1.33 mol) of thionyl chloride, and 0.4 ml (5.0 mmol) of pyridine Is injected into the reaction vessel and 25? It reacted by stirring at 50 degreeC for 18 hours. After completion of the reaction, toluene was added and concentrated by azeotroping excess thionyl chloride with toluene under reduced pressure, and 73.3 g of an oil-like bis (chlorocarbonyl) tricyclo [5,2,1,0 ^2,6 ] decane was obtained. (Yield 100%) was obtained.

Reference Example 3: Synthesis of Photoacid Generator (B) (Q-1)

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. As a result of confirming reaction by HPLC after performing stirring reaction at room temperature for 3 days as it is, the raw material was not detected at all and the product was detected by purity 99% as a single peak. The reaction solution was added dropwise while stirring into 1 L of ion-exchanged water under stirring, and the precipitate was separated by filtration, and thereafter, 500 ml of THF was added thereto, followed by stirring and dissolving. The homogeneous solution was added to a cation exchange resin: Amberlyst 15 (Orga Laboratories) The remaining pyridine was removed through a glass column filled with 100 g. Subsequently, this solution was dripped in 3 L of ion-exchange water under high speed stirring, and the product was precipitated, and this was isolated by filtration and dried in vacuo.

This product has already been coded, 1394 and 1774 ㎝ ㎝ ^-1 in IR spectrum ^{to 1} already appears characteristic absorption of deugi in, that the characteristic absorption of an amide group in the vicinity of 1540 and 1650 ㎝ ㎝ ^{-1 -1} does not exist, And no peak of the protons of the amide and the carboxylic acid in the NMR spectrum.

Next, 65.9 g (0.1 mol) of this product and 53.7 g (0.2 mol) of 1,2-naphthoquinone diazide-4-sulfonyl chlorides were added to 560 g of acetone, and it stirred and dissolved at 20 degreeC. The thing which diluted 21.2 g (0.21 mol) of triethylamine to 106.2 g of acetone was dripped at this at the constant speed over 30 minutes. At this time, the reaction solution was used for 20? Temperature control was carried out in the range of 30 ° C.

After completion of the dropwise addition, the mixture was left to stir for 30 minutes at 20 ° C, 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 obtained filtrate was dripped at 5 L of hydrochloric acid aqueous solution of 0.5 weight% concentration over 1 hour under stirring, and the target substance 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 photosensitive diazoquinone compound (Q-1) was obtained.

Reference Example 4: Synthesis of Photoacid Generator (B) (Q-2)

4,4 '-(1- (2- (4-hydroxyphenyl) -2-propyl) phenyl) ethylidene) bisphenol (manufactured by Honshu Chemical Industries, Ltd.) as a polyhydroxy compound : 30 g (0.0707 mol) of a Tris-PA) compound was added thereto, and 47.49 g of 1,2-naphthoquinone diazide-4-sulfonyl chloride in an amount corresponding to 83.3 mol% of the OH group of the compound was added thereto. Mol) was stirred and dissolved in 300 g of acetone, and then the flask was adjusted to 30 ° C in a thermostat. Next, after dissolving 17.9 g of triethylamine in 18 g of acetone was injected into the dropping funnel, this was added dropwise into the flask over 30 minutes. After completion of the dropwise addition, stirring was continued for 30 minutes, hydrochloric acid was added dropwise thereafter, and stirring was further performed for 30 minutes to terminate the reaction. Thereafter, the mixture was filtered to remove triethylamine hydrochloride. The obtained filtrate was dripped at the 3 L beaker which mixed and stirred 1640 g of pure waters and 30 g of hydrochloric acid, stirring, and obtained the precipitate. After washing with water and filtering this precipitate, it dried under 40 degreeC reduced pressure for 48 hours, and obtained the photo-acid generator (Q-2).

[Reference Example 5: Preparation of Organosilicon Compound (S-1)]

To a 500 ml three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 131.0 g (0.6 mol) of di-t-butyl dicarbonate and 780 g of GBL were added, and 132.8 g of 3-aminopropyltriethoxysilane at room temperature (0.6 Mol) was slowly added dropwise at room temperature. As it dripped, the reaction liquid heated up to about 40 degreeC. Moreover, generation | occurrence | production of carbon dioxide gas was confirmed with progress of reaction. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and then the reaction solution was confirmed by high performance liquid chromatography (HPLC). As a result, no raw materials were detected, and the product product (S-1) was detected with a purity of 98% as a single peak. . Thus, the organosilicon compound S-1 solution was obtained. The obtained reaction solution was adjusted so that S-1 might be 20 weight% with respect to GBL. The structure of S-1 is shown below:

(65)

Reference Example 6: Preparation of Organosilicon Compound (S-2)

132.8 g (gamma) -aminopropyl triethoxysilane and 780 g of (gamma) -aminopropyl triethoxysilane were added to the 500 mL three neck flask with a stirrer, the dropping funnel, and the thermometer, and the flask was adjusted to 30 degreeC in the thermostat. After pouring 71.4 g (0.6 mol) of phenyl isocyanates into the dropping funnel, this was dripped in the flask over 30 minutes, and liquid temperature rose to 50 degreeC. An organosilicon compound S-2 solution was obtained. The obtained reaction solution was adjusted so that S-2 might be 20 weight% with respect to GBL. The structure of S-2 is shown below:

[Formula 66]

[Reference Example 7: Synthesis of hydroxypolyamide resin (A) (P-1)]

3.72 g (0.02 mol) of 4,4-biphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and bis (chlorocarbonyl) prepared in Reference Example 2 in a 500 ml three-necked flask equipped with a Teflon® anchor type stirrer. 3.16 g of pyridine in GBL 94.9 g separately to a solution obtained by mixing and stirring 49.5 g (0.18 mol) of tricyclo [5,2,1,0 ^2,6 ] decane and 22.3 g of GBL at room temperature (around 20-25 ° C) What mixed (0.04 mol) was dripped from the dropping funnel. The time required for dripping was 20 minutes, and reaction liquid temperature was 40 degreeC at the maximum.

After the dropwise addition, the reaction solution was stirred for 1 hour in 2,2-bis (3-amino-4-hydroxyphenyl) -hexa, in a separable flask having a capacity of 2 L equipped with a Teflon (registered trademark) anchor type stirrer separately. Fluoropropane (hereinafter also referred to as "6FAP") 65.9 g (0.18 mol), pyridine 19.0 g (0.24 mol), 395 g GBL and 132 g DMAc were mixed and stirred at room temperature to dissolve the reaction vessel in methanol. It was dripped using the addition funnel to the reaction solution which immersed in the container which added dry ice (henceforth also called "ice bath."), And cooled to -15 degreeC. In the reaction system is -15? It was dripped at the reaction container over 1 hour, maintaining at 0 degreeC. After completion of the dropwise addition, the ice bath was removed and stirred for 1 hour at room temperature. 6.33 g (0.08 mol) of pyridine was also added. Thereafter, the reaction solution was returned to room temperature, and 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 9.49 g (0.12 mol) of pyridine were added thereto. The reaction solution was stirred for 24 hours by immersion in a hot water bath.

Ethanol was added to the reaction solution, the polymer was precipitated and then recovered, and dissolved in 697 g of GBL. Subsequently, it was ion-exchanged with 62.1 g of cation exchange resin (Organo make, Amberlyst A21) and 59.6 g of anion exchange resin (Organo make, Amberlyst 15). This solution was dripped at 12 L of ion-exchange water under high speed stirring, the polymer was dispersed-precipitated, collect | recovered, and it washed with water and dewatered suitably, vacuum-dried, and obtained the powder of hydroxy polyamide resin (P-1).

Thus, the weight average molecular weight (Mw) by GPC (high speed liquid chromatography) of the synthesize | combined hydroxy polyamide resin confirmed that it was a single composition by the single sharp curve of 26,600 in polystyrene conversion. The analysis conditions of GPC are described below.

Column: Showa Electric Works, trade name Shodex 805M / 806M Serial

Eluent: N-methylpyrrolidone 40 ℃

Flow rate: 1.0 ml / min

Detector: Nippon Spectroscopy, trade name RI-930

The ¹³ C-NMR result of the hydroxypolyamide resin P-1 obtained in FIG. 1 is shown. Carbon peaks derived from the biphenyl skeleton were observed around 138 ppm and 150 ppm, and peaks derived from ester groups were observed around 174-176 ppm.

Reference Example 8: Synthesis of Hydroxypolyamide Resin (A) (P-2)]

11.2 g (0.06 mol) of 2,2-biphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and bis (chlorocarbonyl) prepared in Reference Example 2 in a 500 ml three-necked flask equipped with a Teflon® anchor type stirrer. 9.49 g of pyridine in 142.3 g of GBL separately in a solution obtained by mixing and stirring 49.3 g (0.18 mol) of tricyclo [5,2,1,0 ^2,6 ] decane and 66.9 g of GBL at room temperature (around 20-25 ° C). What mixed (0.12 mol) was dripped from the dropping funnel. The time required for dripping was 25 minutes, and reaction liquid temperature was 40 degreeC at the maximum.

After the dropwise addition, the reaction solution was stirred for 1 hour in bis (3-amino-4-hydroxyphenyl) propane (manufactured by Clarity Japan Co., Ltd.) in a separable flask equipped with a Teflon (registered trademark) anchor type stirrer separately. 36.2 g (0.14 mol), 14.8 g (0.19 mol) of pyridine, 217 g of GBL and 72.5 g of DMAc are added thereto, mixed and stirred at room temperature to dissolve the reaction vessel in an ice bath. It was dripped using the dripping funnel to the solution immersed and cooled to -15 degreeC. In the reaction system is -15? It was dripped at the reaction container over 1 hour, maintaining at 0 degreeC. After the dropping is finished, the ice bath is removed and 0? It stirred for 1 hour, maintaining at 10 degreeC, and also added 4.74 g (0.06 mol) of pyridine. Thereafter, the reaction solution was returned to room temperature, and 16.4 g (0.10 mol) of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7.91 g (0.10 mol) of pyridine were added thereto. The reaction solution was stirred for 24 hours by immersion in a hot water bath.

Ethanol was added to the reaction solution, and the polymer was precipitated and recovered. The resulting solution was dissolved in 646 g of GBL. Subsequently, it was ion-exchanged with 62.1 g of cation exchange resin (Organo make, Amberlyst A21) and 59.6 g of anion exchange resin (Organo make, Amberlyst 15). This solution was dripped at 12 L of ion-exchange water under high speed stirring, the polymer was dispersed-precipitated, collect | recovered, and it washed with water and dewatered suitably, vacuum-dried, and obtained the powder of hydroxy polyamide resin (P-2).

The weight average molecular weight (Mw) by GPC of the hydroxy polyamide resin synthesize | combined in this way confirmed that it was a single composition by the single sharp curve of 12,700 in polystyrene conversion. The analysis conditions of GPC are described below.

Column: Showa Electric Works, trade name Shodex 805M / 806M Serial

Eluent: N-methylpyrrolidone 40 ℃

Flow rate: 1.0 ml / min

Detector: Nippon Spectroscopy, trade name RI-930

The ¹³ C-NMR result of the hydroxypolyamide resin P-2 obtained in FIG. 2 is shown. Carbon peaks derived from the biphenyl skeleton were observed around 136 ppm and 146 ppm, and peaks derived from ester groups were observed around 174-176 ppm.

[Reference Example 9: Synthesis of hydroxypolyamide resin (A) (P-3)]

5.77 g (0.04 mol) of 1,4-cyclohexanedimethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and bis (chlorocarb) prepared in Reference Example 2 in a 500 ml three-necked flask equipped with a Teflon® anchor type stirrer. Carbonyl) tricyclo [5,2,1,0 ^2,6 ] 49.5 g (0.18 mol) decane and 44.6 g of GBL were added, and it mixed in and stirred at room temperature (about 20-25 degreeC), and separately in 94.9 g of GBL A mixture of 6.33 g (0.08 mol) of pyridine was added dropwise from the dropping funnel. The time required for dripping was 20 minutes, and reaction temperature was 40 degreeC at the maximum.

After the dropwise addition, the reaction solution was stirred for 1 hour in a separable flask equipped with a Teflon (registered trademark) anchor stirrer separately in a capacity of 2 L, 6FAP 58.6 g (0.16 mol), pyridine 16.9 g (0.21 mol), GBL 350 117 g of g and DMAc were added thereto, mixed and stirred at room temperature to dissolve, and the reaction vessel was immersed in a vessel (hereinafter referred to as an "ice bath") in which dry ice was added to methanol and cooled to -15 ° C. It was dripped using the dropping funnel. In the reaction system is -15? It was dripped at the reaction container over 1 hour, maintaining at 0 degreeC. After completion of the dropwise addition, the ice bath was removed, stirred at room temperature for 1 hour, and 6.33 g (0.08 mol) of pyridine was further added.

Ethanol was added to the reaction solution, the polymer was precipitated and then recovered, and dissolved in 697 g of GBL. Subsequently, it was ion-exchanged with 62.1 g of cation exchange resin (Organo make, Amberlyst A21) and 59.6 g of anion exchange resin (Organo make, Amberlyst 15). This solution was dripped at 12 L of ion-exchange water under high speed stirring, the polymer was dispersed-precipitated, collect | recovered, and it washed with water and dewatered suitably, vacuum-dried, and obtained the powder of hydroxy polyamide resin (P-3).

Thus, the weight average molecular weight (Mw) by GPC (high-speed liquid chromatography) of the synthesize | combined hydroxy polyamide resin confirmed that it was a single composition by the single sharp curve of 27,000 in polystyrene conversion. The analysis conditions of GPC are described below.

Column: Showa Electric Works, trade name Shodex 805M / 806M Serial

Eluent: N-methylpyrrolidone 40 ℃

Flow rate: 1.0 ml / min

Detector: Nippon Spectroscopy, trade name RI-930

The result of ¹³ C-NMR of hydroxypolyamide resin P-3 obtained in FIG. 3 is shown. Peaks derived from the methylene group at the α position of the oxygen atom of the ester group were observed around 66 ppm and 69 ppm, and peaks derived from the ester group were observed around 174-176 ppm.

Reference Example 10 Synthesis of Hydroxypolyamide Resin (A) (P-4)

The following structure in a 500 ml three-necked flask equipped with a Teflon® anchor type stirrer:

(67)

17.6 g (0.04 mol) of Karenz MT BD1 (Showa Denko) (trade name) having 47.6 g of bis (chlorocarbonyl) tricyclo [5,2,1,0 ^2,6 ] decane prepared in Reference Example 2 0.18 mol) and 35.4 g of GBL were added at room temperature (about 20-25 degreeC), and what mixed and stirred pyridine 6.33g (0.08mol) in 94.9g of GBL was dripped separately from the dropping funnel. The time required for dripping was 20 minutes, and reaction liquid temperature was 36 degreeC at the maximum.

After the dropwise addition, the reaction solution was stirred for 1 hour in a separable flask equipped with a Teflon (registered trademark) anchor stirrer separately in a capacity of 2 L, 6FAP 58.6 g (0.16 mol), pyridine 16.9 g (0.21 mol), GBL 350 g and 117 g of DMAc were added thereto, mixed and stirred at room temperature to dissolve, and the reaction vessel was dipped into a reaction solution cooled by dipping in an ice bath using a dropping funnel. In the reaction system is -15? It was dripped at the reaction container over 1 hour, maintaining at 0 degreeC. After the dropping is finished, the ice bath is removed and 0? It stirred for 1 hour, keeping at 10 degreeC, and also 5.27 g (0.07 mol) of pyridine was added. Thereafter, the reaction solution was returned to room temperature, and 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 9.49 g (0.12 mol) of pyridine were added thereto. The reaction solution was stirred for 24 hours by immersion in a hot water bath.

Ethanol was added to the reaction solution, the polymer was precipitated and then recovered, and dissolved in 697 g of GBL. Subsequently, it was ion-exchanged with 62.1 g of cation exchange resin (Organo make, Amberlyst A21) and 59.6 g of anion exchange resin (Organo make, Amberlyst 15). The solution was added dropwise to 12 L of ion-exchanged water under high-speed stirring, the polymer was dispersed and precipitated and recovered, washed with water and dehydrated as appropriate, followed by vacuum drying to obtain a powder of hydroxypolyamide resin (P-4).

Thus, the weight average molecular weight (Mw) by GPC of the hydroxy polyamide resin synthesize | combined confirmed that it was a single composition by the single sharp curve of 27,400 in polystyrene conversion. The analysis conditions of GPC are described below.

Column: Showa Electric Works, trade name Shodex 805M / 806M Serial

Eluent: N-methylpyrrolidone 40 ℃

Flow rate: 1.0 ml / min

Detector: Nippon Spectroscopy, trade name RI-930

The ¹³ C-NMR result of the hydroxypolyamide resin P-4 obtained in FIG. 4 is shown. Peaks derived from ester groups were observed at 170 ppm and around, and peaks derived from thioester groups were observed at around 200 ppm.

[Reference Example 11: Synthesis of hydroxypolyamide resin (A) (P-5)]

5.77 g (0.04 mol) of 1,4-cyclohexanedimethanol (manufactured by Tokyo Kasei Kogyo Co., Ltd.), isophthalic acid chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) in a three-necked flask equipped with a Teflon (registered trademark) anchor type stirrer 18.1 g (0.09 mol) and 72.4 g of GBL were put, and the thing which mixed 6.33 g (0.08 mol) of pyridine in 32.1 g of GBL separately was dripped at the solution stirred and mixed at room temperature (20-25 degreeC back and front) from the dropping funnel. The time required for dripping was 25 minutes, and reaction liquid temperature was 48 degreeC at the maximum.

After the dropwise addition, the reaction solution stirred for 1 hour was separately dissolved with 26.2 g (0.09 mol) of 4,4'-diphenyletherdicarboxylic acid chloride in 124.6 g of GBL, and anchored stirrer of Teflon (registered trademark) separately In a separable flask with a capacity of 2 L, 6FAP 58.6 g (0.16 mol), pyridine 16.9 g (0.21 mol), GBL 350 g and DMAc 117 g were added thereto, mixed and stirred at room temperature, and the reaction vessel was iced. It was dripped at the reaction solution immersed in the bath, and cooled to -15 degreeC using the dropping funnel. In the reaction system is -15? It was dripped at the reaction container over 1 hour, maintaining at 0 degreeC. After the dropping is finished, the ice bath is removed and 0? It stirred for 1 hour, keeping at 10 degreeC, and also 5.27 g (0.07 mol) of pyridine was added. Thereafter, the reaction solution was returned to room temperature, and 21.9 g (0.13 mol) of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10.5 g (0.13 mol) of pyridine were added thereto. The reaction solution was stirred for 24 hours by immersion in a hot water bath.

The polymer was precipitated while the ethanol was added to the reaction solution, and then recovered and dissolved in 626 g of GBL. Subsequently, it was ion-exchanged with 62.1 g of cation exchange resin (Organo make, Amberlyst A21) and 59.6 g of anion exchange resin (Organo make, Amberlyst 15). The solution was added dropwise to 12 L of ion-exchanged water under high-speed stirring, and the polymer was dispersed and precipitated and recovered. After washing with water and dehydrating as appropriate, vacuum-dried to obtain a powder of hydroxypolyamide resin (P-5).

The weight average molecular weight (Mw) by the hydroxy polyamide resin synthesize | combined in this way confirmed that it was a single composition with a single sharp curve of 13,200 in polystyrene conversion. The analysis conditions of GPC are described below.

Column: Showa Electric Works, trade name Shodex 805M / 806M Serial

Eluent: N-methylpyrrolidone 40 ℃

Flow rate: 1.0 ml / min

Detector: Nippon Spectroscopy, trade name RI-930

The ¹³ C-NMR result of the hydroxypolyamide resin P-5 obtained in FIG. 5 is shown. A peak derived from the methylene group at the α position of the oxygen atom of the ester group is observed around 65 to 70 ppm, and a peak derived from the ester group is observed around 165 ppm.

Reference Example 12 Synthesis of Hydroxypolyamide Resin (A) (P-6)

In a 2 L separable flask equipped with a Teflon® anchor type stirrer, 6FAP 73.2 g (0.20 mol), pyridine 21.1 g (0.27 mol), GBL 439 g and DMAc 146 g were added thereto, and room temperature (25 ° C). ) Was dissolved by mixing and stirring. Separately, 6.6 g (0.04 mol) of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 88 g of GBL, dropwise from the dropping funnel. The time required for dripping was 25 minutes, and reaction liquid temperature was 28 degreeC at the maximum.

It was confirmed that the absorption properties of already deugi ^one shown ^- after the addition was completed, the reaction mixture by tangyok After stirring while heating to 50 ℃ 18 hours, by measuring the IR spectra of the reaction solution was 1385 ㎝ ^-1 and 1772 ㎝.

Subsequently, this was cooled to 8 degreeC by the water bath, and what melt | dissolved 53.1 g (0.18 mol) of 4,4'- diphenyl ether dicarboxylic acid chlorides in 212 g of GBL separately from this was dripped. The time required for dripping was 60 minutes, and reaction liquid temperature was 12 degreeC at the maximum.

After depositing a polymer while ethanol was added to the reaction solution, this was recovered and dissolved in 671 g of GBL. Subsequently, it was ion-exchanged with 62.1 g of cation exchange resin (Organo make, Amberlyst A21) and 59.6 g of anion exchange resin (Organo make, Amberlyst 15). This solution was dripped at 12 L of water under high-speed stirring, the polymer was dispersed and precipitated, this was recovered, and after washing with water and dehydration as appropriate, it was vacuum dried to obtain a PBO precursor as a hydroxypolyamide resin (P-6). The weight average molecular weight (Mw) by GPC of the hydroxy polyamide resin synthesize | combined in this way confirmed that a single composition was obtained by the single sharp curve of 14,000 in polystyrene conversion. The analysis conditions of GPC are described below.

Column: Showa Electric Works, trade name Shodex 805M / 806M Serial

Eluent: N-methylpyrrolidone 40 ℃

Flow rate: 1.0 ml / min

Detector: Nippon Spectroscopy, trade name RI-930

Reference Example 13: Synthesis of Hydroxypolyamide Resin (A) (P-7)]

73.3 g (0.20 mol) of 6FAP, 21.1 g (0.27 mol) of pyridine, 440 g of GBL, and 147 g of DMAc were dissolved in a 2-liter separable flask equipped with a Teflon® anchor type stirrer. After 6FAP was dissolved, the reaction vessel was cooled by dipping into a vessel in which dry ice was added to methanol. 47.5 g (0.18 mol) of bis (chlorocarbonyl) tricyclo [5,2,1,0 ^2,6 ] decane prepared in Reference Example 2 was dissolved in 142 g of GBL, and -10? It was dripped at the reaction container over 30 minutes, maintaining at -19 degreeC. After completion of dropping, the reaction vessel was immersed in an ice bath, and 0? It stirred for 2 hours, maintaining at 10 degreeC, and also 9.49 g (0.12 mol) of pyridine was added to the reaction container.

Ethanol was added to the reaction solution to precipitate the polymer, which was then recovered and dissolved in 696 g of GBL. Subsequently, it was ion-exchanged with 62.1 g of cation exchange resin (Organo make, Amberlyst A21) and 59.6 g of anion exchange resin (Organo make, Amberlyst 15). The solution was added dropwise to 12 L of ion-exchanged water under high-speed stirring, and the polymer was dispersed and precipitated and recovered. After washing with water and dehydrating as appropriate, vacuum drying was carried out to obtain a PBO precursor as a hydroxypolyamide resin (P-7). Thus, the weight average molecular weight (Mw) by GPC of the synthesize | combined hydroxy polyamide resin confirmed that a single composition was obtained by the single sharp curve of 36,800 in polystyrene conversion. The analysis conditions of GPC are described below.

Column: Showa Electric Works, trade name Shodex 805M / 806M Serial

Eluent: N-methylpyrrolidone 40 ℃

Flow rate: 1.0 ml / min

Detector: Nippon Spectroscopy, trade name RI-930

Reference Example 14 Synthesis of Hydroxypolyamide Resin (A) (P-8)

51.7 g (0.20 mol) of BAP, 21.1 g (0.27 mol) of pyridine, 310 g of GBL, and 103 g of DMAc were added and dissolved in a 2-liter separable flask equipped with a Teflon® anchor type stirrer. After BAP was dissolved, the reaction vessel was cooled by immersing in a vessel in which dry ice was added to methanol. 47.5 g (0.18 mol) of bis (chlorocarbonyl) tricyclo [5,2,1,0 ^2,6 ] decane prepared in Reference Example 2 was dissolved in 142 g of GBL, and -10? It was dripped at the reaction container over 30 minutes, maintaining at -19 degreeC. After completion of dropping, the reaction vessel was immersed in a bath, and 0? It stirred for 2 hours, maintaining at 10 degreeC, and also 9.49 g (0.12 mol) of pyridine was added to the reaction container.

Ethanol was added to the reaction solution to precipitate a polymer, and this was recovered and dissolved in 671 g of GBL. Subsequently, it was ion-exchanged with 62.1 g of cation exchange resin (Organo make, Amberlyst A21) and 59.6 g of anion exchange resin (Organo make, Amberlyst 15). The solution was added dropwise to 12 L of ion-exchanged water under high-speed stirring, and the polymer was dispersed and precipitated and recovered. After washing with water and dehydrating as appropriate, vacuum drying was performed to obtain a PBO precursor as hydroxypolyamide resin P-8. Thus, the weight average molecular weight (Mw) by GPC of the synthesize | combined hydroxy polyamide resin confirmed that a single composition was obtained by the single sharp curve of 36,800 in polystyrene conversion. The analysis conditions of GPC are described below.

Column: Showa Electric Works, trade name Shodex 805M / 806M Serial

Eluent: N-methylpyrrolidone 40 ℃

Flow rate: 1.0 ml / min

Detector: Nippon Spectroscopy, trade name RI-930

<Preparation of positive type photosensitive resin composition>

[Example 1? 6, Comparative Example 1? 4]

Example 1? 6 and Comparative Example 1? As a positive photosensitive resin composition of 4, the said Reference Example 7? Naphth which is a photo-acid generator (B) obtained by the said Reference Example 3 or 4 of the quantity shown to the following Table 1 with respect to 100 mass parts of hydroxy polyamide resins (A) obtained in 14 (P-1-P-8) The toquinone diazide compound (Q-1 or Q-2) and the organosilicon compounds S-1 and S-2 obtained in the reference examples 5 and 6 were dissolved in 15 parts by mass GBL, respectively, and the resin concentration was 35% by mass. Phosphorus alkali-soluble polymer solution was produced, and it filtered after that by 1 micrometer filter.

<Evaluation of the photosensitive resin composition>

(1) Evaluation of patterning characteristics (sensitivity, developing residual ratio)

ㆍ Prefabrication film production and film thickness measurement

Example 1 above? 6 and Comparative Example 1? The positive photosensitive resin composition of 4 was spin-coated to a 6-inch-silicon wafer with the spin coater (Clean Track Mark 8 by Tokyo Electron Co., Ltd.), and prebaked at 125 degreeC on a hotplate for 180 second, and the film for evaluation was obtained. The initial film thickness of each composition was adjusted so that it might be set to 7 micrometers by the resin film thickness after hardening when cured at 320 degreeC for 1 hour. The film thickness was measured by a film thickness measuring device (manufactured by Dainippon Screen Manufacturer, Lambda Ace).

Exposure

The exposure dose was 250 mJ / cm 2? Using a stepper (NSR2005i8A manufactured by Nikon Corporation) having an exposure wavelength of i line (365 nm) through a reticle in which a test pattern was formed on the coating film. Exposure was carried out in steps of 800 mJ / cm 2.

ㆍ Phenomenon

Using an alkali developer (AZ Electronic Materials, AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide aqueous solution), the film thickness after development under the conditions of 23 ° C. was 85% of the initial film thickness (conventional development residual film rate). Or the developing time was adjusted so that it might be 97%, and it developed, it rinsed with pure water, and formed the positive relief pattern.

[Sensitivity (mJ / cm 2)]

In the coating film produced on the said conditions, the minimum exposure amount which can remove the 3.5 micrometer square relief pattern of an exposure part completely was evaluated as a sensitivity. The results are shown in Table 2 below.

[Residual residual film rate (%)]

It calculated | required by (film thickness after image development) / (initial film thickness) x100. The results are shown in Table 2 below.

(2) Measurement of glass transition temperature (Tg) of cured film

Example 1 above? 6 and Comparative Example 1? The positive photosensitive resin composition of 4 was apply | coated by a spin coater (Clean Track Mark 8 by Tokyo Electron Co., Ltd.) on a 6-inch silicon wafer, and it dried at 125 degreeC for 180 second, and then heated up oven (Kyo Thermo Systems Co., Ltd.). (VF200B) was used, and it heated at 320 degreeC in nitrogen atmosphere for 1 hour, and obtained the cured film with a film thickness of 10.0 micrometers.

This cured film was cut into 3 mm width, it was immersed in the dilute hydrofluoric acid solution overnight, the film piece was peeled off, and the dried thing was nitrogen flow volume 50 ml / min using a TMA apparatus (Shimadzu Corporation, TMA-50), and the temperature increase rate 10 The glass transition temperature (Tg) was measured by the conditions of ° C / min. The results are shown in Table 2 below.

(3) Measurement of elastic modulus and elongation of cured film

Example 1 above? 6 and Comparative Example 1? The positive photosensitive resin composition of 4 was apply | coated by a spin coater (Clean Track Mark 8 by Tokyo Electron Co., Ltd.) on a 6-inch silicon wafer, and it dried at 125 degreeC for 180 second, and then heated up oven (Kyo Thermo Systems Co., Ltd.). Manufacture, VF200B), and it heated at 320 degreeC in nitrogen atmosphere for 1 hour, and obtained the heat resistant cured film with a film thickness of 10.0 micrometers.

This cured film was cut into 3 mm width, it was immersed in the dilute hydrofluoric acid solution overnight, the film piece was peeled off, and the dried thing was cut so that it might be 50 mm in length, and it used TENSILON (made by Orient Tech Co., Ltd., UTM-II-20). , The elasticity modulus and elongation of the cured film were measured at a test rate of 40 mm / min and an initial weight of 0.5 fs. The results are shown in Table 2 below.

(4) room temperature 4 weeks viscosity change rate

Example 1 above? 6 and Comparative Example 1? A sample in which the positive photosensitive resin composition of 4 was allowed to stand at room temperature for 3 days was used as a sample after preparation, and then, a sample left for 4 weeks at room temperature was used as a sample after 4 weeks, and a viscometer with a warm water group ( The viscosity in 23 degreeC was measured using the Toki Sangyo company TV-22.

The viscosity change rate of room temperature for 4 weeks was calculated | required by [(viscosity of the sample after 4 weeks)-(viscosity of the sample immediately after adjustment)] / (viscosity of the sample immediately after adjustment) * 100. The results are shown in Table 2 below.

Depending on the difference of the hydroxypolyamide resin (A) having a similar skeleton, the above-mentioned Example 1? The positive photosensitive resin composition obtained in 6 is comparative example 1? Compared with the positive photosensitive resin composition obtained in 4, all had achieved high sensitivity despite the high residual film ratio, and also the viscosity change rate after 4 weeks became low, and it turns out that storage stability improved.

Here, if the acid chloride which comprises the carboxylic acid unit for forming the amide structure in a comparative example consists of an hydroxypolyamide resin (A) which has a pseudo frame | skeleton, it will also be an acid chloride in an Example. It consists of an aromatic group and means similar in this respect. In this case, Example 1? The skeleton of the hydroxypolyamide resin (A) of 4 is similar to that in Comparative Example 3 and Comparative Example 4, and the skeleton of the hydroxypolyamide resin (A) of Examples 5 and 6 is similar to that of Comparative Example 1 and Similar to that of Comparative Example 2.

[Example 1? 6, Example 7? 20]

Example 1? 6 and Example 7? As a positive photosensitive resin composition of 20, as a positive photosensitive resin composition, the said Reference Example 7? Naphthoquinone which is a photo-acid generator (B) obtained by the said Reference Example 4 of the quantity shown in the following Table 3 with respect to 100 mass parts of hydroxy polyamide resins (A) obtained in 11 (P-1-P-5) Diazide compound (Q-2), 15 parts by mass of each of the organosilicon compounds S-1 and S-2 obtained in Reference Example 5 and Reference Example 6 above, and a compound for promoting solubility in the following aqueous alkali solution (C -1-C-6) {Example 7? 20 only} was dissolved in GBL to prepare an alkali-soluble polymer solution having a resin concentration of 35% by mass, and prepared by filtration with a 1 μm filter.

(C-1) 4-hexyl resorcinol

(C-2) 2,2'-dihydroxydiphenylmethane

(C-3) EP4000B (Asahi Organic Materials Industry: Trade Name)

(C-4) EP4080G (Asahi Organic Materials Industry: Trade Name)

(C-5) m-toluic acid

(C-6) m-tolyl acetic acid

(C-7) α-methoxyphenylacetic acid

(C-8) benzenesulfonic acid

<Evaluation of the photosensitive resin composition>

(1) Evaluation of patterning characteristics (sensitivity, development time)

ㆍ Prefabrication film production and film thickness measurement

Example 1 above? 6 and Example 7? The positive photosensitive resin composition of 20 was spin-coated to a 6 inch silicon wafer with the spin coater (Clean Track Mark 8 by Tokyo Electron Co., Ltd.), and prebaked at 125 degreeC on a hotplate for 180 second, and the film for evaluation was obtained. The initial film thickness of each composition was adjusted so that it might be set to 7 micrometers by the resin film thickness after hardening when cured at 320 degreeC for 1 hour. The film thickness was measured by a film thickness measuring device (manufactured by Dainippon Screen Manufacturer, Lambda Ace).

Exposure

Stepper which has an exposure wavelength of i line (365 nm) through the reticle in which the test pattern was formed in this coating film. (NSR2005i8A, manufactured by Nikon Corporation), the exposure dose was 250 mJ / cm 2? Exposure was carried out in steps of 800 mJ / cm 2.

ㆍ Phenomenon

This was developed using an alkali developer (AZ Electronic Materials, AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide aqueous solution) under development at 23 ° C. so as to adjust the developing time so that the film thickness was 97%, and developed. Rinse to form a positive relief pattern.

[Sensitivity (mJ / cm 2)]

In the coating film produced on the said conditions, the minimum exposure amount which can melt | dissolve and remove the 3.5 micrometer square relief pattern of an exposure part completely was evaluated as a sensitivity. The results are shown in Table 4 below.

[Development time (seconds)]

The time in the case of developing the coating film produced on the said conditions was made into developing time (second). The results are shown in Table 4 below.

In the same hydroxypolyamide resin (A), the said Example 7? The positive photosensitive resin composition obtained in 20 is Example 1? By addition of the compound (C) which promotes the solubility to aqueous alkali solution. Compared with the positive photosensitive resin composition obtained in step 6, the developing time was short and high sensitivity was achieved under the same developing residual film ratio.

[Examples 8, 14, 17? 19 and 21? 34]

Examples 8, 14, 17? 19 and 21? As a positive photosensitive resin composition of 34, the said Reference Example 7? Naphtho which is a photo-acid generator (B) obtained by the said Reference Example 4 of the quantity shown in the following Table 5 with respect to 100 mass parts of hydroxy polyamide resins (A) obtained in 11 (P-1-P-5) Quinone diazide compound (Q-2), 15 parts by mass of each of the organosilicon compounds S-1 and S-2 obtained in Reference Example 5 and Reference Example 6, and compound (C) having solubility in aqueous alkali solution ( Compound (D-1? D-10) which causes crosslinking reaction by 10 parts by mass of C-5) and the following heat {Example 21? 34 only} was dissolved in GBL to prepare an alkali-soluble polymer solution having a resin concentration of 35% by mass, and was filtered through a 1 μm filter to prepare.

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

(D-2) the following formula:

(68)

TMOM-BP (Honshu Chemical Industry: Trade Name)

(D-3) 4,4'-bis (methoxymethyl) biphenyl

(D-4) the following formula:

[Formula 69]

TML-BPAF-MF (Honshu Chemical Industry: Trade Name)

(D-5) 1,3,4,6-tetrakis (methoxymethyl) glycoluril

(D-6) Hexamethoxymethylmelamine

(D-7) TRIAM705 (Wako Junyaku: Product Name)

(D-8) trimethylolpropane trimethacrylate

(D-9) the following formula:

(70)

Represented by OXT121 (Toa Synthesis: trade name)

(D-10) 9,10-epoxy-1,5-cyclododecadiene

<Evaluation of the photosensitive resin composition>

(1) Patterning characteristic evaluation (sensitivity)

ㆍ Prefabrication film production and film thickness measurement

Examples 8, 14 and 17 above; 19 and 21? 34 positive photosensitive resin composition was spin-coated to a 6 inch silicon wafer with a spin coater (Clean Track Mark 8 by Tokyo Electron Co., Ltd.), and prebaked at 125 degreeC on a hotplate for 180 second to obtain the film for evaluation (Example 25 However, it prebaked for 180 second at 105 degreeC on the hotplate, and obtained the film for evaluation.). The initial film thickness of each composition was adjusted so that it might be set to 7 micrometers by the resin film thickness after hardening when cured at 320 degreeC for 1 hour. The film thickness was measured by a film thickness measuring device (manufactured by Dainippon Screen Manufacturer, Lambda Ace).

Exposure

The exposure dose was 250 mJ / cm 2? Using a stepper (NSR2005i8A manufactured by Nikon Corporation) having an exposure wavelength of i line (365 nm) through a reticle in which a test pattern was formed on the coating film. Exposure was carried out in steps of 800 mJ / cm 2.

ㆍ Phenomenon

This was developed using an alkali developer (AZ Electronic Materials, AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide aqueous solution) under development at 23 ° C. so as to adjust the developing time so that the film thickness was 97%, and developed. Rinse to form a positive relief pattern.

[Sensitivity (mJ / cm 2)]

In the coating film produced on the said conditions, the minimum exposure amount which can melt | dissolve and remove the 3.5 micrometer square relief pattern of an exposure part completely was evaluated as a sensitivity. The results are shown in Table 6 below.

(2) Measurement of residual film rate at curing

The sample in which the positive relief pattern obtained by the said (1) patterning characteristic evaluation was formed was heated at 320 degreeC under nitrogen atmosphere for 1 hour using the temperature rising oven (VF200B by Koyo Thermo Systems, Inc.).

The residual film rate (%) at the time of curing was defined as (film thickness of curing after curing) / (film thickness of relief pattern after development) × 100. The results are shown in Table 6 below.

In the same hydroxypolyamide resin (A), in Example 21? The positive photosensitive resin composition obtained in 34 is Example 8, 14, and 17? The residual film rate at the time of hardening improved and the sensitivity further improved by adding the compound (D) component which raise | generates a crosslinking reaction by heat compared with the positive photosensitive resin composition obtained by 19.

[Examples 22, 28, 31 and 33? 42]

Examples 22, 28, 31 and 33? As a positive photosensitive resin composition of 42, the said Reference Example 7? Naphtho which is a photo-acid generator (B) obtained by the said Reference Example 4 of the quantity shown in the following Table 7 with respect to 100 mass parts of hydroxy polyamide resins (A) obtained in 11 (P-1-P-5) Quinone diazide compound (Q-2), 15 parts by mass of each of the organosilicon compounds S-1 and S-2 obtained in Reference Example 5 and Reference Example 6, and compound (C) for promoting solubility in aqueous alkali solution ( 20 mass parts of the compound (D) which generate | occur | produces a crosslinking reaction by 10 mass parts of said C-5), and heat (D-2), and a compound (E-1-E-4) which generate | occur | produces an acid by heat {Example 35? 42 only} was dissolved in GBL to prepare an alkali-soluble polymer solution having a resin concentration of 35% by mass, and was prepared by filtration with a 1 μm filter.

(E-1) Methanesulfonic acid 2-methoxyethyl

(E-2) methyl p-toluenesulfonic acid

(E-3) p-toluenesulfonic acid 2-methoxyethyl

(E-4) 2,4-butanesultone

<Evaluation of the photosensitive resin composition>

(1) patterning characteristics evaluation

ㆍ Prefabrication film production and film thickness measurement

Examples 22, 28, 31 and 33 above; The positive photosensitive resin composition of 42 was spin-coated to a 6-inch silicon wafer by the spin coater (Clean Track Mark 8 by Tokyo Electron Co., Ltd.), and prebaked at 125 degreeC on a hotplate for 180 second, and the film for evaluation was obtained. The initial film thickness of each composition was adjusted so that it might be set to 7 micrometers by the resin film thickness after hardening when cured at 320 degreeC for 1 hour. The film thickness was measured by a film thickness measuring device (manufactured by Dainippon Screen Manufacturer, Lambda Ace).

Exposure

The exposure dose was 250 mJ / cm 2? Using a stepper (NSR2005i8A manufactured by Nikon Corporation) having an exposure wavelength of i line (365 nm) through a reticle in which a test pattern was formed on the coating film. Exposure was carried out in steps of 800 mJ / cm 2.

ㆍ Phenomenon

This was developed using an alkali developer (AZ Electronic Materials, AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide aqueous solution) under development at 23 ° C. so as to adjust the developing time so that the film thickness was 97%, and developed. Rinse to form a positive relief pattern.

(2) Measurement of residual film rate at curing

The sample in which the positive relief pattern obtained by said (1) patterning characteristic evaluation was formed was heated at 320 degreeC under nitrogen atmosphere for 1 hour using the temperature rising oven (The Koyo Thermosystems company make, VF200B).

The residual film rate (%) at the time of curing was defined as (film thickness of curing after curing) / (film thickness of relief pattern after development) × 100. The results are shown in Table 8 below.

(3) Evaluation of adhesiveness after curing

Pressurize the cured film obtained by heating the sample which formed the positive type relief pattern obtained by said (1) patterning characteristic evaluation at 250 degreeC for 1 hour in nitrogen atmosphere using a temperature rising oven (VF200B by Koyo Thermo Systems Co., Ltd.). After 100 hours of treatment with a cooker (131 ° C, 2.0 atmospheres), a cutter knife was used to make 100 squares 1 mm wide by a checkerboard scale test (JIS K 5400), and a cellophane (registered trademark) tape was applied from above. It peeled after sticking and counted the number of squares which remained on the board | substrate, without sticking to a cellophane (trademark) tape, and evaluated the adhesiveness after curing. Table 8 below shows the number of squares remaining on the silicon wafer after the tape peel test. The larger the number, the better the adhesion.

In the same hydroxypolyamide resin (A), the said Example 35? The positive photosensitive resin composition obtained in 42 is cured under the above conditions by adding a compound (E) component that generates an acid by heat, as compared with the positive photosensitive resin compositions obtained in Examples 22, 28, 31, 33 and 34. Later adhesion was further improved.

Example 43? 47, comparative example 5? 7]

Reference Example 7? With respect to the hydroxypolyamide resin (A) obtained in 14 (P-1-P-8), the powder of each obtained hydroxypolyamide resin was made into the concentration of 35 mass% of resin solid content, and it turned out to gamma-butyrolactone. When it melt | dissolves and adds 15 mass parts of naphthoquinone diazide compounds (Q-2) with respect to the refractive index (n _r1 ) of an alkali-soluble polymer and 100 mass parts of said alkali-soluble polymers using the following film thickness measuring apparatus. The refractive index (n _r2 ) of the photosensitive resin composition of was measured. The results are shown in Table 9 and Table 10.

Contact film thickness measuring instrument: manufactured by KLA TENCOR, P-15

Non-contact film thickness measuring instrument: Dainippon Screen Manufacturer, Lambda Ace

Industrial availability

The photosensitive resin composition of the present invention is a surface protective film, an interlayer insulating film, and an insulating film for redistribution, a protective film for flip chip devices, a protective film for a device having a bump structure, an interlayer insulating film for a multilayer circuit, a cover coat of a flexible copper plate. And a solder resist film, a liquid crystal aligning film, etc. can be used preferably.

Claims (12)

General formula (1) below:
[Formula 1]

{Wherein Z ₁ , Z ₂ and Z ₃ are each independently a divalent organic group, at least one of Z ₁ , Z ₂ and Z ₃ has an alicyclic structure or an aliphatic structure, and m ₁ is 0 or It is an integer of 1.} and the following general formula (2):
(2)

{Wherein Z ₁ , Z ₂ and Z ₃ are each independently a divalent organic group, at least one of Z ₁ , Z ₂ and Z ₃ has an alicyclic structure or an aliphatic structure, and m ₁ is 0 or It is an integer of 1.} The photosensitive resin composition containing the hydroxy polyamide resin (A) which has at least 1 sort (s) of structure chosen from the group which consists of a structure shown by this, and a photo-acid generator (B). The method of claim 1,
The hydroxypolyamide resin (A) is represented by the following general formula (3):
(3)

{In formula, X <_1> and Y <_1> are 2? It is a tetravalent organic group, R <_1> ? Each R ₃ independently represents a hydrogen atom or 1? 10 is a hydrocarbon group, m ₂ is 1? N ₁ is an integer of 1 or 2, n ₂ ? n ₄ are each independently 0? At least one of the structures represented by Y ₁ (OR ₁ ) _{n 2} (COOR ₃ ) _n 4 in the formula is the general formula (1) or the following general formula (4):
[Chemical Formula 4]

(Wherein, Y ₂ is a divalent tetravalent organic group having at least two carbon atoms, Z ₁ is a divalent organic group, Y ₂ And at least _one of Z ₁ has an alicyclic structure or an aliphatic structure, and R ₄ and R ₅ each independently represent a hydrogen atom or a carbon number of 1? It is a hydrocarbon group of 10, and m <_3> is 1? Is an integer of 100, and n ₅ and n ₆ are each independently 0? Or an above general formula (2) or the following general formula (5):
[Chemical Formula 5]

(Wherein, Y ₂ is a divalent tetravalent organic group having at least two carbon atoms, Z ₁ is a divalent organic group, at least one of Y ₂ and Z ₁ has an alicyclic structure or an aliphatic structure, R ₄ and R ₅ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, m ₃ is an integer of 1 to 100, and n ₅ and n ₆ are each independently an integer of 0 to 2. The photosensitive resin composition which has a structure shown by}. The method of claim 1,
The said photo-acid generator (B) is a naphthoquinone diazide compound, and content of this naphthoquinone diazide compound is 1? With respect to 100 mass parts of said hydroxy polyamide resins (A). It is 50 mass parts, and the said photosensitive resin composition is a compound (C) 1? Which promotes the solubility to aqueous alkali solution with respect to 100 mass parts of said hydroxy polyamide resins (A). The photosensitive resin composition which further contains 100 mass parts. The method of claim 3, wherein
The photosensitive resin composition whose compound (C) which promotes the solubility with respect to the said aqueous alkali solution is a compound containing at least 1 sort (s) of group chosen from the group which consists of a phenolic hydroxyl group, a carboxyl group, and a sulfonyl group. The method of claim 1,
Compound (D) 1 which causes crosslinking reaction by heat with respect to 100 mass parts of said hydroxy polyamide resins (A). The photosensitive resin composition which further contains 50 mass parts. The method of claim 5, wherein
The compound (D) which causes a crosslinking reaction by the said heat is an epoxy compound, an oxetane compound, a melamine compound, an alkenyl compound, following General formula (6)
[Formula 6]

{In formula, R <_6> is a hydrogen atom or the monovalent group chosen from the group which consists of a methyl group, an ethyl group, n-propyl group, and isopropyl group, and R <_7> is a hydrogen atom, a hydroxyl group, and carbon number 1? At least one monovalent organic group selected from the group consisting of 10 alkyl groups, alkoxy groups, ester groups and urethane groups, n ₇ is 1? Is an integer of 5 and n ₈ is 0? Is an integer of 4, where n ₇ + n ₈ = 5 and m ₄ is 1? Is an integer of 4 and Z ₄ is CH ₂ OR ₆ when m ₄ = 1 Or R ₇ And m ₄ = 2? When 4, single bond or 2? Tetravalent organic group, wherein CH ₂ OR ₆ and R ₇ When there are a plurality of R ₆ and R ₇ May be the same as or different from each other.} A compound having a structure represented by Formula (7):
[Formula 7]

{In formula, R <_8> and R <_9> is respectively independently a hydrogen atom or a carbon number of 1? A compound selected from the group consisting of a hydrocarbon group of ₁₀ and R ₁₀ CO-, wherein R ₁₀ is a hydrocarbon group of 1 to ₁₀ carbon atoms. 8) :
[Chemical Formula 8]

{Wherein, D ₁ is the number of carbon atoms 1? 6 is a functional group selected from the group consisting of an alkyl group, an alkenyl group, and a crosslinkable organic group, M ₁ is a group selected from the group consisting of -CH _2- , -O-, and -S-, and Z ₅ is 2 Is an organic group, and n ₉ is 0? Is an integer of 4, D ₁ is the case that a plurality, a plurality of D ₁ will be the same or different.} With at least one compound of the photosensitive resin composition of which is selected from the group consisting of a compound having a structure shown. The method of claim 1,
Compound (E) which generates an acid by heat with respect to 100 weight part of said hydroxy polyamide resins (A) 0.1? The photosensitive resin composition which further contains 30 mass parts. The following process:
(1) Process of forming the photosensitive resin layer which consists of the photosensitive resin composition of any one of Claims 1-7 on a board | substrate,
(2) exposing step;
(3) developing process,
(4) heat-processing the obtained relief pattern,
Method of producing a cured relief pattern comprising a. The hardening relief pattern manufactured by the method of Claim 8. A semiconductor element, and the cured film formed on the semiconductor element, Comprising: The cured film is a cured relief pattern of Claim 9, The semiconductor device characterized by the above-mentioned.  A display element, and the cured film formed on the semiconductor element, Comprising: The cured film is a cured relief pattern of Claim 9, The display device characterized by the above-mentioned. Photosensitivity containing at least one alkali-soluble polymer and naphthoquinone diazide compound selected from the group consisting of a polybenzoxazole precursor having a (thio) ester structure, a polyimide precursor, and a phenol group-containing polyimide in the main chain As the resin composition,
(i) the following steps (a), (b) and (c):
(a) The alkali-soluble polymer is dissolved in γ-butyrolactone at a concentration of 35% by mass of a resin solid to prepare a resin solution:
(b) The resin solution prepared in the above (a) was applied onto a 6-inch silicon wafer, prebaked at 125 ° C. for 180 seconds, and the film thickness when measured using a contact film thickness meter was 10 μm. To form a film of ± 0.2 μm; And
(c) The film thickness obtained by measuring the film after prebaking by arbitrary refractive index (n _f1 ) using a non-contact film thickness meter was made into T _f1 , and obtained by measuring by the contact film thickness meter in (b). The refractive index (n _r1 ) obtained when the film thickness is T _r1 is expressed by the following equation:
n _r1 = n _f1 × T _f1 / T _r1
Obtained by;
The refractive index (n _r1 ) of the alkali-soluble polymer obtained by performing the procedure in order was 1.570? Is in the range of 1.650,
(ii) the following (a '), (b') and (c '):
(a ') 100 mass parts of the said alkali-soluble polymer is melt | dissolved in (gamma) -butyrolactone at the density | concentration of 35 mass% of resin solid content, 15 mass parts of said naphthoquinone diazide compounds are further dissolved, and the solution of the photosensitive resin composition is produced. ;
(b ') When the solution of the photosensitive resin composition produced by said (a') was apply | coated on a 6 inch silicon wafer, it prebaked for 125 degreeC 180 second, and measured using a contact film thickness meter. To form a film having a film thickness of 10 µm ± 0.2 µm; And
(c ') non-contact to the film using a thickness meter, a film after pre-baking at any of the refractive index the film thickness obtained by measuring a (n _f2) to T _f2, and the (b' contact film measured by the thickness meter in) The true refractive index (n _r2 ), which is obtained when the film thickness obtained by making T _r2 is expressed by the following equation:
n _r2 = n _f2 × T _f2 / T _r2
Obtained by;
The refractive index (n _r2 ) of the said photosensitive resin composition obtained by carrying out in order, and the refractive index (n _r1 ) of the said alkali-soluble polymer are the following conditions:
{Refractive index (n _r1 ) / refractive index (n _r2 ) of the photosensitive resin composition} of an alkali-soluble polymer} × 100 = 1.0? 3.0 (%)
The photosensitive resin composition satisfying the.

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