KR101781702B1

KR101781702B1 - Photosensitive resin composition

Info

Publication number: KR101781702B1
Application number: KR1020157006158A
Authority: KR
Inventors: 마사키 혼다; 다카유키 가나다; 마사히코 요시다; 도모시게 유노쿠치; 도모히토 오구라
Original assignee: 아사히 가세이 이-매터리얼즈 가부시키가이샤
Priority date: 2012-09-18
Filing date: 2013-09-13
Publication date: 2017-09-25
Also published as: CN104641293A; JP6587661B2; TW201421161A; KR20170084364A; JPWO2014046062A1; KR101900636B1; TWI559089B; WO2014046062A1; JP2018022171A; CN109298601A; JP6348419B2; KR20150042820A; CN104641293B

Abstract

Provided is a photosensitive resin composition having a high residual film ratio and high sensitivity, and having a uniform surface after development. (a) a compound represented by the following general formula (1):

Wherein R ₁ and R ₂ each independently represent a divalent to octavalent organic group having 2 to 60 carbon atoms and R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a C 1-20 D and e each independently represent an integer of 0 to 2 and may not be 0 at the same time, f and g are each independently an integer of 0 to 4, and n is a positive integer) , (B) a quinone diazide compound, and (c) a phenol resin having a specific structure.

Description

[0001] PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to, for example, an insulating material for electronic components, and a photosensitive resin composition used for forming a relief pattern such as a passivation film, a buffer coat film, and an interlayer insulating film in a semiconductor device.

2. Description of the Related Art Polyimide resins, polybenzoxazole resins, and the like, which have excellent heat resistance, electrical characteristics, and mechanical characteristics, have been widely used in surface protective films and interlayer insulating films used in semiconductor devices in the past. Since these resins are low in solubility in various solvents, they are often provided as a composition dissolved in a solvent in the form of a precursor.

In recent years, countermeasures for de-organic solvents have been demanded from a rise in environmental problems, etc., and various heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution have been proposed in the same manner as photoresists.

Among them, various methods for using a hydroxypolyamide resin soluble in an alkaline aqueous solution which becomes a heat resistant resin after heat curing with a photoacid generator such as a naphthoquinone diazide compound have been proposed.

The development mechanism of this photosensitive resin composition is such that the dissolution rate of the naphthoquinone diazide compound (that is, the photosensitive diazoquinone compound) and the polybenzoxazole (PBO) precursor in the unexposed portion is small in the alkaline aqueous solution, The photosensitive diazoquinone compound is chemically changed to an indenecarboxylic acid compound to increase the dissolution rate of the exposed portion in the alkaline aqueous solution. By using the difference in dissolution rate between the exposed portion and the unexposed portion with respect to the developing solution, it is possible to manufacture a relief pattern composed of the unexposed portion.

The above-described composition can form a positive relief pattern by exposure and development with an alkaline aqueous solution. In addition, the thermally cured film characteristics are obtained by heating.

However, in the manufacturing process of semiconductors and the like, fine processing is progressing at present, and the interval between the pattern and the pattern is shortened. Therefore, in the unexposed portion adjacent to the opened exposed portion, even if the dissolution rate of the unexposed portion is small, the contact with the developer comes not only from the top of the film but also from the side face at the time of development, The shape of the semiconductor device becomes excessively thin, thereby lowering the reliability of the semiconductor package in the manufacturing process of the semiconductor device.

Therefore, it is necessary to develop the developing solution without substantially dissolving the unexposed portion (this phenomenon is referred to as high developing residual film ratio, and in this disclosure, 95 to 100% of the developing residual film ratio is defined as high developing residual film ratio).

However, when the developing residual film ratio is increased, a high exposure amount is required for development of the exposed portion (this is referred to as a low sensitivity).

Discloses a system in which a phenolic resin is added to a heat-resistant resin precursor as a method of making a film having high adhesiveness and high sensitivity at the time of development. Specifically, a photosensitive resin composition containing a polyamic acid silyl ester, a diazonaphthoquinone sulfonic acid ester and a phenol novolac resin (Patent Document 1), a hydroxypolyamide resin, a photosensitive diazonaphthoquinone compound and a specific phenol (Patent Document 2), a photosensitive resin composition containing a hydroxypolyamide resin having a specific structure, a quinone diazide compound, a novolac resin and / or a polyhydroxystyrene (Patent Document 3) .

Further, a photosensitive resin composition containing a phenol resin, a photosensitive diazoquinone compound, a polyfunctional methylol compound, and a solvent in a polyamide resin having a phenolic hydroxyl group (Patent Document 4) has been proposed.

In addition, a photosensitive resin composition (Patent Document 5) using a hydroxypolyamide having at least one ester or thioester structure in the polymer main skeleton is described as a technique of making a goosan film and high sensitivity.

Japanese Patent Publication No. 3369344 Japanese Patent Publication No. 3966667 Japanese Patent Publication No. 4548001 Japanese Laid-Open Patent Publication No. 2005-250160 International publication No. 2011/135887 pamphlet

However, in the phenol resins described in Patent Documents 1 to 5, since the surface of the film after coating with the resin composition is uniform, but the compatibility with the hydroxypolyamide resin is low, the surface of the film after development becomes whitened, There is a problem that it occurs.

Accordingly, an object of the present invention is to provide a photosensitive resin composition having a high developing residual film ratio, high sensitivity, and uniform surface after development.

The inventors of the present invention have conducted intensive studies and have found that the above problems can be solved by using a combination of a hydroxypolyamide derivative and a phenol resin having a specific structure in view of the problems of the prior art described above, . That is, the present invention is as follows.

[One]

(a) a compound represented by the following general formula (1):

[Chemical Formula 1]

Wherein R ₁ and R ₂ each independently represent a divalent to octavalent organic group having 2 to 60 carbon atoms and R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a C 1-20 D and e each independently represent an integer of 0 to 2 and may not be 0 at the same time, f and g are each independently an integer of 0 to 4, and n is a positive integer)

A polymer having a structural unit as a main component,

(b) a quinone diazide compound,

(c) a phenolic resin,

(C) the phenolic resin is represented by the following general formulas (2), (3), and (4)

(2)

(Wherein R ₇ and R ₈ each independently represent a monovalent organic group having 1 to 10 carbon atoms, h and j are each independently an integer of 1 to 3, i and k are independently integers of 0 to 2 4, 1? (J + k)? 4, m1 is 0 or a positive integer, and m2 is a positive integer.

(3)

(Wherein R ₉ and R ₁₀ each independently represent a monovalent organic group having 1 to 10 carbon atoms, l is 2 or 3, p is an integer of 1 to 3, and o and q are each independently 0 to 2 4, 1? (P + q)? 4, m3 is a positive integer, and m4 is 0 or a positive integer.

[Chemical Formula 4]

(Wherein R ₁₁ and R ₁₂ each independently represent a monovalent organic group having 1 to 10 carbon atoms, r and u are each independently an integer of 1 to 3, s and v are each independently an integer of 0 to 2 M + 5 is a positive integer, and m6 is a positive integer, and m11 is a positive integer, and P < (r + s) ₁ is a monovalent hydrocarbon group of 1 to 20 carbon atoms which may be substituted with a hydroxyl group, a carboxyl group or an amino group)

[Chemical Formula 5]

{Wherein, R ₁₃ each independently represents a monovalent organic group having a carbon number of 1 ~ 10, w is an integer from 1 ~ 3, x is an integer from 0 to 2, and satisfies 1 ≤ (w + x) ≤ 4 M7 is a positive integer, m8 is 0 or a positive integer, and Y is a group represented by the following formula (5 '):

[Chemical Formula 6]

(P ₄ and P ₅ are each independently a hydrogen atom, a monovalent aliphatic group which may be substituted with fluorine having 1 to 20 carbon atoms, or a substituted or unsubstituted monovalent aromatic group having 6 to 20 carbon atoms)

Is a divalent organic group selected from the group consisting of

Wherein the positive photosensitive resin composition has a structure represented by at least one of the following groups:

[2]

Wherein the phenol resin is represented by the following general formula (4 '):

(7)

(Wherein R ₁₁ and R ₁₂ each independently represent a monovalent organic group having 1 to 10 carbon atoms, r, t and u are each independently an integer of 1 to 3, and s and v are each independently 0 to 2 (R + s)? 4, 1? (U + v)? 4, m5 is 0 or a positive integer, and m6 is a positive integer.

Is a positive photosensitive resin composition according to [1].

[3]

Wherein the phenol resin is at least one selected from the group consisting of the general formula group (5), wherein Y is a group represented by the following general formula (5 "):

[Chemical Formula 8]

(P ₄ and P ₅ are the same as defined in the above sikgun 5 'respectively)

Is a positive photosensitive resin composition according to [1].

[4]

The positive photosensitive resin composition according to any one of the above items [1] to [3], wherein R ₁ or R _{2 in} the general formula (1) or both have an ester bond.

[5]

Wherein R ₁ or R ₂ in the general formula (1) is a group represented by the following general formula (6):

[Chemical Formula 9]

(Wherein R ₁₈ , R ₁₉ and R ₂₀ each independently represent a divalent organic group having 2 to 60 carbon atoms, at least one of R ₁₈ , R ₁₉ and R ₂₀ has an alicyclic or aliphatic structure, and m Is 0 or 1)

Is a positive photosensitive resin composition according to any one of the above [1] to [4].

[6]

R < ₃ > or R < ₄ > in the general formula (1)

[Chemical formula 10]

(Wherein R ₂₁ represents a monovalent organic group having 1 to 19 carbon atoms)

Is a positive photosensitive resin composition according to any one of the above [1] to [5].

[7]

(A) a step of forming, on a substrate, a photosensitive resin layer composed of the photosensitive resin composition according to any one of the above [1] to [6]

(B) a step of exposing the photosensitive resin layer,

(C) a step of removing the exposed portion with a developer to obtain a relief pattern, and

(D) heating the relief pattern.

[8]

A cured relief pattern produced by the method described in [7] above.

[9]

A semiconductor device comprising a semiconductor element and a cured film formed on the semiconductor element, wherein the cured film is the cured relief pattern described in the above [8].

[10]

A display body device comprising a display body element and a cured film formed on the display body element, wherein the cured film is the cured relief pattern described in the above [8].

[11]

A cured film containing at least one resin selected from the group consisting of polyimide and polybenzoxazole, and a phenolic resin,

The cured film, under the following conditions,

Plasma species: microwave

Process gas: O ₂

Processing time: 60 seconds

Of 0.5 to 5.0 nm when measured using an atomic force microscope (AFM) after the dry etching treatment of the cured film.

[12]

The cured film according to the above-mentioned [11], wherein the rate of change in weight loss when heat-treated at 240 캜 for 10 hours in an air atmosphere is 0.1 to 3.0%.

[13]

The cured film according to the above [11] or [12], wherein the cured film contains 20 to 200 parts by mass of the phenol resin per 100 parts by mass of at least one resin selected from the group consisting of polyimide and polybenzoxazole.

According to the present invention, it is possible to provide a photosensitive resin composition having a high developing residual rate and a high sensitivity, which can prevent whitening after development and have uniform surfaces.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing ¹³ C-NMR results of the hydroxypolyamide resin (P-2) obtained in Synthesis Example 6. FIG.
2 is a diagram showing the ¹ H-NMR results of the phenol resin (N-1) obtained in Synthesis Example 8.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, exemplary forms (hereinafter abbreviated as "embodiments") for carrying out the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications may be made within the scope of the present invention.

In the present embodiment, the photosensitive resin composition comprises (a) a compound represented by the general formula (1):

(11)

(B) a quinone diazide compound (hereinafter also referred to as a quinone diazide compound (b)), (c) a phenol resin (hereinafter also referred to as " , And phenol resin (c)). Here, the main component means 50% by mass or more. Hereinafter, these structures and other components will be described in detail. Unless otherwise specified in the present specification, the structures represented by the same symbols in the general formula may be the same or different from each other when a plurality of structures exist in the molecule. The repeating arrangement in the case where two or more repeating units are present is not limited as long as there is no special mention, and may be random, block, or alternating.

The polymer (a) in the present invention is a polymer having as a main component a structural unit of repeating number n in the general formula (1) (also referred to as a structural unit represented by the general formula (1) in the present disclosure) The catalyst can be a polymer having an imide ring, an oxazole ring, or the like. Preferable examples of the polymer (a) include a polyimide precursor polyamide acid, a polyamide acid ester, and a polyhydroxyamide of a polybenzoxazole precursor. When the polymer (a) is a polymer having a cyclic structure, heat resistance and solvent resistance are remarkably improved. In the polymer (a), one structural unit represented by the general formula (1) may be used, or two or more structural units may be used. When two or more kinds of structural units are present, the arrangement of the structural units may be a block or random, and the number of repeating units n is the total number of repeating units of two or more structural units.

The polymer comprising a structural unit represented by the general formula (1) as a main component is prepared from a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid and a derivative thereof and bis (aminophenol), and a phenol group Having a polyamide structure which is a precursor of polybenzoxazole (hereinafter also referred to as PBO) having a phenolic group or a polyamide structure having a phenol group, which is produced from a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid and a derivative thereof and diaminophenol, Amide structure is preferable.

Repeating unit represented by the general formula (1), for example R ₁ (OR ₃₎ _d (COOR ₅₎ _f (COOH), a dicarboxylic acid, R ₂ (NH ₂₎ having the structure of _{2 2} (OR ₄₎ _e (COOR _< ₆ _> ) _g structure.

In the general formula (1), n is not limited as long as it is a positive integer, but is preferably 1 to 1000, more preferably 3 to 50, and most preferably 3 to 30 from the viewpoint of developability .

R ₂ (NH ₂ ) ₂ (OR ₄ ) _e (COOR ₆ ) _g structure.

Examples of the bisaminophenol compound in which R ₄ is a hydrogen atom and e is 2 include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydro 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino Dihydroxydiphenyl sulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2- Hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxy Phenyl ether, 1,4-diamino-2,5-di De-hydroxy benzene, 1,3-diamino-2,4-dihydroxy-benzene, and 1,3-diamino-4,6-dihydroxy-benzene, and to the R ₂ sikgun:

[Chemical Formula 12]

And a bisaminophenol compound which is a tetravalent organic group selected from the group consisting of

Of these bisaminophenol compounds, particularly preferred from the viewpoint of solubility in an alkali developing solution and heat resistance are compounds in which R ₂ is a tetravalent organic group selected from the above group.

In the bis (aminophenol) (e.g., R ₂ (NH ₂₎ ₂ (OR ₄₎ _e (COOR that the R ₂ in the ₆₎ _g structure selected from the sikgun), and combining a benzene ring to each other The substituent may be an amino group at the meta position, a hydroxyl group at the para position, or a hydroxyl group at the meta position or an amino group at the para position, but from the viewpoint of solubility in solvents, The position is preferably a hydroxyl group.

Also, as a diamine having a structure of R ₂ (NH ₂ ) ₂ (OR ₄ ) _e (COOR ₆ ) _g ,

[Chemical Formula 13]

(Wherein X ₃ is a tetravalent organic group having 2 to 60 carbon atoms)

(Hereinafter referred to as " diamine having a PBO precursor structure in the molecule ") having two sets of amide bonds in the ortho position and a phenolic hydroxyl group in the molecule represented by the formula

X ₃ is not limited as long as it is a tetravalent organic group having 2 to 60 carbon atoms, but from the viewpoint of solubility and heat resistance to an alkaline developer, it is preferable that the structure is exemplified as a preferable organic group represented by R ₂ described above.

As a preferable structure of a diamine having a PBO precursor structure in a molecule, more specifically, the following structure may be mentioned.

[Chemical Formula 14]

As a method for producing the compound represented by the above structure, there can be mentioned a method in which two molecules of nitrobenzoic acid are reacted with the above-mentioned bisaminophenol, followed by reduction of the nitro group to an amino group.

The diamines having a structure of R ₂ (NH ₂ ) ₂ (OR ₄ ) _e (COOR ₆ ) _g include the following structures:

[Chemical Formula 15]

(Wherein Y ₃ represents a divalent organic group having 2 to 60 carbon atoms)

Can be used.

Y ₃ in the above structure is not limited as long as it is a divalent organic group having 2 to 60 carbon atoms, but from the viewpoint of solubility and heat resistance to an alkali developer, examples of organic groups represented by R ₁ include at least one organic group Lt; / RTI >

Preferable examples of such a compound include the following structures specifically.

[Chemical Formula 16]

Such a compound can be obtained, for example, by reacting a dicarboxylic acid dichloride compound with two molecules of nitroaminophenol and reducing the nitro group to an amino group.

Further, as a diamine having a structure of R ₂ (NH ₂ ) ₂ (OR ₄ ) _e (COOR ₆ ) _g , a compound having two sets of polyimide precursor structures in the molecule (hereinafter referred to as "bisamino Phenol ") may also be used. Examples of such compounds include, but are not limited to, the following structures:

[Chemical Formula 17]

(Wherein Y ₄ represents a tetravalent organic group having 4 to 60 carbon atoms and R ₆ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms)

. &Lt; / RTI >

More specific examples of such a compound include the following structures.

[Chemical Formula 18]

(R < ₆ > represents hydrogen or a monovalent hydrocarbon group of 1 to 20 carbon atoms)

Examples of the method for producing bisaminophenol having a PI precursor structure in a molecule include a method in which a tetracarboxylic acid dianhydride is reacted with a monoalcohol or a dicarboxylic acid which is substituted with a monoamine or the like, And an aniline having a nitro group, followed by reduction of the nitro group.

Next, diamines having both of e and g as a diamine having a structure of R ₂ (NH ₂ ) ₂ (OR ₄ ) _e (COOR ₆ ) _g as a raw material will be explained. Such diamines are advantageous in the case of adjusting the solubility in an alkali developing solution. As these diamine compounds, aromatic diamines and the like can be mentioned. An aromatic diamine is advantageous in terms of heat resistance.

Examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether , 4,4'-diaminodiphenyl ether, 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'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2'-bis (4-aminophenyl) propane, 2,2'- (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl- Bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis Aminobenzyl) benzene, imino-di-p-phenylenediamine, 1,5-diaminonaph (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl) -1,3,3- 4,4'-diaminodiphenylurea, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenylurea, Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] benzophenone, 4,4'-bis (4-aminophenoxy) diphenyl sulfone, (4-aminobenzyl) phenoxy] diphenyl sulfone, 4,4'-diaminobiphenyl, 4,4'-diamino Benzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, o-toluidine sulfone, 2,2 Bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) 4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 4, 4'-di- (3-aminophenoxy) diphenyl sulfone and 4,4'-diaminobenzanilide.

The hydrogen atoms of the aromatic nuclei of the aromatic diamine may be substituted with a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group or a phenyl group.

Silicon diamine may be selected as part or all of the diamine. Examples of silicone diamines include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethyldisiloxane, bis , Bis (? -Aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane and bis (? -Aminopropyl) tetraphenyldisiloxane.

Next, the dicarboxylic acid having the structure of R ₁ (OR ₃ ) _d (COOR ₅ ) _f (COOH) ₂ will be described.

D = f = 0 in R ₁ (OR ₃ ) _d (COOR ₅ ) _f (COOH) ₂ . Such a dicarboxylic acid is advantageous in the case of adjusting the solubility in an alkali developing solution. As R ₁ in the case of d = f = 0, the following structure can be mentioned.

[Chemical 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 k L ₁ bonded to the ring carbon each independently represent a 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),

[Chemical Formula 20]

(Wherein n ₁₀ is an integer of 1 to 12), and

[Chemical Formula 21]

(Wherein L ₂ , L ₃ and L ₄ each independently represents a hydrogen atom or a methyl group, and L ₅ represents a hydrogen atom, a methyl group or a hydroxyl group).

Among them, bis (carboxy) tricyclo [5,2,1,02,6] decane is a representative example of a dicarboxylic acid having a tricyclodecane skeleton. As a production example of the compound, a synthetic example of a pamphlet of International Publication No. 2009/081950 can be exemplified.

Further, as the dicarboxylic acid in the case of d = 0 and f = 2 in R ₁ (OR ₃ ) _d (COOR ₅ ) _f (COOH) ₂ , the tetracarboxylic acid dianhydride is reacted with a monoalcohol, A dicarboxylic acid that has been converted to an amine or the like may be used. Examples of the monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, benzyl alcohol and the like. Examples of the monoamine include butylamine and aniline. Examples of the above tetracarboxylic acid dianhydride include compounds represented by the following formulas.

[Chemical Formula 22]

(Wherein B is selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C (CF ₃ ) ₂ -, and -COO- Lt; / RTI >

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

As the dicarboxylic acid in the case of R ₁ (OR ₃ ) _d (COOR ₅ ) _f (COOH) ₂ where R ₃ is hydrogen, d = 1 or 2 and f = 2, The dicarboxylic acid having an amide bond and a phenolic hydroxyl group at ortho positions of each other may be used. As such a dicarboxylic acid, for example, a compound represented by the following formula can be mentioned.

(23)

(Wherein X ₅ represents a trivalent or tetravalent organic group having at least two carbon atoms, R ₅ represents a monovalent hydrocarbon group of 1 to 20 carbon atoms, and n ₁₁ represents an integer of 1 or 2)

A process for producing the compound represented by the above formula include, for example, the structure of the of R ₂ (NH ₂₎ ₂ (OH), bis (aminophenol) or R ₂ (NH ₂₎ having the structure of ₂ ₂ (OH) Can be reacted with diaminophenol having two molecules of trimellitic acid chloride and further reacting an acid anhydride with an alcohol.

As a polycondensation method of the dicarboxylic acid and the bisaminophenol compound (diamine) for synthesizing the polyhydroxyamide, dicarboxylic acid and thionyl chloride are used to obtain diacid chloride, and bisaminophenol (diamine ), Or a method of polycondensation of dicarboxylic acid and bisaminophenol (diamine) by dicyclohexylcarbodiimide, and the like. In the method using dicyclohexylcarbodiimide, hydroxybenzotriazole may also be simultaneously operated.

In the present embodiment, it is preferable that R ₁ and / or R ₂ in the general formula (1) have a structure having an ester bond. When R ₁ and / or R ₂ of the polymer having the main structural unit represented by the general formula (1) according to the present embodiment has an ester structure, compatibility with the phenol resin (c) to be described later is good, A specific effect that the surface state becomes particularly good is exhibited. The reason for this is not clear, but the present inventors have estimated the following reasons. The polymer having a structural unit represented by the general formula (1) as a main component has an amide bond, and because of the polarity of the amide, the bond between the amide-amide is strong, so that the polymer tends to associate with the polymer and is highly compatible with the phenol resin It does not. On the other hand, the polarity of the ester and the phenol resin are close to each other and the amide bond ratio is relatively decreased, so that the compatibility between the polymer (a) and the phenol resin (c) is enhanced.

Examples of the ester structure include a structure represented by the following general formula (6)

&Lt; EMI ID =

(Wherein Ar ₁ and Ar ₂ each independently represent an aromatic group)

.

From the viewpoint of lithography, it is more preferable that R ₁ or R ₂ in the general formula (1) has a structure represented by the following general formula (6).

(25)

Structure represented by the above general formula (6) include, for example, (α) R ₁₉ and R in the general formula (6) and containing a hydroxyl group having the structure R ₁₈ in the compound, (β), the formula (6) _And at least one carboxylic acid compound selected from the group consisting of a polyvalent carboxylic acid having a structure of formula (I) and a derivative thereof.

Hereinafter, the hydroxyl group-containing compound having the structure of (?) R ₁₈ will be described.

R ₁₈ is a residue derived from a divalent phenol compound or an alcohol compound. Examples of the hydroxyl group-containing compound having the structure of R ₁₈ include a phenol compound and an alcohol compound. Specific examples of the divalent phenol compound include hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylmethane Methylenebis (2-methylphenol), 4,4'-methylenebis (2,6-dimethylphenol), 2,2'-methylenebis (6-tert- , 4,4'-dihydroxydiphenyl propane, TM124 (Degussa Japan: trade name), 2,2-bis (4-hydroxyphenyl) butane, 4,4'- (3-dimethylbutylidene) diphenol, 4,4 '- (2-ethylhexylidene) diphenol, hexestrol, 2,2- Bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis 4-hydroxyphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 4, 4'-butylidenebis (6-tert-butyl-m-cresol), 1,1- (4-hydroxyphenyl) cyclohexane, 4,4 '- (? - methylbenzylidene) bisphenol, 1,3- Bis (4-hydroxyphenyl) fluorene, 4,4'-dihydroxytetraphenylmethane, 4,4'-dihydroxydiphenyl hexafluoropropane, 4,4'-dihydroxybenzophenone, 4 Dihydroxydiphenyl ether, 1,3-bis (4-hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenyl sulfone, bis (4-hydroxyphenyl) sulfide, di Phenol acid and the like.

As the phenol compound, a phenol compound containing a functional group may also be used. Examples of the functional group include an amide group, an imide group, a urea group, a urethane group and an ether group.

Specific examples of the dihydric alcohol compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-pentanediol, 1,2- 1,2-decanediol, 1,2-dodecanediol, 2,5-hexanediol, cis-2-butene-1,4-diol, 2,2- 2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,5-hexadiene-3,4-diol, 2,5- Dimethyl-3-hexyne-2,5-diol, 2,4,7,9-tetramethyl-5-decyne-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- menthan- Dimethoxybenzyl alcohol, and butyroin.

As the alcohol compound, an alcohol compound containing a functional group may be used similarly to the phenol compound. Examples of the functional group include an amide group, an imide group, a urea group, a urethane group and an ether group.

Next, at least one carboxylic acid compound selected from the group consisting of polyvalent carboxylic acids having a structure of (R) ₁₉ and R ₂₀ and derivatives thereof will be described.

R < ₁₉ > and R < ₂₀ > may be a divalent carboxylic acid, and concretely, a divalent carboxylic acid having a moiety having the same structure as that listed above as an example of R < ₁ > Carboxylic acids can be used.

In the case where R ₁ and / or R ₂ have an ester bond in the polymer having a structural unit represented by the above general formula (1) as a main component, more preferably R ₁ or R ₂ is a group represented by the general formula (6) Structure is advantageous in terms of i-line transmittance.

In the general formula (6), at least one of R ₁₈ , R ₁₉ and R ₂₀ has an alicyclic structure or an aliphatic structure, particularly from the viewpoint of i-line transmittance and high sensitivity. In this disclosure, " aliphatic " means a chain aliphatic unless otherwise specified. In particular, it is preferable that R ₁₈ in the general formula (6) is an aromatic group, and R ₁₉ and R ₂₀ both have an alicyclic structure or an aliphatic structure (that is, R ₁₉ and R ₂₀ do not have an aromatic structure). In this case, it is advantageous in terms of additional i-line transmittance and high sensitivity.

From the viewpoint of solubility in a solvent, the number of carbon atoms of R ₁₈ is preferably 2 to 30, and the number of carbon atoms of R ₁₉ and R ₂₀ is preferably 2 to 15, respectively. R ₁₈ , R ₁₉ and R ₂₀ preferably contain 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 group.

From the viewpoint of further improvement in i-line transmittance and lithography performance, R ₁₈ in the general formula (6) is more preferably selected from the structures represented by the following general formula (8), and R ₁₉ and R ₂₀ each represent a general formula ) Is more preferable.

(26)

(Wherein R ₁₆ represents a divalent hydrocarbon group of 1 to 18 carbon atoms, and R ₁₇ independently represents a hydrogen atom or a monovalent organic group of 1 to 17 carbon atoms)

(27)

(Wherein A ₁ is selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C (CF ₃ ) ₂ - L ₁ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; k = 4; a plurality of L _{1 s} present may be the same or different; and L ₂ to L ₄ each independently , L ₅ represents a hydrogen atom, a methyl group or a hydroxyl group, and n ₁₀ represents an integer of 1 to 12)

The ratio of the ester group-containing structure represented by the general formula (6) in the polymer containing the structural unit represented by the general formula (1) is preferably 5 to 80 moles in view of good solubility in an alkali developing solution and mechanical properties of the resulting resin film. %.

R ₃ and / or R ₄ in the polymer having a structural unit represented by the general formula (1) as a main component are represented by the following general formula (7):

(28)

As shown in Fig.

The structure of R ₂₁ is not particularly limited, but is preferably an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 10 carbon atoms, and these hydrogen atoms may be replaced by a chlorine atom, a fluorine atom, a bromine atom, a methoxy group, And a phenyl group. From the viewpoint of suppressing the shrinkage upon curing, the number of carbon atoms of R ₂₁ is preferably from 1 to 19, more preferably from 1 to 10, still more preferably from 1 to 6, more specifically R ₂₁ is a methyl group, And a phenyl group.

The ratio of the number of groups represented by the general formula (7) in the number of R ₃ and R ₄ in the polymer having the structural unit represented by the general formula (1) as a main component is preferably from 0.1% And preferably 10 mol%.

The introduction of the group represented by the general formula (7) as R ₃ and / or R ₄ of the polymer having the structural unit represented by the general formula (1) as a main component is preferably carried out by mixing the polymer (a) with a phenol resin (c) So that the surface condition after development becomes particularly good. The reason for this is not clear, but the present inventors have estimated the following reasons. The polymer having a structural unit represented by the general formula (1) as a main component has an amide bond, and because of the polarity of the amide, the bond between the amide-amide is strong, so that the polymer tends to associate with the polymer and is highly compatible with the phenol resin It does not. On the other hand, when the ester structure is introduced by the structure of the general formula (7), the ester has a polarity close to that of the phenol resin, and the amide bond ratio is relatively decreased. ) Is increased.

The polymer (a) having a structural unit represented by the above-described general formula (1) as a main component may be sealed with an end group of an organic group (hereinafter referred to as " sealant ").

In the polycondensation of hydroxypolyamide, when the dicarboxylic acid component is used in an excessive molar amount relative to the sum of the bisaminophenol component and the diamine component, a compound having an amino group or a hydroxyl group is used as an encapsulating agent . Examples of the compound include aniline, ethynyl aniline, norbornenamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, and hydroxyethyl acrylate. .

Conversely, when the sum of the bisaminophenol component and the diamine component is used in excess of the molar amount of the dicarboxylic acid component, the compound having an ester group is preferably a compound having an acid anhydride, a carboxylic acid, an acid chloride, an isocyanate group or the like Or the like is preferably used. Examples of the compound include benzoyl chloride, norbornene dicarboxylic acid anhydride, norbornenecarboxylic acid, ethynylphthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic acid anhydride, Methylcyclohexanedicarboxylic acid anhydride, cyclohexene dicarboxylic acid anhydride, methacryloyloxyethyl methacrylate, phenylisocyanate, mesyl chloride, and tosyl chloride.

The polymer (a) having a structural unit represented by the general formula (1) as a main component may contain an additional structural unit other than the structural unit represented by the general formula (1) within the range not impairing the effect of the present invention . Examples of the added structural unit include a polyhydroxyimide structure, a polyester structure, and a polyamide structure not containing a hydroxyl group. The proportion of the structural unit represented by the general formula (1) in the polymer (a) is more than 50% by mass, the developed residual film ratio is high, the sensitivity is high, the surface after development is uniform, the shape of the cured relief pattern is good Is preferably 75 to 100% by mass, more preferably 90 to 100% by mass from the viewpoint of obtaining a photosensitive resin composition which does not cause metal corrosion after etching with the fluorine-based compound gas.

The polystyrene reduced weight average molecular weight of the polymer (a) having a structural unit represented by the above general formula (1) as a main component by gel permeation chromatography (hereinafter also referred to as "GPC") is preferably 3,000 to 70,000, More preferably 50,000. The weight average molecular weight is preferably 3,000 or more from the viewpoint of the physical properties of the cured relief pattern, and is preferably 70,000 or less from the viewpoint of resolution. As the developing solvent for GPC, tetrahydrofuran (hereinafter also referred to as "THF") and N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP") are recommended. The molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As a standard monodisperse polystyrene, it is recommended to choose STANDARD SM-105 as a standard sample of organic solvent system manufactured by Showa Denko KK.

(b) a quinone diazide compound

As the quinone diazide compound (b), various compounds which act as photoacid generators can be used. Among them, a naphthoquinone diazide compound (NQD compound) is preferable, and 1,2-naphthoquinone di Compounds having a zid structure are preferred. Examples of the compound having a 1,2-naphthoquinone diazide structure include 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and polyhydroxy At least one NQD compound selected from the group consisting of 1,2-naphthoquinonediazide-5-sulfonic acid ester of the compound is preferable.

The NQD compound can be obtained by condensing naphthoquinonediazide sulfonic acid compound with chlorosulfonic acid or thionyl chloride with sulfonyl chloride and condensing naphthoquinonediazide sulfonyl chloride with a polyhydroxy compound according to a conventional method . For example, when a polyhydroxy compound and a predetermined amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride are reacted with dioxane, acetone , Tetrahydrofuran, or the like in the presence of a basic catalyst such as triethylamine, esterification is carried out, and the obtained product is washed with water and dried to obtain an NQD compound.

Examples of preferred NQD compounds include those represented by the following general formula groups.

[Chemical Formula 29]

(Wherein Q is a hydrogen atom, or the group of the following formulas:

(30)

, All the Q groups may not be hydrogen atoms at the same time)

In addition, a naphthoquinone diazide sulfonyl ester compound containing a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be used, or a 4-naphthoquinone diazide sulfonyl ester compound An ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be mixed and used.

The amount of the quinone diazide compound (b) to be added to the entire alkali-soluble resin is preferably 1 to 100 parts by mass based on 100 parts by mass of the total amount of the polymer (a) and the phenol resin (c) having the structural unit represented by the formula (1) To 50 parts by mass is preferable, and 5 parts by mass to 30 parts by mass is more preferable. When the amount of the quinone diazide compound (b) is 1 part by mass or more, the resin has good patterning property, and when it is 50 parts by mass or less, the tensile elongation of the film after curing is good and the developing residue (scum) .

(c) phenol resin

The phenol resin (c) in the present embodiment has a structure represented by at least one selected from the group consisting of the following general formulas (2), (3) and (4) and general formula group (5).

(31)

(32)

(33)

(34)

(35)

Is a divalent organic group selected from the group consisting of

The phenol resin (c) has a dissolution inhibiting effect for the quinone diazide compound (b), while the unexposed portion has a dissolution promoting effect, and the contrast can be generated to form a pattern. However, since general phenol resins such as cresol / formaldehyde novolak resin and phenol / formaldehyde novolac resin are poor in compatibility with the polymer (a), the film obtained by coating the photosensitive resin composition is uniform, There is a problem that the surface is whitened in the subsequent film.

On the other hand, the phenol resin having a structure represented by at least one of the general formulas (2), (3), and (4) and the general formula group (5) has high compatibility with the polymer (a). Therefore, according to the photosensitive resin composition of the present embodiment, whitening does not occur after development, and a film having a uniform surface can be formed. When the compatibility of the polymer (a) with the phenol resin is poor, the white pigment after development causes phase separation in the film, resulting in irregularities in the film surface after development due to the difference in solubility between the polymer (a) and the phenolic resin . According to the present embodiment, by combining the polymer (a) and the phenol resin (c), these whitening and surface roughness can be prevented, and a uniform surface film can be formed. The reason for this is not clear, but the present inventors have estimated the following reasons. In general, the material is considered to be easy to mix as the polarity is closer. It is generally considered that the polarity of the phenol resin (c) used in the present invention is close to that of the polymer (a) or that the phenol resin (c) It seems to be because it is a configuration.

The content of the phenolic resin (c) in the present embodiment is preferably in the range of 20 to 200 parts by mass based on 100 parts by mass of the polymer (a). The content thereof is preferably 20 parts by mass or more from the viewpoint of sensitivity, and 200 parts by mass or less is preferable from the viewpoint of heat resistance. The content thereof is more preferably 50 to 150 parts by mass, and still more preferably 50 to 100 parts by mass from the viewpoint of heat resistance.

In the general formula (2), from the viewpoint of sensitivity, i and k are preferably 0 or 1, and R ₇ and R ₈ are each preferably a methyl group or an ethyl group. From the viewpoint of the pattern shape after curing, it is preferable that h and j are 1 or 2, respectively. The total number of m1 and m2 is preferably 5 or more, more preferably 10 or more, further preferably 20 or more from the viewpoint of heat resistance, and is preferably 300 or less, more preferably 250 Or less, more preferably 200 or less. The ratio (m1 / m2) of m1 to m2 is preferably 1/99 or more, more preferably 10/90 or more, further preferably 20/80 or more, from the viewpoint of alkali solubility, , Preferably 90/10 or less, more preferably 80/20 or less, further preferably 70/30 or less.

The structure represented by the general formula (2) is more preferably a structure represented by the following formula.

(36)

(Wherein m9 and m10 are each independently 0 or a positive integer, and m9 and m10 are not 0 at the same time, the sum of m9 and m10 is the same as m1 in the general formula (2) Lt; / RTI > is as defined in general formula (2)

In the general formula (3), from the viewpoint of sensitivity, it is preferable that o and q are each 0 or 1, and R ₉ and R ₁₀ are each preferably a methyl group or an ethyl group. From the viewpoint of the pattern shape after curing, l is preferably 2, and p is preferably 1 or 2. When p and q in the structural unit represented by the repeating number m4 are each 1, it is preferable that R ₁₀ is in a meta position or a para position with respect to the phenolic hydroxyl group. The total number of m3 and m4 is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more from the viewpoint of heat resistance, and is preferably 300 or less, more preferably 250 or less, Or less, more preferably 200 or less. When 1 is 2 or 3 and p is 1, the ratio (m 3 / m 4) of m 3 to m 4 is preferably 10/90 or more, more preferably 20/80 or more, from the viewpoint of alkali solubility Or more, more preferably 30/70 or more, and from the viewpoint of heat resistance, it is preferably 99/1 or less, more preferably 90/10 or less, still more preferably 80/20 or less. When l is 3 and p is 2, the m3 / m4 ratio is preferably 10/90 or more, more preferably 20/80 or more, still more preferably 30/70 or more from the viewpoint of alkali solubility , Preferably 80/20 or less, more preferably 70/30 or less, further preferably 60/40 or less from the viewpoint of heat resistance.

The structure represented by the general formula (3) is more preferably a structure represented by the following formula.

(37)

(Wherein m3 and m4 are the same as defined in the general formula (3)),

In the general formula (4), from the viewpoint of sensitivity, s and v are preferably 0 or 1, and R ₁₁ and R ₁₂ are each preferably a methyl group or an ethyl group. From the viewpoint of the pattern shape after curing, r and u are preferably 1 or 2, respectively. The total number of m5 and m6 is preferably 5 or more, more preferably 7 or more, further preferably 10 or more from the viewpoint of heat resistance, and is preferably 300 or less, more preferably 250 Or less, more preferably 200 or less. The ratio of m5 to m6 (m5 / m6) is preferably not less than 1/99, more preferably not less than 10/90, further preferably not less than 20/80 from the viewpoint of the film stress, , Preferably 90/10 or less, more preferably 80/20 or less, further preferably 70/30 or less. It is preferable that P ₁ is a hydroxyphenyl group in view of the surface state after development and the adhesive strength of the cured film and the diaphragm film. m11 is preferably 1 to 3 from the viewpoint of alkali solubility of the composition.

The structure represented by the general formula (4) is more preferably a structure represented by the following general formula (4 ') in view of the sensitivity of the composition and the pattern shape after curing.

(38)

In the general formula (4 '), s and v are preferably 0 or 1, and R ₁₁ and R ₁₂ are each preferably a methyl group or an ethyl group. From the viewpoint of the pattern shape after curing, r, t and u are preferably 1 or 2, respectively. The total number of m5 and m6 is preferably 5 or more, more preferably 7 or more, further preferably 10 or more from the viewpoint of heat resistance, and is preferably 300 or less, more preferably 250 Or less, more preferably 200 or less. The ratio of m5 to m6 (m5 / m6) is preferably not less than 1/99, more preferably not less than 10/90, further preferably not less than 20/80 from the viewpoint of the film stress, , Preferably 90/10 or less, more preferably 80/20 or less, further preferably 70/30 or less.

The structure represented by the general formula (4 ') is more preferably a structure represented by the following formula.

[Chemical Formula 39]

(Wherein m5 and m6 are the same as defined in formula (4 '))

In the general formula (5), from the viewpoint of sensitivity, x is preferably 0 or 1, and R ₁₃ is preferably a methyl group or an ethyl group. From the viewpoint of the pattern shape after curing, w is preferably 1 or 2. The total number of m7 and m8 is preferably 3 or more, more preferably 5 or more, further preferably 10 or more from the viewpoint of heat resistance, and preferably 300 or less, more preferably 250 Or less, more preferably 200 or less. The ratio (m7 / m8) of m7 to m8 is preferably 10/90 or more, more preferably 20/80 or more, further preferably 30/70 or more, from the viewpoint of heat resistance, , Preferably not more than 99/1.

In the general formula (5), Y is more preferably a structure represented by the following general formula (5 '') in view of the sensitivity of the composition and the pattern shape after curing.

(40)

(P ₄ and P ₅ are the same as defined in the above sikgun 5 'respectively)

P ₄ and P ₅ are each preferably a methyl group or a hydrogen atom from the viewpoint of cost.

Among them, the structure represented by the general formula group (5) is more preferably a structure represented by the following formula.

(41)

(Wherein m7 is the same as defined in General Formula (5)

The phenol resin (c) can be synthesized by polycondensation of various phenol compounds alone or a mixture of a plurality of them by a method known as an aldehyde such as formalin, or by a method in which a phenol compound is polymerized with a polymerization component , And a method of synthesizing by a combination of these methods.

Specific examples of the polymerization component include a compound having two methylol groups in the molecule, a compound having two alkoxymethyl groups in the molecule, and a compound having two haloalkyl groups in the molecule.

Examples of the phenol compound include phenol compounds such as phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 4-methylphenol, 3,5-dimethylphenol, methylenebisphenol, methylenebisp-cresol, bisphenol A, resorcin, catechol, 2- methylresorcin, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, These may be used alone or as a mixture of plural.

Examples of the aldehydes include, in addition to formalin, trioxane, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like. These aldehydes may be used singly or as a mixture of two or more thereof.

Examples of the compound having two methylol groups in the molecule include bis (hydroxymethyl) cresol, 2,6-bis (hydroxymethyl) -4-ethylphenol, 2,6- Butylphenol, 2,6-bis (hydroxymethyl) -4-t-butylphenol, 2,6-bis (hydroxymethyl) Bis (hydroxymethyl) -4-methoxyphenol, 2,6-bis (hydroxymethyl) -4-ethoxyphenol, 2,6- (Hydroxymethyl) -4-n-butoxyphenol, 2,6-bis (hydroxymethyl) -4-t-butoxyphenol and bis (hydroxymethyl) biphenyl.

Examples of the compound having two alkoxymethyl groups in the molecule include bis (methoxymethyl) cresol, 2,6-bis (methoxymethyl) -4-ethylphenol, 2,6- Butylphenol, 2,6-bis (methoxymethyl) -4-t-butylphenol, 2,6-bis (methoxymethyl) Bis (methoxymethyl) -4-methoxyphenol, 2,6-bis (methoxymethyl) -4-ethoxyphenol, 2,6- (Methoxymethyl) -4-n-butoxyphenol, 2,6-bis (methoxymethyl) -4-t-butoxyphenol and bis (methoxymethyl) biphenyl. The number of carbon atoms of the alkoxymethyl group is preferably 1 to 10, more preferably 1 to 2, and most preferably 1, from the viewpoint of the reaction activity.

As the compound having two haloalkyl groups in the molecule, for example, bischloromethylbiphenyl and the like can be given.

The weight average molecular weight of the phenol resin (c) is preferably 1,000 to 50,000, more preferably 2,000 to 20,000. The weight average molecular weight is preferably 1,000 or more from the viewpoint of elongation, and is preferably 50,000 or less from the viewpoint of alkali solubility. The weight average molecular weight is a value obtained in terms of standard polystyrene using GPC.

Other components

In the present invention, it is preferable that the above various components are dissolved in an organic solvent to form a varnish phase and used as a solution of the photosensitive resin composition. Examples of such an organic solvent include N-methyl-2-pyrrolidone,? -Butyrolactone (hereinafter also referred to as "GBL"), cyclopentanone, cyclohexanone, isophorone, N, N-dimethylacetamide (Hereinafter, also referred to as "DMAc"), dimethylimidazolinone, tetramethylurea, dimethylsulfoxide, diethylene glycol dimethyl ether (hereinafter also referred to as "DMDG"), diethylene glycol diethyl ether, diethylene glycol di Propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, Butylene glycol, butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, diisobutyl ketone, 2-Heptanone, 2-methyl-4-heptanone, 3-methyl-4-heptanone, 2-octanone, 3-octanone, 4-octanone, 5-methyl-2-octanone, Rice, etc. may be used alone or in combination.

Among these solvents, a non-amide type solvent is preferable because it has little influence on the photoresist and the like. More specific examples include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofurfuryl alcohol, 2-heptanone, 2-nonanone, and the like. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent to be added is preferably 100 to 2,000 parts by mass based on 100 parts by mass of the total amount of the polymer (a) and the phenol resin (c) having the structural unit represented by the general formula (1) . By changing the amount of the organic solvent added, the viscosity of the photosensitive resin composition solution can be controlled. The addition amount is more preferably 100 to 1,000 parts by mass. By adjusting the amount of the organic solvent to be added, viscosity suitable for the coating apparatus and coating thickness is obtained, and the production of the cured relief pattern can be facilitated.

The photosensitive resin composition according to the present invention may contain a crosslinking agent for the purpose of increasing the chemical resistance of the film (photosensitive resin layer) after heat curing, if necessary. Examples of the crosslinking agent include an aromatic compound having a methylol group and / or an alkoxymethyl group, at least one member selected from the group consisting of a compound in which the N position is substituted with a methylol group and / or an alkoxymethyl group, an epoxy compound, an oxetane compound, And the like can be used.

Among these crosslinking agents, at least one kind of compound selected from the group consisting of an aromatic compound having a methylol group and / or an alkoxymethyl group and a compound having a N-position substituted with a methylol group and / or an alkoxymethyl group is preferable in terms of chemical resistance after thermosetting .

The crosslinking agent may be used alone or in admixture of two or more. The amount of the crosslinking agent is preferably 1 to 100 parts by mass per 100 parts by mass of the total amount of the polymer (a) and the phenol resin (c) having the structural unit represented by the general formula (1) More preferably 3 to 50 parts by mass. When the blending amount is 1 part by mass or more, crosslinking proceeds satisfactorily and the patterning property becomes good. When the blending amount is 100 parts by mass or less, the mechanical properties after curing are maintained well.

In the present invention, a dissolution accelerator can be preferably used. Examples of the dissolution accelerator include a carboxylic acid compound and a phenolic compound.

Examples of the carboxylic acid compound include 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy- -Methoxyphenylacetic acid, 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxyphenylacetic acid, 4-hydroxyphenylacetic acid, 2-methoxy-2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, O-acetyl Hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, mandelic acid, atrolactic acid, O-acetyl Maleic acid, mandelic acid,? -Methoxyphenylacetic acid, O-acetyl mandelic acid,? -Methoxyphenylacetic acid, hexyl dihydroxybenzenecarboxylate, octyl dihydroxybenzenecarboxylate, dihydroxybenzenecarboxylate decyl, Treehi Octyl hexyl glycyrrhinolate, octyl hexyl glycyrrhinolate, octyl hexyl glycyrrhinolate, octyl hexyl glycyrrhinolate, octyl hexyl glycyrrhinolate, octyl hexyl glycyrrhinolate, Dodecyl and fluoroglucinolcarboxylic acid dodecyl, trihydroxybenzene carboxylic acid hexadecyl hexadecylsulfate, and hexadecyl fluoroglucinol carboxylic acid, and the like.

Examples of the phenol compound include a ballast used in the photosensitive diazoquinone compound and a linear phenol compound such as para-cumylphenol, bisphenol, resorcinol, or MtrisPC, MtetraPC (manufactured by Honshu Chemical Industry Co., Ltd.) (Manufactured by Honshu Chemical Industry Co., Ltd.) such as TrisP-HAP, TrisP-PHBA and TrisP-PA, compounds obtained by substituting 2-5 hydrogen atoms of the phenyl group of diphenylmethane with a hydroxyl group, And compounds obtained by substituting 1 to 5 hydrogen atoms of the phenyl group of diphenylpropane with a hydroxyl group. By the addition of the phenolic compound, the adhesion of the relief pattern at the time of development can be improved and the occurrence of residue can be suppressed. The ballast agent refers to a phenol compound which is used as a raw material for the above-described photosensitive diazoquinone compound in which a part of the phenolic hydrogen atoms is a naphthoquinone diazidesulfonic acid esterified phenol compound.

The blending amount of the dissolution promoting agent is preferably from 0 to 50 parts by mass, more preferably from 1 to 30 parts by mass, per 100 parts by mass of the total amount of the polymer (a) and the phenol resin (c) having the structural unit represented by the general formula (1) desirable. When the blending amount is 50 parts by mass or less, the heat resistance of the film after heat curing is good. When the compounding amount is 1 part by mass or more, the effect of accelerating the dissolution of the exposed part in the developer is good.

The photosensitive resin composition according to the present invention may contain an additive such as an alcohol, a dye, a flavor or a surfactant for improving the in-plane uniformity of a coating film or an adhesion aid for enhancing adhesion with a silicon substrate or a copper substrate Or the like.

More specifically, the alcohol preferably has 4 to 14 carbon atoms. Specific examples thereof include cyclopropylcarbinol, 2-cyclohexen-1-ol, cyclohexanemethanol, 4-methyl- -Cyclohexane-1-propanol, 1-cyclohexyl-1-propanol, 1-cyclohexane- - pentanol, 3,3,5-trimethylcyclohexanol, norbornane-2-methanol, cyclooctanol, 2,3,4-trimethyl-3-pentanol, 2,4-hexadiene- cis-2-hexen-1-ol, trans-2-hepten-1-ol, cis- Ethyl-2-methyl-3-pentanol, 2-ethyl-1-hexanol, 2,3-dimethyl-1-heptyl- 2-hexanol, 2,5-dimethyl-2-hexanol, trans, cis-2,6-nonadiene- 4-diol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl- Diol, 1,5-hexadiene-3,4-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,4,7,9-tetramethyl- Diol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanediol, trans-p- menthan-3,8-diol, 2,4-dimethoxybenzyl alcohol, And the like.

Of these, from the viewpoint of in-plane uniformity after application, it is preferable to use 2,3,4-trimethyl-3-pentanol, 2,4-hexadiene-1-ol, cis- Cis-2-butene-1-ol, cis-2-butene-1-ol, cis- Diol, 1,5-hexadiene-3,4-diol, and the like are preferable, and from the viewpoint of adhesion with a substrate, a monoalcohol is more preferable than a diol, and among these, 2,3,4-trimethyl-3-pentanol, 3-ethyl-2-methyl-3-pentanol and glycerol-?,? '- diallyl ether are particularly preferred.

These hydroxyl group-containing compounds may be used alone or in combination of two or more.

The amount of the alcohol to be blended is preferably 0.01 to 70 parts by mass relative to 100 parts by mass of the total amount of the polymer (a) and the phenol resin (c) having the structural unit represented by the general formula (1) More preferably 0.1 to 50 parts by mass, still more preferably 1 to 40 parts by mass, and particularly preferably 5 to 25 parts by mass. When the blending amount of the alcohol is 0.01 part by mass or more, the development residue of the exposed part is small, and when it is 70 parts by mass or less, the tensile elongation of the film after curing is good.

Examples of the dye include methyl violet, crystal violet, malachite green and the like. When blending the dyes, the blending amount is preferably from 0.1 to 10 parts by mass per 100 parts by mass of the total amount of the polymer (a) and the phenol resin (c) having a structural unit represented by the general formula (1) as a main component. When the blending amount is 0.1 parts by mass or more, the visualization effect is satisfactory, and when it is 10 parts by mass or less, the heat resistance of the film after heat curing is good.

As the perfume, terpene compounds can be mentioned, and from the viewpoint of solubility in solvents, monoterpene compounds and sesquiterpene compounds are preferable.

Specifically, there may be mentioned, for example, linalool, isopitol, dihydrolinalol, acetic acid linalyl, linalooloxide, geranilanol, laban dulol, tetrahydrolabanedulol, acetic acid laban dulol, nerol, acetic acid nerol, Citronellal, hydroxycitronellar, dimethyloctanal, citronellic acid, citronellolyl acetate, taracellulose, citrullineacetate, citronellal, citronellal, But are not limited to, trimethylolpropane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, Aldehyde, carbool, piperitol, terpene-4-ol, terpineol, terpenol, dihydroterpineol, sibrole, thymol, borneol, boronyl acetate, isoborneol, isobornyl acetate, Cineol, Phenol, Pinocar Butanol, mirtenal, verbeneol, pinocampeol, camphorsulfonic acid, neroli stone, terpinene, ionone, pinene, campfen, camphorenaldehyde, camphoronic acid, isocamporonic acid, camphoric acid, abietic acid, And the like. These terpene compounds may be used alone or in combination of two or more.

When the perfume is blended, the blending amount is preferably from 0.1 to 70 parts by mass, more preferably from 1 to 50 parts by mass, per 100 parts by mass of the total amount of the polymer (a) and the phenol resin (c) having the structural unit represented by the general formula (1) More preferably 50 parts by mass. When the blending amount is 0.1 part by mass, the effect of the perfume is satisfactory, and when it is 70 parts by mass or less, the heat resistance of the film after heat curing is good.

Examples of the surfactant include polyglycols such as polypropylene glycol and polyoxyethylene lauryl ether, and nonionic surfactants composed of derivatives thereof. Fluorinated surfactants such as FLORAD (trade name, manufactured by Sumitomo 3M Co., Ltd.), Megapack (trade name, manufactured by Dainippon Ink and Chemicals, Incorporated) and LUMI FRON (trade name, manufactured by Asahi Glass Co., Ltd.). Organosiloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corporation), and Granol (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) The addition of the surfactant makes it more difficult to cause the coating film to crater in the edge of the wafer at the time of coating.

The blending amount of the surfactant is preferably 0 to 10 parts by mass, more preferably 0.01 to 1 part by mass (parts by mass) per 100 parts by mass of the total amount of the polymer (a) and the phenol resin (c) having the structural unit represented by the general formula More preferable. When the blending amount is 10 parts by mass or less, heat resistance of the film after heat curing is good. When the blending amount is 0.01 parts by mass or more, the effect of preventing the above-mentioned coating film from being cratered is good.

Examples of the adhesion assisting agent that improves the adhesion between the cured resist pattern and the silicon substrate or the copper substrate include alkylimidazoline, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy polymer, , Tetrazole, oxazole, thiazole, imidazole, and the like.

The organosilicon compound is a compound containing an alkoxyl group having one or more functional groups and a silanol group and is an adhesion assisting agent for enhancing adhesion to a silicon wafer. The number of carbon atoms of the organosilicon compound is preferably 4 to 30, more preferably 4 to 18 from the viewpoint of solubility in solvents.

Specific examples of the compound include 3-mercaptopropyltrimethoxysilane (trade name: KBM803 manufactured by Shin-Etsu Chemical Co., Ltd., trade name: Sara Ace S810 manufactured by Chisso Corporation), 3-mercaptopropyltriethoxysilane (Trade name: SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (trade name: LS1375, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: SIM6474.0 manufactured by Ajax Co., Ltd.), mercaptomethyltrimethoxysilane SIM 6473.5C), mercaptomethyl methyl dimethoxysilane (trade name: SIM 6473.0, manufactured by Ajax Co., Ltd.), 3-mercaptopropyl diethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, Mercaptopropyltrimethoxypropoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3- Mercaptopropyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane, Silane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercapto Butyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, N- (3-triethoxysilylpropyl) urea (trade name: LS3610, manufactured by Shin-Etsu Chemical Co., (Product name: SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- (3-trimethoxysilylpropyl) urea 3-ethoxydimethoxysilylpropyl) urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- Urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- Urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- , N- (3-triethoxysilylbutyl) urea, N- (3-triethoxysilylbutyl) urea, N- Aminophenyltrimethoxysilane (trade name: SLA0599.0, manufactured by Ajax Co., Ltd.), p-aminophenyltrimethoxysilane (manufactured by Ajax Co., Ltd., trade name: SLA0598.0), trimethoxysilane product name SLA0599.1), aminophenyltrimethoxysilane (trade name: SLA0599.2), 2- (trimethoxysilylethyl) pyridine (trade name: SIT8396.0, (3-triethoxysilylmethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, N-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-n-butoxysilane, tetra- Tetrakis (methoxyethoxysilane), tetrakis (methoxy-n-propoxysilane), tetrakis (ethoxyethoxysilane), tetrakis (methoxyethoxyethoxy (Trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) (Triethoxysilyl) octadiene, bis [3- (triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) Propyl] tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxitriethoxysilane, bis (pentadionate) titanium-O, O'-bis (oxyethyl) Propylphenylsilane diol, isopropylphenylsilane diol, n-butyldiphenylsilane diol, isobutylphenylsilane diol, tert-butylphenylsilane diol, ethylphenylsilane diol, But are not limited to, phenyl silane diol, diphenyl silanediol, dimethoxydiphenyl silane, diethoxydiphenyl silane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, Butyl methylphenyl silanol, isobutyl methylphenyl silanol, tert-butyl methylphenyl silanol, ethyl n-propyl Silane compounds such as silanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, But are not limited to, silanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, and the like. These may be used singly or in combination.

Among the organosilicon compounds, among the above-mentioned organosilicon compounds, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane , Diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and silane coupling agents represented by the following structures.

(42)

The organosilicon compound may be used alone or in combination of two or more. When blending the organosilicon compound, the blending amount is preferably 1 to 40 parts by mass based on 100 parts by mass of the total amount of the polymer (a) and the phenol resin (c) having the structural unit represented by the general formula (1) More preferably 2 to 30 parts by mass, and still more preferably 4 to 20 parts by mass. When the compounding amount is 1 part by mass or more, the development residue of the exposed portion is satisfactorily reduced, and adhesion with the silicon substrate is good. On the other hand, when the amount is 40 parts by mass or less, the film after curing has a good tensile elongation, .

Specific examples of the heterocyclic structure compound include 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 1,3-dimethyl-5-pyrazolone, 3,5-dimethylpyrazole, Methyl-1-phenyl-5-pyrazolone, 2-methylimidazole, 1,10-phenanthroline, phenothiazine, phenoxazine, phenoxathine, Mercaptoethanol, mercapto benzothiazole, mercaptobenzoxazole, methyl thiobenzothiazole, dibenzothiazyl disulfide, methyl thio benzimidazole, benzimidazole, phenyl mercaptothiazoline, mercaptophenyl tetrazole, and mercapto Methyl tetrazole and the like. Examples of the benzotriazoles include compounds represented by the following general formulas.

(43)

(Wherein Z ₇ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms and a carboxyl group, and Z ₈ represents a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 5 carbon atoms A monovalent hydrocarbon group, and an aminoalkyl group)

Among the heterocyclic structure compounds, from the viewpoint of the sensitivity on the copper substrate, it is preferable to use 5-mercapto-1-phenyltetrazole, 1,2,3-benzotriazole, benzothiazole, benzoxazole, benzimidazole , And 2-mercaptobenzoxazole are more preferable.

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

The compounding amount in the case of compounding the heterocyclic structure compound is preferably from 0.1 to 30 parts by mass per 100 parts by mass of the total amount of the polymer (a) and the phenol resin (c) having the structural unit represented by the general formula (1) , More preferably from 0.5 to 10 parts by mass. When the compounding amount of the heterocyclic structure compound is 0.1 part by mass or more, the adhesion of the film after heat curing to the copper substrate becomes good, and when it is 30 parts by mass or less, the stability of the composition is good.

&Lt; Method of manufacturing cured relief pattern, and semiconductor device and display body device >

The present invention also provides a method of producing a cured relief pattern,

(A) a step of forming a photosensitive resin layer comprising the photosensitive resin composition of the present invention on a substrate,

(B) a step of exposing the photosensitive resin layer,

(D) a step of heating the relief pattern

/ RTI > The present invention also provides a cured relief pattern produced by the above method. This will be described in detail below.

(A) a step of forming a photosensitive resin layer on a substrate

In this step, the photosensitive resin composition of the present invention is applied to a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate by spin coating using a spin coater, or a coater such as a die coater or a roll coater. This is dried at 50 to 140 캜 using an oven or a hot plate to remove the solvent to form a photosensitive resin layer. A spin coating method using a spin coater is most preferable from the viewpoint of obtaining a coating film having a uniform film thickness.

(B) a step of exposing the photosensitive resin layer

Next, the substrate thus obtained is exposed to actinic radiation using a contact aligner or a stepper via a mask, or directly irradiated with a beam, an electron beam, or an ion beam.

(C) a step of removing the exposed portion with a developer to obtain a relief pattern

Next, development can be carried out by a method such as a dipping method, a paddle method, and a rotary spray method. By the development, the relief pattern can be obtained by eluting and removing the exposed portion from the photosensitive resin layer. Examples of the developing solution include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine, organic amines such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide , And if necessary, an aqueous solution containing an appropriate amount of a water-soluble organic solvent such as methanol, ethanol or the like or a surfactant can be used. Among these, tetramethylammonium hydroxide aqueous solution is preferable, and the concentration of tetramethylammonium hydroxide is preferably 0.5 to 10 mass%, and more preferably 1 to 5 mass%.

(D) a step of heating the relief pattern

Subsequently, the obtained relief pattern is cured by heating to form a heat resistant cured relief pattern containing a resin having an imide ring, an oxazole ring, or the like (for example, a resin having a polybenzoxazole structure). As the heating apparatus, it is possible to use an oven, a hot plate, a vertical furnace, a belt conveyor, and a pressure oven. As the heating method, hot air, infrared rays, and heating by electromagnetic induction are recommended. The temperature is preferably 200 to 450 ° C, more preferably 250 to 400 ° C. The heating time is preferably 15 minutes to 8 hours, more preferably 15 minutes to 4 hours. The atmosphere is preferably an inert gas such as nitrogen or argon.

The present invention also provides a semiconductor device having a semiconductor element and a cured film formed on the semiconductor element, wherein the cured film is a cured relief pattern of the present invention.

The present invention also provides a display body device comprising a display body element and a cured film formed on the display body element, wherein the cured film is a cured relief pattern of the present invention.

An example of the application of a semiconductor device includes a cured film formed on an upper portion of a semiconductor element, and the cured film is a cured relief pattern made of a cured film of the above-mentioned photosensitive resin composition. As the cured film, a protective film such as a passivation film on a semiconductor element, a buffer coat film formed by forming a cured film of the above-described photosensitive resin composition on a passivation film, or the like can be formed on a circuit formed on a semiconductor element, An insulating film such as an interlayer insulating film formed by forming a cured film of the composition, an a ray shielding film, a planarizing film, a projection (resin post), and a barrier rib.

Examples of the application of the display device device include a protective film formed by forming a cured film of the above-mentioned photosensitive resin composition on a display element, an insulating film or a flattening film for a TFT element or a color filter, a projection for an MVA type liquid crystal display, A barrier rib for an organic EL element cathode, and the like. The method of use is to form a cured film of a patterned photosensitive resin composition on a substrate on which a display element or a color filter is formed in accordance with the use of a semiconductor device by the above-described method.

The photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation of a multilayer circuit, cover coat of a flexible copper clad, a solder resist film, a liquid crystal alignment film of a display device, and the use of a light emitting device.

Another embodiment of the present invention is a cured film containing at least one resin selected from the group consisting of polyimide and polybenzoxazole, and a phenolic resin,

The cured film, under the following conditions,

Plasma species: microwave

Process gas: O₂

Processing time: 60 seconds

(Hereinafter sometimes simply referred to as surface roughness) of 0.5 to 5.0 nm as measured using an atomic force microscope (AFM) after the dry etching treatment of the substrate. More specifically, the surface roughness is measured by a method described in the section of the embodiment of this disclosure, or a method equivalent thereto by a method understood by a person skilled in the art.

The cured film is obtained by applying a photosensitive resin layer composed of a positive photosensitive resin composition to a substrate, followed by exposure, development and curing. The positive photosensitive resin composition may contain at least one resin selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, a quinone diazide compound, a phenol resin, and a solvent.

By setting the surface roughness to the above range, whitening of the cured film can be improved. Although it is not desired to be bound by theory, it is presumed that the surface roughness depends on the compatibility between the components in the positive photosensitive resin composition, in particular, the compatibility of the polyimide precursor and / or the polybenzoxazole precursor with the phenol resin.

In order to improve the sensitivity at the time of curing of the polyimide precursor and / or the polybenzoxazole precursor and the positive photosensitive resin composition containing the phenolic resin, it is effective to increase the amount of the phenolic resin. However, if the amount of the phenol resin is increased, the cured film becomes easily whitened. It is presumed that the whitening is caused by the low compatibility of the polyimide precursor and / or the polybenzoxazole precursor with the phenol resin.

In order to achieve both sensitivity and prevention of whitening, it is effective to appropriately control the type and amount of the phenol resin.

The compatibility of the polyimide precursor and / or the polybenzoxazole precursor with the phenol resin is affected by the skeleton structure (hydroxyl group, ester group, etc.) of the polyimide precursor and / or polybenzoxazole precursor and the skeleton structure (hydroxyl group concentration, Distance, etc.). Thus, for example, it is advantageous to use a relatively large amount of a phenol resin having a specific structure.

As examples of the components advantageous from the above viewpoints, examples of the polyimide precursor and the polybenzoxazole precursor include those described above as the polymer (a) in the " photosensitive resin composition ". Examples of the phenol resin include those described above as the phenol resin (c) in the " photosensitive resin composition ". Examples of the above-mentioned solvent include the above-mentioned organic solvents in the < photosensitive resin composition >.

The surface roughness of the cured film after the dry etching treatment under the above conditions is 5.0 nm or less indicates that the whitening of the cured film after the dry etching treatment is prevented and the yield of the semiconductor process can be improved. The surface roughness is advantageously low, but may be 0.5 nm or more from the viewpoint of adhesion between the cured film and the mold resin. The surface roughness is more preferably 0.5 nm to 4.5 nm, and particularly preferably 0.5 nm to 4.0 nm.

In view of controlling the surface roughness within the above range, the positive photosensitive resin composition is preferably a phenolic resin composition comprising 100 parts by mass of at least one resin selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, And more preferably 20 to 200 parts by mass, particularly preferably 50 to 150 parts by mass of the phenol resin. The phenol resin content of 20 parts by mass or more is advantageous from the viewpoint of sensitivity at the time of curing, and 200 parts by mass or less is advantageous from the viewpoint of heat resistance and further from the viewpoint of preventing whitening of the cured film.

The cured film preferably has a weight loss change rate (hereinafter, simply referred to as a weight loss change rate) of 0.1 to 3.0% when heat-treated at 240 캜 for 10 hours in an air atmosphere. In the present disclosure, the rate of change in weight loss when heat-treated at 240 캜 for 10 hours in an air atmosphere is a value calculated according to the following formula.

Weight reduction rate (%) = {maximum weight during heat treatment (g) - minimum weight during heat treatment (g)} / weight before heat treatment (g) * 100

Further, the weight change rate is measured more specifically by the method described in the section of the embodiment of this disclosure or equivalent method thereof by a person skilled in the art.

In another embodiment of the present invention, there is provided a photosensitive resin composition comprising a positive photosensitive resin composition containing at least one resin selected from a polyimide precursor and a polybenzoxazole precursor, a quinone diazide compound, a phenol resin and a solvent A cured film obtained by applying a layer to a substrate and then performing exposure, development and curing is provided as a cured film having a weight loss change ratio of 0.1 to 3.0% when heat treated at 240 캜 for 10 hours in an air atmosphere.

The rate of change in weight decrease is an index of sensitivity when the photosensitive resin layer is cured, and is dependent on the structure of the polyimide precursor and / or the polybenzoxazole precursor and the phenol resin (in particular, the ester structure). When the cured film is heat-treated at 240 캜 for 10 hours in an air atmosphere, the change in the weight loss of the cured film is 3.0% or less. This means that the cured film is formed from the photosensitive resin layer, that is, Even in a semiconductor process such as a stacked CSP in which a plurality of layers of the attached chips are laminated via a diaphragm film, it is possible to prevent peeling of the diaphragm film, which is thought to be caused by gas generated from the cured film, . The weight decrease rate is preferably low, but may be 0.1% or more, for example. The weight decrease rate is more preferably 0.1 to 2.75%, and particularly preferably 0.1 to 2.5%.

The positive photosensitive resin composition is preferably selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor in terms of controlling the rate of change in the weight loss of the cured film when the film is heat-treated at 240 캜 for 10 hours in an air atmosphere in the above range It is preferable to contain 20 to 200 parts by mass of the phenol resin with respect to 100 parts by mass of at least one kind of resin, particularly preferably 50 to 150 parts by mass of the phenol resin. A phenolic resin content of 20 parts by mass or more is advantageous from the viewpoint of sensitivity, and a content of 200 parts by mass or less is advantageous in view of adhesion strength between the cured film and the diaphragm film.

The use of a quinone diazide compound is preferable from the viewpoint of sensitivity improvement. Specific examples of the quinone diazide compound include those described above in the section of " Photosensitive resin composition ". The content of the quinone diazide compound is preferably from 1 to 50 parts by mass based on 100 parts by mass of the total amount of the at least one resin selected from the group consisting of the polyimide precursor and the polybenzoxazole precursor and the phenol resin And preferably 5 to 30 parts by mass. When the content is 1 part by mass or more, the sensitivity is good, and when it is 50 parts by mass or less, the adhesive strength between the cured film and the diaphragm film is good.

The thickness of the cured film of the present disclosure can be typically 1 to 50 mu m, more preferably 2 to 30 mu m, and still more preferably 3 to 20 mu m. The thickness of 1 mu m or more is advantageous from the viewpoint of the function of the protective film and the insulating film, and the thickness of 50 mu m or less is advantageous from the viewpoint of avoiding unnecessary increase in cost.

Example

Hereinafter, the present invention will be described in detail by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited thereto.

The measurement conditions in the examples are as follows.

&Lt; Weight average molecular weight (Mw) >

GPC, in terms of standard polystyrene (STANDARD SM-105, an organic solvent-based standard sample manufactured by Showa Denko K.K.). The GPC apparatus used and measurement conditions are as follows:

Pump: JASCO PU-980

Detector: JASCO RI-930

Column oven: JASCO CO-965 40 ° C

Column: Two Shodex KD-806M in series

Mobile phase: 0.1 mol / l EtBr / N-methylpyrrolidone

Flow rate: 1.0 ml / min.

&Lt; Evaluation of patterning characteristics (sensitivity, residual film ratio) >

· Preparation of prebake film and measurement of film thickness

The photosensitive resin composition was spin-coated on a 6-inch silicon wafer with a spin coater (Clean Track Mark 8 manufactured by Tokyo Electron Co., Ltd.) and pre-baked on a hot plate at 125 캜 for 180 seconds to obtain a film for evaluation. The initial film thickness of each composition was adjusted so as to have a resin film thickness of 5 占 퐉 after curing at 320 占 폚 for 30 minutes. The film thickness was measured by a film thickness measuring apparatus (Lambda ACE manufactured by Dainippon Screen Corporation).

· Exposure

The exposed film was passed through a reticle having a test pattern formed thereon, and an exposure amount was changed stepwise from 150 mJ / cm 2 to 800 mJ / cm 2 using a stepper (NSR2005i8A manufactured by Nikon Corporation) having an exposure wavelength of i-line (365 nm) Lt; / RTI >

·phenomenon

Developed with a 2.38% tetramethylammonium hydroxide aqueous solution AZ-300MIF (manufactured by AZ Electronic Materials Co., Ltd.) at 23 占 폚 with a developer (D-SPIN) for 80 seconds and rinsed with pure water to form a relief pattern.

[Sensitivity (mJ / cm < 2 >)]

The minimum exposure amount at which the 100 탆 square relief pattern of the exposed area of the coated film prepared under the above conditions was completely dissolved and removed was evaluated as the sensitivity.

[Developed residual film ratio (%)]

(Film thickness after development) / (initial film thickness)} 100.

&Lt; Evaluation of surface state after development &

The film after the development was visually observed, and the film whose surface was whitened was "-2", and the film was observed in darkness at a magnification of 500 times using an optical microscope. The surface was uneven, and when the film was touched with a hand, The film was observed at the darkness at a magnification of 500 at a magnification of 500, and the film was observed at darkness at a magnification of 500 at a magnification of 500 times that there was unevenness on the surface but no contact mark remained when the film was touched by hand, Quot ;, and " +2 "

When the compatibility between the polymer (a) and the phenol resin is poor, phase separation occurs in the film and the surface of the developed film is uneven from the difference in solubility of the polymer (a) and the phenol resin in an alkali developing solution, This is a phenomenon that occurs when there is irregularity in the period of the wavelength range or more (several hundred nm or more). In addition, the contact-state after development has irregularities on the surface of a period of not more than visible light wavelength range (several tens of nm to several hundreds nm) after development due to phase separation, and when the film is touched by hand, the convex portion of the surface is broken, It happens by being born. In the state where the period of the phase separation is several tens nm or less, a contact mark does not occur even if the surface of the developed film is touched, and a uniform film is formed.

&Lt; Evaluation of surface state after cured film dry etching treatment >

[Surface roughness after dry etching]

The photosensitive resin composition obtained in the Examples and Comparative Examples was spin-coated on a 6-inch silicon wafer so that the film thickness after curing became about 10 占 퐉 and prebaked on a hot plate at 120 占 폚 for 180 seconds to form a coating film. The film thickness was measured by a film thickness measuring apparatus (Lambda ACE) manufactured by Dainippon Screen. The coated film was heated in a nitrogen atmosphere at 320 DEG C for 30 minutes to obtain a cured film having a thickness of 10 mu m.

Next, the wafer to which the obtained cured film was attached was dry-etched using a high-density plasma apparatus (apparatus name: SWP, manufactured by Shin-KONJIN Co., Ltd.). The treatment conditions are as follows.

Plasma species: microwave

Process gas: O₂

Stage temperature: 200 캜

Processing time: 60 seconds

Subsequently, surface roughness measurement and whitening evaluation of the surface of the cured film subjected to the dry etching treatment were carried out.

The surface roughness was measured using an atomic force microscope (AFM) (Nanopics 1000, manufactured by Seiko Instruments Inc.), and the arithmetic mean roughness Ra (unit: nm) was measured with respect to the measurement range of 5 탆. NPX1CTP004 was used as a cantilever, and the measurement conditions were a damping mode and a scan speed of 50 sec / frame. The measurement results are shown in Table 4.

[Evaluation of whiteness after dry etching]

The whitening evaluation was carried out by observing the surface of the cured film subjected to the dry etching treatment with an optical microscope (product name: ECLIPSE L200, Nikon Corporation). White pigments were evaluated according to the following criteria. The evaluation results are shown in Table 4.

Good: No abnormality.

Slightly defective: whitening is observed in a part of the cured film.

Bad: White patches are observed at many points in the cured film.

&Lt; Evaluation of adhesion strength of diaphragm film &

[Evaluation of Adhesion Strength of DiaTouch Film]

The photosensitive resin composition obtained in the Examples and Comparative Examples was spin-coated on a 6-inch silicon wafer so that the film thickness after curing became about 10 占 퐉 and prebaked on a hot plate at 120 占 폚 for 180 seconds to form a coating film. The film thickness was measured by a film thickness measuring apparatus (Lambda ACE) manufactured by Dainippon Screen. This coated film was heated at 320 DEG C for 30 minutes in a nitrogen atmosphere to obtain a cured film having a thickness of 10 mu m. Next, the wafer to which the cured film was attached was diced by using a dicing machine (DAD3350, manufactured by Disco) to obtain chips with a cured film of a size 8.0 mm x 8.0 mm x 0.3 mm in thickness.

Subsequently, a die bonding film (product name: DF-375, manufactured by Hitachi Chemical Co., Ltd.) was pasted on a silicon wafer and the cured film chip (size 8.0 mm x 8.0 mm x 0.3 mm thickness (area 64 mm & And a total of 24 silicon wafers having a pitch of 80 占 퐉 were vertically and horizontally arranged in total of 24 silicon wafers were bonded to the silicon wafer under the conditions of a compression temperature of 240 占 폚, a load of 1.96 N, and a compression time of 10 seconds / Die bond film / chip with a cured film attached thereto), and further baking was performed at 180 DEG C for 1 hour.

Here, in the case of a semiconductor in which chips such as stacked CSPs are stacked, the above thermal compression bonding and baking are repeatedly performed. In such a case, the hot pressing at a compression temperature of 240 DEG C, a load of 1.96 N, and a compression time of 10 seconds, and baking at 180 DEG C for 1 hour were repeated ten times.

Next, the adhesive strength of the sample comprising the silicon wafer / die bond film / chip with the cured film was measured. The adhesive strength was measured by heating the sample at 260 캜 using a tabletop type strength tester (product name: universal type bond tester series 4000, manufactured by DAGE). Twenty-four samples were measured for each of the examples and comparative examples, and the average value of the adhesive strength was used. The adhesive strength was evaluated based on the following criteria. The evaluation results are shown in Table 5.

Good: The average value of the adhesive strength is greater than 1 N

Bad: average value of adhesion strength is 1 N or less

For a sample having an average value of adhesive strength of 1 N or less, it is presumed that gas or the like is generated from the cured film during repeated thermocompression bonding and baking, and the bonding strength is lowered.

[Weight change after heat treatment at 240 占 폚 for 10 hours]

The sample for measurement was prepared by the following method. The photosensitive resin composition obtained in Examples and Comparative Examples was spin-coated on a 6-inch silicon wafer substrate having an aluminum vapor deposition layer formed on the outermost surface so that the film thickness after curing would be about 10 占 퐉. Baked to form a coating film. The film thickness was measured by a film thickness measuring apparatus (Lambda ACE) manufactured by Dainippon Screen. This coated film was heated at 320 DEG C for 30 minutes in a nitrogen atmosphere to obtain a cured film having a thickness of 10 mu m. The obtained cured film was cut into a dicing area with a width of 3 mm and then peeled off from the wafer with a dilute hydrochloric acid aqueous solution to obtain a cured film piece having a thickness of about 10 mu m and a width of 3 mm. This cured film was measured for weight change rate when heated at 240 캜 for 10 hours using a thermal analyzer (model name DTG-60, manufactured by Shimadzu Corporation). The measurement conditions were as follows.

Sample length: 10 mm

Static load: 200 g / ㎟

Measuring temperature range: 240 ℃

Temperature rise rate: 0 ° C / minute (constant)

Measurement Atmosphere: Air

The weight change ratio was obtained from the following formula based on the weight of the cured film measured before and after the heat treatment. The measurement results are shown in Table 5.

(%) = (Maximum weight during heat treatment (g) - minimum weight (g) during heat treatment) / weight before heat treatment (g) x 100

[Synthesis Example 1]

&Lt; Synthesis of diamine compound >

18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter also referred to as "6FAP") were dissolved in 100 ml of acetone, 17.4 g Mol) and cooled to -15 < 0 > C. A solution of 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 ml of acetone was added dropwise thereto. After completion of dropwise addition, the mixture was allowed to react at -15 DEG C for 4 hours, and then returned to room temperature. The precipitated white solid was separated by filtration, and vacuum-dried at 50 ° C.

30 g of the solid was put into a stainless steel autoclave of 300 ml of GBL, dispersed in 250 ml of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced thereinto as a balloon, and the reduction reaction was carried out at room temperature. Approximately two hours later, the balloon was confirmed to be no longer clogged and the reaction was terminated. After completion of the reaction, the reaction mixture was filtered to remove the palladium compound as a catalyst and concentrated by a rotary evaporator to obtain a diamine (1) having the following structure. The resulting solid was used directly for the reaction.

(44)

[Synthesis Example 2]

<-Bis (carboxymethyl) Preparation of decane tricyclo [5,2,1,0 ^2,6]>

A separable three-necked glass flask equipped with an anchor stirrer made of Teflon (registered trademark) was charged with 71.9 g of tricyclo [5,2,1,0 ^2,6 ] decane dimethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.366 mol) were dissolved in 1 liter of acetonitrile. To the 1.4 L of ion-exchanged water, 256.7 g (1.808 mol) of disodium hydrogenphosphate and 217.1 g (1.809 mol) of dihydrogenphosphate were dissolved. 2.8 g (0.0179 mol) of 2,2,6,6-tetramethylpiperidin-1-oxyl (hereinafter also referred to as "TEMPO" manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto and dissolved by stirring. 143.2 g (1.267 mol) of 80% sodium chlorite was diluted with 850 ml of ion-exchanged water, and this was added dropwise to the reaction solution. Subsequently, 3.7 ml of a 5 mass% aqueous solution of sodium dihydrochloride diluted with 7 ml of ion-exchanged water was added dropwise to the reaction solution. The reaction solution was kept at 35 to 38 占 폚 by a constant temperature layer and reacted for 20 hours with stirring.

After the reaction, the reaction solution was cooled to 12 캜, and an aqueous solution prepared by dissolving 75 g of sodium sulfite in 300 ml of ion-exchanged water was added dropwise to the reaction solution to inactivate excess sodium chlorite. Then, the solution was washed with 500 ml of ethyl acetate Respectively. Thereafter, 115 ml of 10% hydrochloric acid was added dropwise to adjust the pH of the reaction solution to 3 to 4, and the precipitate was recovered by decantation. This precipitate was dissolved in 200 ml of tetrahydrofuran. Further, the aqueous layer was extracted twice with 500 ml of ethyl acetate, washed with brine, and the precipitate was dissolved in a tetrahydrofuran solution in the same manner. These tetrahydrofuran solutions were mixed and dried with anhydrous sodium sulfate. This solution was concentrated twofold buffer concentrator, by drying, bis (carboxy) tricyclo [5,2,1,0 ^2,6] decane 58.4 g of water to obtain a white crystal (yield: 71.1%).

[Synthesis Example 3]

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, 97 ml (1.33 mol) of thionyl chloride obtained in Synthesis Example 2, 0.4 ml Were charged into a reaction vessel and reacted by stirring at 25 to 50 DEG C for 18 hours. After completion of the reaction, toluene was added and the excess thionyl chloride was removed by azeotropic distillation under reduced pressure to obtain toluene. Thus, bis (chlorocarbonyl) tricyclo [5,2,1,0 ^2,6 ] decane (Yield: 100%).

[Synthesis Example 4]

(1- (2- (4-hydroxyphenyl) -2-propyl) phenyl) ethylidene) bisphenol as a polyhydroxy compound 30 g (0.0707 mol) of a compound represented by the following formula: Tris-PA) was added and to this was added 47.49 g of 1,2-naphthoquinonediazide-4-sulfonyl chloride in an amount corresponding to 83.3 mol% 0.177 mol) in 300 g of acetone was added thereto, and the flask was adjusted to 30 DEG C in a constant-temperature bath. Next, 17.9 g of triethylamine dissolved in 18 g of acetone was poured into the dropping funnel, which was then added dropwise to the flask over 30 minutes. After completion of the dropwise addition, stirring was further continued for 30 minutes, hydrochloric acid was added dropwise, and stirring was further performed for 30 minutes to terminate the reaction. After filtration, the triethylamine hydrochloride was removed. The resulting filtrate was added dropwise to a 3 L beaker mixed with 1640 g of pure water and 30 g of hydrochloric acid with stirring to obtain a precipitate. The precipitate was washed with water and filtered, and then dried at 40 ° C under a reduced pressure for 48 hours to obtain a quinone diazide compound (Q-1).

[Synthesis Example 5]

<Synthesis of hydroxypolyamide resin (P-1)> (a)

13.6 g (0.0225 mol) of the diamine (1) obtained in Synthesis Example 1 and 0.29 g (0.0025 mol) of 4-ethynyl aniline (trade name: P-APAC, manufactured by Fuji Photo Film Co., Ltd.) ) Was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). 7.75 g (0.025 mol) of 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride was added thereto together with 30 g of pyridine, and the mixture was reacted at 60 ° C for 6 hours. After completion of the reaction, the solution was poured into 2 L of water, and the precipitate of the polymer solid was collected by filtration. The polymer solid was dried in a vacuum drier at 50 DEG C for 60 hours to obtain the following formula:

[Chemical Formula 45]

(P-1) having a structure represented by the following formula (1).

The weight average molecular weight (Mw) of the hydroxypolyamide resin (P-1) thus synthesized by GPC was a single sharp curve of 15,700 in terms of polystyrene, and it was confirmed to be a single composition.

[Synthesis Example 6]

< Synthesis of hydroxypolyamide resin (P-2) >

In a 500 ml three-necked flask equipped with a stirrer made of Teflon (registered trademark), 3.72 g (0.02 mol) of 4,4-biphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 47.0 g (0.175 mol) of tricyclo [5,2,1,0 ^2,6 ] decane and 66.9 g of GBL were mixed and stirred at room temperature (around 20 to 25 ° C), and pyridine 9.49 g (0.12 mol) was added dropwise from the dropping funnel. The time required for the dropping was 25 minutes, and the reaction temperature was 40 ° C at the maximum.

After the dropwise addition, the reaction solution was stirred for 1 hour, and then the solution was added to a separable flask having a capacity of 2 L equipped with a Teflon (registered trademark) type stirrer, 2,2-bis (3-amino-4-hydroxyphenyl) , 65.9 g (0.18 mol) of fluoropropane (hereinafter also referred to as "6FAP"), 14.8 g (0.19 mol) of pyridine, 217 g of GBL and 72.5 g of DMAc were mixed and stirred to dissolve the mixture. The solution was immersed in a bath and cooled to -15 캜 using a dropping funnel. The reaction system was kept at -15 to 0 占 폚, and the reaction system was added dropwise to the reaction vessel for 1 hour.

After completion of the dropwise addition, the ice bath was removed, stirred at 0 to 10 캜 for 1 hour, and further added with 4.74 g (0.06 mol) of pyridine. Thereafter, the reaction solution was returned to room temperature, 24.6 g (0.15 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 11.8 g (0.15 mol) Deg.] C, and the reaction solution was stirred for 24 hours.

Ethanol was added to the reaction solution to precipitate a polymer, which was recovered and dissolved in 646 g of GBL. Subsequently, ion exchange was performed with 62.1 g of a cation exchange resin (manufactured by Organo Corporation, Amberlyst A21) and 59.6 g of an anion exchange resin (Amberlyst 15, manufactured by Organo Company). This solution was added dropwise to 12 L of ion-exchanged water under high-speed stirring to disperse and precipitate the polymer, recovered, washed appropriately with water, dehydrated and vacuum-dried to obtain the following formula:

(46)

(Molar ratio n / m = 80/10)

(P-2) having a structure of the hydroxypolyamide (P-2) was obtained.

The weight average molecular weight (Mw) of the hydroxypolyamide resin thus synthesized by GPC was a single sharp curve of 12,700 in terms of polystyrene, and it was confirmed to be a single composition.

¹³ C-NMR results of the hydroxypolyamide resin (P-2) obtained in Fig. 1 are shown. A carbon peak derived from the biphenyl skeleton was observed at about 138 ppm and around 150 ppm, and a peak derived from ester group was observed at around 174 - 176 ppm.

[Synthesis Example 7]

<Synthesis of hydroxypolyamide resin (P-3)> (a)

59 g (0.1 mol) of P-2 prepared in Synthesis Example 6 and 0.94 g (0.1 mol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 1 L separable flask equipped with a stirrer made of Teflon (registered trademark) 0.0093 mol) and GBL (240 g) were mixed and stirred at room temperature to dissolve the solution. Then, a solution of 5 g of GBL dissolved in 1.3 g (0.0093 mol) of benzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise from the dropping funnel to obtain 24 Lt; / RTI >

The reaction solution was ion-exchanged with 3.0 g of a cation exchange resin (Amberlyst A21, manufactured by Organo) and 3.0 g of an anion exchange resin (Amberlyst 15, manufactured by Organo). This solution was added dropwise to 6 liters of ion-exchanged water under high-speed stirring, and the polymer was dispersed and precipitated, recovered, suitably washed with water, dehydrated and vacuum-dried to obtain the following formula:

(47)

(Molar ratio n / m = 80/10)

(P-3) having a structure of the hydroxypolyamide resin (P-3).

The weight average molecular weight (Mw) of the hydroxypolyamide resin (P-3) thus synthesized by GPC was a single sharp curve of 12,800 in terms of polystyrene, and it was confirmed to be a single composition.

[Synthesis Example 8]

First, a separable flask equipped with a 1.0 liter dean-stark apparatus was purged with nitrogen. Then, in the separable flask, 81.3 g (0.738 mol) of resorcin and 4,4'-bis (methoxymethyl ) 84.8 g (0.35 mol) of biphenyl (BMMB), 3.81 g (0.02 mol) of p-toluenesulfonic acid and 116 g of propylene glycol monomethyl ether (PGME) were mixed and stirred at 50 DEG C to dissolve the solids. The dissolving mixed solution was heated to 120 DEG C by an oil bath, and the generation of methanol was confirmed from the reaction solution. The reaction solution was directly stirred at 120 占 폚 for 3 hours.

Next, 24.9 g (0.150 mol) of 2,6-bis (hydroxymethyl) -p-cresol and 499 g of PGME were mixed and stirred in a separate container, and uniformly dissolved therein was introduced into the separable flask Dropwise over 1 hour, and the mixture was further stirred for 2 hours. After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 50 g of PGME was further added thereto and stirred. The reaction dilution was added dropwise to 8 L of water under high-speed stirring to disperse and precipitate the resin. The resin was recovered, washed appropriately with water, dehydrated and vacuum-dried to obtain the following formula:

(48)

(Molar ratio m9 / m10 / m2 = 30/30/70)

To obtain a phenol resin (N-1). The weight average molecular weight of the synthesized resin by GPC was 9,900 in terms of polystyrene.

FIG. 2 shows ¹ H-NMR results of the obtained phenol resin (N-1).

[Synthesis Example 9]

First, a separable flask equipped with a 1.0 liter dean-stark apparatus was purged with nitrogen, and then 99.1 g (0.9 mol) of resorcin and 2,6-bis (hydroxymethyl) 116.0 g (0.7 mol) of p-cresol, 3.81 g (0.02 mol) of p-toluenesulfonic acid and 116 g of propylene glycol monomethyl ether (PGME) were mixed and stirred at 50 DEG C to dissolve the solids. The dissolving mixed solution was heated to 120 DEG C by an oil bath, and the generation of methanol was confirmed from the reaction solution. The reaction solution was directly stirred at 120 占 폚 for 3 hours.

After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 50 g of PGME was further added thereto and stirred. The reaction dilution was added dropwise to 8 L of water under high-speed stirring to disperse and precipitate the resin. The resin was recovered, washed appropriately with water, dehydrated and vacuum-dried to obtain the following formula:

(49)

(Molar ratio m3 / m4 = 50/50)

To obtain a phenol resin (N-2). The weight average molecular weight of the synthesized resin by GPC was 9,400 in terms of polystyrene.

[Synthesis Example 10]

(0.48 mol) of m-cresol and 34.6 g (0.32 mol) of p-cresol in a separable flask equipped with a dean-stark apparatus having a capacity of 1.0 L. Then, in a separable flask, 51.85 g 86.2 g (0.71 mol) of salicylaldehyde and 2.69 g (0.014 mol) of p-toluenesulfonic acid were mixed and stirred. The resulting mixed solution was heated to 100 占 폚 with an oil bath and stirred for 2 hours, followed by stirring at 150 占 폚 for 8 hours while appropriately adding dipropylene glycol dimethyl ether. After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 100 g of PGME was further added thereto and stirred. The reaction dilution was added dropwise to 8 L of water under high-speed stirring to disperse and precipitate the resin. The resin was recovered, washed appropriately with water, dehydrated and vacuum-dried to obtain the following formula:

(50)

(Molar ratio m5 / m6 = 60/40)

To obtain a phenol resin (N-3). The weight average molecular weight of the synthesized resin by GPC was 10,600 in terms of polystyrene.

[Synthesis Example 11]

First, a separable flask equipped with a 1.0 liter capacity Dean Stark apparatus was purged with nitrogen, and then 109.0 g (0.8 mol) of 2,3,5-trimethylphenol, 42.73 g of salicylaldehyde g (0.35 mol) of p-toluenesulfonic acid and 2.69 g (0.014 mol) of p-toluenesulfonic acid were mixed and stirred. The resulting mixed solution was heated to 100 占 폚 with an oil bath and stirred for 2 hours. After stirring for 8 hours at 150 占 폚 while adding dipropylene glycol dimethyl ether as appropriate, the liquid temperature was cooled to 80 占 폚.

Next, 28.4 g of 37% formalin was added dropwise to the separable flask for 1 hour using a dropping funnel, and the mixture was further stirred for 2 hours.

After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 100 g of PGME was further added thereto and stirred. The reaction dilution was added dropwise to 8 L of water under high-speed stirring to disperse and precipitate the resin. The resin was recovered, washed appropriately with water, dehydrated and vacuum-dried to obtain the following formula:

(51)

(Molar ratio M / N = 50/50)

To obtain a phenol resin (N-4). The weight average molecular weight of the synthesized resin by GPC was 9,200 in terms of polystyrene.

[Synthesis Example 12]

(0.8 mol) of fluoroglucinol, 121.2 g (0.5 mol) of 4,4'-bis (methoxymethyl) biphenyl (BMMB) in a separable flask equipped with a dean- 3.9 g (0.025 mol) of diethylsulfuric acid and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 70 DEG C to dissolve the solids to obtain a mixed solution.

The resulting mixed solution was heated to 140 DEG C by an oil bath, and the generation of methanol was confirmed from the reaction solution. The reaction solution was directly stirred at 140 占 폚 for 2 hours.

Next, the reaction vessel was cooled in the atmosphere, and another 100 g of tetrahydrofuran was added thereto and stirred to obtain a reaction dilution liquid. The reaction dilution was added dropwise to 4 L of water under high-speed stirring to disperse and precipitate the resin. The precipitate was recovered, washed appropriately with water, dehydrated and then vacuum-dried to obtain the following formula of fluroglucinol / BMMB:

(52)

To obtain a phenol resin (N-5). The weight average molecular weight of the synthesized resin by GPC was 15,000 in terms of polystyrene.

&Lt; Preparation of positive photosensitive resin composition >

[Example 1]

10 g of P-1 prepared in Synthesis Example 5 and 2 g of N-1 prepared in Synthesis Example 8 were weighed, and 1.68 g of the quinone diazide compound Q-1 prepared in Synthesis Example 4, together with GBL, 20 g And then filtered through a filter of 1 占 퐉 to prepare a positive photosensitive resin composition.

[Example 2]

10 g of P-1 prepared in Synthesis Example 5 and 5 g of N-1 prepared in Synthesis Example 8 were weighed, and GBL, 25 g of Q-1 and 2.1 g of quinone diazide compound Q- And then filtered through a filter of 1 占 퐉 to prepare a positive photosensitive resin composition.

[Example 3]

10 g of P-1 prepared in Synthesis Example 5 and 10 g of N-1 prepared in Synthesis Example 8 were weighed, and 2.8 g of the quinone diazide compound Q-1 prepared in Synthesis Example 4, together with GBL, 33.3 g And then filtered through a filter of 1 占 퐉 to prepare a positive photosensitive resin composition.

delete

[Example 4]

10 g of P-1 prepared in Synthesis Example 5 and 20 g of N-1 prepared in Synthesis Example 8 were weighed, and together with 4.2 g of the quinone diazide compound Q-1 prepared in Synthesis Example 4, 50 g of GBL And then filtered through a filter of 1 占 퐉 to prepare a positive photosensitive resin composition.

[Example 5]

A positive photosensitive resin composition was similarly prepared using N-2 prepared in Synthesis Example 9 instead of N-1 used in Example 1.

[Example 6]

A positive photosensitive resin composition was prepared in the same manner as in Example 2 except that N-2 prepared in Synthesis Example 9 was used instead of N-1.

[Example 7]

A positive photosensitive resin composition was prepared in the same manner as in Example 3 except that N-2 prepared in Synthesis Example 9 was used instead of N-1.

[Example 8]

A positive photosensitive resin composition was similarly prepared using N-2 prepared in Synthesis Example 9 instead of N-1 used in Example 4.

[Example 9]

A positive-type photosensitive resin composition was prepared in the same manner as in Example 1 except that phenol resin AEG018 (trade name, phenol component: bisphenol A, aldehyde component: formaldehyde, manufactured by Guei Chemical Co., Ltd.) was used instead of N-1 used in Example 1 .

[Example 10]

A positive photosensitive resin composition was prepared in the same manner as in Example 2 except that phenol resin AEG018 (trade name, phenol component: bisphenol A, aldehyde component: formaldehyde, manufactured by Genei Chemical Co., Ltd.) was used instead of N-1 used in Example 2 .

[Example 11]

A positive-type photosensitive resin composition was prepared in the same manner as in Example 3 except that phenol resin AEG018 (trade name, phenol component: bisphenol A, aldehyde component: formaldehyde, manufactured by Guei Chemical Co., Ltd.) was used instead of N-1 used in Example 3 .

[Example 12]

A positive photosensitive resin composition was prepared in the same manner as in Example 4 except that phenol resin AEG018 (trade name, phenol component: bisphenol A, aldehyde component: formaldehyde, manufactured by Genei Chemical Co., Ltd.) was used instead of N-1 used in Example 4 .

[Example 13]

The phenol resin AEG024 (trade name, phenol component: m-cresol / p-cresol ratio = 60/40, aldehyde component: formaldehyde / salicylaldehyde ratio = 70/30, Ltd.) was used to prepare a positive photosensitive resin composition in the same manner.

[Example 14]

[Example 15]

[Example 16]

[Example 17]

A positive photosensitive resin composition was similarly prepared using the N-3 prepared in Synthesis Example 10 instead of the N-1 used in Example 1.

[Example 18]

A positive photosensitive resin composition was similarly prepared using the N-3 prepared in Synthesis Example 10 instead of the N-1 used in Example 2.

[Example 19]

A positive photosensitive resin composition was similarly prepared using the N-3 prepared in Synthesis Example 10 instead of the N-1 used in Example 3.

[Example 20]

A positive photosensitive resin composition was similarly prepared using the N-3 prepared in Synthesis Example 10 instead of the N-1 used in Example 4.

[Example 21]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 1.

[Example 22]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 2.

[Example 23]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 3.

[Example 24]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 4.

[Example 25]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 5.

[Example 26]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 6.

[Example 27]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 7.

[Example 28]

A positive photosensitive resin composition was similarly prepared by using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 8.

[Example 29]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 9.

[Example 30]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 10.

[Example 31]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 11.

[Example 32]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 12.

[Example 33]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 13.

[Example 34]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 14.

[Example 35]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 15.

[Example 36]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 16.

[Example 37]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 17.

[Example 38]

A positive photosensitive resin composition was similarly prepared by using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 18.

[Example 39]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 19.

[Example 40]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Example 20.

[Example 41]

A positive photosensitive resin composition was similarly prepared using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 1.

[Example 42]

A positive photosensitive resin composition was similarly prepared using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 2.

[Example 43]

A positive photosensitive resin composition was similarly prepared by using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 3.

[Example 44]

A positive photosensitive resin composition was similarly prepared by using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 4.

[Example 45]

A positive photosensitive resin composition was similarly prepared using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 5.

[Example 46]

A positive photosensitive resin composition was similarly prepared using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 6.

[Example 47]

A positive photosensitive resin composition was similarly prepared using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 7.

[Example 48]

A positive photosensitive resin composition was similarly prepared using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 8.

[Example 49]

A positive photosensitive resin composition was similarly prepared using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 9.

[Example 50]

A positive photosensitive resin composition was similarly prepared using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 10.

[Example 51]

A positive photosensitive resin composition was similarly prepared by using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 11.

[Example 52]

A positive photosensitive resin composition was similarly prepared by using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 12.

[Example 53]

A positive photosensitive resin composition was similarly prepared using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 13.

[Example 54]

A positive photosensitive resin composition was similarly prepared by using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 14.

[Example 55]

A positive photosensitive resin composition was similarly prepared using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 15.

[Example 56]

A positive photosensitive resin composition was similarly prepared by using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 16.

[Example 57]

A positive photosensitive resin composition was similarly prepared by using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 17.

[Example 58]

A positive photosensitive resin composition was similarly prepared using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 18.

[Example 59]

A positive photosensitive resin composition was similarly prepared using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 19.

[Example 60]

A positive photosensitive resin composition was similarly prepared using P-3 prepared in Synthesis Example 7 instead of P-1 used in Example 20.

[Comparative Example 1]

10 g of P-1 prepared in Synthesis Example 5 was weighed and dissolved in 16.7 g of GBL together with 1.4 g of the quinone diazide compound Q-1 prepared in Synthesis Example 4, followed by filtration through a 1 占 퐉 filter, Thereby preparing a positive photosensitive resin composition.

[Comparative Example 2]

10 g of P-1 prepared in Synthesis Example 5 and 2 g of phenol resin EP4000B (trade name: m-cresol / p-cresol ratio = 60/40, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) Was dissolved in 20 g of GBL together with 1.68 g of the quinone diazide compound Q-1, and the mixture was filtered through a 1 占 퐉 filter to prepare a positive photosensitive resin composition.

[Comparative Example 3]

10 g of P-1 prepared in Synthesis Example 5 and 5 g of phenol resin EP4000B (trade name m-cresol / p-cresol ratio = 60/40, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) Was dissolved in 25 g of GBL together with 2.1 g of the quinone diazide compound Q-1, and the mixture was filtered through a 1 탆 filter to prepare a positive photosensitive resin composition.

[Comparative Example 4]

10 g of P-1 prepared in Synthesis Example 5 and 10 g of phenol resin EP4000B (trade name: m-cresol / p-cresol ratio = 60/40, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) Was dissolved in 33.3 g of GBL together with 2.8 g of the quinone diazide compound Q-1 thus prepared, followed by filtration through a 1 占 퐉 filter to prepare a positive photosensitive resin composition.

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[Comparative Example 5]

10 g of the P-1 prepared in Synthesis Example 5 and 20 g of phenol resin EP4000B (trade name: m-cresol / p-cresol ratio = 60/40, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) Was dissolved in 50 g of GBL together with 4.2 g of the quinone diazide compound Q-1 thus prepared, followed by filtration through a 1 占 퐉 filter to prepare a positive photosensitive resin composition.

[Comparative Example 6]

A positive-type photosensitive resin composition was similarly prepared using a phenol resin MXP5560BF (trade name, phenol / m-cresol / p-cresol ratio = 50/30/20) instead of the phenol resin used in Comparative Example 2.

[Comparative Example 7]

A positive-type photosensitive resin composition was similarly prepared using phenol resin MXP5560BF (trade name, phenol / m-cresol / p-cresol ratio = 50/30/20) instead of the phenol resin used in Comparative Example 3.

[Comparative Example 8]

A positive-type photosensitive resin composition was prepared in the same manner using the phenol resin MXP5560BF (trade name, phenol / m-cresol / p-cresol ratio = 50/30/20) instead of the phenol resin used in Comparative Example 4.

[Comparative Example 9]

A positive-type photosensitive resin composition was prepared in the same manner using the phenol resin MXP5560BF (trade name, phenol / m-cresol / p-cresol ratio = 50/30/20) instead of the phenol resin used in Comparative Example 5.

[Comparative Example 10]

A positive photosensitive resin composition was similarly prepared using N-4 prepared in Synthesis Example 11 instead of the phenol resin used in Comparative Example 2.

[Comparative Example 11]

A positive photosensitive resin composition was similarly prepared using the N-4 prepared in Synthesis Example 11 instead of the phenol resin used in Comparative Example 3.

[Comparative Example 12]

A positive photosensitive resin composition was similarly prepared using N-4 prepared in Synthesis Example 11 instead of the phenol resin used in Comparative Example 4.

[Comparative Example 13]

A positive photosensitive resin composition was similarly prepared using the N-4 prepared in Synthesis Example 11 instead of the phenol resin used in Comparative Example 5.

[Comparative Example 14]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Comparative Example 6.

[Comparative Example 15]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Comparative Example 7.

[Comparative Example 16]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Comparative Example 8.

[Comparative Example 17]

A positive photosensitive resin composition was similarly prepared using P-2 prepared in Synthesis Example 6 instead of P-1 used in Comparative Example 9.

[Comparative Example 17]

[Examples 61 to 64]

A positive photosensitive resin composition was similarly prepared using the phenol resin N-5 prepared in Synthesis Example 12 instead of the N-1 used in Examples 1 to 4.

[Examples 65 to 68]

A positive photosensitive resin composition was similarly prepared by using phenol resin N-6 (phenol component: bisphenol S, aldehyde component: formaldehyde, manufactured by Konishi Kagaku Kogyo K.K.) instead of N-1 used in Examples 1 to 4 Lt; / RTI >

[Examples 69 to 72]

A positive photosensitive resin composition was similarly prepared using phenol resin MEH-7600-4H (trade name, manufactured by Guneyi Chemical Co., Ltd.) instead of N-1 used in Examples 1 to 4.

The structure of the above-mentioned phenol resin is shown below.

(53)

Evaluation of the patterning characteristics of the positive photosensitive resin compositions of the prepared Examples 1 to 60, Comparative Examples 1 to 17, and Examples 61 to 72 and evaluation of the surface state after development were carried out. The results are shown in Tables 1, 2 and 3.

[Examples 73 to 92, Comparative Examples 18 to 29]

(Examples 73 to 82 and Comparative Examples 18 to 23), evaluation of the adhesion strength of the diazepam films (Examples 83 to 82 and Comparative Examples 18 to 23) after the dry etching treatment of the cured films obtained from the positive photosensitive resin compositions prepared in the above- 92 and Comparative Examples 24 to 29). The results are shown in Tables 4 and 5.

From the results shown in Tables 1, 2 and 3, it can be seen that Examples 1 to 60 exhibit excellent sensitivity and residual residual film ratio and good surface condition after development. Further, in Examples 21 to 40, the use of the polymer having an ester structure introduced into the polymer skeleton shows that the residual film ratio at the time of development is improved and the surface state after development is better than those of Examples 1 to 20 . Further, in Examples 41 to 60, the residual film ratio at the time of development was improved and the surface condition after development was improved as compared with Examples 21 to 40 by using a polymer having an ester structure introduced into the side chain of the polymer .

From the results shown in Tables 4 and 5, a photosensitive resin composition comprising a positive photosensitive resin composition containing at least one resin selected from a polyimide precursor and a polybenzoxazole precursor, a quinone diazide compound, a phenol resin and a solvent The cured film obtained by applying the resin layer to a substrate, exposing, developing, and curing the substrate shows good surface state after dry etching treatment and good adhesion strength of the diatomic film.

Industrial availability

The photosensitive resin composition of the present invention can be applied to a semiconductor device, a display device device, and a surface protective film of a light emitting device, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, a protective film for a device having a bump structure, A cover coat of a plate, a solder resist film, a liquid crystal alignment film, and the like.

Claims

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(a) a compound represented by the following general formula (1):

Wherein R ₁ and R ₂ each independently represent a divalent to octavalent organic group having 2 to 60 carbon atoms and R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a C 1-20 D and e each independently represent an integer of 0 to 2 and may not be 0 at the same time, f and g are each independently an integer of 0 to 4, and n is a positive integer)
, More than 50 mass% of the structural unit represented by the general formula
(b) a quinone diazide compound,
(c) a phenolic resin,
The phenolic resin (c)
(4 ') < RTI ID = 0.0 >

(Wherein R ₁₁ and R ₁₂ each independently represent a monovalent organic group having 1 to 10 carbon atoms, r, t and u are each independently an integer of 1 to 3, and s and v are each independently 0 to 2 4, 1?? (U + v)? 4, m5 is 0 or a positive integer, and m6 is a positive integer.
Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.

(a) a compound represented by the following general formula (1):

Wherein R ₁ and R ₂ each independently represent a divalent to octavalent organic group having 2 to 60 carbon atoms and R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a C 1-20 D and e each independently represent an integer of 0 to 2 and may not be 0 at the same time, f and g are each independently an integer of 0 to 4, and n is a positive integer)
, More than 50 mass% of the structural unit represented by the general formula
(b) a quinone diazide compound,
(c) a phenolic resin,
(C) the phenol resin is represented by the following general formula (5):

{Wherein, R ₁₃ each independently represents a monovalent organic group having a carbon number of 1 ~ 10, w is an integer from 1 ~ 3, x is an integer of 0 ~ 2, 1 ≤≤ (w + x) ≤≤ 4 M7 is a positive integer, m8 is 0 or a positive integer, and Y is a group represented by the following general formula (5 "):

(P ₄ and P ₅ are each independently a hydrogen atom, a monovalent aliphatic group which may be substituted with fluorine having 1 to 20 carbon atoms, or a substituted or unsubstituted monovalent aromatic group having 6 to 20 carbon atoms)
Lt; / RTI >
Wherein the positive photosensitive resin composition has a structure represented by at least one of the following groups:

3. The method of claim 2,
The general formula ₍₁₎ R 1 or R ₂ or a positive photosensitive resin composition are those of the quantum structure having an ester bond.

3. The method of claim 2,
Wherein R ₁ or R ₂ in the general formula (1) is a group represented by the following general formula (6):

(Wherein R ₁₈ , R ₁₉ and R ₂₀ each independently represent a divalent organic group having 2 to 60 carbon atoms, at least one of R ₁₈ , R ₁₉ and R ₂₀ has an alicyclic or aliphatic structure, and m Is 0 or 1)
Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.

(a) a compound represented by the following general formula (1):

(Wherein R ₁ and R ₂ each independently represent a divalent to octavalent organic group having 2 to 60 carbon atoms,
R ₃ or R ₄ is a group represented by the following general formula (7):

(Wherein R ₂₁ represents a monovalent organic group having 1 to 19 carbon atoms)
&Lt; / RTI >
R ₅ and R ₆ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms,
d and e are each independently an integer of 0 to 2 and may not be 0 at the same time, f and g are each independently an integer of 0 to 4, and n is a positive integer)
, More than 50 mass% of the structural unit represented by the general formula
(b) a quinone diazide compound,
(2), (3), and (4), and the general formula group (5): wherein the phenolic resin (c)

(Wherein R ₇ and R ₈ each independently represent a monovalent organic group having 1 to 10 carbon atoms, h and j are each independently an integer of 1 to 3, i and k are independently integers of 0 to 2 , M 1 is 0 or a positive integer, and m 2 is a positive integer, m 1 and m 2 are positive integers, and m 1 and m 2 are positive integers, The total number is 10 or more, and the ratio of m1 to m2 (m1 / m2) is 80/20 or less)

(Wherein R ₉ and R ₁₀ each independently represent a monovalent organic group having 1 to 10 carbon atoms, l is 2 or 3, p is an integer of 1 to 3, and o and q are each independently 0 to 2 4, 1?? (P + q)? 4, m3 is a positive integer, and m4 is 0 or a positive integer.

(Wherein R ₁₁ and R ₁₂ each independently represent a monovalent organic group having 1 to 10 carbon atoms, r and u are each independently an integer of 1 to 3, s and v are each independently an integer of 0 to 2 , M5 is 0 or a positive integer, m6 is a positive integer, m11 is a positive integer, and m1 is a positive integer. And P ₁ is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group, a carboxyl group or an amino group)

{Wherein, R ₁₃ each independently represents a monovalent organic group having a carbon number of 1 ~ 10, w is an integer from 1 ~ 3, x is an integer of 0 ~ 2, 1 ≤≤ (w + x) ≤≤ 4 M7 is a positive integer, m8 is 0 or a positive integer, and Y is a group represented by the following formula (5 '):

(P ₄ and P ₅ are each independently a hydrogen atom, a monovalent aliphatic group which may be substituted with fluorine having 1 to 20 carbon atoms, or a substituted or unsubstituted monovalent aromatic group having 6 to 20 carbon atoms)
Is a divalent organic group selected from the group consisting of
Wherein the positive photosensitive resin composition has a structure represented by at least one of the following groups:

(a) a compound represented by the following general formula (1):

Wherein R ₁ and R ₂ each independently represent a divalent to octavalent organic group having 2 to 60 carbon atoms and R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a C 1-20 D and e each independently represent an integer of 0 to 2 and may not be 0 at the same time, f and g are each independently an integer of 0 to 4, and n is a positive integer)
, More than 50 mass% of the structural unit represented by the general formula
(b) a quinone diazide compound,
(c) a phenolic resin, (c) the phenolic resin is represented by the following general formulas (3) and (4), and general formula group (5)

(A) a step of forming a photosensitive resin layer composed of the photosensitive resin composition according to claim 2 on a substrate,
(B) a step of exposing the photosensitive resin layer,
(C) a step of removing the exposed portion with a developer to obtain a relief pattern, and
(D) a step of heating the relief pattern
&Lt; / RTI >

A cured relief pattern produced by the method according to claim 8.

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

A display body device comprising a display body element and a cured film formed on the display body element, wherein the cured film is the cured relief pattern according to claim 9.

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