KR20100091115A - Positive photosensitive resin composition - Google Patents

Abstract

PURPOSE: A positive photoresist resin composition, a flat panel display using thereof, and a semiconductor device are provided to secure the high residual film rate without generating development residue, and to improve the coating property after a high temperature baking. CONSTITUTION: A positive photoresist resin composition contains 100 parts of copolymer by weight, 5~50 parts of photoresist by weight including a quinone diazide group, and 1~4 parts of hardener by weight including more than two epoxy resin. The copolymer is formed with the following: a structure unit induced from a fumaric acid diester monomer marked with chemical formula 1; a structure unit induced from an aromatic vinyl monomer marked with chemical formula 2; a structure unit induced from an alpha-beta unsaturated carboxylic acid monomer marked with chemical formula 3; and a structure unit induced from a (meth)acrylic acid ester monomer marked with chemical formula 4.

Description

Positive photosensitive resin composition {POSITIVE PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive resin composition, and more particularly, to a positive photosensitive resin composition. More specifically, the present invention relates to a flat panel display (FPD) or semiconductor device comprising a photosensitive resin composition capable of forming a patterned film by using photolithography technology, and further, an interlayer insulating film or planarization film formed using the photosensitive resin composition. .

Photolithography techniques have conventionally been used to perform microdevice formation or microfabrication in a wide range of fields including the manufacture of semiconductor integrated circuits such as LSIs, the manufacture of FPD display surfaces, and the manufacture of circuit boards such as thermal heads. It is becoming. In this photolithography technique, the photosensitive resin composition is used in order to form a resist pattern. In recent years, as a new use of these photosensitive resin compositions, techniques for forming interlayer insulating films and planarization films such as semiconductor integrated circuits and FPDs have attracted attention. In particular, the market demand for high quality of FPD display surface and shortening of the manufacturing process of a semiconductor element represented by TFT etc. is strong.

In order to achieve high quality of the FPD display surface, it is important to suppress transmission loss in the circuit. For this purpose, an interlayer insulating film or a flattening film having a fine pattern excellent in low dielectric properties has become an essential material. In addition, for shortening of the manufacturing process of a semiconductor device, an inorganic interlayer insulating film such as SiNx formed by vacuum deposition for the purpose of protecting a source or a gate electrode is replaced with an organic interlayer insulating film which can be easily formed by a wet process. Is desired. For this reason, the insulating property equivalent to SiNx is essential for an organic interlayer insulating film, and the interlayer insulating film of low dielectric constant whose dielectric constant is less than 3.0 is required. In order to obtain the interlayer insulation film and the planarization film which have the said low dielectric property, the role of alkali-soluble resin in the photosensitive resin composition is very large, and the research on the photosensitive resin composition used for such use is done.

For example, Patent Literature 1 discloses a photosensitive resin composition having good developability and high resolution by using a radically polymerizable compound having an unsaturated carboxylic acid and an epoxy group as the alkali-soluble resin blended into the photosensitive resin composition for an interlayer insulating film or a planarization film. It is disclosed that the pattern film of can be formed. However, since the structural unit contained in the said alkali-soluble resin is comprised by the (meth) acryloyl group, it is generally known that the photosensitive resin composition which has sufficient low dielectric properties cannot be obtained.

Patent Literature 2 uses a copolymer containing styrene, (meth) acrylic acid, and hydroxyalkyl ester as a structural unit as an alkali-soluble resin blended into the photosensitive resin composition for an interlayer insulating film or a planarization film, thereby reducing the dielectric of the photosensitive resin composition. It is disclosed that the characteristics become good. However, when a large amount of styrene is introduced into the resin, the hydrophobicity of the resin is increased, so that the residual film ratio at the time of development can be kept high, but the development residue is increased to obtain a photosensitive resin composition having sufficient developability. There is a problem that can not be.

In addition, Patent Literature 3 includes an alkali-soluble resin having a fumaric acid diester, a photopolymerizable polyfunctional (meth) acrylate compound, and a photopolymerization initiator to form a protective film for a color filter, a pixel for RGB, a black matrix or a spacer. It is disclosed that favorable developability can be obtained by using a type photosensitive resin composition. However, since the dielectric constant of the photopolymerizable polyfunctional (meth) acrylate contained in this negative photosensitive resin composition is high, there exists a problem that the photosensitive resin composition which has sufficient low dielectric properties cannot be obtained.

For this reason, in the photosensitive resin composition used for interlayer insulation films or planarization films, such as FPD and a semiconductor device, there is no image development residue, high developability, and the high resolution which is excellent in low dielectric properties, maintaining the high residual film rate. Formation of a pattern film is required.

Japanese Patent Publication Hei 7-248629 (2P, 3P and 4P) Japanese Patent Laid-Open No. 2004-4233 (2P, 4P, and 34P) Japanese Patent Publication No. 2007-137947 (2P, 3P, and 5P)

The first object of the present invention is to reduce the coating film properties such as flatness, light transmittance and solvent resistance even after high temperature baking, without developing residue, while maintaining a high residual film ratio in the developing step of forming a pattern film. An object of the present invention is to provide a photosensitive resin composition capable of forming a high resolution pattern film having excellent dielectric properties.

A second object of the present invention is to provide an FPD or semiconductor device having a planarization film or an interlayer insulation film formed of the excellent photosensitive resin composition.

A third object of the present invention is to provide an FPD or semiconductor device having an organic interlayer insulating film that can be easily formed by a wet process without forming an inorganic interlayer insulating film such as SiNx by the excellent photosensitive resin composition.

The photosensitive resin composition which concerns on this invention consists of components (A), (B) and (C) shown below, and the structural ratio of components (B) and (C) is respectively with respect to 100 mass parts of components (A). (B) 5-50 mass parts and (C) 1-40 mass parts.

Component (A) is a structural unit (a1) derived from the fumaric acid diester monomer represented by the following formula (1), a structural unit (a2) derived from the aromatic vinyl monomer represented by the following formula (2), and α represented by the following formula (3) It is a copolymer which consists of a structural unit (a3) derived from the (beta)-unsaturated carboxylic acid monomer, and a structural unit (a4) derived from the (meth) acrylic acid ester monomer represented by following General formula (4), and a structural unit (a1) and a structure It is a copolymer whose total amount of a unit (a2) is 40-85 mass% in this component (A), and the mass ratio (a4) / (a3) of a structural unit (a3) and a structural unit (a4) is 0.2-7.0.

(In formula, each of R <^1> and R <^2> is a C3-C8 branched alkyl group, a C4-C12 cycloalkyl group, or a substituted branched cycloalkyl group.)

(Wherein R ³ is a hydrogen atom or a methyl group, R ⁴ is a C6-C12 aromatic hydrocarbon group)

(Wherein R ⁵ is a hydrogen atom, a methyl group or a carboxymethyl group)

(Wherein R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a C6-C12 aromatic hydrocarbon group, a C1-C12 alkyl group, a C1-C12 branched alkyl group, a C2-C12 hydroxyalkyl group or a main ring configuration Alicyclic hydrocarbon group having 5 to 12 carbon atoms)

Component (B) is a photosensitive agent having a quinonediazide group obtained by esterifying a phenolic compound having a hydroxyl group and a quinonediazide compound.

Component (C) is a hardening | curing agent which has two or more epoxy groups.

The flat panel display of 2nd invention has the layer which hardened the photosensitive resin composition of 1st invention.

The semiconductor device of 3rd invention has the layer which hardened the photosensitive resin composition of 1st invention.

The present invention can achieve the following effects.

According to the photosensitive resin composition of 1st invention, in the image development process which forms the pattern film using the photolithography technique, there is no image development residue, maintaining high residual film rate, and even after high-temperature baking, such as postbaking, flatness, light transmittance, and content It is possible to form a high resolution pattern film excellent in low dielectric properties without impairing coating film properties such as forming properties. And by using this photosensitive resin composition, the FPD and semiconductor device which have the outstanding characteristic can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment which concerns on this invention is described in detail.

The photosensitive resin composition of this embodiment consists of components (A), (B) and (C), and the composition ratio of components (B) and (C) is respectively (B) 5 with respect to 100 mass parts of components (A). 50 mass parts and (C) 1-40 mass parts.

Component (A): The specific copolymer described below.

Component (B): Photosensitive agent with quinonediazide group.

Component (C): Curing agent having two or more epoxy groups.

Each component is demonstrated in order below.

<Component (A): Copolymer>

The copolymer of component (A) is a structural unit (a1) derived from the fumaric acid diester monomer represented by the following general formula (1), a structural unit (a2) derived from the aromatic vinyl monomer represented by the following general formula (2), and the following general formula (3) It is a copolymer which consists of a structural unit (a3) derived from the (alpha), (beta)-unsaturated carboxylic acid monomer shown, and a structural unit (a4) derived from the (meth) acrylic acid ester monomer represented by following formula (4), and a structural unit (a1) ) And the total amount of the structural unit (a2) is 40 to 85 mass% in this component (A), and the mass ratio (a4) / (a3) of the structural unit (a3) and the structural unit (a4) is 0.2 to 7.0.

(Formula 1)

(In formula, each of R <^1> and R <^2> is a C3-C8 branched alkyl group, a C4-C12 cycloalkyl group, or a substituted branched cycloalkyl group.)

(Formula 2)

(Wherein R ³ is a hydrogen atom or a methyl group, R ⁴ is a C6-C12 aromatic hydrocarbon group)

(Formula 3)

(Wherein R ⁵ is a hydrogen atom, a methyl group or a carboxymethyl group)

(Formula 4)

(Wherein R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a C6-C12 aromatic hydrocarbon group, a C1-C12 alkyl group, a C1-C12 branched alkyl group, a C2-C12 hydroxyalkyl group or a main ring configuration Alicyclic hydrocarbon group having 5 to 12 carbon atoms)

The structural units represented by Formulas 1 to 4 are each derived from monomers (monomers for each structural unit) represented by the following Formulas 5 to 8.

(Wherein R ¹ and R ² are each the same as in formula 1. The monomer of formula 5 is called fumaric acid diester monomer.)

(Wherein R ³ and R ⁴ are the same as in formula 2. The monomer of formula 6 is called aromatic vinyl monomer)

(Wherein R ⁵ is the same as in formula 3. The monomer of formula 7 is called α, β-unsaturated carboxylic acid monomer.)

(Wherein R ⁶ and R ⁷ are the same as in formula 4. The monomer of formula 8 is called (meth) acrylic acid ester monomer.)

[Structural Unit (a1) Derived from Fumaric Acid Diester Monomer]

The structural unit (a1) derived from the fumaric acid diester monomer does not have a methylene group in the main chain structure portion, and substituents (COOR ¹ and COOR ² in Chemical Formula 1) are bonded to the carbon of the main chain and constituted of fumaric acid diester. The polymer has an intact backbone structure. Due to the intact main chain structure, molecular chain thermal motility of the main chain is suppressed, and loss to thermal energy in a specific frequency band can be suppressed to obtain good low dielectric properties.

Each of R ¹ and R ² in Chemical Formula 1 is a C3-C8 branched alkyl group, a C4-C12 cycloalkyl group, or a substituted branched cycloalkyl group. R ¹ and R ² are preferably a branched alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or a substituted branched cycloalkyl group. More preferably, they are a 3-5 branched alkyl group or a C6-C8 cycloalkyl group.

When the number of carbon atoms of the branched alkyl group exceeds 8, the polymerizability may deteriorate and problems may occur. Moreover, when carbon number of a cycloalkyl group or a substituted branched cycloalkyl group exceeds 12, there exists a problem that developability becomes inadequate. R ¹ and R ² in Chemical Formula 1 may be the same substituent, or may be a different substituent. It is preferable that R ¹ and R ² are identical to each other for ease of availability.

[Structural Unit (a2) Derived from Aromatic Vinyl Monomer]

The aromatic vinyl monomer which induces a structural unit (a2) can improve the copolymerization reactivity with the fumaric acid diester monomer which induces a structural unit (a1) at the time of superposition | polymerization. Since the fumaric acid diester monomer is a monomer having strong electron acceptability, copolymerization reactivity with a polar monomer such as (meth) acrylic acid ester or acrylonitrile is low, but copolymerization with an electron donating monomer is relatively high. Since the aromatic vinyl monomer which induces a structural unit (a2) has good copolymerizability with all three monomers of a fumaric acid diester monomer, the (alpha), (beta)-unsaturated carboxylic acid monomer, and a (meth) acrylic acid ester monomer, superposition | polymerization is carried out. Each structural unit derived from monomers having different copolymerizability at the time of reaction can be introduced into the polymer smoothly, and a copolymer having uniform properties can be obtained without biasing the distribution in the copolymer composition.

In Formula 2, R ³ is a hydrogen atom or a methyl group, and R ⁴ is an aromatic hydrocarbon group having 6 to 12 carbon atoms. R ³ is preferably a hydrogen atom, and R ⁴ is an aromatic hydrocarbon group having 6 to 10 carbon atoms. When carbon number of R <^4> exceeds 12, developability of the photosensitive resin composition will become inadequate.

(Total amount of (a1) + (a2)]

The total amount of the structural unit (a1) derived from the fumaric acid diester monomer and the structural unit (a2) derived from the aromatic vinyl monomer is 40 to 85 mass%, preferably 45 to 80 mass% in component (A), More preferably, it is 50-75 mass%. When the total amount of (a1) and (a2) is less than 40 mass%, the structural unit (a3) derived from the α, β-unsaturated carboxylic acid monomer and the structural unit (a4) derived from the (meth) acrylic acid ester monomer Since the copolymerizability becomes insufficient and the intact segment in a copolymer decreases, the photosensitive resin composition which has sufficient low dielectric properties cannot be obtained. On the other hand, when it exceeds 85 mass%, since the hydrophobicity of a copolymer becomes high, the developability of the photosensitive resin composition will become inadequate and the image development residue will arise on a pattern.

The preferred composition ratios of (a1) and (a2) in the total amount of (a1) + (a2) of component (A) are molar fractions, preferably (a1) :( a2) = 80:20 to 10:90 More preferably 70:30 to 15:85. When (a1) is more than 80 mol% and (a2) is less than 20 mol%, the polymerization property of (a1) falls in a polymerization reaction, and there exists a problem in copolymerizability. On the other hand, when (a2) exceeds 90 mol% and (a1) is less than 10 mol%, since the structural unit derived from the aromatic vinyl monomer in component (A) increases, hydrophobicity of a copolymer becomes high and photosensitive There exists a possibility that developability of a resin composition may become inadequate.

[Structural unit (a3) derived from α, β-unsaturated carboxylic acid monomer]

The structural unit (a3) derived from the α, β-unsaturated carboxylic acid monomer is a component that contributes to solubility in a developing solution in a developing step. R ⁵ in Formula 3 is a hydrogen atom, a methyl group or a carboxymethyl group. Preferably it is a hydrogen atom or a methyl group, and when using a structural unit of that excepting the above, there exists a problem that copolymerizability with another structural unit cannot be obtained.

The acid value of the copolymer of component (A) can be adjusted with content of the structural unit (a3) derived from this (alpha), (beta)-unsaturated carboxylic acid monomer. The range of the acid value is preferably 50 to 200 mgKOH / g, more preferably 70 to 150 mgKOH / g to adjust the ratio of the structural unit (a3). If the acid value is too low, the solubility in the developer may be insufficient. On the other hand, if the acid value is too high, the residual film ratio at the time of development may decrease.

[Structural unit (a4) derived from (meth) acrylic acid ester monomer]

The structural unit (a4) derived from the (meth) acrylic acid ester monomer is a component that contributes to the adjustment of the developability, in particular, the residual film ratio and the resolution during development. In Formula 4, R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a C6-C12 aromatic hydrocarbon group, a C1-C12 alkyl group, a C1-C12 branched alkyl group, a C2-C12 hydroxyalkyl group or a main ring It is a C5-C12 alicyclic hydrocarbon group. The cyclocyclic alicyclic hydrocarbon group having 5 to 12 carbon atoms may include an additional structure, for example, a double bond in a ring, a side chain of a hydrocarbon group, a side chain of a spiro ring, a crosslinked hydrocarbon group in a ring, and the like. R ⁶ is preferably a methyl group, R ⁷ is preferably an alkyl or branched alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, or a cyclohexyl group, dicyclopentanyl Qi. When carbon number of R <^7> exceeds 12, polymerizability may fall and it may be unsuitable. These (meth) acrylic acid ester monomers which induce the structural unit (a4) can be used alone or in combination of two or more for the purpose of adjusting developability.

[Mass ratio (a4) / (a3)]

The mass ratio (a4) / (a3) of the structural unit (a3) derived from the α, β-unsaturated carboxylic acid monomer and the structural unit (a4) derived from the (meth) acrylic acid ester monomer is 0.2 to 7.0, preferably Is 0.3-6.0, More preferably, it is 0.6-4.0. When the value of the mass ratio (a4) / (a3) is lower than 0.2, the number of structural units derived from the α, β-unsaturated carboxylic acid monomer in the copolymer increases, and the residual film rate during development decreases. On the other hand, when the value of the mass ratio (a4) / (a3) is higher than 7.0, the number of structural units derived from the (meth) acrylic acid ester monomer increases, resulting in insufficient developability, leading to the occurrence of development residue and a decrease in resolution.

Generally known solvents can be used as the polymerization solvent used for obtaining the copolymer of component (A). Specific examples of such a solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, 2-heptanone and cyclohexanone; Amides such as N, N-dimethylacetamide and N-methylpyrrolidone; Lactones, such as (gamma) -butyrolactone, etc. are mentioned. These polymerization solvents can be used individually or in mixture of 2 or more types.

As a polymerization initiator used in order to obtain the copolymer of component (A), what is generally known as a radical polymerization initiator can be used. Specific examples thereof include an azo polymerization initiator, an azo polymerization initiator having no cyano group, an organic peroxide, hydrogen peroxide, and the like. When a peroxide is used as a radical polymerization initiator, this peroxide and a reducing agent can be combined and used as a redox polymerization initiator.

In order to adjust the weight average molecular weight at the time of obtaining the copolymer of component (A), a molecular weight modifier can be used. As a molecular weight regulator, For example, mercaptans, such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert- dodecyl mercaptan, thioglycolic acid, a mercaptopropionic acid; Xanthogens such as dimethyl xanthogen disulfide and diisopropyl xanthogen disulfide; Terpinolene, the (alpha) -methylstyrene dimer, etc. are mentioned.

The weight average molecular weight of the copolymer of component (A) becomes like this. Preferably it is 5,000-60,000, More preferably, it is 5,000-30,000, More preferably, it is 8,000-25,000. If the weight average molecular weight is less than 5,000, pattern flow may occur at the time of post-baking, resulting in insufficient resolution of the pattern film. If it exceeds 60,000, it may be difficult to obtain satisfactory developability due to insufficient solubility in a developer.

<Component (B): Photosensitive Agent with Quinonediazide Group>

When the photosensitive agent having a quinonediazide group of component (B) is exposed through a photomask in an exposure process by photolithography, the photosensitive reaction of the photosensitive agent having a quinonediazide group occurs in the exposed portion to generate a carboxyl group, and the subsequent development. It can melt | dissolve with respect to a developing solution in a process. On the other hand, the unexposed portion can form a film because it has a dissolution inhibiting ability with respect to the developer. That is, since the photosensitive agent which has a quinonediazide group is exposed through a photomask, since the solubility with respect to a developing solution can be distinguished in a subsequent developing process, a pattern film can be obtained.

The photosensitizer which has the quinonediazide group of component (B) can be obtained by esterifying a phenolic compound which has a hydroxyl group, and a quinonediazide compound. Examples of the quinone diazide compound include naphthoquinone diazide sulfonic acid chlorides represented by 1,2-naphthoquinone diazide-5-sulfonyl chloride, 1,2-naphthoquinone diazide-4-sulfonyl chloride, and the like. Quinonediazidesulfonic acid halides such as benzoquinonediazide sulfonic acid chloride are used.

The esterification reaction is carried out at a temperature of about -20 to 60 ° C in the presence of a phenolic compound having a hydroxyl group and a quinonediazidesulfonic acid halide in the presence of a basic catalyst such as sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, triethylamine, and the like. It is carried out by reacting at. Esterification rate can be suitably adjusted by adjusting the quantity of the phenolic compound which has a hydroxyl group, and the quantity of a quinonediazide compound. In this esterification reaction, a mixture having different esterification numbers and esterification positions is obtained. Therefore, esterification rate is represented by the average value of these mixtures. In addition, these reaction products may be used individually by 1 type, and may use 2 or more types together.

The esterification rate of the photosensitive agent which has a quinonediazide group becomes like this. Preferably it is 20-95 mol%, More preferably, it is 35-90 mol%. If the esterification rate is less than 20 mol%, the sensitivity may be lowered. If the esterification rate is higher than 95 mol%, the compatibility of the photosensitizer with respect to the copolymer may deteriorate and the pattern film may be phase separated and become cloudy.

As a phenolic compound which has a hydroxyl group which can be used for the photosensitive agent which has a quinonediazide group, the compound represented by following formula (9) or (10) is preferable.

(In formula, each of R <^8> , R <^9> , R <^10> and R <^11> represents a hydrogen atom or a C1-C2 alkyl group, and each of R <^12> and R <^13> represents a C1-C2 alkyl group. "

(In formula, each of R <^14> , R <^15> , R <^16> , R <^17> , R <^18> , R <^19> and R <^20> represents a hydrogen atom, a C1-C4 alkyl group, or following General formula (11),

In formula, R <^21> represents a hydrogen atom or a C1-C4 alkyl group, each of m and n is an integer of 0-2, and a, b, c, d, e, f, g, and h are a + b ≤ 5, c + d ≤ 5, e + f ≤ 5, g + h ≤ 5 is an integer of 0 to 5, i is an integer of 0 to 2).

As a phenolic compound represented by the said Formula (9), the following compounds are mentioned, for example.

In addition, as the phenolic compound represented by the formula (10), o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, Bisphenol A, B, C, E, F and G, 4,4 ', 4' '-methylidritrisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol , 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4'-[1- [4- [2- ( 4-hydroxyphenyl) -2-propyl] phenyl] ethylidene] bisphenol, 4,4 ', 4' '-ethylidinetrisphenol, 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxy Phenol, 4,4 '-[(2-hydroxyphenyl) methylene] bis [2,3-dimethylphenol], 4,4'-[(3-hydroxyphenyl) methylene] bis [2,6-dimethylphenol ], 4,4 '-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2'-[(2-hydroxyphenyl) methylene] bis [3,5-dimethylphenol ], 2,2 '-[(4-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4'-[(3,4-dihydroxyphenyl) methylene] bis [2,3 , 6-trimethylphenol], 4- [bis (3-cycle Lohexyl-4-hydroxy-6-methylphenyl) methyl] -1,2-benzenediol, 4,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2,3- Benzenetriol, 4,4 '-[(2-hydroxyphenyl) methylene] bis [3-methylphenol], 4,4', 4 ''-(3-methyl-1-propanyl-3-iridine ) Trisphenol, 4,4 ', 4' '-4' ''-(1,4-phenylenedimethylidine) tetrakisphenol, 2,4,6-tris [(3,5-dimethyl-4-hydrate Hydroxyphenyl) methyl] -1,3-benzenediol, 2,4,6-tris [(3,5-dimethyl-2-hydroxyphenyl) methyl] -1,3-benzenediol, 4,4 '-[ 1- [4- [1- [4-hydroxy-3,5-bis [(hydroxy-3-methylphenyl) methyl] phenyl] -1-methylethyl] phenyl] ethylidene] bis [2,6-bis (Hydroxy-3-methylphenyl) methyl] phenol and the like. Among these compounds, 4,4 ', 4' '-methylidritrisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4,4'-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4 '-[1- [4- [2- (4-hydroxyphenyl) -2- Propyl] phenyl] ethylidene] bisphenol, 4,4 ', 4 "-ethylidine trisphenol, etc. are preferable.

Among these phenolic compounds represented by the formula (10), a compound represented by the following formula (15) or the following formula (16) is particularly preferable.

The composition ratio of the photosensitive agent which has the quinonediazide group of the component (B) in the photosensitive resin composition is 5-50 mass parts with respect to 100 mass parts of copolymers of a component (A), Preferably it is 7-45 mass parts, More preferably, Is 10 to 40 parts by mass. When this composition ratio is less than 5 mass parts, there exists a possibility that the fall of a sensitivity or a developing residue may occur, and when it exceeds 50 mass parts, the compatibility of the photosensitive agent with respect to a copolymer may deteriorate, and a pattern film may phase-separate.

<Component (C): Curing Agent Having Two or More Epoxy Groups>

The hardening | curing agent used for the photosensitive resin composition of this invention has two or more epoxy groups. This curing agent can cause a thermosetting reaction at the time of high temperature baking with the carboxyl group of the side chain of a copolymer, and can form a crosslinked film. As a specific example of this hardening | curing agent, a bisphenol-type epoxy resin, a cresol or a phenol novolak-type epoxy resin, a naphthalene-type epoxy resin, an alicyclic epoxy resin, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, glycy Dylamine type epoxy resin, heterocyclic epoxy resin, siloxane type epoxy resin, fluorene type epoxy resin, tetraphenyrolethane type epoxy resin, DPP (di-n-pentylphthalate) type epoxy resin, trishydroxyphenylmethane type epoxy Aromatic polyglycidyl ethers, such as resin and a dicyclopentadiene phenol type epoxy resin, and the aromatic nucleated hydrogenated material of the said epoxy resin can also be used. The curing agent is not limited to these high molecular weight epoxy resins, and may be a low molecular weight epoxy compound. Preferably, a cresol novolak-type epoxy resin, a phenol novolak-type epoxy resin, an alicyclic epoxy resin, etc. are mentioned. Particularly preferably, by using a bisphenol type epoxy resin having two or more epoxy groups, good curability, high light transmittance and solvent resistance can be achieved. These epoxy resins can be used 1 type or in combination of 2 or more types.

The composition ratio of the hardening | curing agent of a component (C) in the photosensitive resin composition is 1-40 mass parts with respect to 100 mass parts of copolymers of a component (A), Preferably it is 5-35 mass parts, More preferably, it is 10-30 mass It is wealth. If the composition ratio is less than 1 part by mass, the solvent resistance of the patterned film (cured film) becomes insufficient, and if it exceeds 40 parts by mass, the compatibility of the curing agent with respect to the copolymer may deteriorate, resulting in phase separation of the patterned film, resulting in turbidity.

<Other ingredients added>

Addition components, such as a solvent, a hardening accelerator, a contrast improver, a compatibilizer, an adhesive improvement aid, and surfactant, can be used for the photosensitive resin composition.

(solvent)

Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, and di Diethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol Propylene glycol monoalkyl ether acetates such as monomethyl ether acetate and propylene glycol monoethyl ether acetate, lactic acid esters such as methyl lactate and ethyl lactate, aromatic hydrocarbons such as toluene and xylene, methyl ethyl ketone and 2-heptanone , Cyclohex And the like can be mentioned ketones such as rice, N, N- dimethylacetamide, N- methylpyrrolidone, etc. amides, γ- butyrolactone, etc. of lactones. These solvents can be used individually or in mixture of 2 or more types.

(Hardening accelerator)

A hardening accelerator can accelerate the crosslinking reaction of the hardening | curing agent of the said component (C), and the side chain carboxyl group of the copolymer of a component (A). As a hardening accelerator, For example, Aromatic sulfonium salts, such as SI-60L, SI-80L, SI-100L, SI-110L (above, Sanshin Chemical Co., Ltd. product); Diazabicyclo undecene salts, such as U-CAT SA102, U-CAT SA106, U-CAT SA506, U-CAT SA603, and U-CAT 5002 (above, manufactured by San Apro Co., Ltd.); And U-CAT 5003, U-CAT 18X, and CPI-210s (above, manufactured by San Apro Co., Ltd.). Moreover, as an imidazole series hardening accelerator, the quazole 1B2PZ [manufactured by Shikoku Chemical Co., Ltd.] is mentioned.

Moreover, the photobase generator etc. which generate | occur | produce a base by irradiating light can also be used. This photobase generator generates bases, such as an amine, at the time of light irradiation by adjusting the conditions at the time of a bleaching process, and can be used as a crosslinking promoter in a subsequent post-baking process. By containing these hardening accelerators in the photosensitive resin composition, since the reaction speed of an epoxy group and a carboxyl group becomes fast, thermal deformation of a pattern film is suppressed in high temperature baking, such as post-baking, and a high resolution pattern film can be obtained.

0.1-15 mass parts is preferable with respect to 100 mass parts of hardening | curing agents of a component (C), and, as for the structural ratio of a hardening accelerator, 1-10 mass parts is more preferable.

(Contrast enhancer)

The phenolic compound which has a hydroxyl group represented by the said Formula (9) or (10) can be mix | blended with the photosensitive resin composition for the purpose of improving contrast. Since the phenolic compound having a hydroxyl group is a low molecule, it is usually suitable for controlling the dissolution rate as a dissolution accelerator in the photosensitive resin composition, or for improving the sensitivity or adjusting the sensitivity of the photosensitive resin composition. Adjustment of these dissolution rates or sensitivity is performed by adjusting the addition amount of a phenolic compound. When improving a dissolution rate and a sensitivity, what is necessary is just to make a large amount, and in the opposite case, to make small addition amount. By using these phenolic compounds, the low molecular weight compound is contained in the resin component which suppresses the dissolution suppression which causes an azocoupling reaction with a photosensitive agent, compared with the case where it is not used, and it makes the difference of the dissolution rate of an exposure part and an unexposed part large. Can increase the contrast, and improve the resolution.

The phenolic compound having a hydroxyl group is preferably the above formula (12), (13), (14), (15) or (16), and is usually used in an amount of 1 to 20 parts by mass based on 100 parts by mass of the copolymer.

(Commercializing agent)

In the photosensitive resin composition, a polycarboxylic acid ester compound in which a part of two or more carboxyl groups represented by the following formula (17) is esterified with a higher alcohol for the purpose of improving the compatibility of components (A), (B) and (C). Can be further formulated.

R ²² is a hydrocarbon group which may be substituted with a hydroxyl group, a halogen, an amino group or a sulfonic acid group, R ²³ is a hydrocarbon group, and p and q are each an integer of 1 or more. R ²² is preferably saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon, and particularly preferably unsaturated hydrocarbon. Although carbon number of R <^23> is not specifically limited, It is preferable that it is 3-16, and it is more preferable that it is 5-12. Furthermore, R ²³ may be a straight chain alkyl group or a branched alkyl group. In addition, p is preferably 1 to 2, q is preferably 1 to 3, and when p is 2 or more, each R ²³ may be the same or different.

Content of a polycarboxylic acid ester compound is 0.01-10 mass parts with respect to 100 mass parts of copolymers of a component (A), Preferably it is 0.5-5 mass parts. When content of a polycarboxylic acid ester compound is more than 10 mass parts, there exists a possibility that the heat resistance of the formed film may deteriorate.

(Adhesive Enhancement Aid and Surfactant)

An adhesive improvement aid, surfactant, etc. can be further mix | blended with the photosensitive resin composition as needed. Examples of the adhesion improving aid include alkylimidazolines, butyric acids, alkyl acids, polyhydroxystyrenes, polyvinyl methyl ethers, t-butyl novolacs, epoxysilanes, epoxy polymers, silane coupling agents, and the like. Examples of the surfactant include nonionic surfactants such as polyglycols and derivatives thereof such as polypropylene glycol or polyoxyethylene lauryl ether, fluorine-containing surfactants such as Florade [trade name, Sumitomo 3M ( Ltd. manufacture], Megapak [brand name, Dainippon Ink and Chemicals Co., Ltd.], sulfon [brand name, Asahi Glass Co., Ltd.] or an organosiloxane surfactant, for example, KP341 [brand name, Shin-Etsu Chemical Co., Ltd. ( NOTE) manufacture] is mentioned.

<Preparation method of photosensitive resin composition>

At the time of preparation of the photosensitive resin composition or its diluent, each component including the said component (A), (B), and (C) may be mix | blended collectively, and may be mix | blended sequentially after melt | dissolving each component in a solvent. In addition, the addition order and working conditions at the time of compounding are not restrict | limited. For example, a resin composition may be prepared by dissolving all components in a solvent at the same time. If necessary, each component may be suitably two or more solutions, and these solutions may be mixed at the time of use (application) to prepare a photosensitive resin composition. It may be.

<Flat Panel Displays and Semiconductor Devices>

A flat panel display and a semiconductor device have a layer which hardened the photosensitive resin composition mentioned above, ie, a planarization film or an interlayer insulation film. At the time of formation of a planarization film and an interlayer insulation film, the solution of the photosensitive resin composition is normally apply | coated on a board | substrate, and prebaking is carried out to form the coating film (photoresist film) of the photosensitive resin composition. Under the present circumstances, the board | substrate with which the photosensitive resin composition is apply | coated can be any well-known board | substrate, such as the board | substrate for conventional FPD or semiconductor device formation, such as glass and silicon. The substrate may be a bare substrate, an oxide film, a nitride film, a metal film, or the like may be formed, or may be a substrate on which a circuit pattern or a semiconductor device is formed. In addition, the temperature of a prebak is 40-140 degreeC normally, and time is about 0 to 15 minutes. Subsequently, after performing pattern exposure to a photoresist film through a predetermined | prescribed mask, it develops using alkaline developing solution, and rinses as needed, and forms the film of the photosensitive resin composition. The film thus formed is exposed to the entire surface and then post-baked to form a pattern film. The exposure amount at the time of whole surface exposure may be 600 mJ / cm <^{2> or} more normally. In addition, a post-baking temperature is 150-250 degreeC normally, Preferably it is 180-230 degreeC, and a post-baking time is 30-90 minutes normally.

The pattern film formed using the photosensitive resin composition is used as a planarization film or interlayer insulation film of FPD, such as a semiconductor device, a liquid crystal display device, and a plasma display. The planarization film and the interlayer insulation film are not independent here, and the pattern film formed of the photosensitive resin composition can be used as the planarization film or the interlayer insulation film. In a semiconductor device or the like, such a film functions as either an interlayer insulating film or a flattening film.

In the formation of the pattern film, a method of applying the photosensitive resin composition or the dilution thereof may be any of spin coating method, roll coating method, land coating method, spray method, cast coating method, immersion coating method, slit coating method, and the like. Method can be used. Moreover, as radiation used for exposure, ultraviolet rays, such as g line | wire, h line | wire, i line | wire, far ultraviolet rays, such as KrF excimer laser beam or ArF excimer laser beam, X-ray, an electron beam, etc. are mentioned, for example.

As the developing method, a method used in developing a conventional photoresist such as a paddle developing method, an immersion developing method, a rocking immersion developing method, and a shower developing method can be used. As the developer, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and sodium silicate, organic amines such as ammonia, ethylamine, propylamine, diethylamine, diethylaminoethanol and triethylamine, and tetramethylammonium hydroxide An aqueous solution in which quaternary amines such as seeds and the like are adjusted to a predetermined concentration can be used.

(Example)

Hereinafter, the said embodiment is demonstrated further more concretely by an Example and a comparative example. "Part" and "%" are all based on mass unless otherwise specified. The measuring method and evaluation method used by each Example and each comparative example are shown below.

<Acid value>

The acid value (mgKOH / g) is tetrahydro according to JIS K0070: 1992 "Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical product". A certain amount of resin was dissolved in a furan (THF) solution, and phenolphthalein was measured by titration with a potassium hydroxide / ethanol solution as an indicator.

<Weight average molecular weight>

The weight average molecular weight (Mw) was measured by RI detector using THF as an eluent, using gel permeation chromatography apparatus HLC-8220GPC manufactured by Toso Corporation, and column SHODEX K801 manufactured by Showa Electric Co., Ltd. It calculated | required by conversion using the analytical curve obtained with a known polystyrene standard.

Synthesis Example 1, Synthesis of Copolymer A-1

540.0 g of ethyl lactate (EL) was injected into a 1000 mL four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, and nitrogen-substituted, and the temperature was raised to 90 ° C in an oil bath.

On the other hand, bis fumarate (4-tert-butylcyclohexyl) (DcHtBF) 71.1g, methacrylic acid (MAA) 38.4g, styrene (St) 18.9g, methacrylic acid 2-hydroxyethyl (HEMA) 71.6g, 2 , 2'-azobisisobutyronitrile [Azo polymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd.] 10.0 g and EL 60.0 g were uniformly mixed in a dropping funnel over 2 hours with a liquid (dropping component) previously mixed. After dripping, it maintained at the same temperature for 8 hours and obtained copolymer A-1.

Synthesis Examples 2 to 9

The copolymers A-2 to A-9 were synthesized in the same manner as in Synthesis Example 1 except that the injection type and amount, dropping, and polymerization temperature shown in Table 1 were changed.

The meaning of abbreviation in Table 1 is as follows.

DcHtBF: Fumaric acid bis (4-tert-butylcyclohexyl)

DcHF: Dicyclohexyl fumaric acid

DiPF: Diisopropyl Fumarate

DsBF: disecbutyl fumarate

DtBF: ditertbutyl fumaric acid

DsAF: fumaric acid disecamyl

St: Styrene

αMeSt: α-methylstyrene

MAA: methacrylic acid

AA: acrylic acid

HEMA: 2-hydroxyethyl methacrylate

HPMA: Methacrylic Acid Hydroxypropyl

MMA: Methyl methacrylate

CHMA: cyclohexyl methacrylate

Hex-O: t-hexyl peroxy-2-ethylhexanoate, peroxide-based polymerization initiator "Perhexyl O" manufactured by Nichiyu Co., Ltd.

Bu-O: t-butylperoxy-2-ethylhexanoate, peroxide polymerization initiator "Perbutyl O" manufactured by Nichiyu Co., Ltd.

AIBN: 2,2'- azobisisobutyronitrile [Azo type polymerization initiator, Wako Pure Chemical Industries, Ltd. manufacture]

PGMEA: propylene glycol monomethyl ether acetate

EL: ethyl lactate

&Lt; Example 1 >

100 g of Copolymer A-1 obtained in Synthesis Example 1, 6.25 g of an esterified product of the compound represented by Formula 15 with 1,2-naphthoquinonediazide-5-sulfonyl chloride, and a phenol represented by Formula 15 1.25 g of a compound, 5 g of Techmoa VG3101L (manufactured by PRINTECH), 0.1 g of U-CAT SA102 (manufactured by San Apro Co., Ltd.) were dissolved in 75.2 g of propylene glycol monomethyl ether acetate and 0.2 g of ethyl lactate, To prevent radiation wrinkles and so-called striation on the resist film during rotation coating, 0.01 g of a fluorine-based surfactant, Megapak R-08 (manufactured by Dainippon Ink and Chemicals, Inc.) is further added. After stirring, the mixture was filtered with a 0.2 µm filter to prepare a dilution of the photosensitive resin composition.

(Formation of a thin film pattern)

The dilution of this photosensitive resin composition was spin-coated on a 4-inch silicon wafer, baked at 100 ° C. for 90 seconds on a hot plate to obtain a 4.2 μm thick thin film. Canon Co., Ltd. g + h + i line mask aligner (PLA-501F) exposes the test patterns of various line widths and contact holes having 1: 1 line width and contact holes at an optimal exposure amount to 0.4 mass%. By developing at 23 DEG C for 60 seconds in an aqueous tetramethylammonium hydroxide solution, a line & space pattern and a contact hole pattern having a line and space width of 1: 1 were formed. After exposing this thin film to PLA-501F for the whole surface, it post-processed by heating at 220 degreeC and 60 minute (s) in oven, and obtained the thin film (pattern film) which has a 3.0-micrometer-thick pattern.

(Evaluation evaluation)

The hole pattern of 10 micrometers was observed in SEM in the pattern produced above. When the residue was seen on the whole hole part surface, x was evaluated, and when a residue was seen only in the interface vicinity of a hole and a board | substrate, (triangle | delta) and when a residue was not seen on the hole part whole surface, developability was evaluated. The results are shown in Table 2.

Dielectric constant evaluation

Except not exposing the test pattern with PLA-501F, the same operation as described above was performed to obtain a 3.0 μm-thick thin film without a pattern on a 4-inch silicon wafer. An electrode was formed on this thin film, and the dielectric constant was computed by the capacitance obtained using the LCR meter (AG-4311) manufactured by Ando Electric Co., Ltd. on the conditions of room temperature and 10 kHz. The results are shown in Table 2.

(Evaluation of transmittance)

A thin film without a pattern was obtained on a glass substrate by performing the same operation as above except using a quartz glass substrate having a length of 70 mm and a width of 70 mm, without exposing the test pattern. And the transmittance | permeability of wavelength 400nm of the light of the glass substrate which has this thin film was measured using the ultraviolet-visible-light spectrophotometer CARY4E (made by Varian company). The results are shown in Table 2.

(Solvent resistance evaluation)

The glass substrate obtained by performing the same operation as the transmittance evaluation was immersed in Remover100 (manufactured by AZ Electronic Materials Co., Ltd.) at 80 ° C for 1 minute, followed by pure rinsing, followed by rebaking at 200 ° C for 15 minutes. It was. And when the transmittance | permeability difference before solvent immersion and the rebaking process is less than 3%, it evaluated as (circle) and the case where the transmittance difference is 3% or more. The results are shown in Table 2.

<Example 2>

A dilution of the photosensitive resin composition was prepared by performing the same operation as in Example 1 except using Copolymer A-2 obtained in Synthesis Example 2. The physical properties similar to Example 1 were evaluated about this photosensitive resin composition, and the result is shown in Table 2.

<Examples 3 to 18>

The dilution of the photosensitive resin composition of Examples 3-18 was prepared by performing the same operation as Example 1 with the combination shown in Table 2 and Table 3. The physical properties similar to Example 1 were evaluated about these photosensitive resin compositions, and the result is shown to Table 2 and Table 3.

<Comparative Examples 1 and 2>

By performing the same operation as in Example 1 with the formulations shown in Table 3, dilutions of the photosensitive resin compositions of Comparative Examples 1 and 2 were prepared. The physical properties similar to Example 1 were evaluated about these photosensitive resin compositions, and the result is shown in Table 3.

From the results shown in Tables 2 and 3, in Examples 1 to 18, there was no developing residue in the developing step of forming the patterned film, and even after high-temperature baking, the coating film properties such as light transmittance and solvent resistance were not impaired. It was confirmed that the characteristics were excellent. In Examples 1 to 18, the remaining film ratio of the pattern film was sufficiently maintained, and the flatness of the pattern film was also good.

On the other hand, from the result shown in Table 3, since the copolymer of component (A) did not contain the structural unit (a1) in the comparative example 1, developability deteriorated. In Comparative Example 2, the dielectric constant deteriorated because the copolymer contained no structural units (a1) and (a2).

Claims (3)

In the photosensitive resin composition which consists of a component (A), (B) and (C),
Component (A) is a structural unit (a1) derived from the fumaric acid diester monomer represented by the following formula (1), a structural unit (a2) derived from the aromatic vinyl monomer represented by the following formula (2), and α represented by the following formula (3) It is a copolymer which consists of a structural unit (a3) derived from the (beta)-unsaturated carboxylic acid monomer, and a structural unit (a4) derived from the (meth) acrylic acid ester monomer represented by following General formula (4), and a structural unit (a1) and a structure It is a copolymer whose total amount of a unit (a2) is 40-85 mass% in the said component (A), and the mass ratio (a4) / (a3) of a structural unit (a3) and a structural unit (a4) is 0.2-7.0,
(Formula 1)

(In formula, each of R <^1> and R <^2> is a C3-C8 branched alkyl group, a C4-C12 cycloalkyl group, or a substituted branched cycloalkyl group.)
(2)

(Wherein R ³ is a hydrogen atom or a methyl group, R ⁴ is a C6-C12 aromatic hydrocarbon group)
(Formula 3)

(Wherein R ⁵ is a hydrogen atom, a methyl group or a carboxymethyl group)
(Formula 4)

(Wherein R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a C6-C12 aromatic hydrocarbon group, a C1-C12 alkyl group, a C1-C12 branched alkyl group, a C2-C12 hydroxyalkyl group or a main ring configuration Alicyclic hydrocarbon group having 5 to 12 carbon atoms)
Component (B) is a photosensitizer which has a quinonediazide group obtained by esterifying a phenolic compound which has a hydroxyl group, and a quinonediazide compound,
Component (C) is a curing agent having two or more epoxy groups,
The composition ratio of component (B) and (C) is 5-50 mass parts of (B) and 1-40 mass parts of (C) with respect to 100 mass parts of components (A), The photosensitive resin composition characterized by the above-mentioned.
Flat panel display which has a layer which hardened the photosensitive resin composition of Claim 1.
The semiconductor device which has a layer which hardened the photosensitive resin composition of Claim 1.