KR20230020332A - Epoxy resin, photosensitive resin composition, resist film, curable composition and cured film - Google Patents

Abstract

The present invention is to provide an epoxy resin capable of suppressing volatilization and sublimation of low-molecular-weight components during heat treatment, and producing a film exhibiting a high refractive index, a low extinction coefficient, and high etching resistance. To this end, provided is an epoxy resin having a structure which has a recurring unit represented by formula (1-1) and of which both ends are represented by formula (1-2).

Description

Epoxy resin, photosensitive resin composition, resist film, curable composition, and cured film

The present invention relates to an epoxy resin, a photosensitive resin composition, a resist film, a curable composition, and a cured film.

In recent years, with the high integration and high speed of LSI, the pattern processing is increasingly required to be miniaturized, and in photolithography using ArF excimer laser light (193 nm), use of optical characteristics of process materials and improvement of process equipment As a result, the intrinsic resolution limit derived from the wavelength of the light source is exceeded.

In the field of photoresist, various methods for forming finer wiring patterns have been developed, and one of them is a multilayer resist method. In the multilayer resist method, one or more layers of an underlayer or the like are formed on a substrate, a resist pattern is formed thereon by ordinary photolithography, and then the wiring pattern is processed and transferred to the substrate by dry etching.

One of the important members in the multilayer resist method is the lower layer film. As characteristics required for the lower layer film, film formability, high dry etching resistance, high refractive index, and low extinction coefficient are required. As a material for an underlayer film that meets the requirements, a novolak resin having a high aromatic ring concentration (for example, Patent Document 1) has been proposed, and a method for producing an underlayer film using a cationically polymerizable compound and a photopolymerization initiator has been proposed. (Patent Document 2).

Japanese Patent Laid-Open No. 2016-206676 International Publication No. 2006/115044

When the novolak resin of Patent Document 1 is used as the material for the lower layer film, when forming the lower layer film on the substrate, heat treatment is generally performed at a high temperature of 170 to 200 ° C. Thus, there is a problem of contaminating the peripheral device.

In Patent Literature 2, since no heat treatment is required to form the lower layer film, the above-mentioned subject of Patent Literature 1 can be solved. However, since low-molecular-weight components volatilize or sublimate during heat treatment (PEB, post-exposure bake) after resist exposure, the problem of contaminating peripheral devices cannot itself be solved. In addition to this, the lower layer film is required to have a reflectance lower than that of the resist film, but there is also a problem in that the lower layer film of Patent Literature 2 cannot satisfy this requirement.

The problem to be solved by the present invention is to provide an epoxy resin capable of producing a film capable of suppressing volatilization and sublimation of low molecular weight components during heat treatment and exhibiting a high refractive index, low extinction coefficient and high etching resistance. is to do

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that volatilization and sublimation of low molecular weight components can be suppressed during heat treatment by using an epoxy resin having a specific structure, resulting in a high refractive index and low extinction. It was found that a film capable of exhibiting high modulus and high etching resistance could be produced, and the present invention was completed.

That is, the present invention has a repeating unit represented by the following general formula (1-1), and relates to an epoxy resin having a structure represented by the following general formula (1-2) at both ends.

(In the above general formulas (1-1) and (1-2),

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently an alkylene group having 1 to 6 carbon atoms;

R ²¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;

R ²² and R ²³ are each independently an alkylene group having 1 to 6 carbon atoms;

X ¹ , X ² and X ³ are each independently an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a halogen atom;

Y is an oxo group,

a, b and c are each independently an integer of 0 to 5)

According to the present invention, an epoxy resin capable of producing a film capable of suppressing volatilization and sublimation of low molecular weight components during heat treatment and exhibiting a high refractive index, low extinction coefficient and high etching resistance can be provided.

1 is a diagram showing the results of ¹³ C-NMR measurement of the epoxy resin of Synthesis Example 1.
Fig. 2 is a diagram showing the results of FD-MS measurement of the epoxy resin of Synthesis Example 1.

Hereinafter, one embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range not impairing the effects of the present invention.

[Epoxy Resin]

The epoxy resin of the present invention has a repeating unit represented by the following general formula (1-1), and both terminals have a structure represented by the following general formula (1-2).

Here, "both ends" means both ends of the main chain (longest molecular chain) of the epoxy resin.

(In the above general formulas (1-1) and (1-2),

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently an alkylene group having 1 to 6 carbon atoms;

R ²¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;

R ²² and R ²³ are each independently an alkylene group having 1 to 6 carbon atoms;

X ^{1 ,} X ² and X ³ are each independently an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a halogen atom;

Y is an oxo group,

* is a bond number bonded to the repeating unit,

a, b and c are each independently an integer of 0 to 5)

In the epoxy resin of the present invention, both terminals have a structure represented by the general formula (1-2), and the cyclic structure formed by R ²² and R ²³ is flexible, so the crystallinity of the epoxy resin is reduced and the coating film property is reduced. can be thought of as improving.

The structures represented by the general formula (1-2) may be the same or different from each other at both ends.

The alkylene group of 1 to 6 carbon atoms of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is preferably an alkylene group of 1 to 3 carbon atoms, more preferably a methylene group.

The alkyl group of 1 to 5 carbon atoms for R ²¹ is preferably an alkyl group of 1 to 3 carbon atoms.

The alkylene group of 1 to 6 carbon atoms for R ²² and R ²³ is preferably an alkylene group of 1 to 3 carbon atoms, more preferably a methylene group.

Examples of the alkyl group for X ¹ , X ² and X ³ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a cyclohexyl group. The number of carbon atoms in the alkyl group is, for example, 1 to 9, preferably 1 to 3.

Examples of the alkoxy group for X ¹ , X ² and X ³ include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group and a cyclohexyloxy group. The number of carbon atoms in the alkoxy group is, for example, 1 to 9, preferably 1 to 3.

Examples of the aryl group for X ¹ , X ² and X ³ include aryl groups having 6 to 14 carbon atoms forming a ring. The said aryl group may have substituents, such as the above-mentioned alkyl group, the above-mentioned alkoxy group, and a hydroxy group. Specific examples of the aryl group include a phenyl group, a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxyalkoxyphenyl group, an alkoxyphenyl group, a tolyl group, a xylyl group, a naphthyl group, a hydroxynaphthyl group, and a dihydroxynaphthyl group.

The aralkyl group of X ¹ , X ² and X ³ means an alkyl group in which at least one hydrogen atom of the alkyl group is substituted with an aryl group. Examples of the aryl group include the same as the aryl group described above.

Specific examples of the aralkyl group represented by X ¹ , X ² and X ³ include phenylmethyl, hydroxyphenylmethyl, dihydroxyphenylmethyl, tolylmethyl, xylylmethyl, naphthylmethyl, hydroxynaphthylmethyl, and dihydroxynaph. ethylmethyl group, phenylethyl group, hydroxyphenylethyl group, dihydroxyphenylethyl group, tolylethyl group, xylylethyl group, naphthylethyl group, hydroxynaphthylethyl group, and dihydroxynaphthylethyl group.

The number of carbon atoms in the aralkyl group is, for example, 7 to 15, preferably 7 to 12.

Examples of the halogen atom for X ¹ , X ² and X ³ include a fluorine atom, a chlorine atom, and a bromine atom.

a, b and c are preferably integers of 0 to 2, more preferably 0 or 1.

The structure represented by the general formula (1-2) is preferably a structure represented by the following general formula (1-3).

(In the above general formula (1-3),

R ¹³ , R ¹⁴ , R ¹⁵ , R ²² and R ²³ are the same as in the above general formula (1-2))

As a specific example of the epoxy resin of this invention, the epoxy resin represented by the following general formula (1) is mentioned.

The weight average molecular weight of the epoxy resin of the present invention is, for example, 500 to 50,000, preferably 500 to 10,000, more preferably 500 to 5,000.

The weight average molecular weight of the epoxy resin of the present invention is measured by the method described in Examples.

[Method for producing epoxy resin]

The epoxy resin of the present invention can be produced by reacting a dihydroxynaphthalene compound and an aldehyde compound in the presence of an alkali catalyst to obtain a dihydroxynaphthalene resin, and reacting the dihydroxynaphthalene resin with epihalohydrin. there is.

As the dihydroxynaphthalene compound, for example, a compound represented by the following general formula (A) can be used, and specific examples thereof include 2,7-dihydroxynaphthalene, methyl-2,7-dihydroxynaphthalene, and ethyl- 2,7-dihydroxynaphthalene, t-butyl-2,7-dihydroxynaphthalene, methoxy-2,7-dihydroxynaphthalene, and ethoxy-2,7-dihydroxynaphthalene. .

The dihydroxynaphthalene compounds used may be used singly or in combination of two or more.

(In the above general formula (A),

X ¹ and a are the same as in the above general formula (1-1))

Examples of the alkali catalyst include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metals such as metal sodium and metal lithium; alkali metal hydrides such as sodium hydride; Alkali metal carbonates, such as sodium carbonate and potassium carbonate, etc. are mentioned.

Alkali catalysts to be used may be used alone or in combination of two or more.

The alkali catalyst may be used in an amount of 0.9 to 5 moles, preferably 1 to 5 moles, more preferably 2 to 5 moles, per 1 mole of the dihydroxynaphthalene compound.

In order to make the epoxy resin of the present invention having the structure represented by the above general formula (1-2) at both ends, an amount different from the so-called "catalyst amount" is used. It is presumed that by using this amount, the electron density at the ortho position after the proton escapes with respect to the hydroxyl group of the dihydroxynaphthalene compound is higher, and the formation of the cyclic structure is promoted.

The aldehyde compound is, for example, a compound represented by R ²¹ CHO (R ²¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), and specific examples thereof include formaldehyde, acetaldehyde, propionaldehyde, n-butylaldehyde, t-butylaldehyde, pentylaldehyde, etc. are mentioned.

Among the above aldehyde compounds, formaldehyde is preferable, and formalin in an aqueous solution state may be used, or paraformaldehyde in a solid state may be used as the formaldehyde.

The aldehyde compound to be used may be used alone or in combination of two or more.

R ²¹ , R ²² , R ²³ and R ²⁴ in the general formulas (1-1) and (1-2) are structures derived from aldehyde compounds.

The amount of the aldehyde compound used is, for example, 0.5 to 4 moles of the aldehyde compound per 1 mole of the dihydroxynaphthalene compound, preferably 0.6 to 4 moles. It is more preferable to use more than 2.0 mol of an aldehyde compound.

Since the structure represented by the general formula (1-2) is formed by the reaction of two aldehyde compounds, the aldehyde compound may be used in the above amount in order to obtain the structure represented by the general formula (1-2) at both terminals. .

When the reaction between the dihydroxynaphthalene compound and the aldehyde compound is carried out by heating and stirring in the presence of an alkali catalyst, the heating temperature may be set in the range of 20 to 150°C, and the reaction time is, for example, in the range of 1 to 10 hours. good to do

In addition, post-processing after reaction can employ a well-known method.

The reaction between the dihydroxynaphthalene compound and the aldehyde compound may be carried out in an organic solvent, and may be carried out using monoalcohols such as methanol, ethanol, and propanol; Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol polyols such as 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, and glycerin; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethylmethyl ether, ethylene glycol mono glycol ethers such as phenyl ether; cyclic ethers such as 1,3-dioxane, 1,4-dioxane, and tetrahydrofuran; glycol esters such as ethylene glycol acetate; Ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, are mentioned.

These solvents may be used independently, respectively, or may be used as a mixed solvent of two or more types.

The epoxy resin of the present invention can be obtained by reacting dihydroxynaphthalene resin with epihalohydrin.

Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, and β-methylepichlorohydrin, and epichlorohydrin is preferable because of its good reactivity.

The epihalohydrin to be used may be used alone or in combination of two or more.

The amount of epihalohydrin used is, for example, 1 to 10 moles of epihalohydrin per mole of phenolic hydroxyl groups in the dihydroxynaphthalene resin, and preferably 2 to 5 moles.

The reaction between the dihydroxynaphthalene resin and epihalohydrin may be carried out in the presence of an alkali catalyst, and the same alkali catalyst as described above can be used as the alkali catalyst.

The amount of alkali catalyst used in the reaction between dihydroxynaphthalene resin and epihalohydrin may be a normal catalytic amount.

The reaction between dihydroxynaphthalene resin and epihalohydrin may be carried out in an organic solvent, and the same organic solvent as described above can be used as the organic solvent.

For the reaction between dihydroxynaphthalene resin and epihalohydrin, known reaction conditions can be employed, and a post-treatment after the reaction can also employ a known method.

When dihydroxynaphthalene resin is reacted with epihalohydrin, an epoxy compound represented by the following general formula (2) in addition to the epoxy resin of the present invention (hereinafter sometimes referred to as “epoxy compound of the present invention”) is also used is obtained

(In the above general formula (2),

R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently an alkylene group having 1 to 6 carbon atoms;

R ²² , R ²³ , R ²⁴ and R ²⁵ are each independently an alkylene group having 1 to 6 carbon atoms;

X ² , X ³ and X ⁴ are each independently an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a halogen atom;

Y is an oxo group,

b, c and d are each independently an integer of 0 to 5)

The epoxy compound of the present invention is preferably contained in a composition containing the epoxy resin of the present invention described later.

The epoxy compound represented by the said general formula (2) is preferably an epoxy compound represented by the following general formula (2-1).

(In the above general formula (2-1),

R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ²² , R ²³ , R ²⁴ and R ²⁵ are the same as in the above general formula (2))

[Photosensitive Resin Composition]

The photosensitive resin composition of the present invention contains the epoxy resin of the present invention and a photosensitizer, and preferably contains the epoxy resin of the present invention, the epoxy compound of the present invention, and a photosensitizer.

Components other than the epoxy resin of the present invention and the epoxy compound of the present invention contained in the photosensitive resin composition of the present invention are described below.

As a photosensitizer, the compound which has a quinonediazide group is mentioned, for example. Specific examples of the compound having a quinonediazide group include aromatic (poly)hydroxy compounds, naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide- Full ester compounds, partial ester compounds, amidates, or partial amidates of sulfonic acids having a quinonediazide group, such as 4-sulfonic acid and orthoanthraquinonediazidesulfonic acid, are exemplified.

Examples of the aromatic (poly)hydroxy compound include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4 ,4'-tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, 2,2' ,3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, 2,3,3',4,4',5'-hexa polyhydroxybenzophenone compounds such as hydroxybenzophenone;

bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(2', 3',4'-trihydroxyphenyl)propane, 4,4'-{1-[4-[2-(4-hydroxyphenyl)-2-propyl]phenyl]ethylidene}bisphenol, 3,3' -bis[(poly)hydroxyphenyl]alkane compounds such as dimethyl-{1-[4-[2-(3-methyl-4-hydroxyphenyl)-2-propyl]phenyl]ethylidene}bisphenol;

Tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxy hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis( Tris such as 4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane and bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane (hydroxyphenyl) methane compounds or their methyl substituents;

Bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4 -Hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2 -Methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-3 -Hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydroxy hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methane compounds such as -2-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane or methyl-substituted products thereof; and the like.

A photosensitizer may be used individually by 1 type, and may use two or more types together.

It is preferable that the compounding quantity of a photosensitive agent is 5-50 mass parts with respect to 100 mass parts of total resin solid content of a photosensitive resin composition from the point which becomes the photosensitive resin composition excellent in photosensitivity.

The photosensitive resin composition of the present invention may contain other resins (X) other than the epoxy resin of the present invention. As the Resin (X), resins soluble in alkaline developing solutions or those soluble in alkaline developing solutions when used in combination with additives such as acid generators can be used.

As resin (X), it is a phenol resin (X-1), for example; Homopolymers or copolymers of hydroxy group-containing styrene compounds such as p-hydroxystyrene and p-(1,1,1,3,3,3-hexafluoro-2-hydroxypropyl)styrene (X-2); What modified|denatured the hydroxyl group of said (X-1) or (X-2) with acid decomposable groups, such as a t-butoxycarbonyl group and a benzyloxycarbonyl group (X-3); (meth)acrylic acid homopolymer or copolymer (X-4); Alternating polymer (X-5) of an alicyclic polymerizable monomer, such as a norbornene compound and a tetracyclododecene compound, and maleic anhydride or maleimide, etc. are mentioned.

In the case of using Resin (X), the blending ratio of the epoxy resin of the present invention and Resin (X) can be arbitrarily adjusted depending on the intended use.

The ratio of the epoxy resin of the present invention to the total of the resin components in the composition may be, for example, 60% by mass or more. The ratio of the epoxy resin of the present invention in the composition is preferably 70% by mass or more, 80% by mass or more, and 90% by mass or more of the total of the resin components in this order.

The photosensitive resin composition of the present invention may contain a surfactant for purposes such as improving film formability and pattern adhesion when used for resist applications and reducing developing defects.

Examples of the surfactant include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ether compounds such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; Sorbitan such as polyoxyethylene/polyoxypropylene block copolymer, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate fatty acid ester compounds; Polyoxyethylene sorbitol, such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. nonionic surfactants such as non-tane fatty acid ester compounds; fluorine-based surfactants having a fluorine atom in the molecular structure, such as a copolymer of a polymerizable monomer having a fluoroaliphatic group and [poly(oxyalkylene)] (meth)acrylate; and silicone surfactants having a silicone structural site in their molecular structure.

Surfactant may be used individually by 1 type, and may use two or more types together.

It is preferable to use content of surfactant in the range of 0.001-2 mass parts with respect to 100 mass parts of total resin solid content in the photosensitive resin composition of this invention.

The photosensitive resin composition of this invention may further contain various additives, such as a dye, a filler, a crosslinking agent, and a dissolution promoter. As these additives, known ones can be used.

The photosensitive resin composition of the present invention may be used by dissolving the epoxy resin of the present invention in an organic solvent.

The epoxy resin of the present invention may be dissolved in an organic solvent to obtain a resist resin composition, and this may be used as a positive resist solution, or the resist resin composition may be coated onto a film and removed from the solvent to be used as a positive resist film. can also Examples of the support film for use as a resist film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. The support film may be a single layer film or a laminated film. In addition, the surface of the support film may be corona treated or coated with a release agent.

Although the organic solvent used for the photosensitive resin composition of this invention is not specifically limited, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, etc. Alkylene glycol monoalkyl ether of; dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; alkylene glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate; Ketone compounds, such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; cyclic ethers such as dioxane; 2-Hydroxymethylpropionate, 2-hydroxyethylpropionate, 2-hydroxy-2-methylethylpropionate, ethoxyethyl acetate, oxyacetate ethyl, 2-hydroxy-3-methylbutanoic acid methyl, 3-methoxy Ester compounds, such as butyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate, are mentioned.

An organic solvent may be used individually by 1 type, and may use 2 or more types together.

The photosensitive resin composition of the present invention can be prepared by blending the above components and mixing them using a stirrer or the like. In addition, when the photosensitive resin composition contains a filler or a pigment, it can be prepared by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three-roll mill.

In a photolithography method using the photosensitive composition of the present invention as a resist resin composition, for example, the resist resin composition is applied onto a silicon substrate photolithography target and prebaked at a temperature of 60 to 150°C. The coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor blade coating.

Regarding the formation of a resist pattern, since the resist resin composition of the present embodiment is of a positive type, a target resist pattern is exposed through a predetermined mask, and the exposed portion is dissolved with an alkaline developer to form a resist pattern. . Since the resist resin composition has high alkali solubility in the exposed area and high alkali resistance in the unexposed area, it is possible to form a resist pattern with excellent resolution.

[Curable Resin Composition]

The curable resin composition of the present invention contains the epoxy resin of the present invention and a curing agent, and preferably contains the epoxy resin of the present invention, the epoxy compound of the present invention, and a curing agent.

Components other than the epoxy resin of the present invention and the epoxy compound of the present invention contained in the curable resin composition of the present invention are described below.

The curing agent is not particularly limited as long as it is a compound capable of causing a curing reaction with the epoxy resin of the present invention, and various compounds can be used, for example, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, resole resins, ( Epoxy resins other than the epoxy resin of the present invention, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, acid anhydrides, and oxazoline compounds.

Examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, a compound obtained by methoxymethylation of 1 to 6 methylol groups of hexamethylolmelamine, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, and hexamethoxymethylmelamine. Compounds in which 1 to 6 methylol groups of methylolmelamine were acyloxymethylated are exemplified.

Examples of the guanamine compound include compounds obtained by methoxymethylation of 1 to 4 methylol groups of tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxymethylbenzoguanamine, and tetramethylolguanamine; Compounds obtained by acyloxymethylation of 1 to 4 methylol groups of methoxyethylguanamine, tetraacyloxyguanamine, and tetramethylolguanamine are exemplified.

Examples of the glycoluril compound include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and 1,3,4 ,6-tetrakis(hydroxymethyl)glycoluril.

Examples of the urea compound include 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, and 1,1,3,3-tetrakis (methoxymethyl) urea. methyl) urea.

Examples of the resol resin include phenol, alkylphenols such as cresol and xylenol, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, naphthol, and dihydroxynaphthalene. and polymers obtained by reacting a phenolic hydroxyl group-containing compound with an aldehyde compound under alkaline catalytic conditions.

Examples of the epoxy resin include diglycidyloxynaphthalene, phenol novolak type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol coaxial novolac type epoxy resin, and naphthol-cresol coaxial type epoxy resin. Novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, 1,1-bis(2,7-diglycidyloxy-1-naphthyl)alkane, naphthylene ether type epoxy resin, triphenyl A methane-type epoxy resin, a dicyclopentadiene-phenol addition reaction type epoxy resin, a phosphorus atom-containing epoxy resin, and a polyglycidyl ether of a cocondensate of a phenolic hydroxyl group-containing compound and an alkoxy group-containing aromatic compound are exemplified.

As for an isocyanate compound, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate are mentioned, for example.

Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, and 4,4'-oxybisazide. .

Examples of the compound containing a double bond such as an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, and 1,4-butanediol divinyl ether. , tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetra Vinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylol-propane trivinyl ether are mentioned.

As an acid anhydride, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4'- aromatic acid anhydrides such as (isopropylidene)diphthalic anhydride and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride; and alicyclic carboxylic acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, decenylsuccinic anhydride, and trialkyltetrahydrophthalic anhydride.

A hardening|curing agent may be used individually by 1 type, and may use two or more types together.

The content of the curing agent is preferably a ratio of 0.5 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin of the present invention, from the viewpoint of obtaining a composition having excellent curability.

Curable resin composition of this invention may contain resin (Y) other than the epoxy resin of this invention. As the resin (Y), for example, various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenolic compounds, modified furnaces of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds Rockfish resin, phenolaralkyl resin (xylock resin), naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, biphenyl-modified phenolic resin, biphenyl-modified naphthol resin, aminotriazine-modified phenolic resin, various and vinyl polymers.

When using resin (Y), the compounding ratio of the epoxy resin of this invention and resin (Y) can be arbitrarily adjusted according to a desired use. For example, the ratio of the epoxy resin of the present invention to the total resin component in the composition may be 60% by mass or more. The ratio of the epoxy resin of the present invention in the composition is preferably 70% by mass or more, 80% by mass or more, and 90% by mass or more of the total of the resin components in this order.

The cured product of the curable composition of the present invention can be suitably used as a resist underlayer film or a resist permanent film.

When the curable composition of the present invention is used for resist underlayer film (BARC film) applications, in addition to the epoxy resin and curing agent of the present invention, other resins (Y), surfactants, dyes, fillers, crosslinking agents, It can be set as the composition for resist underlayer films by adding various additives, such as a dissolution accelerator, and dissolving in an organic solvent.

The organic solvent used for the resist underlayer film composition is not particularly limited, and examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether and propylene glycol monomethyl ether. Alkylene glycol monoalkyl ether; dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; alkylene glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate; Ketone compounds, such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; cyclic ethers such as dioxane; 2-Hydroxymethylpropionate, 2-hydroxyethylpropionate, 2-hydroxy-2-methylethylpropionate, ethoxyethyl acetate, oxyacetate ethyl, 2-hydroxy-3-methylbutanoic acid methyl, 3-methoxy Ester compounds, such as butyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate, are mentioned.

An organic solvent may be used individually by 1 type, and may use two or more types together.

The composition for a resist underlayer film can be prepared by blending the above components and mixing them using a stirrer or the like. In addition, when the resist underlayer film composition contains a filler or a pigment, it can be prepared by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three-roll mill.

In order to form a resist underlayer film from the composition for a resist underlayer film, for example, the above-described composition for a resist underlayer film is applied onto an object to be subjected to photolithography, such as a silicon substrate, and dried under temperature conditions of 100 to 200 ° C. In addition, there is a method of heating and curing under a temperature condition of 250 to 400 ° C. Next, a resist pattern can be formed by a multilayer resist method by carrying out a normal photolithography operation on this lower layer film to form a resist pattern, followed by a dry etching treatment with a halogen-based plasma gas or the like.

When the curable composition of the present invention is used for resist permanent film applications, in addition to the epoxy resin and curing agent of the present invention, other resins (Y), surfactants, dyes, fillers, crosslinking agents, dissolution promoters, etc. It can be set as the composition for permanent resist films by adding an additive and dissolving in an organic solvent. As for the organic solvent used here, the thing similar to the organic solvent used for the composition for resist underlayer films is mentioned.

A method of photolithography using a composition for a resist permanent film is, for example, dissolving and dispersing a resin component and an additive component in an organic solvent, applying the composition onto a silicon substrate photolithography object, and applying the composition at a temperature of 60 to 150°C. Prebaking. The coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor blade coating. Next, when the composition for a permanent resist film is of a positive type, the target resist pattern is exposed through a predetermined mask, and the exposed portion is dissolved with an alkaline developer to form a resist pattern.

A permanent film made of a composition for a resist permanent film is, for example, a solder resist in relation to semiconductor devices, a package material, an underfill material, an adhesive layer of a package such as a circuit element, an adhesive layer between an integrated circuit element and a circuit board, and a thin display typified by LCD and OLED. In terms of relationship, it can be suitably used for a thin film transistor protective film, a liquid crystal color filter protective film, a black matrix, a spacer, and the like.

(Example)

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

In addition, this invention is not limited to the following example. In addition, in the examples of this application, "%" means "mass %".

In this Example, the weight average molecular weight of a compound is a value calculated in terms of polystyrene based on GPC measurement, and the measurement conditions are as follows.

(Gel permeation chromatography (GPC) measurement conditions)

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation

Column: Showa Denko Co., Ltd. "Shodex KF802" (8.0 mmФ × 300 mm)

+ "Shodex KF802" (8.0 mmФ × 300 mm) manufactured by Showa Denko Co., Ltd.

+ "Shodex KF803" (8.0 mmФ × 300 mm) manufactured by Showa Denko Co., Ltd.

+ "Shodex KF804" (8.0 mmФ × 300 mm) manufactured by Showa Denko Co., Ltd.

Detector: RI (Differential Refractometer)

Data processing: "GPC-8020 Model II Version 4.30" manufactured by Tosoh Corporation

Column temperature: 40°C

Developing solvent: tetrahydrofuran

Flow rate: 1.0 mL/min

Injection volume: 0.1mL

Sample: A 0.5% by mass tetrahydrofuran solution filtered through a microfilter in terms of resin solid content

Standard sample: the following monodisperse polystyrene

(use polystyrene)

"A-500" made by Tosoh Corporation

"A-2500" by Tosoh Corporation

"A-5000" manufactured by Toso Co., Ltd.

"F-1" made by Toso Co., Ltd.

"F-2" made by Toso Co., Ltd.

"F-4" made by Toso Co., Ltd.

"F-10" made by Toso Co., Ltd.

"F-20" made by Toso Co., Ltd.

( ¹³ C-NMR measurement)

For the measurement of ^{the 13} C-NMR spectrum, the Acetone-d ₆ solution of the sample was analyzed using “AL-400” manufactured by Nippon Electronics Co., Ltd., and structural analysis was performed. Below, the measurement conditions of ¹³ C-NMR spectrum are shown.

[ ¹³ C-NMR spectrum measurement conditions]

Measurement mode: SGNNE (1H complete decoupling method of NOE cancellation)

Pulse angle: 45℃ pulse

Sample concentration: 30wt%

Total count: 10000 times

(FD-MS measurement)

FD-MS was measured using a dual convergence type mass spectrometer AX505H (FD505H) manufactured by Nihon Denshi Co., Ltd.

(Synthesis Example 1: Synthesis of Epoxy Resin (A-1))

180g (1.13mol) of 2,7-dihydroxynaphthalene, 137g (1.69mol) of 37% formaldehyde solution, 288g of isopropyl alcohol, 48% in a 2,000ml four-necked flask equipped with a thermometer, cooling tube and stirrer After adding 197 g (1.69 mol) of an aqueous solution of potassium hydroxide, the mixture was stirred and reacted under reflux at 85°C for 12 hours. After completion of the reaction, ethyl acetate and water were added, and separation washing was performed 5 times. After distilling off the solvent from the remaining resin solution under reduced pressure, vacuum drying was performed to obtain 214 g of phenol resin (a-1) as a light red powder.

120 g of the obtained phenolic resin (a-1), 830 g (8.97 mol) of epichlorohydrin, 12 g (0.15 mol) of 49% aqueous sodium hydroxide solution, ion exchange 55 g of water was added, and 221 g of isopropanol was added to dissolve it. Thereafter, the temperature was raised to 60°C, 64 g (0.78 mol) of a 49% by mass aqueous solution of sodium hydroxide was added over 30 minutes, and the mixture was further stirred for 1 hour and then washed with water. After repeating this operation once again, the organic layer was recovered and the solvent was distilled off under reduced pressure at 150°C to obtain a powdery epoxy resin (A-1).

It was 1,745 when the weight average molecular weight of the obtained epoxy resin (A-1) was measured. In addition, when FD-MS measurement was performed about the epoxy resin (A-1), peaks were confirmed at 752 and 1320 in the FD-MS spectrum. A separate ¹³ C-NMR measurement was also performed, and the epoxy resin (A-1) was an epoxy resin represented by the following general formula (A-1-1) and an epoxy compound represented by the following general formula (A-1-2) It was confirmed that it was the epoxy composition (A-1) which is a mixture of.

The results of the ¹³ C-NMR measurement are shown in FIG. 1 and the results of the FD-MS measurement are shown in FIG.

(Synthesis Example 2: Synthesis of Epoxy Resin (A-2))

Synthesis was carried out except that 2,7-dihydroxynaphthalene was 180 g (1.13 mol), 37% formaldehyde aqueous solution was 182 g (2.25 mol), isopropyl alcohol was 288 g, and 48% potassium hydroxide aqueous solution was 263 g (2.25 mol). In the same manner as in the synthesis of the phenol resin in Example 1, 223 g of a powdery phenol resin (a-2) was obtained.

Using 15 g of the obtained phenol resin (a-2), 104 g (1.12 mol) of epichlorohydrin, 2.50 g (0.01 mol) of 20% aqueous sodium hydroxide solution, 7 g of ion-exchanged water, and 28 g of isopropanol, 20% hydroxylation A powdery epoxy resin (A-2) was obtained in the same manner as in the synthesis of the epoxy resin in Synthesis Example 1, except that the amount of sodium aqueous solution added was 31 g (0.16 mol).

It was 954 when the weight average molecular weight of the obtained epoxy resin (A-2) was measured. In addition, when FD-MS measurement and ¹³ C-NMR measurement were performed on the epoxy resin (A-2), the epoxy resin (A-2) was an epoxy composition that is a mixture of an epoxy resin and an epoxy compound as in Synthesis Example 1 ( It was confirmed that it was A-2).

(Synthesis Example 3: Synthesis of Epoxy Resin (A-3))

Examples except that 2,7-dihydroxynaphthalene was 180 g (1.13 mol), 37% formaldehyde aqueous solution was 365 g (4.49 mol), isopropyl alcohol was 288 g, and 48% potassium hydroxide aqueous solution was 525 g (4.49 mol). 221 g of powdery phenol resin (a-3) was obtained in the same manner as in the synthesis of the phenol resin in 1.

Using 15 g of the obtained phenol resin (a-3), 104 g (1.12 mol) of epichlorohydrin, 2.50 g (0.01 mol) of 20% aqueous sodium hydroxide solution, 7 g of ion-exchanged water, and 28 g of isopropanol, 20% hydroxide A powdery epoxy resin (A-3) was obtained in the same manner as in the synthesis of the epoxy resin in Synthesis Example 1, except that the amount of sodium aqueous solution added was 31 g (0.16 mol).

It was 954 when the weight average molecular weight of the obtained epoxy resin (A-3) was measured. In addition, when FD-MS measurement and ¹³ C-NMR measurement were performed on the epoxy resin (A-3), the epoxy resin (A-3) was an epoxy composition (a mixture of an epoxy resin and an epoxy compound as in Synthesis Example 1) A-3) was confirmed.

(Synthesis Example 4: Synthesis of Epoxy Resin (A-4))

In a flask equipped with a thermometer, dropping funnel, cooling tube, and stirrer, 150 g (0.94 mol) of 2,7-dihydroxynaphthalene, 84 g (1.03 mol) of 37% formaldehyde aqueous solution, 200 g of isopropyl alcohol, and 48% potassium hydroxide 32 g (0.27 mol) of aqueous solution was put in, and the mixture was stirred while blowing nitrogen under room temperature. Then, it heated up at 85 degreeC and stirred for 12 hours. After completion of the reaction, it was cooled to 40°C, 720 g (7.78 mol) of epichlorohydrin was added dropwise over 1 hour, and after further stirring for 1 hour, water washing was performed. Subsequently, the temperature was raised to 60°C, 52 g (0.64 mol) of a 49% aqueous sodium hydroxide solution was added over 30 minutes, and the mixture was further stirred for 1 hour, followed by washing with water. After repeating this operation once more, the organic layer was recovered and the solvent was distilled off under reduced pressure at 150°C to obtain a powdery epoxy resin (A-4) powder.

It was 832 when the weight average molecular weight of the obtained epoxy resin (A-4) was measured. In addition, when FD-MS measurement and ¹³ C-NMR measurement were performed on the epoxy resin (A-4), the epoxy resin (A-4) was an epoxy composition that is a mixture of an epoxy resin and an epoxy compound as in Synthesis Example 1 ( A-4) was confirmed.

(Synthesis Example 5: Synthesis of Epoxy Resin (A-5))

In a flask equipped with a thermometer, dropping funnel, fractionation tube and stirrer, 150 g (0.94 mol) of 2,7-dihydroxynaphthalene, 58 g (0.71 mol) of 37% formaldehyde aqueous solution, 200 g of isopropyl alcohol, and 49% sodium hydroxide 3.5 g (0.04 mol) of an aqueous solution was introduced, and the mixture was stirred while blowing nitrogen under room temperature. Then, it heated up at 78 degreeC and stirred for 2 hours. After completion of the reaction, it was cooled to 40°C, 732 g (7.91 mol) of epichlorohydrin, 20 g of ion-exchanged water, and 24 g (0.29 mol) of 49% aqueous sodium hydroxide solution were added, followed by stirring for 2 hours, followed by washing with water. After repeating this operation once again, the temperature was raised to 60°C. After the temperature was raised, 57 g (0.70 mol) of a 49% aqueous sodium hydroxide solution was added over 30 minutes, stirred for 1 hour, and then washed with water. After repeating this operation once again, the organic layer was recovered and the solvent was distilled off under reduced pressure at 150°C to obtain a powdery epoxy resin (A-5) powder.

It was 574 when the weight average molecular weight of the obtained epoxy resin (A-5) was measured. In addition, when FD-MS measurement and ¹³ C-NMR measurement were performed on the epoxy resin (A-5), the epoxy resin (A-5) was an epoxy composition that is a mixture of an epoxy resin and an epoxy compound as in Synthesis Example 1 ( A-5) was confirmed.

(Synthesis Comparative Example 1: Preparation of Epoxy Resin (A'-1))

For comparison, N-770 (manufactured by DIC Corporation), which is a phenol novolak-type epoxy resin, was prepared as an epoxy composition (A'-1).

(Synthesis Comparative Example 2: Synthesis of Epoxy Resin (A'-2))

240g (1.50mol) of 2,7-dihydroxynaphthalene, 85g (1.05mol) of 37% formaldehyde solution, 376g of isopropyl alcohol, 48% in a 2,000ml four-necked flask equipped with a thermometer, cooling tube and stirrer After adding 88 g (1.05 mol) of an aqueous solution of potassium hydroxide, the mixture was stirred and reacted under reflux at 75°C for 2 hours. After completion of the reaction, ethyl acetate and water were added, and separation washing was performed 5 times. After distilling off the solvent from the remaining resin solution under reduced pressure, vacuum drying was performed to obtain 245 g of phenol resin (a'-2).

84 g of the obtained phenol resin (a'-2), 463 g (5.0 mol) of epichlorohydrin, and 53 g of n-butanol were added to a 2,000 ml four-necked flask equipped with a thermometer, a condenser and a stirrer, and dissolved. Thereafter, the temperature was raised to 50°C, 220 g (1.10 mol) of a 49% by mass aqueous solution of sodium hydroxide was added over 3 hours, and after further stirring for 1 hour, water washing was performed. After repeating this operation once again, the organic layer was recovered and the solvent was distilled off under reduced pressure at 150°C to obtain a powdery epoxy resin (A'-2).

The obtained epoxy resin (A'-2) was evaluated in the same manner as in Synthesis Example 1. Unlike the results of Synthesis Example 1, the compound represented by the following general formula (A'-2-1) and the following It was confirmed that the epoxy resin composition was a mixture of compounds represented by the general formula (A'-2-2).

(Example 1-5 and Comparative Example 1-2: Evaluation of the amount of volatile components and film formability)

Regarding the epoxy compositions of Synthesis Example 1-5 and Synthesis Comparative Example 1-2, the amount of volatile components and film formability were evaluated by the following methods. The results are shown in Table 1.

(Amount of volatile components)

1.0 g of the epoxy composition was spread on a petri dish to be leveled. In order to sufficiently volatilize moisture and residual solvent, it was dried in a dryer at 200 ° C. for 1 hour. After drying, it was heated in a dryer at 200°C for 1 hour, the amount of weight loss before and after heating was measured, and the amount of volatile components was evaluated according to the following criteria.

○: weight reduction rate is less than 0.1%

×: weight reduction rate of 0.1% or more

(film formation)

An epoxy resin solution in which 1.0 g of the epoxy composition was dissolved in 9.0 g of cyclohexanone was coated on a silicon wafer with a diameter of 6 inches at 1500 rpm for 30 seconds using a spin coater, and prebaked for 60 seconds on a hot plate at 120 ° C. , an epoxy film having a film thickness of about 300 nm was formed.

The presence or absence of striation on the surface of the obtained epoxy film was confirmed visually, and evaluated according to the following criteria.

Excellent : striation not confirmed

Good: Slightly confirmed striation

Bad: Multiple striations confirmed

[Table 1]

From the results of Table 1, it was confirmed that volatilization and sublimation of low molecular weight components at the time of heat treatment can be suppressed in the composition containing the epoxy resin which has a specific cyclic structure at both ends.

(Example 6-10 and Comparative Example 3-4: Preparation and Evaluation of Composition for Forming Lower Layer Film)

10 g of the epoxy composition shown in the table, 5.0 g of photoacid generator solution ("CPI-101A" manufactured by San-Apro Co., Ltd.), 0.1 g of surfactant ("Megapack R-41" manufactured by DIC Corporation), cyclo It was dissolved in 90 g of hexanone, and the resulting solution was microfiltered to prepare a composition for forming a lower layer film.

With respect to the obtained composition for forming an underlayer film, an underlayer film was formed by the following method, and optical characteristics and etching resistance were evaluated. The results are shown in Table 2.

(Evaluation of optical properties)

The composition for forming an underlayer film was applied onto a silicon wafer having a diameter of 6 inches to a thickness of about 300 nm using a spin coater, and then prebaked on a hot plate at 120°C for 60 seconds. Next, the prebaked film was irradiated with ghi rays at 1000 mJ/cm 2 using an exposure apparatus (“Multilite” manufactured by Ushio Denki Co., Ltd.), and post-baked on a hot plate at 250° C. for 90 seconds to prepare a lower layer film. did.

About the produced lower layer film, the refractive index (n value) and extinction coefficient (k value) at a wavelength of 193 nm were measured using a spectroscopic ellipsometer (manufactured by J.A. Woollam: VUV-VASE GEN-1). Regarding the n-value, those of 1.48 or more were evaluated as "○", and those of less than 1.48 were evaluated as "x". About the k value, those less than 0.25 were evaluated as "○", and those of 0.25 or more were evaluated as "x".

(Etching resistance evaluation)

The composition for forming an underlayer film was applied on a silicon wafer having a diameter of 6 inches to a thickness of about 700 nm using a spin coater at 1500 rpm for 30 seconds, and then prebaked on a hot plate at 120°C for 60 seconds. Next, the prebaked film was irradiated with ghi rays at 1000 mJ/cm 2 using an exposure apparatus (“Multilite” manufactured by Ushio Denki Co., Ltd.), and post-baked on a hot plate at 250° C. for 90 seconds to prepare a lower layer film. did.

The prepared lower layer film was etched using an etching apparatus ("EXAM" manufactured by Shinko Seiki Co., Ltd.) under the conditions of CF ₄ : 89 sccm, pressure: 2.0 Pa, RF power: 100 W, and processing time: 180 seconds. The film thickness of the lower layer film before and after the etching process was measured to calculate the etching rate, and the etching resistance was evaluated according to the following criteria.

○: Etching rate is less than 110 nm/min

x: Etching rate of 110 nm/min or more

[Table 2]

From the results in Table 2, it was confirmed that the film using the composition containing an epoxy resin having a specific cyclic structure at both ends had excellent optical characteristics and excellent etching resistance.

Claims (10)

An epoxy resin having a repeating unit represented by the following general formula (1-1) and having a structure represented by the following general formula (1-2) at both ends.

(In the above general formulas (1-1) and (1-2),
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently an alkylene group having 1 to 6 carbon atoms;
R ²¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;
R ²² and R ²³ are each independently an alkylene group having 1 to 6 carbon atoms;
X ¹ , X ² and X ³ are each independently an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a halogen atom;
Y is an oxo group,
a, b and c are each independently an integer of 0 to 5) According to claim 1,
The epoxy resin whose structure represented by the said general formula (1-2) is a structure represented by the following general formula (1-3).

(In the above general formula (1-3),
R ¹³ , R ¹⁴ , R ¹⁵ , R ²² , R ²³ and R ²⁴ are the same as in the above general formula (1-2)) As an epoxy resin containing dihydroxynaphthalene resin and epihalohydrin as reaction components,
The dihydroxynaphthalene resin is a dihydroxynaphthalene resin obtained by reacting a dihydroxynaphthalene compound and an aldehyde compound in the presence of an alkali catalyst, and 0.9 to 5 moles of the alkali catalyst are used per mole of the dihydroxynaphthalene compound. epoxy resin. According to claim 3,
An epoxy resin comprising 0.5 to 4 moles of the aldehyde compound per mole of the dihydroxynaphthalene compound. According to any one of claims 1 to 4,
An epoxy resin having a weight average molecular weight of 500 to 5,000. An epoxy composition containing the epoxy resin according to any one of claims 1 to 5 and an epoxy compound represented by the following general formula (2).

(In the above general formula (2),
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently an alkylene group having 1 to 6 carbon atoms;
R ²² , R ²³ , R ²⁴ and R ²⁵ are each independently an alkylene group having 1 to 6 carbon atoms;
X ² , X ³ and X ⁴ are each independently an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a halogen atom;
Y is an oxo group,
b, c and d are each independently an integer of 0 to 5) A photosensitive resin composition comprising the epoxy resin according to any one of claims 1 to 5 or the epoxy composition according to claim 6, and a photosensitizer. A resist film using the photosensitive resin composition according to claim 7. A curable composition comprising the epoxy resin according to any one of claims 1 to 5 or the epoxy composition according to claim 6, and a curing agent. A cured film of the curable composition according to claim 9.

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