CN113348188B - Phenolic hydroxyl group-containing resin, photosensitive composition, resist film, curable composition, and cured product - Google Patents

Phenolic hydroxyl group-containing resin, photosensitive composition, resist film, curable composition, and cured product Download PDF

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CN113348188B
CN113348188B CN201980089823.7A CN201980089823A CN113348188B CN 113348188 B CN113348188 B CN 113348188B CN 201980089823 A CN201980089823 A CN 201980089823A CN 113348188 B CN113348188 B CN 113348188B
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resin
compound
photosensitive composition
hydroxyl group
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CN113348188A (en
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今田知之
长田裕仁
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DIC Corp
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DIC Corp
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/18Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenols substituted by carboxylic or sulfonic acid groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28Chemically modified polycondensates
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/039Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Materials For Photolithography (AREA)

Abstract

To provide a phenolic hydroxyl group-containing resin which has high heat resistance and exhibits excellent alkali developability when used as a resist material, there is provided a phenolic hydroxyl group-containing resin which is a reaction product of a novolak type phenolic resin (C) containing an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) as essential reaction raw materials and an alcohol compound (X). In the formula (1), R 1 and R 2 are an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group or a halogen atom. m, n and p are integers from 0 to 4. R 3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural part having 1 or more substituents selected from an alkoxy group, a halogen group and a hydroxyl group on a hydrocarbon group. R 4 is a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom.

Description

Phenolic hydroxyl group-containing resin, photosensitive composition, resist film, curable composition, and cured product
Technical Field
The invention relates to a phenolic hydroxyl group-containing resin, a photosensitive composition, a resist film, a curable composition and a cured product.
Background
In the field of photoresists, various methods for forming resist patterns, which are subdivided according to the use and function, have been developed successively, and with this, the performances required for the resin materials for resists have been also highly diversified. For example, as a resist used for manufacturing a semiconductor such as an IC or LSI, manufacturing a display device such as an LCD, manufacturing a printing original plate, or the like, a positive photoresist obtained by using an alkali-soluble resin and a photosensitive agent such as a1, 2-naphthoquinone diazide compound is known.
As the alkali-soluble resin, a positive photoresist composition obtained using a cresol novolac type epoxy resin has been proposed (for example, refer to patent documents 1 and 2).
Positive photoresist compositions obtained using cresol novolac type epoxy resins have been developed for the purpose of improving developability such as sensitivity, but in recent years, there is a tendency for higher integration of semiconductors and finer patterns, and more excellent sensitivity has been demanded. However, the positive photoresist composition obtained using the cresol novolac type epoxy resin has a problem that sufficient sensitivity corresponding to the thinning is not obtained. Further, although various heat treatments are performed in the manufacturing process of semiconductors and the like, higher heat resistance is also required, there is a problem that a positive photoresist composition obtained using a cresol novolac type epoxy resin has insufficient heat resistance.
As a method for manufacturing a structure patterned by a photoresist, there is a wafer level packaging technique. The wafer level packaging technology is a mounting technology for manufacturing a semiconductor package by performing resin sealing, rewiring, electrode formation in a wafer state, and singulation by dicing.
In the wafer level package, as the wiring density increases, an electrochemical deposition method is used for electronic wiring (for example, refer to non-patent document 1). Gold bumps, copper pillars and copper leads used in the reconfiguration of wafer level packages require a mold (gold) of the resist to be electroplated. The resist is very thick when compared to the resist used in IC fabrication. The pattern size of the resist mold and the thickness of the resist layer are, for example, 2 μm to 100 μm, and it is necessary to pattern the photoresist to a high aspect ratio (resist thickness relative to the line size).
Regarding patterning of a photoresist having a high aspect ratio, it has been proposed to use aliphatic polyaldehyde as a linking agent for m-cresol or p-cresol in the synthesis of a novolak resin (for example, refer to patent document 3). However, there is a problem that it is difficult to combine heat resistance and alkali dissolution rate, which are important characteristics for thick film resists.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2008-0881197
Patent document 2: japanese patent laid-open No. 2002-107925
Patent document 3: japanese patent laid-open No. 9-6003
Non-patent literature
Non-patent literature 1:Gary Solomon,Electrochemically deposited solder bumps for wafer-level packaging,PACKAGING/ASSEMBLY,Solid State Technology,pages 83,84,86,88April 2001
Disclosure of Invention
Problems to be solved by the invention
The problem to be solved by the present invention is to provide a phenolic hydroxyl group-containing resin which has high heat resistance and exhibits excellent alkali developability when used as a resist material.
Solution for solving the problem
The present inventors have conducted intensive studies to solve the above problems, and as a result, found that: the present invention has been accomplished in view of the above problems, and has an object to provide a phenolic hydroxyl group-containing resin which is a reaction product of a triaryl compound having a carboxyl group and an aliphatic aldehyde, wherein part or all of the carboxyl groups in the reaction product are esterified with an alcohol compound, and which is excellent in heat resistance and alkali developability.
That is, the present invention relates to a phenolic hydroxyl group-containing resin which is a reaction product of a novolak-type phenol resin (C) containing an aromatic compound (a) represented by the following formula (1) and an aliphatic aldehyde (B) as essential reaction raw materials and an alcohol compound (X).
(In the formula (1), R 1 and R 2 each independently represent an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom.
M, n and p each independently represent an integer of 0 to 4.
When there are a plurality of R 1, the plurality of R 1 are optionally the same or different.
When there are a plurality of R 2, the plurality of R 2 are optionally the same or different.
R 3 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural part having 1 or more substituents selected from an alkoxy group, a halogen group and a hydroxyl group on a hydrocarbon group.
R 4 represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom.
When there are a plurality of R 4, the plurality of R 4 are optionally the same or different. )
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a phenolic hydroxyl group-containing resin having high heat resistance and exhibiting excellent alkali developability when used as a resist material.
Drawings
FIG. 1 is a view showing a GPC chart of a phenolic trinuclear compound (A-1) containing carboxylic acid.
FIG. 2 is a diagram showing a 13 C-NMR spectrum of a phenolic trinuclear compound (A-1) containing a carboxylic acid.
FIG. 3 is a GPC chart showing a novolak type phenol resin (C-1).
FIG. 4 is a diagram showing a 13 C-NMR spectrum of a novolak type phenol resin (C-1).
FIG. 5 is a GPC chart showing an esterified novolak-type phenol resin (Z-1).
FIG. 6 is a diagram showing 13 C-NMR spectrum of esterified novolak-type phenol resin (Z-1).
FIG. 7 is a GPC chart showing an esterified novolak-type phenol resin (Z-2).
FIG. 8 is a diagram showing 13 C-NMR spectrum of esterified novolak-type phenol resin (Z-2).
FIG. 9 is a GPC chart showing an esterified novolak-type phenol resin (Z-3).
FIG. 10 is a diagram showing 13 C-NMR spectrum of esterified novolak-type phenol resin (Z-3).
FIG. 11 is a GPC chart showing a novolak resin (C' -2).
FIG. 12 is a GPC chart showing a novolak resin (C' -3).
Detailed Description
An embodiment of the present invention will be described below. The present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within a range that does not impair the effects of the present invention.
[ Phenolic hydroxyl group-containing resin ]
The phenolic hydroxyl group-containing resin of the present invention is a reaction product of a novolak-type phenol resin (C) containing an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) as essential reaction raw materials and an alcohol compound (X).
(In the formula (1), R 1 and R 2 each independently represent an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom.
M, n and p each independently represent an integer of 0 to 4.
When there are a plurality of R 1, the plurality of R 1 are optionally the same or different.
When there are a plurality of R 2, the plurality of R 2 are optionally the same or different.
R 3 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural part having 1 or more substituents selected from an alkoxy group, a halogen group and a hydroxyl group on a hydrocarbon group.
R 4 represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom.
When there are a plurality of R 4, the plurality of R 4 are optionally the same or different. )
The phenolic hydroxyl group-containing resin of the present invention has a triarylmethane structure. Since the triarylmethane structure contains aromatic rings at a high density, the phenolic hydroxyl group-containing resin of the present invention has very high heat resistance.
In the triarylmethane structure of formula (1), two hydroxyl groups and carboxyl groups are respectively substituted on different aromatic rings, and strong hydrogen bonds are not formed. Thus, the phenolic hydroxyl group-containing resin of the present invention can maintain good proton dissociability and can exhibit excellent alkali developability. Further, since a part or all of carboxyl groups in the triarylmethane structure are esterified by the reaction with the alcohol compound (X), an extreme polarity change can be induced before and after hydrolysis of the ester group (before and after formation of carboxyl groups), and a good development contrast can be obtained.
[ Novolak-type phenol resin ]
The novolac type phenolic resin (C) is a resin containing an aromatic compound (a) represented by the following formula (1) and an aliphatic aldehyde (B) as essential reaction raw materials.
(In the formula (1), R 1 and R 2 each independently represent an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom.
M, n and p each independently represent an integer of 0 to 4.
When there are a plurality of R 1, the plurality of R 1 are optionally the same or different.
When there are a plurality of R 2, the plurality of R 2 are optionally the same or different.
R 3 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural part having 1 or more substituents selected from an alkoxy group, a halogen group and a hydroxyl group on a hydrocarbon group.
R 4 represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom.
When there are a plurality of R 4, the plurality of R 4 are optionally the same or different. )
In the formula (1), examples of the aliphatic hydrocarbon group having 1 to 9 carbon atoms of R 1、R2、R3 and R 4 include an alkyl group having 1 to 9 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, and a cycloalkyl group having 3 to 9 carbon atoms.
Examples of the alkoxy group of R 1、R2 and R 4 in the formula (1) include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and cyclohexyloxy.
In the above formula (1), examples of the aryl group for R 1 and R 2 include phenyl, tolyl, xylyl, naphthyl and anthracenyl.
In the above formula (1), examples of the aralkyl group of R 1 and R 2 include benzyl, phenylethyl, phenylpropyl, naphthylmethyl and the like.
In the formula (1), examples of the halogen atom of R 1、R2 and R 4 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
In the above formula (1), examples of the "structural part having 1 or more substituents selected from the group consisting of an alkoxy group, a halogen group and a hydroxyl group on a hydrocarbon group" of R 3 include alkoxyalkoxy groups such as a haloalkyl group, a haloaryl group, a 2-methoxyethoxy group and a 2-ethoxyethoxy group; alkyl alkoxy substituted with hydroxy, and the like.
In the above formula (1), m and n are each preferably an integer of 2 or 3.
When m and n are each 2, it is preferable that each of two R 1 and two R 2 is independently an alkyl group having 1 to 3 carbon atoms. At this time, it is preferable that two R 1 and two R 2 are bonded to the 2, 5-positions of the phenolic hydroxyl group, respectively.
In the above formula (1), p is preferably an integer of 0, 1 or 2.
The aromatic compound (a) represented by the formula (1) may be used alone or in combination with a plurality of compounds having different molecular structures.
The aromatic compound (a) represented by the formula (1) can be produced, for example, by a condensation reaction of an alkyl-substituted phenol (a 1) and an aromatic aldehyde (a 2) having a carboxyl group.
The aromatic compound (a) represented by the formula (1) can be produced, for example, by a condensation reaction of an alkyl-substituted phenol (a 1) and an aromatic ketone (a 3) having a carboxyl group.
The alkyl-substituted phenol (a 1) is an alkyl-substituted phenol, and examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, preferably a methyl group.
Specific examples of the alkyl-substituted phenol (a 1) include monoalkylphenols such as o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-octylphenol, p-t-butylphenol, o-cyclohexylphenol, m-cyclohexylphenol, and p-cyclohexylphenol; dialkylphenols such as 2, 5-xylenol, 3, 4-xylenol, 2, 4-xylenol, and 2, 6-xylenol; trialkylphenols such as 2,3, 5-trimethylphenol and 2,3, 6-trimethylphenol. Among these, dialkylphenols are preferable, and 2, 5-xylenol and 2, 6-xylenol are more preferable.
The alkyl-substituted phenol (a 1) may be used alone or in combination of 1 or more than 2.
Examples of the aromatic aldehyde (a 2) having a carboxyl group include: a compound having a formyl group on a benzene ring of benzene, phenol, resorcinol or the like; compounds having an alkyl group, an alkoxy group, a halogen atom, or the like in addition to the formyl group.
Specific examples of the aromatic aldehyde (a 2) having a carboxyl group include 4-formylbenzoic acid, 2-formylbenzoic acid, 3-formylbenzoic acid, methyl 4-formylbenzoate, ethyl 4-formylbenzoate, propyl 4-formylbenzoate, isopropyl 4-formylbenzoate, butyl 4-formylbenzoate, isobutyl 4-formylbenzoate, tert-butyl 4-formylbenzoate, cyclohexyl 4-formylbenzoate, tert-octyl 4-formylbenzoate and the like. Of these, 4-formylbenzoic acid is preferred.
The aromatic aldehyde (a 2) having a carboxyl group may be used alone or in combination of 1 or more.
The aromatic ketone (a 3) having a carboxyl group is a compound having at least 1 carboxyl group and a carbonyl group on an aromatic ring.
Specific examples of the aromatic ketone (a 3) having a carboxyl group include, for example, 2-acetylbenzoic acid, 3-acetylbenzoic acid, methyl 4-acetylbenzoate and 2-acetylbenzoate, ethyl 2-acetylbenzoate, propyl 2-acetylbenzoate, isopropyl 2-acetylbenzoate, butyl 2-acetylbenzoate, isobutyl 2-acetylbenzoate, tert-butyl 2-acetylbenzoate, cyclohexyl 2-acetylbenzoate, tert-octyl 2-acetylbenzoate and the like. Of these, 2-acetylbenzoic acid and 4-acetylbenzoic acid are preferable.
The aromatic ketone (a 3) may be used alone or in combination of 1 or more than 2.
Specific examples of the aliphatic aldehyde (B) include formaldehyde, paraformaldehyde, 1,3, 5-trioxane, acetaldehyde, propionaldehyde, tetramethylene oxide, polyoxymethylene, chloral, hexamethylenetetramine, glyoxal, n-butyraldehyde, hexanal, allylaldehyde, crotonaldehyde, and acrolein.
The aliphatic aldehyde compound (B) may be used alone or in combination of 1 or more than 2.
The aliphatic aldehyde (B) is preferably 1 or more selected from formaldehyde and paraformaldehyde, more preferably formaldehyde.
When formaldehyde and an aliphatic aldehyde other than formaldehyde are used as the aliphatic aldehyde (B), the amount of the aliphatic aldehyde other than formaldehyde is preferably in the range of 0.05 to 1 mole relative to 1 mole of formaldehyde.
The method for producing the novolak-type phenol resin (C) preferably includes the following three steps 1 to 3.
(Process 1)
The aromatic compound (a) is obtained by heating and polycondensing the alkyl-substituted phenol (a 1) and the aromatic aldehyde (a 2) having a carboxyl group in the presence of an acid catalyst, if necessary, with a solvent in the range of 60 to 140 ℃.
(Process 2)
The aromatic compound (a) obtained in step 1 is separated from the reaction solution.
(Step 3)
The aromatic compound (a) and the aliphatic aldehyde (B) separated in step 2 are heated and polycondensed in the presence of an acid catalyst at 60 to 140 ℃ using a solvent as needed, thereby obtaining a novolac type phenol resin (C).
Examples of the acid catalyst used in the steps 1 and 3 include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, and manganese acetate. The acid catalyst may be used in an amount of 1 or 2 or more. Among these acid catalysts, sulfuric acid and p-toluenesulfonic acid are preferable in step 1, and sulfuric acid, oxalic acid and zinc acetate are preferable in step 3, from the viewpoint of excellent activity. The acid catalyst may be added before the reaction or during the reaction.
Examples of the solvent used in the steps 1 and 3 as needed include monohydric alcohols such as methanol, ethanol, and propanol; polyhydric alcohols such as ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, and glycerin; glycol ethers such as 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, and ethylene glycol monophenyl ether; cyclic ethers such as 1, 3-dioxane and 1, 4-dioxane; glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Among these solvents, 2-ethoxyethanol is preferred because of its excellent solubility in the resulting compound.
The ratio [ (a 1)/(a 2) ] of the feed of the alkyl-substituted phenol (a 1) to the aromatic aldehyde (a 2) having a carboxyl group in the step 1 is preferably in the range of 1/0.2 to 1/0.5, more preferably in the range of 1/0.25 to 1/0.45 in terms of a molar ratio, from the viewpoints of the removability of the unreacted alkyl-substituted phenol (a 1), the yield of the product and the purity of the reaction product being excellent.
The feed ratio [ (A)/(B) ] of the aromatic compound (A) to the aliphatic aldehyde (B) in the step 3 is preferably in the range of 1/0.5 to 1/1.2, more preferably in the range of 1/0.6 to 1/0.9 in terms of molar ratio, from the viewpoint of suppressing excessive polymerization (gelation) and obtaining a resin having an appropriate molecular weight for the phenolic resin for resists.
As a method for separating the aromatic compound (a) from the reaction solution in the step 2, for example, the following method can be mentioned: the reaction solution is put into a poor solvent (S1) in which the reaction product is not dissolved or is hardly dissolved, and the resulting precipitate is collected by filtration, and then dissolved in a solvent (S2) in which the reaction product is soluble and which is also miscible with the poor solvent (S1), and put into the poor solvent (S1) again, and the resulting precipitate is collected by filtration.
The poor solvent (S1) used in this case includes, for example, water; monohydric alcohols such as methanol, ethanol, and propanol; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene. Among these poor solvents (S1), water and methanol are preferable in that the acid catalyst can be removed at the same time and efficiently. On the other hand, examples of the solvent (S2) include monohydric alcohols such as methanol, ethanol, and propanol; polyhydric alcohols such as ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, and glycerin; glycol ethers such as 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, and ethylene glycol monophenyl ether; cyclic ethers such as 1, 3-dioxane and 1, 4-dioxane; glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. In the case of using water as the poor solvent (S1), acetone is preferable as the poor solvent (S2). The poor solvent (S1) and the solvent (S2) may be used alone or in combination of 1 or more.
In the case of using an aromatic hydrocarbon such as toluene or xylene as a solvent in the steps 1 and 3, if the heating is performed at 80 ℃ or higher, the aromatic compound (a) produced by the reaction is dissolved in the solvent, and therefore, the crystals of the aromatic compound (a) are precipitated by directly cooling, and the aromatic compound (a) can be separated by filtering the crystals. In this case, the poor solvent (S1) and the solvent (S2) may not be used.
The aromatic compound (a) represented by the formula (1) can be obtained by the separation method of the step 2.
The purity of the aromatic compound (a) is preferably 90% or more, more preferably 94% or more, particularly preferably 98% or more, as calculated from a Gel Permeation Chromatography (GPC) spectrum. The purity of the aromatic compound (a) can be determined from the area ratio of the GPC spectrum, and is measured under measurement conditions described below.
The weight average molecular weight (Mw) of the novolak type phenol resin (C) is preferably in the range of 2,000 to 35,000, more preferably in the range of 2,000 to 25,000.
The weight average molecular weight (Mw) of the novolak type phenol resin (C) is measured by gel permeation chromatography (hereinafter abbreviated as "GPC") under the following measurement conditions.
(Measurement conditions of GPC)
Measurement device: HLC-8220GPC manufactured by Tosoh Co., ltd "
Column: shodex KF802 (8.0 mm. Phi. Times.300 mm) manufactured by Showa Denko Co., ltd.)
"Shodex KF802" manufactured by Showa Denko Co., ltd., (8.0 mm. Phi. Times.300 mm)
"Shodex KF803" manufactured by Shodex Co., ltd., (8.0 mm. Phi. Times.300 mm)
"Shodex KF804" manufactured by Showa Denko Co., ltd. (8.0 mm. Phi. Times.300 mm)
Column temperature: 40 DEG C
A detector: RI (differential refractometer)
And (3) data processing: GPC-8020 model II version 4.30 manufactured by Tosoh Co., ltd "
Developing solvent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Sample: a tetrahydrofuran solution (100. Mu.l) having a resin solid content of 0.5% by mass was filtered through a microfilter
Standard sample: the monodisperse polystyrene described below
(Standard sample: monodisperse polystyrene)
"A-500" manufactured by Tosoh Co., ltd "
"A-2500" manufactured by Tosoh Co., ltd "
"A-5000" manufactured by Tosoh Co., ltd "
"F-1" manufactured by Tosoh Co., ltd "
F-2 manufactured by Tosoh Co., ltd "
F-4 manufactured by Tosoh Co., ltd "
F-10 manufactured by Tosoh Co., ltd "
F-20 manufactured by Tosoh Co., ltd "
[ Alcohol Compound (X) ]
The phenolic hydroxyl group-containing resin of the present invention is a reaction product of a novolak type phenolic resin (C) and an alcohol compound (X). The reaction between the novolak-type phenol resin (C) and the alcohol compound (X) is, for example, a dehydration esterification reaction.
Examples of the alcohol compound (X) include aliphatic alcohols having 10 or less carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, ethylene glycol, propylene glycol, and trimethylolpropane; an aromatic alcohol having 10 or less carbon atoms such as benzyl alcohol; ether alcohols having 10 or less carbon atoms, which contain an ether bond, such as 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methoxy-1-butanol, and 2-isopropoxyethyl alcohol; ketoalcohols having 10 or less carbon atoms, such as 3-hydroxy-2-butanone, which contain a ketone group; and ester alcohols having 10 or less carbon atoms including an ester group such as methyl hydroxyisobutyrate. Among these, aliphatic alcohols having 10 or less carbon atoms and ether alcohols having 10 or less carbon atoms are preferable, and ethanol, n-propanol, isopropanol (2-propanol), n-butanol, isobutanol (2-methyl-2-propanol), t-butanol and 2-ethoxyethyl alcohol (2-ethoxyethyl alcohol) (2-ethoxyethanol ) are more preferable.
The alcohol compound (X) may be used alone or in combination of 1 or more than 2.
The dehydration esterification reaction can be carried out by stirring a mixture of the novolak type phenol resin (C) and the alcohol compound (X) in the presence of an acid catalyst.
Examples of the acid catalyst include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used alone or in combination of 1 or more than 2.
The reaction temperature is not particularly limited, and may be, for example, 10℃to 60℃and is preferably room temperature since no special apparatus is required.
In the dehydration-esterification reaction of the novolak-type phenol resin (C) with the alcohol compound (X), the carboxyl group in the novolak-type phenol resin (C) derived from the aromatic compound (A) represented by the above formula (1) reacts with the alcohol compound (X) to form an ester bond with dehydration.
The ratio of the novolac-type phenolic resin (C) to the alcohol compound (X) in the dehydration esterification reaction is not particularly limited, and for example, the ratio of the novolac-type phenolic resin to the alcohol=1/0.5 to 1/10 by weight is defined.
The phenolic hydroxyl group-containing resin of the present invention is a resin having a structure obtained by esterifying a part or all of the carboxyl groups of the novolak type phenol resin (C), and the esterification rate of the carboxyl groups of the novolak type phenol resin (C) is preferably 5 to 90 mol%, more preferably 10 to 85 mol% or 5 to 70 mol%.
The esterification rate of the phenolic hydroxyl group-containing resin of the present invention was confirmed by the method described in examples.
The number average molecular weight (Mn) of the phenolic hydroxyl group-containing resin of the present invention is preferably in the range of 500 to 7,000, more preferably in the range of 1,000 to 5,000.
The weight average molecular weight (Mw) of the phenolic hydroxyl group-containing resin of the present invention is preferably in the range of 3,000 to 20,000, more preferably in the range of 5,000 to 15,000.
The number average molecular weight and the weight average molecular weight of the phenolic hydroxyl group-containing resin of the present invention are measured by gel permeation chromatography (hereinafter abbreviated as "GPC") in the same manner as the novolak type phenolic resin (C).
[ Photosensitive composition ]
The photosensitive composition of the present invention comprises the phenolic hydroxyl group-containing resin of the present invention and a photoacid generator.
The photoacid generator is not particularly limited, and known photoacid generators can be used, and examples thereof include organic halides, sulfonates, onium salts, diazonium salts, and disulfone compounds.
Specific examples of the photoacid generator include the following.
Halogenated alkyl-containing s-triazine derivatives such as tris (trichloromethyl) s-triazine, tris (tribromomethyl) s-triazine, tris (dibromomethyl) s-triazine, 2, 4-bis (tribromomethyl) -6-p-methoxyphenyl s-triazine, and (2- [2- (5-methylfuran-2-yl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine;
Halogen-substituted paraffin compounds such as1, 2,3, 4-tetrabromobutane, 1, 2-tetrabromoethane, carbon tetrabromide and iodoform; halogen-substituted cyclic alkane compounds such as hexabromocyclohexane, hexachlorocyclohexane and hexabromocyclododecane;
halogenated alkyl-containing benzene derivatives such as bis (trichloromethyl) benzene and bis (tribromomethyl) benzene; halogenated alkyl group-containing sulfone compounds such as tribromomethylphenyl sulfone and trichloromethylphenyl sulfone; halogen-containing sulfolane compounds such as 2, 3-dibromosulfolane; halogenated alkyl group-containing isocyanurate compounds such as tris (2, 3-dibromopropyl) isocyanurate;
sulfonium salts such as triphenylsulfonium chloride, diphenyl-4-methylphenylsulfonium triflate, triphenylsulfonium mesylate, triphenylsulfonium triflate, triphenylsulfonium para-toluenesulfonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroarsenate, and triphenylsulfonium hexafluorophosphonate;
Iodonium salts such as diphenyliodonium triflate, diphenyliodonium p-toluenesulfonate, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphonate, and the like;
Sulfonate compounds such as methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, phenyl p-toluenesulfonate, 1,2, 3-tris (p-toluenesulfonyloxy) benzene, benzoin p-toluenesulfonate, methyl methanesulfonate, ethyl methanesulfonate, butyl methanesulfonate, 1,2, 3-tris (methanesulfonyloxy) benzene, phenyl methanesulfonate, benzoin methanesulfonate, methyl triflate, ethyl triflate, butyl triflate, 1,2, 3-tris (trifluoromethanesulfonyl) benzene, phenyl triflate, benzoin triflate and the like; disulfone compounds such as diphenyl disulfone;
Bis (phenylsulfonyl) diazomethane, bis (2, 4-dimethylphenylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, cyclohexylsulfonyl- (2-methoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (3-methoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (4-methoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2-methoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (3-methoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (4-methoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2-fluorophenylsulfonyl) diazomethane, cyclohexylsulfonyl- (3-fluorophenylsulfonyl) diazomethane, cyclohexylsulfonyl- (4-fluorophenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2-fluorophenylsulfonyl) diazomethane, cyclopentylsulfonyl- (3-fluorophenylsulfonyl) diazomethane, cyclohexylsulfonyl- (4-fluorophenylsulfonyl) diazomethane, cyclohexylsulfonyl-4-trifluoromethylsulfonyl-diazomethane, cyclopentylsulfonyl- (2-chlorophenyl sulfonyl) diazomethane, cyclopentylsulfonyl- (3-chlorophenyl sulfonyl) diazomethane, cyclopentylsulfonyl- (4-chlorophenyl sulfonyl) diazomethane, cyclohexylsulfonyl- (2-trifluoromethylphenyl sulfonyl) diazomethane, cyclohexylsulfonyl- (3-trifluoromethylphenyl sulfonyl) diazomethane, cyclohexylsulfonyl- (4-trifluoromethylphenyl sulfonyl) diazomethane, cyclopentylsulfonyl- (2-trifluoromethylphenyl sulfonyl) diazomethane, cyclopentylsulfonyl- (3-trifluoromethylphenyl sulfonyl) diazomethane, cyclohexylsulfonyl- (3-trifluoromethylsulfonyl) diazomethane cyclopentylsulfonyl- (4-trifluoromethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2-trifluoromethoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (3-trifluoromethoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (4-trifluoromethoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2-trifluoromethoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (3-trifluoromethoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (4-trifluoromethoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2, 4, 6-trimethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2, 3, 4-trimethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2, 4, 6-triethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2, 3, 4-triethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2, 4, 6-trimethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2, 3, 4-trimethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2, 4, 6-triethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2, 3, 4-triethylphenylsulfonyl) diazomethane, phenylsulfonyl- (2-methoxyphenylsulfonyl) diazomethane, phenylsulfonyl- (3-methoxyphenylsulfonyl) diazomethane, phenylsulfonyl- (4-methoxyphenylsulfonyl) diazomethane, bis (2-methoxyphenylsulfonyl) diazomethane, bis (3-methoxyphenylsulfonyl) diazomethane, 4-trimethylphenylsulfonyl, 2, 4-triethylphenylsulfonyl, 4-trifluoromethanesulfonyl, sulfone diazide compounds such as 2, 4-dimethylphenylsulfonyl- (2, 4, 6-trimethylphenylsulfonyl) diazomethane, 2, 4-dimethylphenylsulfonyl- (2, 3, 4-trimethylphenylsulfonyl) diazomethane, phenylsulfonyl- (2-fluorophenylsulfonyl) diazomethane, phenylsulfonyl- (3-fluorophenylsulfonyl) diazomethane, and phenylsulfonyl- (4-fluorophenylsulfonyl) diazomethane;
O-nitrobenzyl ester compounds such as o-nitrobenzyl p-toluenesulfonate;
Sulfonyl hydrazide compounds such as N, N' -bis (phenylsulfonyl) hydrazide;
Salts formed by sulfonium cations such as triarylsulfonium and triarylalkyl sulfonium and sulfonates such as fluoroalkanesulfonate, arenesulfonate and alkane sulfonate, namely sulfonium salts;
Salts formed by iodonium cations such as diaryliodonium and sulfonates such as fluoroalkanesulfonate, arenesulfonate, and alkane sulfonate, i.e., iodonium salts;
Bis (alkylsulfonyl) diazomethane, bis (cycloalkylsulfonyl) diazomethane, bis (perfluoroalkylsulfonyl) diazomethane, bis (arylsulfonyl) diazomethane, bis (aralkylsulfonyl) diazomethane, and the like;
an N-sulfonyloxy imide compound formed by a combination of a dicarboxylic acid imide compound and a sulfonic acid ester (salt) such as a fluorinated alkane sulfonic acid ester (salt), an aromatic hydrocarbon sulfonic acid ester (salt), an alkane sulfonic acid ester (salt), or the like;
benzoin tosylate, benzoin mesylate, benzoin butane sulfonate and the like benzoin sulfonate compounds;
Polyhydroxy aromatic hydrocarbon sulfonate (salt) compounds obtained by substituting all hydroxyl groups of polyhydroxy aromatic hydrocarbon compounds with sulfonate (sulfosalt) such as fluoroalkanesulfonate (salt), arenesulfonate (salt), alkane sulfonate (salt) and the like;
Nitrobenzyl sulfonate compounds such as (poly) nitrobenzyl fluoro alkane sulfonate, (poly) nitrobenzyl arene sulfonate and (poly) nitrobenzyl alkane sulfonate;
Fluorinated alkane benzyl sulfonate compounds such as (poly) fluorinated alkane benzyl sulfonate, (poly) fluorinated alkane benzyl sulfonate, and (poly) fluorinated alkane benzyl sulfonate;
bis (arylsulfonyl) alkane compounds;
bis-O- (arylsulfonyl) - α -dialkylglyoxime, bis-O- (arylsulfonyl) - α -bicycloalkyl glyoxime, bis-O- (arylsulfonyl) - α -dialkylglyoxime, bis-O- (alkylsulfonyl) - α -bicycloalkyl glyoxime, bis-O- (alkylsulfonyl) - α -dialkylglyoxime, bis-O- (fluoroalkylsulfonyl) - α -bicycloalkyl glyoxime, bis-O- (fluoroalkylsulfonyl) - α -dialkylsulfonyl) - α -dialkylglyoxime, bis-O- (fluoroalkylsulfonyl) - α -dialkylglyoxime, bis-O- (arylsulfonyl) - α -dialkyldioxime, bis-O- (arylsulfonyl) - α -bicycloalkyl dioxime, bis-O- (arylsulfonyl) - α -dialkyldioxime, bis-O- (alkylsulfonyl) - α -dialkyldioxime, bis-O- (fluoroalkylsulfonyl) - α -dialkylsulfonyl, bis-dialkylsulfonyl) - α -dialkylsulfonyl, bis-aryl- α -dialkylsulfonyl, bis-sulfonyl) - α -dialkylsulfonyl, bis-aryl- α -dialkylsulfonyl, bis-sulfonyl, and bis-aryl-sulfonyl- α -dialkylglyoxime, oxime compounds such as bis-O- (fluoroalkyl sulfonyl) - α -dicycloalkyl dioxime, bis-O- (fluoroalkyl sulfonyl) - α -diaryl dioxime, and the like;
Modified oxime compounds such as arylsulfonyloxyiminoarylacetonitrile, alkylsulfonyloxyiminoarylacetonitrile, fluoroalkylsulfonyliminoarylacetonitrile, ((arylsulfonyl) oxyimino-thiophen-ylidene) arylacetonitrile, ((alkylsulfonyl) oxyimino-thiophen-ylidene) arylacetonitrile, ((fluoroalkylsulfonyl) oxyimino-thiophen-ylidene) arylacetonitrile, bis (arylsulfonyloxyimino) arylene diacetonitrile, bis (alkylsulfonyloxyimino) arylene diacetonitrile, bis (fluoroalkylsulfonyloxy imino) arylene diacetonitrile, arylfluoroalkyl-O- (alkylsulfonyl) oxime, arylfluoroalkyl-O- (arylsulfonyl) oxime, and arylfluoroalkanone-O- (fluoroalkylsulfonyl) oxime.
The photoacid generator may be used alone or in combination of 1 or more than 2.
The content of the photoacid generator in the photosensitive composition of the present invention is, for example, in the range of 0.1 to 20 parts by mass, preferably in the range of 0.1 to 10 parts by mass, relative to 100 parts by mass of the resin solid content in the photosensitive composition.
By setting the content of the photoacid generator in the above range, the photosensitive composition of the present invention can be produced into a photosensitive composition having high photosensitivity.
The photosensitive composition of the present invention may contain the phenolic hydroxyl group-containing resin of the present invention and the photoacid generator, and may optionally contain other components.
Examples of the other components include an organic alkali compound, a resin other than the phenolic hydroxyl group-containing resin of the present invention, a sensitizer, a surfactant, a dye, a filler, a crosslinking agent, and a dissolution accelerator.
The photosensitive composition of the present invention may contain an organic base compound for neutralizing an acid generated by the photoacid generator at the time of exposure. By including the organic alkali compound in the photosensitive composition of the present invention, it is possible to obtain an effect of preventing a dimensional change of the resist pattern due to movement of the acid generated by the photoacid generator.
Specific examples of the organic base compound include pyrimidine compounds such as pyrimidine, (poly) aminopyrimidine, (poly) hydroxypyrimidine, (poly) amino (poly) alkylpyrimidine, (poly) amino (poly) alkoxypyrimidine, (poly) hydroxy (poly) alkylpyrimidine, and (poly) hydroxy (poly) alkoxypyrimidine; pyridine compounds such as pyridine, (poly) alkylpyridine and dialkylaminopyridine; amine compounds having a hydroxyalkyl group, such as a polyalkanolamine, a tris (hydroxyalkyl) aminoalkyl, and a bis (hydroxyalkyl) iminotris (hydroxyalkyl) alkane; amino aryl compounds such as aminophenol, and the like.
The organic base compound may be used alone or in combination of 1 or more than 2.
The content of the organic base compound in the photosensitive composition of the present invention is preferably in the range of 0.1 to 100 mol%, more preferably in the range of 1 to 50 mol%, based on 1 mol of the photoacid generator.
The photosensitive composition of the present invention may contain other resins than the phenolic hydroxyl group-containing resin of the present invention.
The other resin is not particularly limited, and is, for example, a resin soluble in an alkali developer or a resin soluble in an alkali developer by being used in combination with an additive such as a photoacid generator.
The other resins include: phenolic resins other than the phenolic hydroxyl group-containing resins of the present invention; homopolymers or copolymers of a hydroxyl-containing styrene compound such as p-hydroxystyrene or p- (1, 3-hexafluoro-2-hydroxypropyl) styrene; a resin obtained by modifying a hydroxyl group in the phenolic resin or the polymer of the hydroxyl-containing styrene compound with an acid-decomposable group such as t-butoxycarbonyl group or benzyloxycarbonyl group; homopolymers or copolymers of (meth) acrylic acid; and alternating polymers of alicyclic polymerizable monomers such as norbornene compounds and tetracyclododecene compounds with maleic anhydride or maleimide.
Specific examples of the phenolic resin other than the phenolic hydroxyl group-containing resin of the present invention include phenol novolac resins, cresol novolac resins, naphthol novolac resins, copolycondensed novolac resins obtained by using various phenolic compounds, aromatic hydrocarbon formaldehyde resin modified phenolic resins, dicyclopentadiene phenol addition resins, phenol aralkyl resins (Xylock resins), naphthol aralkyl resins, trimethylol methane resins, tetraphenolethane (tetraphenylolethane) resins, biphenyl modified phenolic resins (polyhydric phenol compounds obtained by joining phenol cores with a bisphenol), biphenyl modified naphthol resins (polyhydric phenol compounds obtained by joining phenol cores with a bisphenol), aminotriazine modified phenolic resins (polyhydric phenol compounds obtained by joining phenol cores with a melamine, benzoguanamine, etc.), alkoxy group-containing aromatic ring modified phenolic resins (polyhydric phenol compounds obtained by joining phenol cores with a formaldehyde and alkoxy group-containing aromatic rings), and the like.
Among the specific examples of the phenolic resins other than the phenolic hydroxyl group-containing resin of the present invention, cresol novolak resins and resol resins of cresols and other phenolic compounds are preferred from the viewpoint of forming a photosensitive composition excellent in balance of developability, heat resistance and fluidity.
Specifically, the cresol novolac resin or the resol resin of cresol and other phenolic compounds is a novolac resin obtained by using 1 or more kinds of cresol and aldehyde compounds selected from the group consisting of o-cresol, m-cresol and p-cresol as necessary reaction raw materials, and using other phenolic compounds in an appropriate combination.
The other resins may be used alone or in combination of at least 2 kinds.
The content of the other resin in the photosensitive composition of the present invention is not particularly limited and may be arbitrarily set according to the intended use. For example, the proportion of the phenolic hydroxyl group-containing resin of the present invention in the total of the resin components in the photosensitive composition of the present invention may be set to 60 mass% or more, and preferably 80 mass% or more.
The photosensitive composition of the present invention may contain a photosensitive agent commonly used in a resist material. The sensitizer is, for example, a compound having a quinone diazide group.
Specific examples of the compound having a quinone diazide group include an ester compound or an amidated compound of an aromatic (poly) hydroxy compound and a sulfonic acid compound having a quinone diazide group. The ester compound also includes a partial ester compound, and the amidate compound also includes a partial amidate compound.
Specific examples of the sulfonic acid compound having a quinone diazide group include naphthoquinone-1, 2-diazide-5-sulfonic acid, naphthoquinone-1, 2-diazide-4-sulfonic acid, ortho-anthraquinone-diazide sulfonic acid, and 1, 2-naphthoquinone-2-diazide-5-sulfonic acid.
Specific examples of the sulfonic acid compound having a quinone diazide group described above may use a halide compound further substituted with halogen.
Examples of the aromatic (poly) hydroxy compound include 2,3, 4-trihydroxybenzophenone, 2,4 '-trihydroxybenzophenone, 2,4, 6-trihydroxybenzophenone, 2,3, 4-trihydroxy-2' -methylbenzophenone, 2,3,4 '-tetrahydroxybenzophenone, 2',4,4 '-tetrahydroxybenzophenone, 2,3', 4', 6-pentahydroxybenzophenone, 2',3,4 '-pentahydroxybenzophenone, 2',3,4, 5-pentahydroxybenzophenone, 2,3', polyhydroxy benzophenone compounds such as 4,4',5', 6-hexahydroxybenzophenone, 2,3', 4',5' -hexahydroxybenzophenone;
Bis [ (poly) hydroxyphenyl ] alkane compounds such as 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'- {1- [4- [ 2- (4-hydroxyphenyl) -2-propyl ] phenyl ] ethylene } bisphenol, and 3,3' -dimethyl- {1- [4- [ 2- (3-methyl-4-hydroxyphenyl) -2-propyl ] phenyl ] ethylene } bisphenol;
Tris (hydroxyphenyl) methane compounds such as tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-3, 5-dimethylphenyl) -2-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -3, 4-dihydroxyphenyl methane, bis (4-hydroxy-3, 5-dimethylphenyl) -3, 4-dihydroxyphenyl methane or methyl substituents thereof;
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-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 (3-hydroxyphenyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methane compounds such as bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxyphenyl methane and bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenyl methane, methyl substituents thereof, and the like.
The above-mentioned photosensitizers may be used alone or in combination of 1 or more than 2.
The content of the photosensitive agent in the photosensitive composition of the present invention is preferably 5 to 50 parts by mass relative to 100 parts by mass of the total resin components of the photosensitive composition of the present invention, from the viewpoint of forming a photosensitive composition excellent in photosensitivity.
The photosensitive composition of the present invention may contain a surfactant. When the photosensitive composition of the present invention is used for a resist application, the effect of improving film forming property and pattern adhesion, reducing development defects, and the like can be obtained by including the surfactant in the photosensitive composition of the present invention.
The surfactant may be any known surfactant. Examples of the surfactant include nonionic surfactants, fluorine surfactants, and silicone surfactants.
The surfactant may be used alone or in combination of at least 2 kinds.
The content of the surfactant in the photosensitive composition of the present invention is preferably 0.001 to 2 parts by mass based on 100 parts by mass of the total resin components of the photosensitive composition of the present invention.
The photosensitive composition of the present invention is preferably prepared in a state in which the phenolic hydroxyl group-containing resin of the present invention is dissolved in an organic solvent.
Examples of the organic solvent include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl 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; ester compounds such as methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate.
The organic solvents may be used alone or in combination of at least 1 kind and at least 2 kinds.
The content of the organic solvent in the photosensitive composition of the present invention is not particularly limited, and for example, the content may be set to an amount capable of dissolving all of the phenolic hydroxyl group-containing resin of the present invention in the photosensitive composition.
The photosensitive composition of the present invention can be produced by mixing the above components and mixing the components with a stirrer or the like. When the photosensitive composition of the present invention contains a filler or pigment, it can be produced by dispersing or mixing the filler or pigment using a dispersing device such as a dissolver, a homogenizer, or a three-roll mill.
The photosensitive composition of the present invention can be used as a resist material.
When the photosensitive composition of the present invention is used as a resist material, the photosensitive composition of the present invention may be used as a coating material as it is, or the photosensitive composition of the present invention may be applied to a support film, and the resulting coating film may be desolvated to prepare a resist film.
Examples of the support 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 formed of a plurality of films. In addition, the surface of the aforementioned support film may be corona-treated or coated with a release agent.
Typical photolithography methods using the photosensitive composition of the present invention include, for example, the following methods.
First, the photosensitive composition of the present invention is applied to an object to be subjected to photolithography, such as a silicon substrate, a silicon carbide substrate, or a gallium nitride substrate, and prebaked at a temperature of 60 to 150 ℃. The coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, or blade coating. Then, the resist pattern is formed by exposing the resist pattern to light and developing the resist pattern with an alkali developer.
When the photosensitive composition of the present invention is used for a resist permanent film, a crosslinking agent may be contained.
Examples of the crosslinking agent include the same as the curing agent contained in the curable composition described later.
The crosslinking agent may be used alone or in combination of 1 or more than 2.
The method of forming the resist permanent film includes, for example, the following methods.
First, the photosensitive composition of the present invention is applied to an object to be subjected to photolithography, such as a silicon substrate, a silicon carbide substrate, or a gallium nitride substrate, and prebaked at a temperature of 60 to 150 ℃. The coating method is the same as previously enumerated. Then, the resist pattern is formed by exposing the resist pattern to light and then thermally curing the resist pattern at a temperature of 110 to 210 ℃ and then developing the resist pattern with an alkali developer. Or it may be developed with an alkali developer after exposure and then thermally cured at a temperature of 110 to 210 ℃.
Specific examples of the resist permanent film include solder resist, packaging material, underfill material, packaging adhesive layer for circuit element, adhesive layer for integrated circuit element and circuit substrate, and the like in semiconductor device. In addition, thin displays typified by LCDs and OELDs include thin film transistor protective films, liquid crystal color filter protective films, black matrices, spacers, and the like.
[ Curable composition ]
The curable composition of the present invention comprises the phenolic hydroxyl group-containing resin of the present invention and a curing agent.
The curing agent is not particularly limited as long as it is a compound capable of undergoing a curing reaction with the phenolic hydroxyl group-containing resin of the present invention, and examples thereof include melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, resol resins, epoxy compounds, isocyanate compounds, azide compounds, compounds containing a double bond such as an alkenyl ether group, acid anhydrides, oxazoline compounds, and the like.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound obtained by methoxymethylating 1 to 6 methylol groups of hexamethylol melamine, a compound obtained by acyloxymethylating 1 to 6 methylol groups of hexamethylol melamine, and the like.
Examples of the guanamine compound include tetramethylol guanamine, tetramethylol methyl benzoguanamine, compounds obtained by methoxymethylation of 1 to 4 methylol groups of tetramethylol guanamine, compounds obtained by acyloxymethylation of 1 to 4 methylol groups of tetramethylol guanamine, and the like.
Examples of the glycoluril compound include 1,3,4, 6-tetra (methoxymethyl) glycoluril, 1,3,4, 6-tetra (butoxymethyl) glycoluril, and 1,3,4, 6-tetra (hydroxymethyl) glycoluril.
Examples of the urea compound include 1, 3-bis (hydroxymethyl) urea, 1, 3-tetra (butoxymethyl) urea, and 1, 3-tetra (methoxymethyl) urea.
Examples of the resol resin include polymers obtained by reacting phenol-containing compounds such as alkylphenols, e.g., phenol, cresol, xylenol, etc., phenylphenol, resorcinol, bisphenol a, bisphenol F, etc., naphthol, dihydroxynaphthalene, etc., with aldehyde compounds under the condition of an alkaline catalyst.
Examples of the epoxy compound include diglycidyl oxy naphthalene, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol-phenol co-condensation novolac type epoxy resin, naphthol-cresol co-condensation novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, 1-bis (2, 7-diglycidyl oxy-1-naphthyl) alkane, naphthalene ether type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, epoxy resin containing a phosphorus atom, polyglycidyl ether of a co-condensate of a phenolic hydroxyl group-containing compound and an aromatic compound containing an alkoxy group, and the like.
Examples of the isocyanate compound include toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.
Examples of the azide compound include 1,1 '-biphenyl-4, 4' -bisazide, 4 '-methylenebisazide, and 4,4' -oxybispentazide.
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-propylene glycol divinyl ether, 1, 4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1, 4-cyclohexanediol divinyl ether, 1, 4-cyclohexanedimethanol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol pentavinyl ether, and trimethylolpropane trivinyl ether.
Examples of the acid anhydride include aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, 4'- (isopropylidene) diphthalic anhydride, and 4,4' - (hexafluoroisopropylidene) diphthalic anhydride; alicyclic carboxylic anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and trialkyltetrahydrophthalic anhydride.
Among the above curing agents, glycoluril compounds, urea compounds and resol resins are preferable, and glycoluril compounds are more preferable, in view of obtaining a cured product having high curability and excellent heat resistance.
The above-mentioned curing agents may be used alone or in combination of 1 or more than 2.
The content of the curing agent in the curable composition of the present invention is preferably 0.5 to 50 parts by mass based on 100 parts by mass of the total resin components of the curable composition of the present invention.
The curable composition of the present invention may contain the phenolic hydroxyl group-containing resin of the present invention and the curing agent, and may optionally contain other components.
Examples of the other components include resins other than the phenolic hydroxyl group-containing resin of the present invention, curing accelerators, surfactants, dyes, fillers, crosslinking agents, and dissolution accelerators.
The curable composition of the present invention may contain other resins than the phenolic hydroxyl group-containing resin of the present invention.
Examples of the other resins include addition polymerization resins of an alicyclic diene compound such as a novolak resin and dicyclopentadiene with a phenol compound, modified novolak resins of a phenolic hydroxyl group-containing compound and an aromatic compound containing an alkoxy group, phenol aralkyl resins (Xylock resins), naphthol aralkyl resins, trimethylol methane resins, tetraphenolethane (tetraphenylolethane) resins, biphenyl modified phenolic resins, biphenyl modified naphthol resins, aminotriazine modified phenolic resins, vinyl polymers, and the like.
Specific examples of the novolak resin include: and a polymer obtained by reacting a phenol-containing compound such as alkylphenol, phenylphenol, resorcinol, bisphenol A, bisphenol F, naphthol, or dihydroxynaphthalene with an aldehyde compound in the presence of an acid catalyst.
Specific examples of the vinyl polymer include homopolymers of vinyl compounds such as polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetradodecene, polynorbornene, and poly (meth) acrylate, and copolymers thereof.
The other resins may be used alone or in combination of at least 2 kinds.
The content of the other resin in the curable composition of the present invention is not particularly limited and may be arbitrarily set according to the intended use. For example, the other resin is preferably 0.5 to 100 parts by mass per 100 parts by mass of the phenolic hydroxyl group-containing resin of the present invention contained in the curable composition of the present invention.
The curable composition of the present invention may contain a curing accelerator.
Specific examples of the curing accelerator include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, manganese acetate, and the photoacid generator.
The curing accelerator may be used alone or in combination of 1 or more than 2.
The content of the curing accelerator in the curable composition of the present invention is not particularly limited, but is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the resin solid content of the curable composition of the present invention.
The curable composition of the present invention is preferably in a state in which the phenolic hydroxyl group-containing resin of the present invention is dissolved in an organic solvent.
Examples of the organic solvent include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl 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; ester compounds such as methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate.
The organic solvents may be used alone or in combination of at least 1 kind and at least 2 kinds.
The content of the organic solvent in the curable composition of the present invention is not particularly limited, and for example, the content may be set to an amount capable of dissolving all of the phenolic hydroxyl group-containing resin of the present invention in the curable composition.
The curable composition of the present invention can be produced by mixing the above components and mixing the components with a stirrer or the like. When the curable composition of the present invention contains a filler or pigment, the curable composition can be produced by dispersing or mixing the filler or pigment using a dispersing device such as a dissolver, a homogenizer, or a three-roll mill.
The curable composition of the present invention is useful as a resist material, and the cured product of the curable composition of the present invention is useful as a resist.
When the curable composition of the present invention is used as a resist material, the curable composition of the present invention may be used as a coating material as it is, or the curable composition of the present invention may be applied to a support film, and the resulting coating film may be desolvated to prepare a resist film.
Examples of the support 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 formed of a plurality of films. In addition, the surface of the aforementioned support film may be corona-treated or coated with a release agent.
When the curable composition of the present invention is used for a resist underlayer film, the following examples are given as examples of a method for producing a resist underlayer film.
The resist underlayer film is formed by the following method: the curable composition of the present invention is applied to an object to be subjected to photolithography, such as a silicon substrate, a silicon carbide substrate, or a gallium nitride substrate, and dried at a temperature of 100 to 200 ℃, and then cured by heating at a temperature of 250 to 400 ℃. Then, a resist pattern is formed by performing a normal photolithography operation on the underlayer film, and a dry etching process is performed by using a halogen-based plasma gas or the like, thereby forming a resist pattern by a multilayer resist method.
The method of curing the curable composition of the present invention is not particularly limited, and the composition may be cured by an appropriate method such as heat curing or photo curing depending on the type of the curing agent, the type of the curing accelerator, and the like. The curing conditions such as the heating temperature, time, light type during photo-curing, and exposure time during thermal curing can be appropriately adjusted according to the type of the curing agent, the type of the curing accelerator, and the like.
Examples
Hereinafter, the present invention will be specifically described with reference to examples and comparative examples.
The number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the resins prepared in the examples were measured using the following GPC measurement conditions.
[ Measurement conditions of GPC ]
Measurement device: HLC-8220GPC manufactured by Tosoh Co., ltd "
Column: shodex KF802 (8.0 mm. Phi. Times.300 mm) manufactured by Showa electric Co., ltd.), "Shodex KF803 (8.0 mm. Phi. Times.300 mm) manufactured by Showa electric Co., ltd.)," Shodex KF804 (8.0 mm. Phi. Times.300 mm) manufactured by Showa electric Co., ltd.)
Column temperature: 40 DEG C
A detector: RI (differential refractometer)
And (3) data processing: GPC-8020 model II version 4.30 manufactured by Tosoh Co., ltd "
Developing solvent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Sample: sample obtained by filtering tetrahydrofuran solution having 0.5 mass% in terms of resin solid content with microfilter
Injection amount: 0.1mL
Standard sample: the monodisperse polystyrene described below
(Standard sample: monodisperse polystyrene)
"A-500" manufactured by Tosoh Co., ltd "
"A-2500" manufactured by Tosoh Co., ltd "
"A-5000" manufactured by Tosoh Co., ltd "
"F-1" manufactured by Tosoh Co., ltd "
F-2 manufactured by Tosoh Co., ltd "
F-4 manufactured by Tosoh Co., ltd "
F-10 manufactured by Tosoh Co., ltd "
F-20 manufactured by Tosoh Co., ltd "
Further, in the measurement of the C-NMR spectrum of 13 in the examples, a solution of DMSO-d 6 in the sample was analyzed by using "AL-400" manufactured by Japanese electronics Co., ltd. The measurement conditions of 13 C-NMR spectrum are shown below.
[ 13 C-NMR Spectroscopy conditions ]
Measurement mode: SGNNE (NOE-free 1H decoupling method)
Pulse angle: pulse at 45 DEG C
Sample concentration: 30wt%
Cumulative number of times: 10000 times
Synthesis example 1 Synthesis of Carboxylic acid-containing phenolic trinuclear Compound
To a 2000ml four-necked flask equipped with a cooling tube, 293.2g (2.4 mol) of 2, 5-xylenol and 150g (1 mol) of 4-formylbenzoic acid were charged and dissolved in 500ml of acetic acid. While cooling in an ice bath, 5ml of sulfuric acid was added thereto, and the mixture was heated at 100℃for 2 hours with a mantle heater, followed by stirring to react. After the reaction, the obtained solution was subjected to reprecipitation with water to obtain a crude product. The crude product was redissolved in acetone, and after further reprecipitation with water, the resultant product was collected by filtration and dried under vacuum to obtain 283g of the precursor compound (A-1) as pale pink crystals.
As a result of carrying out 13 C-NMR spectrometry on the obtained precursor compound (A-1), it was confirmed that it was a compound represented by the following structural formula. Further, the GPC purity calculated from the GPC chart was 97.9%. The GPC chart of the precursor compound (A-1) is shown in FIG. 1, and the 13 C-NMR chart is shown in FIG. 2.
Production example 1 Synthesis of Carboxylic acid-containing novolak-type phenol resin
A1000 ml four-necked flask equipped with a cooling tube was charged with 188g of the precursor compound (A-1) and 16g of 92% paraformaldehyde (B-1), and then dissolved in 500ml of acetic acid. After adding 10ml of sulfuric acid while cooling in an ice bath, the mixture was heated to 80℃in an oil bath and stirred for 4 hours to react. After the reaction was completed, water was added to the resulting solution to reprecipitate the crude product. The crude product was redissolved in acetone, reprecipitated with water, and the precipitate was collected by filtration and dried under vacuum to obtain 182g of an orange powder of novolak-type phenol resin (C-1).
The resulting novolak-type phenol resin (C-1) had a number average molecular weight (Mn) of 3946, a weight average molecular weight (Mw) of 8504 and a polydispersity (Mw/Mn) of 2.16.
GPC spectra of the obtained novolak type phenol resin (C-1) are shown in FIG. 3, and 13 C-NMR spectra are shown in FIG. 4.
EXAMPLE 1 preparation of esterified novolak-type phenol resin (Z-1)
Into a 300ml four-necked flask equipped with a cooling tube, 20g of the carboxylic acid-containing novolak type phenol resin (C-1) obtained in production example 1 and 100ml of 2-ethoxyethanol were charged, and after cooling in an ice bath, 1ml of sulfuric acid was added, and then stirring was continued at room temperature for 4 hours to react. After the completion of the reaction, sulfuric acid was deactivated with 10ml of triethylamine, and water was added to the resulting solution to reprecipitate the crude product. The crude product was redissolved in acetone, reprecipitated with water, and the precipitate was collected by filtration and dried under vacuum to obtain 21.3g of novolak-type esterified phenol resin (Z-1) as a pale orange powder.
The obtained esterified novolak-type phenol resin (Z-1) had a number average molecular weight (Mn) of 3183, a weight average molecular weight (Mw) of 5180 and a polydispersity (Mw/Mn) of 1.62. The esterification rate of the obtained esterified novolak-type phenol resin (Z-1) was 52% as calculated by 13 C-NMR.
GPC spectra of the esterified novolak-type phenol resin (Z-1) are shown in FIG. 5. FIG. 6 shows a 13 C-NMR spectrum of an esterified novolak-type phenol resin (Z-1).
In addition, the esterification rate was calculated from the ratio of the integrated value of carbonyl carbon derived from carboxyl group observed at 167 to 175ppm to the integrated value of carbonyl carbon derived from ester group observed at 155 to 164 ppm.
EXAMPLE 2 Synthesis of esterified novolak-type phenol resin (Z-2)
The reaction was carried out in the same manner as in example 1 except that 100ml of 2-propanol was used instead of 100ml of 2-ethoxyethanol, to thereby obtain 18.3g of esterified novolak-type phenol resin (Z-2) as a pale orange powder.
The obtained novolak-type esterified phenol resin (Z-2) had a number average molecular weight (Mn) of 1772, a weight average molecular weight (Mw) of 2554 and a polydispersity (Mw/Mn) of 1.44. The esterification rate of the obtained esterified novolak-type phenol resin (Z-2) as calculated by 13 C-NMR was 35%.
GPC spectra of the esterified novolak-type phenol resin (Z-2) are shown in FIG. 7. FIG. 8 shows a 13 C-NMR spectrum of an esterified novolak-type phenol resin (Z-2).
EXAMPLE 3 Synthesis of esterified novolak-type phenol resin (Z-3)
The reaction was carried out in the same manner as in example 1 except that 100ml of 2-methyl-2-propanol was used instead of 100ml of 2-ethoxyethanol, to thereby obtain 19.2g of an esterified novolak-type phenol resin (Z-3) as a pale orange powder.
The resulting esterified novolak-type phenol resin (Z-3) had a number average molecular weight (Mn) of 1074, a weight average molecular weight (Mw) of 1466 and a polydispersity (Mw/Mn) of 1.36. The esterification rate of the obtained esterified novolak-type phenol resin (Z-3) as calculated by 13 C-NMR was 15%.
The GPC chart of the esterified novolak-type phenol resin (Z-3) is shown in FIG. 9. FIG. 10 shows the 13 C-NMR spectrum of the esterified novolak-type phenol resin (Z-3).
Comparative example 1 Synthesis of novolak resin (C' -2)
552G (4 mol) of 2-hydroxybenzoic acid, 498g (3 mol) of 1, 4-bis (methoxymethyl) benzene, 2.5g of p-toluenesulfonic acid and 500g of toluene were charged into a 2L four-necked flask equipped with a stirrer and a thermometer, and the temperature was raised to 120℃to effect a methanol removal reaction. The temperature was raised and the reaction was distilled under reduced pressure, and the reaction was carried out at 230℃for 6 hours under reduced pressure to give 882g of a pale yellow solid novolak resin (C' -2).
The novolak resin (C' -2) had a number average molecular weight (Mn) of 1016, a weight average molecular weight (Mw) of 2782 and a polydispersity (Mw/Mn) of 2.74. The GPC chart of the novolak resin (C' -2) is shown in FIG. 11.
Comparative example 2 Synthesis of novolak resin (C' -3)
To a 2L four-necked flask equipped with a stirrer and a thermometer were charged 648g (6 mol) of m-cresol, 432g (4 mol) of p-cresol, 2.5g (0.2 mol) of oxalic acid and 492g of 42% formaldehyde, and the temperature was raised to 100℃to react the mixture. The mixture was dehydrated to 200℃under normal pressure, distilled at 230℃for 6 hours under reduced pressure to give 736g of novolak-type phenol resin (C' -3) in a pale yellow solid state.
The novolak resin (C' -3) had a number average molecular weight (Mn) of 1450, a weight average molecular weight (Mw) of 10316 and a polydispersity (Mw/Mn) of 7.116. The GPC chart of the novolak resin (C' -3) is shown in FIG. 12.
EXAMPLE 4 preparation of photosensitive composition
20 Parts by mass of the esterified novolak-type phenol resin (Z-1) prepared in example 1 was dissolved in 75 parts by mass of Propylene Glycol Monomethyl Ether Acetate (PGMEA), and 5 parts by mass of a photoacid generator was added to the solution to dissolve the same. The obtained solution was subjected to fine filtration with a disc filter made of polytetrafluoroethylene having a size of 0.1. Mu.m, to prepare a photosensitive composition.
As the photoacid generator, "TME-triazine" (2- [2- (5-methylfuran-2-yl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine) manufactured by Sanko chemical industries, ltd.
The photosensitive composition thus obtained was used for the following evaluation. The results are shown in Table 1.
(1) Evaluation of alkali developability
The obtained photosensitive composition was coated on a 5-inch silicon wafer with a thickness of about 1 μm by a spin coater, and dried on a heating plate at 110℃for 60 seconds to form a resin film on the silicon wafer. This operation was repeated to prepare a plurality of evaluation wafers.
The evaluation wafer was immersed in an alkali developer (2.38% aqueous tetramethylammonium hydroxide solution) for 60 seconds, and dried on a heating plate at 110 ℃ for 60 seconds after the immersion. The film thickness before and after immersion in the developer was measured, and the difference was divided by 60 to obtain the alkali developability
Two wafers for evaluation were prepared, and one wafer was used as a "non-exposure sample". The other block was used as an "exposed sample", and a ghi ray lamp (Multi-Light, manufactured by USHIO Motor Co., ltd.) was used to irradiate 200mJ/cm 2 of ghi rays, followed by heat treatment at 110℃for 120 seconds. Both the "unexposed sample" and the "exposed sample" were immersed in an alkali developer (2.38% aqueous tetramethylammonium hydroxide solution) for 60 seconds, and then dried on a heating plate at 110℃for 60 seconds. The film thickness of each sample before and after immersion in the developer was measured, and the difference was divided by 60 to obtain an alkali developability
The evaluation wafer was immersed in an alkali developer (15% sodium carbonate aqueous solution) for 60 seconds, and dried on a heating plate at 110 ℃ for 60 seconds after the immersion. The film thickness before and after immersion in the developer was measured, and the difference was divided by 60 to obtain the alkali developability
Two wafers for evaluation were prepared, and one wafer was used as a "non-exposure sample". The other block was used as an "exposed sample", and a ghi ray lamp (Multi-Light, manufactured by USHIO Motor Co., ltd.) was used to irradiate 200mJ/cm 2 of ghi rays, followed by heat treatment at 110℃for 120 seconds. Both the "unexposed sample" and the "exposed sample" were immersed in an alkali developer (15% sodium carbonate aqueous solution) for 60 seconds, and then dried on a heating plate at 110℃for 60 seconds. The film thickness of each sample before and after immersion in the developer was measured, and the difference was divided by 60 to obtain an alkali developability
(2) Evaluation of Heat resistance
The resulting photosensitive composition was coated on a 5-inch silicon wafer with a thickness of up to about 1 μm using a spin coater, and dried on a heating plate at 110℃for 60 seconds. The resin film on the wafer was scraped, and the glass transition temperature (Tg) thereof was measured and evaluated.
The glass transition temperature (Tg) was measured using a Differential Scanning Calorimeter (DSC) (Q100 manufactured by TA Instruments Co., ltd.) under a nitrogen atmosphere at a temperature ranging from-100 to 200℃and a temperature rise of 10℃per minute. The glass transition temperature was evaluated as "o" when 150 ℃ or higher, and as "x" when less than 150 ℃.
Examples 5 to 6 and comparative examples 3 to 5
Photosensitive compositions were prepared and evaluated in the same manner as in example 4, except that the resins shown in table 1 were used instead of the esterified novolak type phenol resin (Z-1). The results are shown in Table 1.
TABLE 1
As shown in the results in table 1, it can be seen that: the photosensitive compositions of comparative examples 3 to 5 were confirmed to be alkali-soluble in the stage before exposure, and were unable to function as photosensitive compositions. On the other hand, it can be seen that: the photosensitive compositions of examples 4 to 6 were not alkali-eluted at the stage before exposure, and the alkali-eluted by exposure was found to be able to obtain a good development contrast. This is presumably because: the acid of the photoacid generator caused hydrolysis of the ester groups of the esterified novolak-type phenol resins of examples 1-3 to form carboxyl groups, thereby effecting a polarity change.

Claims (7)

1. A photosensitive composition comprising a phenolic hydroxyl group-containing resin which is a reaction product of a novolak type phenol resin (C) containing an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) as essential reaction raw materials and an alcohol compound (X) and a photoacid generator,
In the formula (1), R 1 and R 2 each independently represent an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom;
m, n and p each independently represent an integer of 0 to 4;
when there are a plurality of R 1, the plurality of R 1 are optionally the same or different;
When there are a plurality of R 2, the plurality of R 2 are optionally the same or different;
r 3 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural part having 1 or more substituents selected from the group consisting of an alkoxy group, a halogen group and a hydroxyl group on a hydrocarbon group;
r 4 represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom;
When there are a plurality of R 4, the plurality of R 4 are optionally the same or different.
2. The photosensitive composition according to claim 1, wherein the aromatic compound (a) is a reaction product of 1 or more selected from the group consisting of an aromatic aldehyde having a carboxyl group and an aromatic ketone having a carboxyl group, and an alkyl-substituted phenol compound.
3. The photosensitive composition according to claim 2, wherein the aromatic aldehyde having a carboxyl group is formylbenzoic acid.
4. The photosensitive composition according to any one of claims 1 to 3, wherein the aliphatic aldehyde (B) is 1 or more selected from formaldehyde and paraformaldehyde.
5. The photosensitive composition according to any one of claims 1 to 3, wherein the alcohol compound (X) is 1 or more selected from an aliphatic alcohol having 10 or less carbon atoms and an ether alcohol having 10 or less carbon atoms.
6. The photosensitive composition according to any one of claims 1 to 3, wherein the esterification rate of the carboxyl groups of the novolak-type phenol resin (C) is 5 to 70 mol%.
7. A resist film formed from the photosensitive composition according to claim 1.
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