CN109790264B - Phenolic hydroxyl group-containing resin and resist material - Google Patents
Phenolic hydroxyl group-containing resin and resist material Download PDFInfo
- Publication number
- CN109790264B CN109790264B CN201780060031.8A CN201780060031A CN109790264B CN 109790264 B CN109790264 B CN 109790264B CN 201780060031 A CN201780060031 A CN 201780060031A CN 109790264 B CN109790264 B CN 109790264B
- Authority
- CN
- China
- Prior art keywords
- group
- phenolic hydroxyl
- hydroxyl group
- containing resin
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/34—Cyanuric or isocyanuric esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/36—Chemically modified polycondensates by etherifying
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Materials For Photolithography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The purpose of the present invention is to provide a phenolic hydroxyl group-containing resin having excellent fluidity and a cured product having high heat resistance and dry etching resistance, a curable composition containing the same, and a resist material, wherein the phenolic hydroxyl group-containing resin is represented by the following structural formula (1) (wherein X represents a hydrocarbon group having 1 to 14 carbon atoms; R1Each independently is any of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. m is 0, 1 or 2, and n is 0 or an integer of 1 to 4. ) The reaction product of a binaphthol compound (a1) and a cyanuric halide (a2) has a polydispersity (Mw/Mn) in the range of 1.01 to 1.30.
Description
Technical Field
The present invention relates to a phenolic hydroxyl group-containing resin which has excellent fluidity and gives a cured product having high heat resistance and dry etching resistance, a curable composition containing the same, and a resist material.
Background
In the field of photoresists, various methods for forming resist patterns, which are subdivided into functions according to the use, have been developed, and the required performance of resin materials for resists has been highly diversified and diversified. For example, a resin material for pattern formation is required to have high developability capable of forming a fine pattern on a highly integrated semiconductor accurately and with high production efficiency. In applications called underlayer films, antireflection films, BARC films, hard masks, and the like, dry etching resistance, low reflectivity, high fluidity that can be applied to a substrate surface having irregularities, and the like are required. In addition, in applications called permanent resists, toughness such as substrate conformability is required in addition to high heat resistance. Further, from the viewpoint of quality reliability, long-term storage stability under various environments in various countries is also one of important properties.
As one of resin materials suitable for photoresists, naphthol novolac type resin is known (see patent document 1 below). The naphthol novolac type resin has a feature of being excellent in dry etching resistance due to a rigid naphthalene skeleton, but has low fluidity, so that the coating property on the surface of a substrate having irregularities is low, and the surface smoothness of the obtained film is insufficient.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2010-248435
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object of the present invention is to provide a phenolic hydroxyl group-containing resin which has excellent fluidity and gives a cured product having high heat resistance and dry etching resistance, a curable composition containing the same, and a resist material.
Means for solving the problems
As a result of intensive studies to solve the above problems, the present inventors have found that a phenolic hydroxyl group-containing resin which is a reaction product of a binaphthol compound and a cyanuric halide and has a polydispersity (Mw/Mn) in the range of 1.01 to 1.30 has high fluidity, and therefore has excellent coatability on a substrate surface having irregularities, and a cured product has excellent heat resistance and dry etching resistance, and have completed the present invention.
That is, the present invention relates to a phenolic hydroxyl group-containing resin which is a reaction product of a bis-naphthol compound (a1) represented by the following structural formula (1) and cyanuric halide (a2), and has a polydispersity (Mw/Mn) in the range of 1.01 to 1.30.
(wherein X represents a hydrocarbon group having 1 to 14 carbon atoms R1Each independently is any of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. m is 0, 1 or 2, and n is 0 or an integer of 1 to 4. )
The present invention also relates to a curable composition containing the above-mentioned phenolic hydroxyl group-containing resin and a curing agent.
The present invention also relates to a cured product of the curable composition.
The present invention also relates to a resist material using the curable composition.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a phenolic hydroxyl group-containing resin, a curable composition containing the same, and a resist material, which have excellent fluidity and give a cured product having high heat resistance and dry etching resistance, can be provided.
Drawings
FIG. 1 is a GPC chart of the phenolic hydroxyl group-containing resin (1) obtained in example 1.
Detailed Description
The phenolic hydroxyl group-containing resin is characterized by being a reaction product of a bis-naphthol compound (a1) represented by the following structural formula (1) and cyanuric halide (a2), and having a polydispersity (Mw/Mn) in the range of 1.01 to 1.30.
(wherein X represents a hydrocarbon group having 1 to 14 carbon atoms R1Each independently is any of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. m is 0, 1 or 2, and n is 0 or an integer of 1 to 4. )
The above-mentioned binaphthol compound (a1) can be obtained, for example, by a method of reacting a 2-naphthol compound with an aldehyde compound. The aforementioned 2-naphthol compound means 2-naphthol or 2-naphthol having one or more R's in the aforementioned formula (1) on the aromatic nucleus1The substituent compounds shown may be used alone in 1 kind, or in combination of 2 or more kinds.
R in the aforementioned formula (1)1Each independently is any of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. Specific examples of the aliphatic hydrocarbon group include methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, and the like. Specific examples of the alkoxy group include methoxy, ethoxy, propoxy and butoxy. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a structural site obtained by substituting the aromatic nucleus thereof with the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, and the like. Specific examples of the aralkyl group include a phenylmethyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and a structural site obtained by substituting the above-mentioned aliphatic hydrocarbon group, alkoxy group, halogen atom, etc. on the aromatic nucleus thereof. Among them, from the viewpoint of higher heat resistance of the cured product, it is preferable that both n and m in the structural formula (1) are 0. That is, 2-naphthol is preferably used as the reaction raw material of the above-mentioned bisnaphthol compound (a 1).
Examples of the aldehyde compound include formaldehyde, trioxymethylene, acetaldehyde, propionaldehyde, tetraoxymethylene (tetraoxymethylene), polyoxymethylene, trichloroacetaldehyde, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, hexanal, allylaldehyde, benzaldehyde, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, crotonaldehyde, and acrolein. These may be used alone or in combination of 2 or more. Among them, formaldehyde is preferably used in view of excellent reactivity. That is, X in the structural formula (1) is preferably a methylene group. The formaldehyde may be used as formalin in an aqueous solution or as paraformaldehyde in a solid state, or both.
The reaction of the 2-naphthol compound with the aldehyde compound is preferably carried out at a temperature of about 80 to 120 ℃ by gradually raising the temperature from room temperature in the presence of an alkali catalyst, from the viewpoint of obtaining the target dinaphthol compound (a1) in high yield. The reaction may be carried out in an organic solvent as required.
The reaction ratio of the 2-naphthol compound and the aldehyde compound is preferably in the range of 0.45 to 0.55 mol of the aldehyde compound per 1 mol of the 2-naphthol compound.
Examples of the base catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, and pyridine. These may be used alone or in combination of 2 or more. The amount of the alkali catalyst added is preferably in the range of 0.05 to 3 mass% with respect to the total mass of the reaction raw materials.
Examples of the organic solvent include methanol, ethanol, propanol, butanol, ethyl lactate, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, propylene glycol (trimethylene glycol), diethylene glycol, polyethylene glycol, glycerol, 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 monophenyl ether, diethylene glycol ethylmethyl ether, propylene glycol monomethyl ether, 1, 3-dioxane, 1, 4-dioxane, tetrahydrofuran, ethylene glycol acetate, acetone, ethyl acetate, and the like, Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, and the like. These solvents may be used alone, or a mixed solvent of 2 or more kinds may be used. Among them, alcohol solvents such as methanol, ethanol, propanol, and butanol are preferable in terms of obtaining the bis-naphthol compound (a1) in high yield. The amount of the organic solvent is preferably in the range of 0.5 to 5 times the total mass of the reaction raw materials.
After the reaction is completed, the reaction product is purified by washing with water, reprecipitation, or the like, whereby the high purity bis-naphthol compound (a1) can be obtained. The purity of the bisnaphthol compound (a1) is preferably 90% or more, more preferably 99% or more, as calculated from the area ratio in the GPC diagram, from the viewpoint of forming a phenolic hydroxyl group-containing resin having excellent balance between flowability and heat resistance and dry etching resistance of a cured product.
In the present invention, the purity of the bis-naphthol compound (a1) and the content of each component in the phenolic hydroxyl group-containing resin are calculated from the area ratio of the figures obtained by GPC measurement under the following conditions. The weight average molecular weight (Mw), the number average molecular weight (Mn), and the polydispersity number (Mw/Mn) of the phenolic resin containing a phenolic hydroxyl group are values measured by GPC under the following conditions.
[ side Condition of GPC ]
A measuring device: HLC-8220GPC, manufactured by Tosoh corporation "
Column: shorex KF802 (8.0 mm. phi. times.300 mm) manufactured by Shorey K.K. + Shorex KF803 (8.0 mm. phi. times.300 mm) manufactured by Shorey K.K. + Shorex KF804 (8.0 mm. phi. times.300 mm) manufactured by Shorey K.K.)
Column temperature: 40 deg.C
A detector: RI (differential refractometer)
Data processing: "GPC-8020 model II version 4.30" manufactured by Tosoh corporation "
Developing solvent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Sample preparation: the resulting tetrahydrofuran solution (0.5 mass% in terms of resin solid content) was filtered through a microfilter (100. mu.l)
Standard sample: the following monodisperse polystyrene
(Standard sample: monodisperse polystyrene)
"A-500" made by Tosoh corporation "
"A-2500" made by Tosoh corporation "
"A-5000" manufactured by Tosoh corporation "
"F-1" made by Tosoh corporation "
"F-2" made by Tosoh corporation "
"F-4" made by Tosoh corporation "
"F-10" made by Tosoh corporation "
"F-20" made by Tosoh corporation "
The method for reacting the bis-naphthol compound (a1) with the cyanuric halide (a2) is not particularly limited, and examples thereof include a method in which the reaction is carried out in the presence of a hydrogen halide scavenger at a temperature of about 50 to 100 ℃. The reaction may be carried out in an organic solvent as required.
The reaction ratio between the bis-naphthol compound (a1) and the cyanuric halide (a2) is preferably in the range of 1.5 to 5, more preferably in the range of 2.0 to 3.5, in terms of easily adjusting the polydispersity (Mw/Mn) of the obtained phenolic hydroxyl group-containing resin to the range of 1.0 to 1.5.
Examples of the hydrogen halide scavenger include tertiary amine compounds such as trimethylamine and triethylamine, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and basic compounds. The amount of addition thereof is preferably in the range of 1 to 2 moles per 1 mole of the cyanoureahalide (a 2).
The organic solvent is preferably a hydrophobic solvent, and examples thereof include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. The organic solvent is preferably used in an amount of 0.5 to 5 times the total mass of the reaction raw materials.
After the reaction, the reaction product was washed with water to remove the salt formed. The phenolic hydroxyl group-containing resin of the present invention preferably has a content of a component having a number average molecular weight (Mn) of 500 or less in a range of 0.1 to 3.0%, more preferably 0.1 to 2.8%, and particularly preferably 0.3 to 2.0% as calculated from an area ratio in a GPC diagram, from the viewpoint of more excellent balance between flowability and heat resistance and dry etching resistance of a cured product. The content of the component having a number average molecular weight (Mn) of 500 or less can be prepared by increasing the number of times of washing with water, performing reprecipitation, or the like.
The phenolic hydroxyl group-containing resin of the present invention preferably contains a polynuclear compound (A) represented by the following structural formula (2) as an essential component.
(wherein X represents a hydrocarbon group having 1 to 14 carbon atoms R1Each independently is any of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. m is 0, 1 or 2, and n is 0 or an integer of 1 to 4. )
The content of the polynuclear compound (a) is preferably 35% or more, more preferably in the range of 35 to 90%, and particularly preferably in the range of 55 to 80% as calculated from the area ratio of the GPC chart, from the viewpoint of forming a phenolic hydroxyl group-containing resin having a more excellent balance between flowability and heat resistance and dry etching resistance of a cured product.
The phenolic hydroxyl group-containing resin of the present invention may contain, for example, a component in which a part to all of the phenolic hydroxyl groups in the structural formula (1) are substituted with the structural sites represented by the following structural formula (3) in addition to the polynuclear compound (a) represented by the structural formula (1).
(wherein X represents a hydrocarbon group having 1 to 14 carbon atoms R1Each independently is any of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. m is 0, 1 or 2, and n is 0 or an integer of 1 to 4. )
In particular, from the viewpoint of more excellent heat resistance and dry etching resistance of the cured product, it is preferable to contain a compound (B) in which one phenolic hydroxyl group in the structural formula (1) is substituted by the structural formula (3) together with the polynuclear compound (a). In this case, the total content of the polynuclear compound (A) and the compound (B) in the phenolic hydroxyl group-containing resin is preferably in the range of 50 to 99%, more preferably in the range of 60 to 99%, and particularly preferably in the range of 80 to 99% as calculated from the area ratio of a GPC chart.
The phenolic hydroxyl group-containing resin of the present invention preferably has a weight average molecular weight (Mw) in the range of 980 to 1,200 as measured by GPC under the aforementioned conditions. The phenolic hydroxyl group-containing resin of the present invention is characterized in that the polydispersity (Mw/Mn) is in the range of 1.01 to 1.30, and the polydispersity (Mw/Mn) is more preferably in the range of 1.01 to 1.25, and particularly preferably in the range of 1.01 to 1.20, from the viewpoint of forming a phenolic hydroxyl group-containing resin having a better balance between flowability and heat resistance and dry etching resistance of a cured product.
The phenolic hydroxyl group-containing resin of the present invention described in detail above can be used for various applications such as paints, adhesives, electric and electronic members, photoresists, and liquid crystal alignment films, as in the case of ordinary phenol resins.
The curable composition of the present invention contains the above-mentioned phenolic hydroxyl group-containing resin of the present invention and a curing agent as essential components. The curable composition of the present invention may contain another resin (C) in addition to the phenolic hydroxyl group-containing resin of the present invention. Examples of the other resin (C) used here include various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, modified novolak resins of compounds containing a phenolic hydroxyl group and aromatic compounds containing an alkoxy group, phenol aralkyl resins (Xylock resins), naphthol aralkyl resins, trimethylolmethane resins, tetrahydroxyphenyl ethane resins, biphenyl-modified phenolic resins, biphenyl-modified naphthol resins, aminotriazine-modified phenolic resins, and various vinyl polymers.
More specifically, the various novolak resins include polymers obtained by reacting an aldehyde compound with a phenolic hydroxyl group-containing compound such as phenol, cresol, xylenol and other alkylphenols, phenylphenol, resorcinol, biphenyl, bisphenol a, bisphenol F and other bisphenols, naphthol, dihydroxynaphthalene and other bisphenols under the presence of an acid catalyst.
Examples of the various vinyl polymers include homopolymers of vinyl compounds such as polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polycyclododecene, polytricycloterpene (polytricycloene), and poly (meth) acrylate, and copolymers thereof.
When the other resin is used, the blending ratio of the phenolic hydroxyl group-containing resin of the present invention and the other resin (C) may be arbitrarily set according to the application, and from the viewpoint of more remarkably exhibiting the excellent heat resistance effect exhibited by the present invention, the other resin (C) is preferably used in a ratio of 0.5 to 100 parts by mass with respect to 100 parts by mass of the phenolic hydroxyl group-containing resin of the present invention.
The curing agent used in the present invention is not particularly limited as long as it is a compound that can cause a curing reaction with the phenolic hydroxyl group-containing resin of the present invention, and various compounds can be used. The method for curing the curable composition of the present invention is not particularly limited, and the curable composition can be cured by an appropriate method such as thermal curing or photo curing depending on the type of the curing agent, the type of the curing accelerator described later, and the like. The heating temperature and time for thermal curing, the type of light for photo-curing, the exposure time and other curing conditions are appropriately adjusted depending on the type of curing agent, the type of curing accelerator described later and the like.
Specific examples of the curing agent 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, hexamethoxy methyl melamine, a compound obtained by methoxymethylation of 1 to 6 methylol groups of hexamethylol melamine, hexamethoxy ethyl melamine, hexaacyloxymethyl melamine, and a compound obtained by acyloxymethylation of 1 to 6 methylol groups of hexamethylol melamine.
Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl benzoguanamine, a compound in which 1 to 4 methylol groups of tetramethylol guanamine are methoxymethylated, tetramethoxyethyl guanamine, tetraacyloxy guanamine, and a compound in which 1 to 4 methylol groups of tetramethylol guanamine are acyloxymethylated.
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, 1,3, 3-tetra (butoxymethyl) urea, and 1,1,3, 3-tetra (methoxymethyl) urea.
Examples of the resol resin include polymers obtained by reacting an aldehyde compound with a phenolic hydroxyl group-containing compound such as phenol, cresol, xylenol and other alkylphenols, phenylphenol, resorcinol, biphenyl, bisphenol a, bisphenol F and other bisphenols, naphthol, dihydroxynaphthalene and other bisphenols under the presence of an alkaline catalyst.
Examples of the epoxy compound include diglycidyl ether oxynaphthalene, phenol novolac type epoxy resins, cresol novolac type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolac type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, 1-bis (2, 7-diglycidyl ether oxy-1-naphthyl) alkane, naphthylene ether type epoxy resins, triphenylmethane type epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, phosphorus atom containing epoxy resins, polyglycidyl ethers of polycondensates of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, 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 '-methylidene bisazide, and 4, 4' -oxybis azide.
Examples of the compound having 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, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, and the like.
Examples of the acid anhydride include aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4 '- (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, dodecenylsuccinic anhydride, and trialkyltetrahydrophthalic anhydride.
Among these, glycoluril compounds, urea compounds, and resol resins are preferable, and glycoluril compounds are particularly preferable, from the viewpoint of forming a curable composition having excellent curability and heat resistance of a cured product.
The amount of the curing agent to be blended in the curable composition of the present invention is preferably 0.5 to 50 parts by mass relative to 100 parts by mass of the total of the phenolic hydroxyl group-containing resin of the present invention and the other resin (C) in view of forming a composition having excellent curability.
The curable composition of the present invention may contain a curing accelerator in accordance with the curing agent. When the curable composition of the present invention is thermally cured, an acid compound such as acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, manganese acetate, or the like is preferably used as a curing accelerator. On the other hand, when the curable composition of the present invention is photocured, a photoacid generator is preferably used as the curing accelerator. Examples of the photoacid generator include sulfonium salt compounds such as tris (4-methylphenyl) sulfonium trifluoromethanesulfonate and tris (4-methylphenyl) sulfonium hexafluorophosphate; iodonium salt compounds such as bis [ 4-n-alkylphenyl ] iodonium hexafluorophosphate, bis [ 4-n-alkylphenyl ] iodonium hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium bis (perfluorobutanesulfonyl) imide and bis [ 4-n-alkylphenyl ] iodonium tetrakis (pentafluorophenyl) borate (the n-alkyl group in each compound preferably has 10 to 13 carbon atoms); chloromethyl triazine compounds such as 2- [2- (furan-2-yl) ethynyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (methylfuran-2-yl) ethynyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- (methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (4-methoxyphenyl) ethynyl ] -4, 6-bis (trichloromethyl) -s-triazine, and 2- [2- (3, 4-dimethoxyphenyl) ethynyl ] -4, 6-bis (trichloromethyl) -s-triazine. The curing accelerators may be used individually or in combination of 2 or more. The amount of the curing accelerator added is preferably in the range of 0.1 to 10% by mass relative to the total of the resin component and the curing agent component in the curable composition.
The curable composition of the present invention may be diluted with an organic solvent. The organic solvent to be used is not particularly limited, and examples thereof 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 (oxy acetic acid ethyl ester), methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate, and ethyl lactate, which may be used alone or in combination of 2 or more.
As described above, the phenolic hydroxyl group-containing resin of the present invention can be used in various applications such as paints, adhesives, electric and electronic members, photoresists, and liquid crystal alignment films, and among these, the phenolic hydroxyl group-containing resin is particularly suitable as a resist material for applications utilizing the characteristics of excellent fluidity and high heat resistance and dry etching resistance of a cured product, and can be used in various resist members such as a resist underlayer film and a permanent resist film in addition to a general interlayer insulating film.
When the phenolic hydroxyl group-containing resin of the present invention is used as a resist material, the method of using the resin is various, and examples thereof include: a method of using the composition as a positive photoresist material in combination with a photosensitizer or the like, a method of using the composition as a thermosetting resin material in combination with a curing agent, a method of using the composition as a negative photoresist material in combination with a curing agent and a photosensitive curing accelerator, and the like. Among them, a method of using a thermosetting resin material in combination with a curing agent and a method of using a negative photoresist material in combination with a curing agent and a photosensitive curing accelerator are preferable because of the characteristics of excellent fluidity and high heat resistance and dry etching resistance of a cured product.
Examples of the sensitizer include compounds having a quinonediazide group such as ester compounds or amide compounds of aromatic (poly) hydroxy compounds and quinonediazide-containing sulfonic acids such as naphthoquinone-1, 2-diazide-5-sulfonic acid, naphthoquinone-1, 2-diazide-4-sulfonic acid, and o-anthraquinone diazide sulfonic acid.
When the phenolic hydroxyl group-containing resin of the present invention is used for a positive photoresist, a positive photoresist composition can be produced by mixing the phenolic hydroxyl group-containing resin of the present invention, the other resin (C), the sensitizer, and the other additive, dissolving them in an organic solvent, and mixing them with a stirrer or the like. When the filler or pigment is contained, it is preferable to disperse or mix the filler or pigment using a dispersing device such as a dissolver, a homogenizer, or a triple roll mill.
As an example of lithography using the positive photoresist composition, for example, the positive photoresist composition is applied to an object to be subjected to lithography, such as a silicon substrate, a silicon carbide substrate, or a gallium nitride substrate, and prebaked at a temperature of 60 to 150 ℃. Next, the resist pattern is exposed to light, and then the exposed portion is dissolved in an alkali developer to produce a resist pattern.
When the curable composition of the present invention is used for a resist underlayer film, the phenolic hydroxyl group-containing resin of the present invention, the other resin (C), the curing agent, the curing accelerator, and the other additive are blended, dissolved in an organic solvent, and mixed by using a stirrer or the like to produce a resist underlayer film composition. When the filler or pigment is contained, it is preferable to disperse or mix the filler or pigment using a dispersing device such as a dissolver, a homogenizer, or a triple roll mill.
As an example of a method for producing a resist underlayer film from the resist underlayer film composition, a resist underlayer film is formed by, for example, the following methods: the resist underlayer film composition is applied to an object to be subjected to photolithography, such as a silicon substrate, a silicon carbide substrate, or a gallium nitride substrate, dried at a temperature of 100 to 200 ℃, and then cured by heating at a temperature of 250 to 400 ℃. Next, a resist pattern is formed on the underlayer film by a general photolithography process, and a resist pattern by a multilayer resist method can be formed by dry etching treatment with a halogen-based plasma gas or the like.
When the curable composition of the present invention is used for a permanent resist film, the phenolic hydroxyl group-containing resin of the present invention, the other resin (C), the curing agent, the curing accelerator, and the other additive are blended, dissolved in an organic solvent, and mixed by using a stirrer or the like to produce a composition for a resist underlayer film. When the filler or pigment is contained, it is preferable to disperse or mix the filler or pigment using a dispersing device such as a dissolver, a homogenizer, or a triple roll mill.
As an example of lithography using the composition for a permanent resist film, for example, the composition for a permanent resist film is applied to an object to be subjected to lithography, such as a silicon substrate, a silicon carbide substrate, or a gallium nitride substrate, and prebaked at a temperature of 60 to 150 ℃. Then, acid is generated by light through the resist pattern, and then, the resist pattern is thermally cured at a temperature of 110 to 210 ℃, and the unexposed portion is dissolved by an alkali developer, thereby forming a resist pattern. The permanent film formed from the composition for a permanent resist film can be suitably used for a package adhesive layer such as a solder resist, a sealing material, an underfill material, a circuit element, or an adhesive layer between an integrated circuit element and a circuit board, for example, in the case of a semiconductor device; as for thin displays represented by LCDs, OELDs, it can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, black matrices, spacers, and the like.
Examples
The present invention will be described in more detail below with reference to specific examples.
In this example, the purity of the compound and the content of each component in the resin were calculated from the area ratio of the graph obtained by GPC measurement under the following conditions. The weight average molecular weight (Mw), the number average molecular weight (Mn), and the polydispersity number (Mw/Mn) of the resin were values measured by GPC under the following conditions.
[ side Condition of GPC ]
A measuring device: HLC-8220GPC, manufactured by Tosoh corporation "
Column: shorex KF802 (8.0 mm. phi. times.300 mm), manufactured by Shorey electric corporation, and Shorex KF802 (8.0 mm. phi. times.300 mm), manufactured by Shorey electric corporation
"Shodex KF 803" (8.0 mm. phi. times.300 mm) manufactured by Showa Denko K.K. + and "Shodex KF 804" (8.0 mm. phi. times.300 mm) manufactured by Showa Denko K.K.)
Column temperature: 40 deg.C
A detector: RI (differential refractometer)
Data processing: "GPC-8020 model II version 4.30" manufactured by Tosoh corporation "
Developing solvent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Sample preparation: a tetrahydrofuran solution of 0.5 mass% in terms of resin solid content was filtered through a microfilter
Injection amount: 0.1mL
Standard sample: the following monodisperse polystyrene
(Standard sample: monodisperse polystyrene)
"A-500" made by Tosoh corporation "
"A-2500" made by Tosoh corporation "
"A-5000" manufactured by Tosoh corporation "
"F-1" made by Tosoh corporation "
"F-2" made by Tosoh corporation "
"F-4" made by Tosoh corporation "
"F-10" made by Tosoh corporation "
"F-20" made by Tosoh corporation "
Production example 1 production of Binaphthol Compound (a1)
Into a 2000ml 4-neck flask equipped with a condenser tube, 600 parts by mass of isopropyl alcohol, 576 parts by mass of 2-naphthol, 144 parts by mass of 41.5% formalin, and 10 parts by mass of a 48% aqueous sodium hydroxide solution were charged. After the temperature was raised from room temperature (about 25 ℃) to 100 ℃ for 2 hours while stirring, stirring was continued for 3 hours while refluxing. After cooling to room temperature, the precipitated reaction product was filtered under reduced pressure with a suction filter, and the cake-like residue was washed 5 times with 500 parts by mass of ion-exchanged water. The obtained cake was vacuum-dried at 80 ℃ for 72 hours to obtain 550 parts by mass of a white binaphthol compound (a 1). The obtained bisnaphthol compound (a1) had a number average molecular weight (Mn) of 351, a weight average molecular weight (Mw) of 352 and a polydispersity (Mw/Mn) of 1.00.
Example 1 production of phenolic hydroxyl group-containing resin (1)
Into a 1000ml 4-neck flask equipped with a condenser were charged 152 parts by mass of the obtained binaphthol compound (a1), 31 parts by mass of cyanuric chloride, and 500 parts by mass of methyl ethyl ketone, and the mixture was stirred and dissolved. Heating to 50-70 deg.c and adding triethylamine in 52 weight portions for 60 min. After the end of the dropwise addition, stirring was continued at 70 ℃ for 5 hours. Then, 200 parts by mass of water was added to dissolve triethylamine hydrochloride, liquid separation was performed, and the water layer was discarded. Further, after washing with the same amount of water for 2 times, methyl ethyl ketone was recovered by distillation, and reprecipitation was performed for 2 times with a mixed solvent of methanol/water (mass ratio) 10/1, and the precipitate was recovered and dried under reduced pressure to obtain 113 parts by mass of phenolic hydroxyl group-containing resin (1). The obtained phenolic hydroxyl group-containing resin (1) had a number average molecular weight (Mn) of 963, a weight average molecular weight (Mw) of 1,050, a polydispersity (Mw/Mn) of 1.09, and a content of components having a number average molecular weight (Mn) of 500 or less of 0.8%. The content of the polynuclear compound (a) in the phenolic hydroxyl group-containing resin (1) was 59.2%, and the total content of the polynuclear compound (a) and the compound (B) was 85.5%. The GPC diagram of the phenolic hydroxyl group-containing resin (1) is shown in fig. 1.
Example 2 production of phenolic hydroxyl group-containing resin (2)
92 parts by mass of a phenolic hydroxyl group-containing resin (2) was obtained in the same manner as in example 1, except that the amount of the bis-naphthol compound (a1) added in example 1 was changed from 152 parts by mass to 114 parts by mass. The obtained phenolic hydroxyl group-containing resin (2) had a content of 2.8% of components having a number average molecular weight (Mn) of 1,013, a weight average molecular weight (Mw) of 1,252, a polydispersity (Mw/Mn) of 1.24, and a number average molecular weight (Mn) of 500 or less. The phenolic hydroxyl group-containing resin (2)) had a polynuclear compound (a) content of 37.9% and a total content of the polynuclear compound (a) and the compound (B) of 61.5%.
Comparative production example 1 production of phenolic hydroxyl group-containing resin (1')
Into a 1L 4-neck flask equipped with a thermometer, a condenser and a stirrer were charged 144 parts by mass of 2-naphthol, 400 parts by mass of n-butanol, 96 parts by mass of water and 27.7 parts by mass of 92% paraformaldehyde. Subsequently, 2.4 parts by mass of p-toluenesulfonic acid monohydrate was added under stirring. Then, the temperature was raised to 100 ℃ with stirring, and the reaction was carried out for 2 hours. After the reaction was completed, 200 parts by mass of n-butanol was added, the solution in the system was washed with water until the washing water became neutral, and then the solvent was removed from the organic layer under heating and reduced pressure to obtain 153g of a phenolic hydroxyl group-containing resin (' 1). GPC of the phenolic hydroxyl group-containing resin (1') showed a component content of 5.2 mass% with a number average molecular weight (Mn) of 955, a weight average molecular weight (Mw) of 1,427, a polydispersity (Mw/Mn) of 1.49, and Mn of 500 or less.
Comparative production example 2 production of phenolic hydroxyl group-containing resin (2')
Into a 1000ml 4-neck flask equipped with a condenser were charged 152 parts by mass of the obtained binaphthol compound (a1), 31 parts by mass of cyanuric chloride, and 500 parts by mass of methyl ethyl ketone, and the mixture was stirred and dissolved. Heating to 50-70 deg.c and adding triethylamine in 52 weight portions for 60 min. After the end of the dropwise addition, stirring was continued at 70 ℃ for 5 hours. Then, 200 parts by mass of water was added to dissolve triethylamine hydrochloride, liquid separation was performed, and the water layer was discarded. After washing with water in the same amount for 2 times, methyl ethyl ketone was recovered by distillation and dried under reduced pressure to obtain 124 parts by mass of a phenolic hydroxyl group-containing resin (2'). The obtained phenolic hydroxyl group-containing resin (2') had a content of components having a number average molecular weight (Mn) of 958, a weight average molecular weight (Mw) of 1,258, a polydispersity (Mw/Mn) of 1.31, and a number average molecular weight (Mn) of 500 or less of 12.3%. The content of the polynuclear compound (a) in the phenolic hydroxyl group-containing resin (1) was 51.4%, and the total content of the polynuclear compound (a) and the compound (B) was 72.0%.
Examples 3 and 4 and comparative examples 1 and 2
The phenolic hydroxyl group-containing resins obtained in examples 1 and 2 and comparative production examples 1 and 2 were evaluated in accordance with the following procedures. The results are shown in Table 1.
Production of thermosetting composition
1.6 parts by mass of a phenolic hydroxyl group-containing resin, 0.4 part by mass of a curing agent ("1, 3,4, 6-tetrakis (methoxymethyl) glycoluril", manufactured by Tokyo chemical industry Co., Ltd.), and 0.1 part by mass of p-toluenesulfonic acid were dissolved in 100 parts by mass of propylene glycol monomethyl ether acetate, and the resulting solution was filtered through a 0.2 μm membrane filter to obtain a thermosetting composition.
Evaluation of sublimation resistance
The thermosetting composition thus obtained was applied to a 5-inch silicon wafer by a spinner, and dried on a hot plate at 110 ℃ for 180 seconds in an atmosphere having an oxygen concentration of 20% by volume. Subsequently, the cured film was heated and cured at 210 ℃ for 60 seconds to obtain a cured coating film having a film thickness of 0.3. mu.m. The mass of the wafer before and after the curing process at 210 ℃ was measured, and the amount of mass reduction during the curing process was calculated and evaluated according to the following criteria.
A: the mass loss in the curing process at 210 ℃ for 60 seconds is 3% or less
B: the mass reduction in the curing process at 210 ℃ for 60 seconds is more than 3 percent
Evaluation of Heat resistance
The thermosetting composition thus obtained was applied to a 5-inch silicon wafer by a spinner, and dried on a hot plate at 110 ℃ for 180 seconds in an atmosphere having an oxygen concentration of 20% by volume. Subsequently, the cured film was heated and cured at 210 ℃ for 60 seconds to obtain a cured coating film having a film thickness of 0.3. mu.m. The obtained cured coating film was scraped off from the wafer, and the amount of mass loss at 240 ℃ when the temperature was raised under the following conditions was measured using a differential thermal weight simultaneous measurement apparatus (TG/DTA), and evaluated according to the following criteria.
[ conditions for measuring amount of mass loss ]
The measuring instrument: "TG/DTA 6200" manufactured by Seiko Instruments Inc "
Measurement range: room temperature to 400 DEG C
Temperature rise rate: 10 ℃/min
[ evaluation standards ]
A: the mass loss at 240 ℃ is 5 mass% or less
B: the mass decrease at 240 ℃ is more than 5 mass%
Evaluation of fluidity
Is formed with
On a silicon wafer having a hole pattern with a depth of 300nm and a diameter of 5 inches, the thermosetting composition obtained before application by a spinner was dried on a hot plate at 110 ℃ for 180 seconds in an atmosphere with an oxygen concentration of 20% by volume, and then cured by heating at 210 ℃ for 60 seconds to obtain a cured coating film with a thickness of 0.3. mu.m. The silicon wafer was cut on the line of the hole pattern, and the cross section was observed with a laser microscope ("VK-X200" manufactured by KEYENCE CORPORATION) to evaluate whether or not the inflow of the curable composition into the hole pattern was sufficient under the following conditions.
A: the whole hole is filled with the solidified material
B: the entire hole may not be filled with the cured product and may have a void.
Evaluation of Dry etching resistance
A cured coating was provided on a silicon wafer in the same manner as in the evaluation of heat resistance. Using an etching apparatus ("EXAM" manufactured by Shen Steel Mill Co., Ltd.), CF4/Ar/O2(CF4: 40 mL/min, Ar: 20 mL/min, O2: 5 mL/min, pressure: 20Pa, RF output: 200W, processing time: 40 seconds, temperature: the cured coating film on the wafer was etched at 15 ℃. The film thickness before and after the etching treatment at this time was measured, and the etching rate was calculated to evaluate the etching resistance. The evaluation criteria are as follows.
A: etching rate of 150 nm/min or less
B: etching rate exceeding 150 nm/min
[ Table 1]
TABLE 1
| Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| Phenolic hydroxyl group-containing resin | (1) | (2) | (1’) | (2’) |
| Resistance to sublimation | A | A | B | B |
| Heat resistance | A | A | B | B |
| Fluidity of the resin | A | A | B | A |
| Dry etching resistance | A | A | A | A |
Examples 5 and 6 and comparative examples 3 and 4
The phenolic hydroxyl group-containing resins obtained in examples 1 and 2 and comparative production examples 1 and 2 were evaluated in accordance with the following procedures. The results are shown in Table 2.
Production of Photocurable composition
1.6 parts by mass of a phenolic hydroxyl group-containing resin, 0.4 parts by mass of a curing agent (1, 3,4, 6-tetrakis (methoxymethyl) glycoluril, manufactured by Tokyo chemical industry Co., Ltd.), and 0.2 parts by mass of a photoacid generator were dissolved in 100 parts by mass of propylene glycol monomethyl ether acetate, and the resulting solution was filtered with a 0.2 μm membrane filter to obtain a thermosetting composition.
As the photoacid generator, SANWA CHEMICAL co was used, ltd, product "TFE-Triazine" (2- [2- (furan-2-yl) ethynyl ] -4, 6-bis (trichloromethyl) -s-Triazine).
Evaluation of alkali developability [ ADR (nm/s) ]
The photosensitive composition obtained above was coated on a 5-inch silicon wafer with a thickness of about 1 μm by a spin coater, and dried on a hot plate at 110 ℃ for 60 seconds. This was immersed in an alkali developing solution (2.38% aqueous tetramethylammonium hydroxide solution) for 60 seconds, and then dried on a hot plate at 110 ℃ for 60 seconds. The film thickness before and after immersion in the developer was measured, and the difference was divided by 60 to obtain a value as the alkali developability [ ADR (nm/s) ].
Evaluation of light sensitivity
The photosensitive composition obtained above was coated on a 5-inch silicon wafer with a thickness of about 1 μm by a spin coater, and dried on a hot plate at 110 ℃ for 60 seconds. On the wafer, let the line-space (line and space) be 1: 1. and the line width is in the range of 1 μm in 1 ~ 10 μm resist pattern corresponding to the mask close contact, using ghi lamp (USHIO INC manufacturing "multi light") irradiation ghi line, at 140 degrees C, 60 seconds conditions for heat treatment. Subsequently, the substrate was immersed in an alkali developing solution (2.38% aqueous tetramethylammonium hydroxide solution) for 60 seconds, and then dried on a hot plate at 110 ℃ for 60 seconds.
The exposure amount to ghi line is from 30mJ/cm2At 5mJ/cm2The exposure amount (Eop exposure amount) capable of faithfully reproducing the line width of 3 μm when the width of (1) is increased was evaluated.
Evaluation of resolution
The photosensitive composition obtained above was coated on a 5-inch silicon wafer with a thickness of about 1 μm by a spin coater, and dried on a hot plate at 110 ℃ for 60 seconds. A photomask was placed on the wafer, and ghi line 200mJ/cm was irradiated2After curing at 210 ℃ for 180 seconds, an alkali development operation was carried out. The pattern state was confirmed with a laser microscope ("VK-X200" manufactured by KEYENCE CORPORATION), and the evaluation was performed using a as a when the pattern state could be resolved at L/S of 5 μm and using B as a when the pattern state could not be resolved at L/S of 5 μm.
[ Table 2]
TABLE 2
Claims (6)
1. A phenolic hydroxyl group-containing resin which is a reaction product of a binaphthol compound (a1) represented by the following structural formula (1) and cyanuric halide (a2) and has a polydispersity Mw/Mn in the range of 1.01 to 1.30 and a content of a component having a number average molecular weight Mn of 500 or less in the range of 0.1 to 3.0% as calculated from an area ratio in a GPC chart,
wherein X represents a hydrocarbon group having 1 to 14 carbon atoms, and R1Each independently is any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group and an aralkyl group, m is 0, 1 or 2, and n is 0 or an integer of 1 to 4.
2. The phenolic hydroxyl group-containing resin according to claim 1, which contains, as an essential component, a polynuclear compound (A) represented by the following structural formula (2) in an amount of 35% or more as calculated from an area ratio in a GPC chart,
wherein X represents a hydrocarbon group having 1 to 14 carbon atoms, and R1Each independently is any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group and an aralkyl group, m is 0, 1 or 2, and n is 0 or an integer of 1 to 4.
3. The phenolic hydroxyl group-containing resin according to claim 1, which comprises a polynuclear compound (A) represented by the following structural formula (2) and a compound (B) having one phenolic hydroxyl group in the structural formula (2) substituted by the following structural formula (3) as essential components, and the total content of the both is in the range of 50 to 99% as calculated from the area ratio in a GPC chart,
in the formula (2), X represents a C1-14 alkyl group, R1Each independently is any one of aliphatic hydrocarbon group, alkoxy group, halogen atom, aryl group and aralkyl group, m is 0, 1 or 2, n is 0 or an integer of 1 to 4,
in the formula (3), X represents a C1-14 alkyl group, R1Each independently is any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group and an aralkyl group, R is a halogen atom, m is 0, 1 or 2, and n is 0 or an integer of 1 to 4.
4. A curable composition comprising the phenolic hydroxyl group-containing resin according to any one of claims 1 to 3 and a curing agent.
5. A cured product of the curable composition according to claim 4.
6. The curable composition according to claim 4, which is a resist material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-197203 | 2016-10-05 | ||
| JP2016197203 | 2016-10-05 | ||
| PCT/JP2017/034062 WO2018066372A1 (en) | 2016-10-05 | 2017-09-21 | Phenolic hydroxyl group-containing resin and resist material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109790264A CN109790264A (en) | 2019-05-21 |
| CN109790264B true CN109790264B (en) | 2021-09-21 |
Family
ID=61832133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780060031.8A Active CN109790264B (en) | 2016-10-05 | 2017-09-21 | Phenolic hydroxyl group-containing resin and resist material |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6341349B1 (en) |
| KR (1) | KR102432123B1 (en) |
| CN (1) | CN109790264B (en) |
| TW (1) | TWI772327B (en) |
| WO (1) | WO2018066372A1 (en) |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4678453B2 (en) * | 2000-05-31 | 2011-04-27 | Ｄｉｃ株式会社 | Polyvalent hydroxy compound and production method thereof, epoxy resin composition and cured product thereof |
| JP4678455B2 (en) * | 2000-06-29 | 2011-04-27 | Ｄｉｃ株式会社 | Polyvalent hydroxy compound and production method thereof, epoxy resin composition and cured product thereof |
| JP4237558B2 (en) * | 2003-06-30 | 2009-03-11 | 株式会社日清製粉グループ本社 | Method for producing frozen bread dough |
| WO2005114331A1 (en) * | 2004-05-21 | 2005-12-01 | Mitsubishi Gas Chemical Company, Inc. | Resist compound and resist composition |
| JP2007291246A (en) * | 2006-04-25 | 2007-11-08 | Mitsubishi Chemicals Corp | Azo dye, composition for anisotropic dye film having the dye, anisotropic dye film, and polarizing element |
| JP4586039B2 (en) | 2007-04-06 | 2010-11-24 | 大阪瓦斯株式会社 | Phenolic resin and method for producing the same |
| JP5229879B2 (en) * | 2007-06-08 | 2013-07-03 | 日本化薬株式会社 | (Meth) acrylate compound, resin composition containing the same, and cured product thereof |
| WO2009038126A1 (en) * | 2007-09-20 | 2009-03-26 | Nissan Chemical Industries, Ltd. | Resist underlayer film forming composition containing branched polyhydroxystyrene |
| JP5549107B2 (en) | 2009-04-20 | 2014-07-16 | Ｄｉｃ株式会社 | Method for producing novolac resin |
| WO2012017816A1 (en) * | 2010-08-06 | 2012-02-09 | Dic株式会社 | Novel phenol resin, curable resin composition, cured article thereof, and printed wiring board |
| JP2012219090A (en) * | 2011-04-14 | 2012-11-12 | Shikoku Chem Corp | Isocyanurate compound |
| JP5965733B2 (en) | 2012-06-12 | 2016-08-10 | 富士フイルム株式会社 | Pattern forming method and electronic device manufacturing method |
| JP6244134B2 (en) | 2013-08-02 | 2017-12-06 | 富士フイルム株式会社 | Pattern forming method and electronic device manufacturing method |
-
2017
- 2017-09-19 TW TW106132111A patent/TWI772327B/en active
- 2017-09-21 KR KR1020197000935A patent/KR102432123B1/en active IP Right Grant
- 2017-09-21 JP JP2018506623A patent/JP6341349B1/en active Active
- 2017-09-21 CN CN201780060031.8A patent/CN109790264B/en active Active
- 2017-09-21 WO PCT/JP2017/034062 patent/WO2018066372A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| TW201815890A (en) | 2018-05-01 |
| KR102432123B1 (en) | 2022-08-16 |
| JPWO2018066372A1 (en) | 2018-10-04 |
| TWI772327B (en) | 2022-08-01 |
| JP6341349B1 (en) | 2018-06-13 |
| KR20190067151A (en) | 2019-06-14 |
| CN109790264A (en) | 2019-05-21 |
| WO2018066372A1 (en) | 2018-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10414850B2 (en) | Resin containing phenolic hydroxyl groups, and resist film | |
| TWI763715B (en) | Resin and resist material containing phenolic hydroxyl group | |
| JP6816471B2 (en) | Phenolic hydroxyl group-containing compounds and resist materials | |
| CN113348188B (en) | Phenolic hydroxyl group-containing resin, photosensitive composition, resist film, curable composition, and cured product | |
| JP5939450B1 (en) | Phenolic hydroxyl group-containing resin, production method thereof, photosensitive composition, resist material, coating film, curable composition and cured product thereof, and resist underlayer film | |
| JP6274366B1 (en) | Novolac resin and resist material | |
| JP6269904B1 (en) | Method for producing novolac resin | |
| CN109790264B (en) | Phenolic hydroxyl group-containing resin and resist material | |
| JP6590085B2 (en) | Phenolic hydroxyl group-containing resin and resist material | |
| JP7380951B2 (en) | Phenolic hydroxyl group-containing resin | |
| JP6863077B2 (en) | Dendrimer type resin and resist material | |
| US20180334523A1 (en) | Novolac resin and resist film | |
| JP6590084B2 (en) | Phenolic hydroxyl group-containing resin and resist material | |
| JP6328350B2 (en) | Novolac resin and resist material | |
| TW201815949A (en) | Resin composition and resist film | |
| JP2023022510A (en) | Epoxy resin, photosensitive resin composition, resist film. curable composition, and cured film | |
| JP6828279B2 (en) | Novolac type resin and resist film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |