WO2012115029A1 - Photoresist resin composition - Google Patents

Photoresist resin composition Download PDF

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Publication number
WO2012115029A1
WO2012115029A1 PCT/JP2012/053943 JP2012053943W WO2012115029A1 WO 2012115029 A1 WO2012115029 A1 WO 2012115029A1 JP 2012053943 W JP2012053943 W JP 2012053943W WO 2012115029 A1 WO2012115029 A1 WO 2012115029A1
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WIPO (PCT)
Prior art keywords
photoresist
parts
phenol resin
composition
resin composition
Prior art date
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PCT/JP2012/053943
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French (fr)
Japanese (ja)
Inventor
今村　裕治
Original Assignee
住友ベークライト株式会社
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Application filed by 住友ベークライト株式会社 filed Critical 住友ベークライト株式会社
Priority to CN201280006326.4A priority Critical patent/CN103329042B/en
Priority to KR1020137020868A priority patent/KR20140043322A/en
Priority to JP2013501019A priority patent/JP6003881B2/en
Publication of WO2012115029A1 publication Critical patent/WO2012115029A1/en

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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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
    • 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
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/23—Azo-compounds
    • C08K5/235—Diazo and polyazo compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • the present invention relates to a photoresist resin composition.
  • This application claims priority based on Japanese Patent Application No. 2011-039818 filed in Japan on February 25, 2011 and Japanese Patent Application No. 2011-115661 filed in Japan on May 24, 2011. Is incorporated herein by reference.
  • a fine circuit pattern such as a liquid crystal display device circuit or a semiconductor integrated circuit is formed into a desired shape pattern through the steps described below.
  • a photoresist composition is uniformly coated or applied on the insulating film or conductive metal film.
  • the coated photoresist composition is exposed and developed in the presence of a mask having a predetermined shape.
  • the metal film or the insulating film is removed using the patterned photoresist film as a mask, and then the remaining photoresist film is removed to form a fine circuit on the substrate.
  • Such a photoresist composition is classified into a negative type and a positive type depending on whether the exposed portion or the photoresist film is soluble or insoluble.
  • a photosensitizer having a quinonediazide group such as a naphthoquinonediazide compound and an alkali-soluble resin (for example, a novolac-type phenolic resin) are used.
  • a positive photoresist composition having such a composition exhibits high resolving power due to development with an alkaline solution after exposure. For this reason, this positive photoresist composition is used for the production of semiconductors such as IC and LSI, the production of liquid crystal display screen devices such as LCDs, and the production of printing masters.
  • the novolac type phenol resin has many aromatic rings and thus has high heat resistance against plasma dry etching. Therefore, a large number of positive photoresists containing a novolac type phenol resin and a naphthoquinone diazide photosensitizer have been developed and put to practical use, and have achieved great results.
  • photoresist compositions for liquid crystal display device circuits include sensitivity of the formed resist film, development contrast, resolution, adhesion to the substrate, residual film ratio, heat resistance, and circuit line width.
  • An example is CD uniformity.
  • a photoresist composition for a thin film transistor liquid crystal display device circuit requires a high sensitivity for a resist film formed therefrom. Since the substrate of the thin film transistor liquid crystal display device circuit has a large area, if the sensitivity of the resist film is low, the exposure time in the production line becomes long and the production efficiency is lowered. Further, the sensitivity and the remaining film rate are in an inversely proportional relationship, and the higher the sensitivity, the lower the remaining film rate tends to decrease.
  • a novolac type phenol resin obtained by reacting m / p-cresol and formaldehyde in the presence of an acid catalyst is generally used. Then, in order to adjust or improve the characteristics of the photoresist, the ratio of m / p-cresol used as the raw material phenols, the type of the raw material phenols, the molecular weight of the phenol resin, the molecular weight distribution, etc. are studied. I came. In Patent Document 1 below, in order to improve the photoresist characteristics, a positive photoresist in which a high-ortho-type novolac resin with a small amount of binuclear components is blended is used.
  • Patent Document 1 discloses a resist that is excellent in resolving power (pattern shape), heat resistance, and sensitivity, and that is less susceptible to oven contamination due to a low molecular weight volatile component during the resist coating drying process, and also has excellent workability.
  • Patent Document 2 discloses a method of fractionating a novolac resin to improve photoresist characteristics. Such content is well known to those skilled in the art. In general, improvement of the sensitivity of the photoresist is achieved by lowering the molecular weight of the novolak resin. However, this method has a problem that the heat resistance of the resist film is lowered or the remaining film ratio of the unexposed portion is lowered.
  • An object of the present invention is to provide a resin composition for a photoresist having good sensitivity / resolution, high residual film property, and other characteristics that are not inferior to those of general-purpose ones.
  • Embodiments described herein relate generally to a photoresist resin composition.
  • the photoresist resin composition of the embodiment of the present invention includes one or two selected from metacresol, paracresol, 3,5-xylenol and 2,3,5-trimethylphenol, and aldehydes in the presence of an acid catalyst.
  • a high ortho novolak type phenol resin obtained by reaction at a temperature of 110-220 ° C., a naphthoquinonediazide derivative and a solvent are contained.
  • the high ortho novolac type phenol resin used in the embodiment of the present invention is one or two selected from metacresol, paracresol, 3,5-xylenol and 2,3,5-trimethylphenol, and aldehydes as acid catalysts. It is a resin obtained by reacting at a temperature of 110-220 ° C. in the presence. When the reaction is first performed at a high temperature of 110 to 220 ° C., the reaction in the vicinity of the phenolic hydroxyl group occurs preferentially, and therefore, a resin having a higher ortho-ratio than the usual one can be easily obtained.
  • 3,5-xylenol or 2,3,5-trimethylphenol tends to increase the ortho ratio because the reaction at the para-position is inhibited by the steric hindrance of the methyl group.
  • This reaction is preferably carried out at 110-220 ° C, more preferably in the range of 120-150 ° C.
  • a high ortho novolac type phenol resin having an ortho conversion rate of 23% or more can be obtained.
  • the weight ratio of the metacresol and paracresol used in the embodiment of the present invention is preferably 75:25 to 50:50, and more preferably 70:30 to 55:45. It is preferable that the weight ratio is in the above range because the resolution and the remaining film ratio are improved in a high sensitivity region.
  • the total amount of the metacresol and paracresol used in the embodiment of the present invention and the weight ratio of one or two selected from 3,5-xylenol and 2,3,5-trimethylphenol are 95: 5 to 60:40. It is preferable that the ratio is 90: 7 to 70:30. It is preferable that the weight ratio is in the above range because the resolution and the remaining film ratio are improved in a high sensitivity region.
  • aldehydes used for the said high ortho novolak type phenol resin For example, formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, benzaldehyde, salicylaldehyde, etc. are mentioned. Among these, formaldehyde, paraformaldehyde, acetaldehyde, and salicylaldehyde are preferable. Thereby, when used as a photoresist composition, high sensitivity can be achieved.
  • the formaldehyde source is not particularly limited, but any formaldehyde can be used as long as it generates formaldehyde, such as formalin (aqueous solution), paraformaldehyde, hemi-formal with alcohols, and trioxane.
  • an acid catalyst is generally used.
  • the acid catalyst for synthesizing the high ortho novolak type phenol resin is not particularly limited, and examples thereof include weak acids such as organic carboxylic acids such as oxalic acid and acetic acid. Among these, it can also be used individually or in mixture of 2 or more types.
  • the amount of the acid catalyst used is not particularly limited, but is preferably 0.01 to 5% by weight based on the phenols. Further, when a photoresist resin is used in the photoresist composition, a small amount of catalyst remains in the resin because of the characteristics of the photoresist.
  • reaction solvent used for embodiment of this invention it is a moderately non-polar solvent, for example, hexane, benzene, xylene, etc. are mentioned. By using these, it becomes possible to keep the ortho-ratio of the resin high.
  • the ortho-formation rate of the high ortho novolak type phenol resin used in the embodiment of the present invention is preferably 23-50%, more preferably 25-45%. These ortho-conversion rates can generally be analyzed using 13 C-NMR. Thereby, when used as a photoresist, high sensitivity and high residual film ratio can be maintained, and high resolution can be obtained.
  • the high ortho novolac type phenol resin used in the embodiment of the present invention preferably has a weight average molecular weight measured by GPC of 1,000 to 10,000, more preferably 2500 to 8,000, and the weight average molecular weight is within the above range. By doing so, the sensitivity, the remaining film rate, and the resolution can be improved.
  • the weight average molecular weight was calculated based on a calibration curve prepared using a polystyrene standard. GPC measurement can be performed using tetrahydrofuran as an elution solvent, a flow rate of 1.0 ml / min, and a column temperature of 40 ° C. using a differential refractometer as a detector.
  • An apparatus that can be used is, for example, 1) Body: “HLC-8020” manufactured by TOSOH 2) Detector: “UV-8011” manufactured by TOSOH with wavelength set to 280 nm 3) Analytical column: “SHODEX KF-802, KF-803, KF-805” manufactured by Showa Denko KK can be used.
  • the photoresist resin composition of the embodiment of the present invention preferably contains 21.7 to 28.3 g / 100 g of a high ortho novolac type phenol resin as a weight ratio (g / 100 g) to the weight of the solvent.
  • a more preferred high ortho novolak type phenol resin content is 25.0 to 27.0 g / 100 g.
  • a diazonaphthoquinone-5-sulfonic acid chloride or diazonaphthoquinone-4-sulfonic acid derivative such as a ballast such as an alcohol or a phenol derivative and a tetrahydrofuran or dioxane or the like is used. It can be obtained by esterification in a solvent in the presence of a basic catalyst such as triethylamine.
  • a basic catalyst such as triethylamine.
  • polyhydroxybenzophenone such as hydroxybenzophenone and dihydroxybenzophenone, naphthol, hydroquinone, pyrogallol, bisphenol A, p-cresol polymer, and derivatives thereof.
  • the esterification rate can be controlled by adjusting the molar ratio of diazonaphthoquinone sulfonic acid chloride to ballast.
  • These naphthoquinone diazides may be one kind or a mixture of two or more kinds.
  • the photoresist resin composition of the embodiment of the present invention preferably contains 3.3 to 9.9 g / 100 g of naphthoquinonediazide derivative as a weight ratio (g / 100 g) to the weight of the solvent.
  • a more preferred naphthoquinonediazide derivative content is 4.6 to 6.6 g / 100 g.
  • the solvent to be blended in the composition of the embodiment of the present invention is not particularly limited as long as it dissolves the high ortho novolak type phenol resin and the naphthoquinone diazide derivative. In the embodiment of the present invention, these components are used dissolved in a solvent.
  • Examples of the solvent used in the embodiment of the present invention include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, di Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol 20-3-monomethyl ether, methyl pyruvate, ethyl pyruvate , Methyl-3-methoxypropionate and the like can be used alone or in combination.
  • composition of the embodiment of the present invention includes, if necessary, a stabilizer such as an antioxidant, a plasticizer, a surfactant, an adhesion improver, a dissolution accelerator and the like.
  • a stabilizer such as an antioxidant, a plasticizer, a surfactant, an adhesion improver, a dissolution accelerator and the like.
  • Various additives may be used.
  • the method for preparing the composition according to the embodiment of the present invention is not particularly limited. However, in the case where a filler and a pigment are not added to the composition, the above-described components may be mixed and stirred by a usual method.
  • the pigment when added, for example, it may be dispersed and mixed using a dispersing device such as a dissolver, a homogenizer, or a three roll mill. Moreover, you may further filter using a mesh filter, a membrane filter, etc. as needed.
  • composition of the embodiment of the present invention thus obtained is exposed through a mask, a structural change occurs in the composition in the exposed area, and the solubility in an alkali developer is increased. Can be promoted. On the other hand, in the non-exposed area, low solubility in an alkali developer is maintained, so that a resist function can be imparted due to the difference in solubility thus generated.
  • the naphthoquinone diazide derivative in the composition undergoes a chemical change by light irradiation, and is dissolved in an alkali developer together with a novolac resin in a later development step and exposed.
  • the target pattern can be obtained by development.
  • Synthesis of high ortho novolac type phenol resin (Synthesis Example 1) A 3 L 4-neck flask equipped with a stirrer, thermometer and heat exchanger was charged with 600 parts of m-cresol, 400 parts of p-cresol, 100 parts of 3,5-xylenol, 200 parts of hexane, and 5.5 parts of oxalic acid. After the temperature was raised to 130 ° C., 547 parts of 37% formalin was gradually added over 3 hours, followed by reaction for 2 hours while dehydrating. Thereafter, dehydration was performed under normal pressure to an internal temperature of 170 ° C., and dehydration / demonomerization was further performed under reduced pressure of 9.3 ⁇ 10 3 Pa to 200 ° C. to obtain 950 parts of phenol resin B having a weight average molecular weight of 4200.
  • composition for photoresist (Example 1) After dissolving 20 parts of phenol resin for photoresist obtained in Synthesis Example 1 and 4 parts of 2,3,4-trihydroxy-benzophenone ester of naphthoquinone 1,2-diazide-5-sulfonic acid in 76 parts of PGMEA, Filtration was performed using a 1 ⁇ m membrane filter to prepare a photoresist composition.
  • Example 2 A composition was prepared in the same manner as in Example 1 except that the photoresist phenol resin obtained in Synthesis Example 2 was used as the photoresist phenol resin.
  • Example 3 A composition was prepared in the same manner as in Example 1 except that the photoresist phenol resin obtained in Synthesis Example 3 was used as the photoresist phenol resin.
  • Example 4 A composition was prepared in the same manner as in Example 1 except that the photoresist phenol resin obtained in Synthesis Example 4 was used as the photoresist phenol resin.
  • Example 1 A composition was prepared in the same manner as in Example 1 except that the photoresist phenol resin obtained in Comparative Synthesis Example 1 was used as the photoresist phenol resin.
  • Comparative Example 2 A composition was prepared in the same manner as in Example 1 except that the photoresist phenol resin obtained in Comparative Synthesis Example 2 was used as the photoresist phenol resin.
  • Comparative Example 3 A composition was prepared in the same manner as in Example 1 except that the photoresist phenol resin obtained in Comparative Synthesis Example 3 was used as the photoresist phenol resin.
  • Comparative Example 4 A composition was prepared in the same manner as in Example 1 except that the photoresist phenol resin obtained in Comparative Synthesis Example 4 was used as the photoresist phenol resin.
  • a photoresist composition was applied on a 3-inch silicon wafer with a spin coater so as to have a thickness of about 1 ⁇ m, and dried on a hot plate at 110 ° C. for 100 seconds.
  • the wafer was immersed in a developing solution (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, washed with water, and dried on a hot plate at 110 ° C. for 100 seconds.
  • the ratio of the film thickness after development to the film thickness before development was expressed as a percentage, and was defined as the remaining film ratio.
  • the degree of remaining film (resistance) when used as a photosensitizer and a photoresist can be understood, and the higher the numerical value, the higher the remaining film rate.
  • the photoresist composition was applied to a 3-inch silicon wafer with a spin coater so as to have a thickness of about 1.5 ⁇ m, and dried on a hot plate at 110 ° C. for 100 seconds. Then repeated test chart mask on the silicon wafer was irradiated 5mJ / cm 2, 10mJ / cm 2, 15mJ / cm 2 of ultraviolet light, respectively, using a developing solution (2.38% tetramethylammonium hydroxide aqueous solution) 60 Developed for seconds. The obtained pattern was evaluated according to the following criteria by observing the pattern shape with a scanning electron microscope. A An image can be formed at 10 mJ / cm 2 .
  • an image can be formed at 20 mJ / cm 2.
  • An image cannot be formed at C 20 mJ / cm 2 , and an image can be formed at 25 mJ / cm 2 .
  • the photoresist composition prepared above was applied onto a silicon wafer using a spin coater and pre-baked at 110 ° C. for 100 seconds to form a resist film having a thickness of 1.5 ⁇ m. This was exposed using ultraviolet rays through a pattern mask in which a line width of 100 to 1 ⁇ m was engraved. Immediately after the exposure, the film was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, washed with water and dried to obtain a positive pattern. At that time, the minimum resolution of the photoresist pattern that can be resolved with a constant exposure amount is defined as the limit resolution.
  • Examples 1 to 4 are photoresist resin compositions of the present invention, and have an excellent remaining film ratio and resolution as compared with Comparative Examples 1 to 4 which are not the resin composition of the present invention. I was able to prove it.
  • Comparative Example 1 2,3-xylenol was used instead of 3,5-xylenol, but the residual film ratio was low and the limit resolution was high.
  • Comparative Examples 2 and 3 2,5-xylenol was used instead of 3,5-xylenol, but the residual film ratio was low and the limit resolution was high.
  • Comparative Example 4 neither xylenol nor trimethylphenol was used, but the remaining film rate was low and the limit resolution was also high.
  • the resin composition for photoresists of the present invention has good thermal stability, high sensitivity, high resolution, and high residual film properties, so it is suitable for manufacturing fine circuits of liquid crystal display circuits and semiconductor integrated circuits. Can be used.

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

Abstract

Provided is a photoresist resin composition having excellent sensitivity and resolution and high film retention, as well as other properties that are at least commensurate with those of the commonly used compositions. The photoresist resin composition contains a high-ortho-novolac phenol resin, a naphthoquinone diazide derivative, and a solvent, the high-ortho-novolac phenol resin being obtained by reacting an aldehyde and one or two compounds selected from meta-cresol, para-cresol, 3,5-xylenol, and 2,3,5-trimethylphenol in the presence of an acid catalyst at a temperature of 110-220°C.

Description

フォトレジスト用樹脂組成物Resin composition for photoresist
　本発明はフォトレジスト用樹脂組成物に関する。
　本願は、２０１１年２月２５日に日本に出願された特願２０１１－０３９８１８号、および２０１１年５月２４日に日本に出願された特願２０１１－１１５６６１に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a photoresist resin composition.
This application claims priority based on Japanese Patent Application No. 2011-039818 filed in Japan on February 25, 2011 and Japanese Patent Application No. 2011-115661 filed in Japan on May 24, 2011. Is incorporated herein by reference.
　液晶表示装置回路または半導体集積回路のように微細な回路パターンは、以下に説明する工程を経て目的とする形状パターンに作られる。まず、基板上に絶縁膜または導電性金属膜を形成する。次に、この絶縁膜又は導電性金属膜上にフォトレジスト組成物を均一にコーティングまたは塗布する。次に、所定の形状のマスク存在下でコーティングされたフォトレジスト組成物を露光して現像する。その後、パターンが形成されたフォトレジスト膜をマスクとして用いて金属膜または絶縁膜を除去した後、残存するフォトレジスト膜を除去して基板上に微細回路を形成する。このようなフォトレジスト組成物は露光される部分やフォトレジスト膜が可溶か不溶によって、ネガ形とポジ形に分類される。 A fine circuit pattern such as a liquid crystal display device circuit or a semiconductor integrated circuit is formed into a desired shape pattern through the steps described below. First, an insulating film or a conductive metal film is formed on the substrate. Next, a photoresist composition is uniformly coated or applied on the insulating film or conductive metal film. Next, the coated photoresist composition is exposed and developed in the presence of a mask having a predetermined shape. Thereafter, the metal film or the insulating film is removed using the patterned photoresist film as a mask, and then the remaining photoresist film is removed to form a fine circuit on the substrate. Such a photoresist composition is classified into a negative type and a positive type depending on whether the exposed portion or the photoresist film is soluble or insoluble.
　一般にポジ型フォトレジスト組成物には、ナフトキノンジアジド化合物等のキノンジアジド基を有する感光剤とアルカリ可溶性樹脂（例えば、ノボラック型フェノ－ル樹脂）とが用いられている。このような組成からなるポジ型フォトレジスト組成物は、露光後にアルカリ溶液による現像によって高い解像力を示す。そのため、このポジ型フォトレジスト組成物は、ＩＣ、ＬＳＩ等の半導体製造、ＬＣＤ等の液晶表示画面機器の製造及び印刷原版の製造等に利用されている。また、ノボラック型フェノ－ル樹脂は、芳香環を多く持つので、プラズマドライエッチングに対し、高い耐熱性を有している。そのため、これまでノボラック型フェノ－ル樹脂とナフトキノンジアジド系感光剤とを含有する数多くのポジ型フォトレジストが開発、実用化され、大きな成果を挙げてきている。 Generally, in a positive photoresist composition, a photosensitizer having a quinonediazide group such as a naphthoquinonediazide compound and an alkali-soluble resin (for example, a novolac-type phenolic resin) are used. A positive photoresist composition having such a composition exhibits high resolving power due to development with an alkaline solution after exposure. For this reason, this positive photoresist composition is used for the production of semiconductors such as IC and LSI, the production of liquid crystal display screen devices such as LCDs, and the production of printing masters. In addition, the novolac type phenol resin has many aromatic rings and thus has high heat resistance against plasma dry etching. Therefore, a large number of positive photoresists containing a novolac type phenol resin and a naphthoquinone diazide photosensitizer have been developed and put to practical use, and have achieved great results.
　液晶表示装置回路用フォトレジスト組成物の実用面での重要な特性としては、形成されたレジスト膜の感度、現像コントラスト、解像度、基板との接着力、残膜率、耐熱性、および回路線幅均一度（CD uniformity）が挙げられる。。特に、薄膜トランジスタ液晶表示装置回路用フォトレジスト組成物には、そこから形成されるレジスト膜に高い感度が要求される。薄膜トランジスタ液晶表示装置回路の基板は面積が大きいために、レジスト膜の感度が低いと、生産ラインでの露光時間が長くなり、生産効率が低下する。また、感度と残膜率とは反比例関係にあり、感度が高ければ残膜率は減少する傾向を示す。 Important practical characteristics of photoresist compositions for liquid crystal display device circuits include sensitivity of the formed resist film, development contrast, resolution, adhesion to the substrate, residual film ratio, heat resistance, and circuit line width. An example is CD uniformity. . In particular, a photoresist composition for a thin film transistor liquid crystal display device circuit requires a high sensitivity for a resist film formed therefrom. Since the substrate of the thin film transistor liquid crystal display device circuit has a large area, if the sensitivity of the resist film is low, the exposure time in the production line becomes long and the production efficiency is lowered. Further, the sensitivity and the remaining film rate are in an inversely proportional relationship, and the higher the sensitivity, the lower the remaining film rate tends to decrease.
　液晶表示装置回路用ポジ型フォトレジストには、ｍ／ｐ－クレゾ－ルとホルムアルデヒドとを酸触媒の存在下で反応させて得られたノボラック型フェノ－ル樹脂が一般に使用されている。そして、フォトレジストの特性を調整または向上させるために、原料フェノール類として用いるｍ／ｐ－クレゾ－ルの比率や、原料フェノール類の種類、フェノ－ル樹脂の分子量、分子量分布等の検討がなされてきた。下記特許文献１では、フォトレジスト特性を向上させるために、２核体成分の少ないハイオルソ型ノボラック樹脂を配合したポジ型フォトレジストを用いている。特許文献１には、解像力（パターン形状）、耐熱性、および感度に優れ、かつレジスト塗膜の乾燥工程時には、低分子量揮発成分によるオーブン汚れの少なく、作業性にも優れるレジストが開示されている。また、特許文献２には、フォトレジスト特性を向上させるために、ノボラック樹脂を分溜（Fractionation）処理する方法が開示されている。前記の内容は当分野の従事者には広く知られている。一般的にフォトレジストの感度の向上はノボラック樹脂の分子量を低くすることにより達成される。しかし、この手法には、レジスト膜の耐熱性が低下したり、未露光部の残膜率が低下したりする問題がある。さらに、この手法では、露光部と未露光部との溶解速度差が充分に取れないため、露光部と未露光部との現像コントラストの低下し、結果として解像度が低下する問題が生じる。一方、ノボラック樹脂の分子量を高くすると、レジスト膜の耐熱性および解像度は改善されるが、レジスト膜の感度が低下する。すなわち、ある特定の特性を向上させようとすると、別の特性が悪化するというきわめて深刻な不都合を生じる。これまで、様々な改良が試みられたにも関わらず、レジスト膜の感度、残膜率、現像コントラスト、解像度、基板との接着力、回路線幅均一度などのような、液晶表示装置回路用フォトレジスト組成物に求められる特性のいずれか一つを犠牲にせずに、他のいずれかの特性を向上させる手法は、未だ確立されていない。上記の複数の特性がバランス良く、高いレベルで保たれている液晶表示装置回路用フォトレジスト組成物に対する要求は続いている。 As the positive photoresist for liquid crystal display device circuits, a novolac type phenol resin obtained by reacting m / p-cresol and formaldehyde in the presence of an acid catalyst is generally used. Then, in order to adjust or improve the characteristics of the photoresist, the ratio of m / p-cresol used as the raw material phenols, the type of the raw material phenols, the molecular weight of the phenol resin, the molecular weight distribution, etc. are studied. I came. In Patent Document 1 below, in order to improve the photoresist characteristics, a positive photoresist in which a high-ortho-type novolac resin with a small amount of binuclear components is blended is used. Patent Document 1 discloses a resist that is excellent in resolving power (pattern shape), heat resistance, and sensitivity, and that is less susceptible to oven contamination due to a low molecular weight volatile component during the resist coating drying process, and also has excellent workability. . Patent Document 2 discloses a method of fractionating a novolac resin to improve photoresist characteristics. Such content is well known to those skilled in the art. In general, improvement of the sensitivity of the photoresist is achieved by lowering the molecular weight of the novolak resin. However, this method has a problem that the heat resistance of the resist film is lowered or the remaining film ratio of the unexposed portion is lowered. Furthermore, in this method, since the difference in dissolution rate between the exposed portion and the unexposed portion cannot be sufficiently obtained, the development contrast between the exposed portion and the unexposed portion is lowered, resulting in a problem that the resolution is lowered. On the other hand, when the molecular weight of the novolak resin is increased, the heat resistance and resolution of the resist film are improved, but the sensitivity of the resist film is lowered. That is, trying to improve a certain characteristic causes a very serious inconvenience that another characteristic deteriorates. Despite various attempts so far, for liquid crystal display device circuits such as resist film sensitivity, residual film ratio, development contrast, resolution, adhesion to the substrate, circuit line width uniformity, etc. A technique for improving any of the other characteristics without sacrificing any one of the characteristics required for the photoresist composition has not yet been established. There is a continuing demand for a photoresist composition for a liquid crystal display device circuit in which the above-mentioned plurality of characteristics are well balanced and maintained at a high level.
特開平７－１１０５７６号公報JP-A-7-110576 特表２００２－５０８４１５号公報Special table 2002-508415 gazette
　本発明の目的は良好な感度・解像度、高残膜性をもち、その他特性についても汎用のものより劣ることのないフォトレジスト用樹脂組成物を提供することにある。 An object of the present invention is to provide a resin composition for a photoresist having good sensitivity / resolution, high residual film property, and other characteristics that are not inferior to those of general-purpose ones.
　このような目的は、下記の本発明の態様［１］から［４］により達成される。
［１］メタクレゾール、パラクレゾール、３，５－キシレノール及び２，３，５－トリメチルフェノールから選ばれる一種又は二種、並びにアルデヒド類を酸触媒の存在下、１１０－２２０℃の温度下で反応して得られるハイオルソノボラック型フェノール樹脂、ナフトキノンジアジド誘導体及び溶媒を含有することを特徴とするフォトレジスト用樹脂組成物。
［２］メタクレゾールとパラクレゾールとの重量比率が７５：２５から５０：５０である前記［１］記載のフォトレジスト用樹脂組成物。
［３］メタクレゾールとパラクレゾールの合計量と、３，５－キシレノール及び／または２，３，５-トリメチルフェノールとの重量比率が９５：５から６０：４０である前記［１］又は［２］記載のフォトレジスト用樹脂組成物。
［４］［１］から［３］のいずれか１つに記載のフォトレジスト用樹脂組成物を用いてなるフォトレジスト。
　本願明細書において「ハイオルソノボラック型フェノール樹脂」とは、オルソ化率が２３％以上のノボラック型フェノール樹脂を意味する。 Such an object is achieved by the following embodiments [1] to [4] of the present invention.
[1] Reaction of one or two selected from metacresol, paracresol, 3,5-xylenol and 2,3,5-trimethylphenol, and aldehydes in the presence of an acid catalyst at a temperature of 110-220 ° C A resin composition for photoresists, comprising a high-ortho novolak-type phenolic resin, a naphthoquinonediazide derivative, and a solvent.
[2] The resin composition for photoresists according to [1], wherein the weight ratio of metacresol to paracresol is 75:25 to 50:50.
[3] The above [1] or [2], wherein the weight ratio of the total amount of metacresol and paracresol to 3,5-xylenol and / or 2,3,5-trimethylphenol is 95: 5 to 60:40 ] The resin composition for photoresists of description.
[4] A photoresist using the photoresist resin composition according to any one of [1] to [3].
In the present specification, the “high ortho novolak type phenol resin” means a novolac type phenol resin having an ortho conversion rate of 23% or more.
　本発明により、良好な感度、解像度、高残膜性をもち、その他特性についても汎用のものより劣ることのないフォトレジスト用樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a resin composition for a photoresist that has good sensitivity, resolution, high residual film property, and other properties that are not inferior to general-purpose ones.
　以下に、本発明の実施形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
　本発明の実施形態は、フォトレジスト用樹脂組成物に関するものである。
　本発明の実施形態のフォトレジスト用樹脂組成物は、メタクレゾール、パラクレゾール、３，５－キシレノール及び２，３，５－トリメチルフェノールから選ばれる一種又は二種、並びにアルデヒド類を酸触媒の存在下、１１０－２２０℃の温度下で反応して得られるハイオルソノボラック型フェノール樹脂、ナフトキノンジアジド誘導体及び溶媒を含有する。 Embodiments described herein relate generally to a photoresist resin composition.
The photoresist resin composition of the embodiment of the present invention includes one or two selected from metacresol, paracresol, 3,5-xylenol and 2,3,5-trimethylphenol, and aldehydes in the presence of an acid catalyst. A high ortho novolak type phenol resin obtained by reaction at a temperature of 110-220 ° C., a naphthoquinonediazide derivative and a solvent are contained.
　本発明の実施形態に用いるハイオルソノボラック型フェノール樹脂は、メタクレゾール、パラクレゾール、３，５－キシレノール及び２，３，５－トリメチルフェノールから選ばれる一種又は二種、並びにアルデヒド類を酸触媒の存在下、１１０－２２０℃の温度下で反応して得られる樹脂である。初めに１１０-２２０℃の高温で反応させることにより、フェノール性水酸基近傍での反応が優先的に起こるため、通常のものより、オルソ化率の高い樹脂が得られやすい。また、３，５－キシレノールまたは２，３，５－トリメチルフェノールはメチル基の立体障害により、パラ位での反応が阻害されるため、オルソ化率を高めやすい。本反応は１１０-２２０℃で行うことが好ましいが、１２０－１５０℃の範囲で行うことがより好ましい。
　前記の条件で本反応を行うことにより、オルソ化率２３％以上のハイオルソノボラック型フェノール樹脂を得ることができる。
　本発明の実施形態に用いる前記メタクレゾールとパラクレゾールとの重量比率は７５：２５から５０：５０であることが好ましく、さらに７０：３０から５５:４５であることがより好ましい。重量比率が前記の範囲にあることによって高感度領域で解像度、残膜率が良くなり好ましい。
　本発明の実施形態に用いる前記メタクレゾールとパラクレゾールの合計量と、３，５－キシレノール及び２，３，５-トリメチルフェノールから選ばれる一種又は二種の重量比率は９５：５から６０：４０であることが好ましく、さらに９０：７から７０：３０であることがより好ましい。重量比率が前記の範囲にあることによって高感度領域で解像度や残膜率が良くなり好ましい。 The high ortho novolac type phenol resin used in the embodiment of the present invention is one or two selected from metacresol, paracresol, 3,5-xylenol and 2,3,5-trimethylphenol, and aldehydes as acid catalysts. It is a resin obtained by reacting at a temperature of 110-220 ° C. in the presence. When the reaction is first performed at a high temperature of 110 to 220 ° C., the reaction in the vicinity of the phenolic hydroxyl group occurs preferentially, and therefore, a resin having a higher ortho-ratio than the usual one can be easily obtained. In addition, 3,5-xylenol or 2,3,5-trimethylphenol tends to increase the ortho ratio because the reaction at the para-position is inhibited by the steric hindrance of the methyl group. This reaction is preferably carried out at 110-220 ° C, more preferably in the range of 120-150 ° C.
By carrying out this reaction under the above conditions, a high ortho novolac type phenol resin having an ortho conversion rate of 23% or more can be obtained.
The weight ratio of the metacresol and paracresol used in the embodiment of the present invention is preferably 75:25 to 50:50, and more preferably 70:30 to 55:45. It is preferable that the weight ratio is in the above range because the resolution and the remaining film ratio are improved in a high sensitivity region.
The total amount of the metacresol and paracresol used in the embodiment of the present invention and the weight ratio of one or two selected from 3,5-xylenol and 2,3,5-trimethylphenol are 95: 5 to 60:40. It is preferable that the ratio is 90: 7 to 70:30. It is preferable that the weight ratio is in the above range because the resolution and the remaining film ratio are improved in a high sensitivity region.
　前記ハイオルソノボラック型フェノール樹脂に用いられるアルデヒド類としては特に限定されないが、例えば、ホルムアルデヒド、アセトアルデヒド、プロピルアルデヒド、ブチルアルデヒド、ベンズアルデヒド、サリチルアルデヒドなどが挙げられる。
　これらの中でも、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、サリチルアルデヒドが好ましい。これにより、フォトレジスト組成物として用いたときに高感度とすることができる。なお、ホルムアルデヒドを用いる場合は、ホルムアルデヒド源としては特に限定されないが、ホルマリン（水溶液）、パラホルムアルデヒド、アルコール類とのヘミホルマール、トリオキサンなど、ホルムアルデヒドを発生するものであれば使用できる。 Although it does not specifically limit as aldehydes used for the said high ortho novolak type phenol resin, For example, formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, benzaldehyde, salicylaldehyde, etc. are mentioned.
Among these, formaldehyde, paraformaldehyde, acetaldehyde, and salicylaldehyde are preferable. Thereby, when used as a photoresist composition, high sensitivity can be achieved. When formaldehyde is used, the formaldehyde source is not particularly limited, but any formaldehyde can be used as long as it generates formaldehyde, such as formalin (aqueous solution), paraformaldehyde, hemi-formal with alcohols, and trioxane.
　前記フェノール類とアルデヒド類との反応には、酸触媒が一般的に使用される。前記ハイオルソノボラック型フェノール樹脂を合成するための酸触媒としては、特に限定はされないが、例えば、蓚酸、酢酸などの有機カルボン酸といった弱酸が挙げられる。これらの中から、単独あるいは２種以上を混合して使用することもできる。酸触媒の使用量は特に限定されないが、フェノール類に対して０．０１～５重量％であることが好ましい。また、フォトレジスト用樹脂をフォトレジスト組成物に用いる時にはフォトレジストの特性のために樹脂に残留している触媒は少量であることが好ましい。もちろん樹脂を合成する過程で、一般的な除去方法（中和、水洗やフィルターろ過等）により除去してもよい。また、本発明の実施形態に使用される反応溶媒としては、適度に非極性な溶媒で、例えばヘキサン、ベンゼン、キシレンなどが挙げられる。これらを用いることで樹脂のオルソ化率を高く維持することが可能になる。 In the reaction between the phenols and aldehydes, an acid catalyst is generally used. The acid catalyst for synthesizing the high ortho novolak type phenol resin is not particularly limited, and examples thereof include weak acids such as organic carboxylic acids such as oxalic acid and acetic acid. Among these, it can also be used individually or in mixture of 2 or more types. The amount of the acid catalyst used is not particularly limited, but is preferably 0.01 to 5% by weight based on the phenols. Further, when a photoresist resin is used in the photoresist composition, a small amount of catalyst remains in the resin because of the characteristics of the photoresist. Of course, in the process of synthesizing the resin, it may be removed by a general removal method (neutralization, water washing, filter filtration, etc.). Moreover, as a reaction solvent used for embodiment of this invention, it is a moderately non-polar solvent, for example, hexane, benzene, xylene, etc. are mentioned. By using these, it becomes possible to keep the ortho-ratio of the resin high.
　本発明の実施形態に用いられるハイオルソノボラック型フェノール樹脂のオルソ化率としては２３－５０％が好ましく、さらには２５－４５％が好ましい。これらオルソ化率については一般的に１３Ｃ－ＮＭＲを用いて分析することが出来る。これにより、フォトレジストとして用いたときに高感度、高残膜率保持することが出来、高解像度を得ることが出来る。 The ortho-formation rate of the high ortho novolak type phenol resin used in the embodiment of the present invention is preferably 23-50%, more preferably 25-45%. These ortho-conversion rates can generally be analyzed using 13 C-NMR. Thereby, when used as a photoresist, high sensitivity and high residual film ratio can be maintained, and high resolution can be obtained.
　本発明の実施形態に用いるハイオルソノボラック型フェノール樹脂としては、ＧＰＣにより測定される重量平均分子量が１０００～１００００であることが好ましく、さらに好ましくは２５００～８０００であり、重量平均分子量を上記範囲とすることで、感度、残膜率、解像度を向上させることができる。上記重量平均分子量は、ポリスチレン標準物質を用いて作成した検量線をもとに計算した。ＧＰＣ測定はテトラヒドロフランを溶出溶媒とし、流量１．０ｍｌ／ｍｉｎ、カラム温度４０℃の条件で示差屈折計を検出器として用いて実施することができる。用いることのできる装置は、例えば、
１）本体：ＴＯＳＯＨ社製・「ＨＬＣ－８０２０」
２）検出器：波長２８０ｎｍにセットしたＴＯＳＯＨ社製・「ＵＶ－８０１１」
３）分析用カラム：昭和電工社製・「ＳＨＯＤＥＸ　ＫＦ－８０２、ＫＦ－８０３、ＫＦ－８０５」をそれぞれ使用することができる。
　本発明の実施形態のフォトレジスト用樹脂組成物は、溶媒の重量に対する重量比（ｇ／１００ｇ）として、２１．７から２８．３ｇ／１００ｇのハイオルソノボラック型フェノール樹脂を含むことが好ましい。さらに好ましいハイオルソノボラック型フェノール樹脂含有量は、２５．０から２７．０ｇ／１００ｇである。 The high ortho novolac type phenol resin used in the embodiment of the present invention preferably has a weight average molecular weight measured by GPC of 1,000 to 10,000, more preferably 2500 to 8,000, and the weight average molecular weight is within the above range. By doing so, the sensitivity, the remaining film rate, and the resolution can be improved. The weight average molecular weight was calculated based on a calibration curve prepared using a polystyrene standard. GPC measurement can be performed using tetrahydrofuran as an elution solvent, a flow rate of 1.0 ml / min, and a column temperature of 40 ° C. using a differential refractometer as a detector. An apparatus that can be used is, for example,
1) Body: "HLC-8020" manufactured by TOSOH
2) Detector: “UV-8011” manufactured by TOSOH with wavelength set to 280 nm
3) Analytical column: “SHODEX KF-802, KF-803, KF-805” manufactured by Showa Denko KK can be used.
The photoresist resin composition of the embodiment of the present invention preferably contains 21.7 to 28.3 g / 100 g of a high ortho novolac type phenol resin as a weight ratio (g / 100 g) to the weight of the solvent. A more preferred high ortho novolak type phenol resin content is 25.0 to 27.0 g / 100 g.
　次に本発明の実施形態に用いるナフトキノンジアジド誘導体としては、例えば、ジアゾナフトキノン－５－スルフォン酸クロリドまたはジアゾナフトキノン－４－スルフォン酸クロリドの誘導体をアルコールまたはフェノール誘導体等のバラストとテトラヒドロフランまたはジオキサン等の溶媒中において、トリエチルアミン等の塩基性触媒の存在下反応させてエステル化を行って得ることができる。このバラストの化学構造としては種々の化学構造の化合物が使用できる。例えば、ヒドロキシベンゾフェノン、ジヒドロキシベンゾフェノン等のポリヒドロキシベンゾフェノン、ナフトール、ヒドロキノン、ピロガロール、ビスフェノールＡ、p-クレゾールポリマー、及びこれらの誘導体である。また、この反応においては、ジアゾナフトキノンのスルフォン酸クロリドとバラストのモル比を調整することでエステル化率をコントロールすることができる。これらのナフトキノンジアジドは、１種類でも２種類以上の混合物でもかまわない。
　本発明の実施形態のフォトレジスト用樹脂組成物は、溶媒の重量に対する重量比（ｇ／１００ｇ）として、３．３から９．９ｇ／１００ｇのナフトキノンジアジド誘導体を含むことが好ましい。さらに好ましいナフトキノンジアジド誘導体含有量は、４．６から６．６ｇ／１００ｇである。 Next, as the naphthoquinonediazide derivative used in the embodiment of the present invention, for example, a diazonaphthoquinone-5-sulfonic acid chloride or diazonaphthoquinone-4-sulfonic acid derivative such as a ballast such as an alcohol or a phenol derivative and a tetrahydrofuran or dioxane or the like is used. It can be obtained by esterification in a solvent in the presence of a basic catalyst such as triethylamine. As the chemical structure of this ballast, compounds having various chemical structures can be used. For example, polyhydroxybenzophenone such as hydroxybenzophenone and dihydroxybenzophenone, naphthol, hydroquinone, pyrogallol, bisphenol A, p-cresol polymer, and derivatives thereof. In this reaction, the esterification rate can be controlled by adjusting the molar ratio of diazonaphthoquinone sulfonic acid chloride to ballast. These naphthoquinone diazides may be one kind or a mixture of two or more kinds.
The photoresist resin composition of the embodiment of the present invention preferably contains 3.3 to 9.9 g / 100 g of naphthoquinonediazide derivative as a weight ratio (g / 100 g) to the weight of the solvent. A more preferred naphthoquinonediazide derivative content is 4.6 to 6.6 g / 100 g.
　本発明の実施形態の組成物に配合される溶媒は、前記ハイオルソノボラック型フェノール樹脂とナフトキノンジアジド誘導体とを溶解するものであれば特に限定されない。本発明の実施形態においてはこれらの成分を溶媒に溶解して使用する。本発明の実施形態に用いる溶媒としては、Ｎ－メチル－２－ピロリドン、γ－ブチロラクトン、Ｎ，Ｎ－ジメチルアセトアミド、ジメチルスルホキシド、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、乳酸メチル、乳酸エチル、乳酸ブチル、メチル－１，３－ブチレングリコールアセテート、１，３－ブチレングリコール20－３－モノメチルエーテル、ピルビン酸メチル、ピルビン酸エチル、メチル－３－メトキシプロピオネート等を単独または混合して使用できる。 The solvent to be blended in the composition of the embodiment of the present invention is not particularly limited as long as it dissolves the high ortho novolak type phenol resin and the naphthoquinone diazide derivative. In the embodiment of the present invention, these components are used dissolved in a solvent. Examples of the solvent used in the embodiment of the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, di Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol 20-3-monomethyl ether, methyl pyruvate, ethyl pyruvate , Methyl-3-methoxypropionate and the like can be used alone or in combination.
　なお、本発明の実施形態の組成物には、以上説明した成分のほかにも、必要により、酸化防止剤などの安定剤、可塑剤、界面活性剤、密着性向上剤、溶解促進剤などの種々の添加剤を使用してもよい。 In addition to the above-described components, the composition of the embodiment of the present invention includes, if necessary, a stabilizer such as an antioxidant, a plasticizer, a surfactant, an adhesion improver, a dissolution accelerator and the like. Various additives may be used.
　本発明の実施形態の組成物の調製方法としては特に限定されないが、組成物に充填材、顔料を添加しない場合には、上記の成分を通常の方法で混合・攪拌するだけでよく、充填材、顔料を添加する場合には、例えば、ディゾルバー、ホモジナイザー、３本ロールミル等の分散装置を用いて分散、混合させればよい。また、必要に応じて、さらにメッシュフィルター、メンブレンフィルター等を用いて濾過してもよい。 The method for preparing the composition according to the embodiment of the present invention is not particularly limited. However, in the case where a filler and a pigment are not added to the composition, the above-described components may be mixed and stirred by a usual method. When the pigment is added, for example, it may be dispersed and mixed using a dispersing device such as a dissolver, a homogenizer, or a three roll mill. Moreover, you may further filter using a mesh filter, a membrane filter, etc. as needed.
　このようにして得られた本発明の実施形態の組成物に対して、マスクを介して露光を行うことで、露光部においては組成物に構造変化が生じ、アルカリ現像液に対しての溶解性を促進することができる。一方、非露光部においてはアルカリ現像液に対する低い溶解性を保持しているため、こうして生じた溶解性の差により、レジスト機能を付与することができる。 When the composition of the embodiment of the present invention thus obtained is exposed through a mask, a structural change occurs in the composition in the exposed area, and the solubility in an alkali developer is increased. Can be promoted. On the other hand, in the non-exposed area, low solubility in an alkali developer is maintained, so that a resist function can be imparted due to the difference in solubility thus generated.
　本発明の実施形態の組成物をフォトレジストとして使用した場合、光の照射により組成物中のナフトキノンジアジド誘導体が化学変化を起こし、後の現像工程においてノボラック樹脂と共にアルカリ現像液に溶解し、露光されなかった部分との間に明確な溶解速度差を生ずることで、目的とするパターンを現像により得ることができる。 When the composition of the embodiment of the present invention is used as a photoresist, the naphthoquinone diazide derivative in the composition undergoes a chemical change by light irradiation, and is dissolved in an alkali developer together with a novolac resin in a later development step and exposed. By producing a clear difference in dissolution rate from the unexposed portion, the target pattern can be obtained by development.
　以下、本発明の実施形態を合成例および実施例により説明する。しかし本発明はこれらの合成例および実施例によって限定されるものではない。また、合成例、実施例及び比較例に記載されている「部」及び「％」は、すべて「重量部」及び「重量％」を示す。但し、ホルマリン水溶液の濃度（％）を除く。 Hereinafter, embodiments of the present invention will be described with reference to synthesis examples and examples. However, the present invention is not limited by these synthesis examples and examples. Further, “parts” and “%” described in the synthesis examples, examples and comparative examples all represent “parts by weight” and “% by weight”. However, the concentration (%) of the formalin aqueous solution is excluded.
１．ハイオルソノボラック型フェノール樹脂の合成
（合成例１）
　攪拌装置、温度計、熱交換器を備えた３Ｌの４口フラスコにｍ－クレゾール６００部、ｐ－クレゾール４００部、３，５－キシレノール１００部、ヘキサン２００部、シュウ酸５．５部を仕込み、温度を１３０℃まで昇温させた後、３７％ホルマリン５４７部を３時間かけて徐々に添加し、脱水しながらその後２時間反応させた。この後、内温１７０℃まで常圧下で脱水し、さらに９．３×１０３Ｐａの減圧下で２００℃まで脱水・脱モノマーを行い、重量平均分子量４２００のフェノール樹脂Ｂ９５０部を得た。 1. Synthesis of high ortho novolac type phenol resin (Synthesis Example 1)
A 3 L 4-neck flask equipped with a stirrer, thermometer and heat exchanger was charged with 600 parts of m-cresol, 400 parts of p-cresol, 100 parts of 3,5-xylenol, 200 parts of hexane, and 5.5 parts of oxalic acid. After the temperature was raised to 130 ° C., 547 parts of 37% formalin was gradually added over 3 hours, followed by reaction for 2 hours while dehydrating. Thereafter, dehydration was performed under normal pressure to an internal temperature of 170 ° C., and dehydration / demonomerization was further performed under reduced pressure of 9.3 × 10 3 Pa to 200 ° C. to obtain 950 parts of phenol resin B having a weight average molecular weight of 4200.
（合成例２）
　攪拌装置、温度計、熱交換器を備えた３Ｌの４口フラスコにｍ－クレゾール６００部、ｐ－クレゾール４００部、３，５－キシレノール２００部、ヘキサン２００部、シュウ酸６．０部を仕込み、温度を１１５℃まで昇温させた後、３７％ホルマリン５５７部を３時間かけて徐々に添加し、脱水しながらその後２時間反応させた。この後、内温１７０℃まで常圧下で脱水し、さらに９．３×１０３Ｐａの減圧下で２００℃まで脱水・脱モノマーを行い、重量平均分子量３５００のフェノール樹脂Ｂ１０００部を得た。
（合成例３）
　攪拌装置、温度計、熱交換器を備えた３Ｌの４口フラスコにｍ－クレゾール６００部、ｐ－クレゾール４００部、３，５－キシレノール３００部、ヘキサン２００部、シュウ酸６．５部を仕込み、温度を１３０℃まで昇温させた後、３７％ホルマリン５８５部を３時間かけて徐々に添加し、脱水しながらその後２時間反応させた。この後、内温１７０℃まで常圧下で脱水し、さらに９．３×１０３Ｐａの減圧下で２００℃まで脱水・脱モノマーを行い、重量平均分子量２６００のフェノール樹脂Ｂ９９０部を得た。 (Synthesis Example 2)
A 3 L 4-neck flask equipped with a stirrer, thermometer and heat exchanger was charged with 600 parts of m-cresol, 400 parts of p-cresol, 200 parts of 3,5-xylenol, 200 parts of hexane, and 6.0 parts of oxalic acid. After the temperature was raised to 115 ° C., 557 parts of 37% formalin was gradually added over 3 hours, followed by reaction for 2 hours while dehydrating. Thereafter, dehydration was performed under normal pressure to an internal temperature of 170 ° C., and dehydration / demonomerization was further performed under reduced pressure of 9.3 × 10 3 Pa to 200 ° C. to obtain 1000 parts of phenol resin B having a weight average molecular weight of 3500.
(Synthesis Example 3)
A 3 L 4-neck flask equipped with a stirrer, thermometer, and heat exchanger was charged with 600 parts of m-cresol, 400 parts of p-cresol, 300 parts of 3,5-xylenol, 200 parts of hexane, and 6.5 parts of oxalic acid. After raising the temperature to 130 ° C., 585 parts of 37% formalin was gradually added over 3 hours, followed by reaction for 2 hours while dehydrating. Thereafter, dehydration was performed under normal pressure to an internal temperature of 170 ° C., and dehydration / demonomerization was further performed to 200 ° C. under reduced pressure of 9.3 × 10 3 Pa to obtain 990 parts of phenol resin B having a weight average molecular weight of 2600.
（合成例４）
　攪拌装置、温度計、熱交換器を備えた３Ｌの４口フラスコにｍ－クレゾール６００部、ｐ－クレゾール４００部、２，３，５－トリメチルフェノール１００部、ヘキサン２００部、シュウ酸５．５部を仕込み、温度を１３０℃まで昇温させた後、３７％ホルマリン５３４部を３時間かけて徐々に添加し、脱水しながらその後２時間反応させた。この後、内温１７０℃まで常圧下で脱水し、さらに９．３×１０３Ｐａの減圧下で２００℃まで脱水・脱モノマーを行い、重量平均分子量２７００のフェノール樹脂Ｂ１０００部を得た。 (Synthesis Example 4)
In a 3 L four-necked flask equipped with a stirrer, thermometer and heat exchanger, 600 parts of m-cresol, 400 parts of p-cresol, 100 parts of 2,3,5-trimethylphenol, 200 parts of hexane, oxalic acid 5.5 Then, after the temperature was raised to 130 ° C., 534 parts of 37% formalin was gradually added over 3 hours, followed by reaction for 2 hours while dehydrating. Thereafter, dehydration was performed under normal pressure to an internal temperature of 170 ° C., and dehydration / demonomerization was further performed to 200 ° C. under a reduced pressure of 9.3 × 10 3 Pa to obtain 1000 parts of phenol resin B having a weight average molecular weight of 2700.
（比較合成例１）
　攪拌装置、温度計、熱交換器を備えた３Ｌの４口フラスコにｍ－クレゾール６００部、ｐ－クレゾール４００部、２，３－キシレノール１００部、ヘキサン２００部、シュウ酸５．５部を仕込み、温度を１３０℃まで昇温させた後、３７％ホルマリン５８８部を３時間かけて徐々に添加し、脱水しながらその後２時間反応させた。この後、内温１７０℃まで常圧下で脱水し、さらに９．３×１０３Ｐａの減圧下で２００℃まで脱水・脱モノマーを行い、重量平均分子量３５００のフェノール樹脂Ｂ９５０部を得た。 (Comparative Synthesis Example 1)
A 3 L 4-neck flask equipped with a stirrer, thermometer and heat exchanger was charged with 600 parts of m-cresol, 400 parts of p-cresol, 100 parts of 2,3-xylenol, 200 parts of hexane, and 5.5 parts of oxalic acid. After raising the temperature to 130 ° C., 588 parts of 37% formalin was gradually added over 3 hours, followed by reaction for 2 hours while dehydrating. Thereafter, dehydration was performed under normal pressure to an internal temperature of 170 ° C., and dehydration / demonomerization was further performed to 200 ° C. under a reduced pressure of 9.3 × 10 3 Pa to obtain 950 parts of phenol resin B having a weight average molecular weight of 3500.
（比較合成例２）
　攪拌装置、温度計、熱交換器を備えた３Ｌの４口フラスコにｍ－クレゾール６００部、ｐ－クレゾール４００部、２，５－キシレノール１００部、ヘキサン２００部、シュウ酸５．５部を仕込み、温度を１３０℃まで昇温させた後、３７％ホルマリン５８８部を３時間かけて徐々に添加し、脱水しながらその後２時間反応させた。この後、内温１７０℃まで常圧下で脱水し、さらに９．３×１０３Ｐａの減圧下で２００℃まで脱水・脱モノマーを行い、重量平均分子量３６００のフェノール樹脂Ｂ９５０部を得た。
（比較合成例３）
　攪拌装置、温度計、熱交換器を備えた３Ｌの４口フラスコにｍ－クレゾール６００部、ｐ－クレゾール４００部、２，５－キシレノール３００部、ヘキサン２００部、シュウ酸６．５部を仕込み、温度を１３０℃まで昇温させた後、３７％ホルマリン６８４部を３時間かけて徐々に添加し、脱水しながらその後２時間反応させた。この後、内温１７０℃まで常圧下で脱水し、さらに９．３×１０３Ｐａの減圧下で２００℃まで脱水・脱モノマーを行い、重量平均分子量３４００のフェノール樹脂Ｂ９８０部を得た。 (Comparative Synthesis Example 2)
A 3 L 4-neck flask equipped with a stirrer, thermometer and heat exchanger was charged with 600 parts of m-cresol, 400 parts of p-cresol, 100 parts of 2,5-xylenol, 200 parts of hexane, and 5.5 parts of oxalic acid. After raising the temperature to 130 ° C., 588 parts of 37% formalin was gradually added over 3 hours, followed by reaction for 2 hours while dehydrating. Thereafter, dehydration was performed under normal pressure to an internal temperature of 170 ° C., and dehydration / demonomerization was further performed under reduced pressure of 9.3 × 10 3 Pa to 200 ° C. to obtain 950 parts of phenol resin B having a weight average molecular weight of 3600.
(Comparative Synthesis Example 3)
A 3 L 4-neck flask equipped with a stirrer, thermometer, and heat exchanger was charged with 600 parts of m-cresol, 400 parts of p-cresol, 300 parts of 2,5-xylenol, 200 parts of hexane, and 6.5 parts of oxalic acid. After raising the temperature to 130 ° C., 684 parts of 37% formalin was gradually added over 3 hours, followed by reaction for 2 hours while dehydrating. Thereafter, dehydration was performed under normal pressure to an internal temperature of 170 ° C., and dehydration / demonomerization was further performed to 200 ° C. under a reduced pressure of 9.3 × 10 3 Pa to obtain 980 parts of phenol resin B having a weight average molecular weight of 3400.
（比較合成例４）
　攪拌装置、温度計、熱交換器を備えた３Ｌの４口フラスコにｍ－クレゾール６００部、ｐ－クレゾール４００部、ヘキサン２００部、シュウ酸５．０部を仕込み、温度を１３０℃まで昇温させた後、３７％ホルマリン５１０部を３時間かけて徐々に添加し、脱水しながらその後２時間反応させた。この後、内温１７０℃まで常圧下で脱水し、さらに９．３×１０３Ｐａの減圧下で２００℃まで脱水・脱モノマーを行い、重量平均分子量５５００のフェノール樹脂Ｂ９００部を得た。 (Comparative Synthesis Example 4)
A 3 L 4-neck flask equipped with a stirrer, thermometer and heat exchanger was charged with 600 parts of m-cresol, 400 parts of p-cresol, 200 parts of hexane, and 5.0 parts of oxalic acid, and the temperature was raised to 130 ° C. After that, 510 parts of 37% formalin was gradually added over 3 hours, followed by reaction for 2 hours while dehydrating. Thereafter, dehydration was performed under normal pressure to an internal temperature of 170 ° C., and dehydration / demonomerization was further performed to 200 ° C. under a reduced pressure of 9.3 × 10 3 Pa to obtain 900 parts of phenol resin B having a weight average molecular weight of 5500.
２．ハイオルソノボラック型フェノール樹脂の評価
１３Ｃ－ＮＭＲによるオルソ化率（o-o’結合率）の測定
　核磁気共鳴分光分析（ＮＭＲ、日本電子データム(株)製ＪＮＭ－ＡＬ３００）を使用し、得られた結果から、樹脂のo-p、p-p’、o-o’の各結合率を求めた。測定条件としては積算回数を１００００回で行った。合成例１から３の樹脂のオルソ化率はそれぞれ２７％、３０％、２５％であった。比較合成例１から３の樹脂のオルソ化率は２１％、２０％、２１％であった。 2. Evaluation of high ortho novolac type phenolic resin
Measurement of Orthogonalization Rate (o-o 'Bond Rate) by 13 C-NMR Using nuclear magnetic resonance spectroscopy (NMR, JNM-AL300 manufactured by JEOL Datum Co., Ltd.) , P-p ′, and o-o ′ were determined. As measurement conditions, the number of integrations was 10,000. The orthorectification rates of the resins of Synthesis Examples 1 to 3 were 27%, 30%, and 25%, respectively. The orthorectification rates of the resins of Comparative Synthesis Examples 1 to 3 were 21%, 20%, and 21%.
４．フォトレジスト用組成物の調製
（実施例１）
　合成例１で得られたフォトレジスト用フェノール樹脂２０部、およびナフトキノン１,２－ジアジド－５－スルホン酸の２,３,４－トリヒドロキシ－ベンゾフェノンエステル４部をＰＧＭＥＡ７６部に溶解した後、０．１μｍのメンブレンフィルターを用いてろ過し、フォトレジスト用組成物を調製した。 4). Preparation of composition for photoresist (Example 1)
After dissolving 20 parts of phenol resin for photoresist obtained in Synthesis Example 1 and 4 parts of 2,3,4-trihydroxy-benzophenone ester of naphthoquinone 1,2-diazide-5-sulfonic acid in 76 parts of PGMEA, Filtration was performed using a 1 μm membrane filter to prepare a photoresist composition.
（実施例２）
　フォトレジスト用フェノール樹脂として、合成例２で得られたフォトレジスト用フェノール樹脂を用いた他は、実施例１と同様にして組成物を調製した。
（実施例３）
　フォトレジスト用フェノール樹脂として、合成例３で得られたフォトレジスト用フェノール樹脂を用いた他は、実施例１と同様にして組成物を調製した。
（実施例４）
　フォトレジスト用フェノール樹脂として、合成例４で得られたフォトレジスト用フェノール樹脂を用いた他は、実施例１と同様にして組成物を調製した。 (Example 2)
A composition was prepared in the same manner as in Example 1 except that the photoresist phenol resin obtained in Synthesis Example 2 was used as the photoresist phenol resin.
(Example 3)
A composition was prepared in the same manner as in Example 1 except that the photoresist phenol resin obtained in Synthesis Example 3 was used as the photoresist phenol resin.
Example 4
A composition was prepared in the same manner as in Example 1 except that the photoresist phenol resin obtained in Synthesis Example 4 was used as the photoresist phenol resin.
（比較例１）
　フォトレジスト用フェノール樹脂として、比較合成例１で得られたフォトレジスト用フェノール樹脂を用いた他は、実施例１と同様にして組成物を調製した。
（比較例２）
　フォトレジスト用フェノール樹脂として、比較合成例２で得られたフォトレジスト用フェノール樹脂を用いた他は、実施例１と同様にして組成物を調製した。
（比較例３）
　フォトレジスト用フェノール樹脂として、比較合成例３で得られたフォトレジスト用フェノール樹脂を用いた他は、実施例１と同様にして組成物を調製した。
（比較例４）
　フォトレジスト用フェノール樹脂として、比較合成例４で得られたフォトレジスト用フェノール樹脂を用いた他は、実施例１と同様にして組成物を調製した。 (Comparative Example 1)
A composition was prepared in the same manner as in Example 1 except that the photoresist phenol resin obtained in Comparative Synthesis Example 1 was used as the photoresist phenol resin.
(Comparative Example 2)
A composition was prepared in the same manner as in Example 1 except that the photoresist phenol resin obtained in Comparative Synthesis Example 2 was used as the photoresist phenol resin.
(Comparative Example 3)
A composition was prepared in the same manner as in Example 1 except that the photoresist phenol resin obtained in Comparative Synthesis Example 3 was used as the photoresist phenol resin.
(Comparative Example 4)
A composition was prepared in the same manner as in Example 1 except that the photoresist phenol resin obtained in Comparative Synthesis Example 4 was used as the photoresist phenol resin.
　実施例１～４、及び比較例１～４で得られたフォトレジスト組成物を用いて、下記に示す特性評価を行った。結果を表１に示す。 Using the photoresist compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4, the following characteristics were evaluated. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
５．特性の評価方法 5). Evaluation method of characteristics
（１）残膜率測定方法
　フォトレジスト組成物を３インチシリコンウエハ上に約１μｍの厚さになるようにスピンコーターで塗布し、１１０℃のホットプレート上で１００秒間乾燥させた。そのウエハを現像液（２．３８％水酸化テトラメチルアンモニウム水溶液）に６０秒間浸した後、水で洗浄し、１１０℃のホットプレート上で１００秒間乾燥させた。現像前の膜厚に対する、現像後の膜厚の比を百分率で表し、残膜率とした。これにより、感光剤とフォトレジストとして用いたときの残膜（耐性）の程度がわかり、数値が高いほど残膜率が高いことを示す。 (1) Method for measuring remaining film ratio A photoresist composition was applied on a 3-inch silicon wafer with a spin coater so as to have a thickness of about 1 μm, and dried on a hot plate at 110 ° C. for 100 seconds. The wafer was immersed in a developing solution (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, washed with water, and dried on a hot plate at 110 ° C. for 100 seconds. The ratio of the film thickness after development to the film thickness before development was expressed as a percentage, and was defined as the remaining film ratio. As a result, the degree of remaining film (resistance) when used as a photosensitizer and a photoresist can be understood, and the higher the numerical value, the higher the remaining film rate.
（２）感度の測定方法
　フォトレジスト組成物を３インチのシリコンウエハに約１．５μｍの厚さになるようにスピンコーターで塗布し、１１０℃のホットプレート上で１００秒間乾燥させた。次いでこのシリコンウエハにテストチャートマスクを重ね、５ｍＪ／ｃｍ２，１０ｍＪ／ｃｍ２，１５ｍＪ／ｃｍ２の紫外線をそれぞれ照射し、現像液（２．３８％の水酸化テトラメチルアンモニウム水溶液）を用い６０秒間現像した。得られたパターンを走査型電子顕微鏡でパターン形状を観察することにより以下の基準で評価した。
Ａ　１０ｍＪ／ｃｍ２で画像が形成できる。
Ｂ　１５ｍＪ／ｃｍ２では画像形成不可、２０ｍＪ／ｃｍ２で画像が形成できる。
Ｃ　２０ｍＪ／ｃｍ２では画像形成不可、２５ｍＪ／ｃｍ２で画像が形成できる。 (2) Method of measuring sensitivity The photoresist composition was applied to a 3-inch silicon wafer with a spin coater so as to have a thickness of about 1.5 μm, and dried on a hot plate at 110 ° C. for 100 seconds. Then repeated test chart mask on the silicon wafer was irradiated 5mJ / cm 2, 10mJ / cm 2, 15mJ / cm 2 of ultraviolet light, respectively, using a developing solution (2.38% tetramethylammonium hydroxide aqueous solution) 60 Developed for seconds. The obtained pattern was evaluated according to the following criteria by observing the pattern shape with a scanning electron microscope.
A An image can be formed at 10 mJ / cm 2 .
B 15 mJ / cm 2 in the image forming impossible, an image can be formed at 20 mJ / cm 2.
An image cannot be formed at C 20 mJ / cm 2 , and an image can be formed at 25 mJ / cm 2 .
（３）解像度の測定
　上記調製したフォトレジスト組成物を、スピンコーターを用いてシリコンウエハ上に塗布し、１１０℃、１００秒間プリベークして、膜厚１．５μｍのレジスト膜を形成した。これに１００～１μｍの線幅が刻まれたパターンマスクを介し、紫外線を用いて露光した。露光後、直ちに２．３８ｗｔ％のテトラメチルアンモニウムハイドロオキサイト水溶液により、２３℃で６０秒間現像し、水洗、乾燥を行い、ポジ型パターンを得た。その際、一定の露光量で解像される最小のフォトレジストパターンの寸法を限界解像度とした。
　表１の結果から、実施例１～４は、本発明のフォトレジスト用樹脂組成物であり、本発明の樹脂組成物でない比較例１～４に比べて、優れた残膜率、解像度を持つものであることが証明できた。
　一方、比較例１は３，５－キシレノールに替えて２，３－キシレノールを用いたものであるが、残膜率が低く、限界解像度も高いものであった。
　比較例２および３は３，５－キシレノールに替えて２，５－キシレノールを用いたものであるが、残膜率が低く、限界解像度も高いものであった。
　比較例４はキシレノール、トリメチルフェノールのいずれも用いないものであるが、同様に残膜率が低く、限界解像度も高いものであった。 (3) Measurement of resolution The photoresist composition prepared above was applied onto a silicon wafer using a spin coater and pre-baked at 110 ° C. for 100 seconds to form a resist film having a thickness of 1.5 μm. This was exposed using ultraviolet rays through a pattern mask in which a line width of 100 to 1 μm was engraved. Immediately after the exposure, the film was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, washed with water and dried to obtain a positive pattern. At that time, the minimum resolution of the photoresist pattern that can be resolved with a constant exposure amount is defined as the limit resolution.
From the results shown in Table 1, Examples 1 to 4 are photoresist resin compositions of the present invention, and have an excellent remaining film ratio and resolution as compared with Comparative Examples 1 to 4 which are not the resin composition of the present invention. I was able to prove it.
On the other hand, in Comparative Example 1, 2,3-xylenol was used instead of 3,5-xylenol, but the residual film ratio was low and the limit resolution was high.
In Comparative Examples 2 and 3, 2,5-xylenol was used instead of 3,5-xylenol, but the residual film ratio was low and the limit resolution was high.
In Comparative Example 4, neither xylenol nor trimethylphenol was used, but the remaining film rate was low and the limit resolution was also high.
　本発明のフォトレジスト用樹脂組成物は、良好な熱安定性を有し、かつ高感度・高解像度で高残膜性を有することから、液晶表示装置回路や半導体集積回路の微細回路製造に好適に用いることができる。 The resin composition for photoresists of the present invention has good thermal stability, high sensitivity, high resolution, and high residual film properties, so it is suitable for manufacturing fine circuits of liquid crystal display circuits and semiconductor integrated circuits. Can be used.

Claims (4)

  1. 　メタクレゾール、パラクレゾール、３，５－キシレノール及び２，３，５－トリメチルフェノールから選ばれる一種又は二種、並びにアルデヒド類を酸触媒の存在下、１１０－２２０℃の温度下で反応して得られるハイオルソノボラック型フェノール樹脂、ナフトキノンジアジド誘導体及び溶媒を含有することを特徴とするフォトレジスト用樹脂組成物。 Obtained by reacting one or two selected from metacresol, paracresol, 3,5-xylenol and 2,3,5-trimethylphenol, and aldehydes in the presence of an acid catalyst at a temperature of 110-220 ° C. A resin composition for photoresists, comprising: a high-ortho novolak-type phenol resin, a naphthoquinone diazide derivative, and a solvent.
  2. 　メタクレゾールとパラクレゾールとの重量比率が７５：２５から５０：５０である請求項１記載のフォトレジスト用樹脂組成物。 The resin composition for a photoresist according to claim 1, wherein the weight ratio of metacresol to para-cresol is 75:25 to 50:50.
  3. 　メタクレゾールとパラクレゾールの合計量と、３，５－キシレノール及び／または２，３，５-トリメチルフェノールとの重量比率が９５：５から６０：４０である請求項１又は２記載のフォトレジスト用樹脂組成物。 3. The photoresist according to claim 1, wherein the total amount of metacresol and paracresol and the weight ratio of 3,5-xylenol and / or 2,3,5-trimethylphenol is 95: 5 to 60:40. Resin composition.
  4. 　請求項１～３のいずれか１項に記載のフォトレジスト用樹脂組成物を用いてなるフォトレジスト。 A photoresist comprising the photoresist resin composition according to any one of claims 1 to 3.
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JP2014214256A (en) * 2013-04-26 2014-11-17 明和化成株式会社 Photoresist resin and photoresist composition using the same
JP2016018168A (en) * 2014-07-10 2016-02-01 日油株式会社 Photosensitive resin composition and use of the same

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CN111303362B (en) * 2018-12-12 2023-05-30 上海飞凯材料科技股份有限公司 Phenolic resin, preparation method thereof and photoresist
CN111538211B (en) * 2020-05-25 2023-04-21 苏州理硕科技有限公司 Phenolic resin photoresist composition and preparation method thereof
CN114874405A (en) * 2022-05-31 2022-08-09 杭摩科技新材料(阜阳)有限公司 Thermoplastic phenolic resin and preparation process thereof

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JP2014214256A (en) * 2013-04-26 2014-11-17 明和化成株式会社 Photoresist resin and photoresist composition using the same
JP2016018168A (en) * 2014-07-10 2016-02-01 日油株式会社 Photosensitive resin composition and use of the same

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