WO2016103850A1 - Résine phénolique de type novolaque, composition photosensible, matériau de réserve, film de revêtement et film de revêtement de réserve - Google Patents

Résine phénolique de type novolaque, composition photosensible, matériau de réserve, film de revêtement et film de revêtement de réserve Download PDF

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WO2016103850A1
WO2016103850A1 PCT/JP2015/078589 JP2015078589W WO2016103850A1 WO 2016103850 A1 WO2016103850 A1 WO 2016103850A1 JP 2015078589 W JP2015078589 W JP 2015078589W WO 2016103850 A1 WO2016103850 A1 WO 2016103850A1
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formula
group
general formula
same
compound
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PCT/JP2015/078589
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今田　知之
教夫 長江
勇介 佐藤
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Dic株式会社
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    • 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
    • C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
    • 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

Definitions

  • the present invention uses a novolak-type phenol resin suitable for obtaining a resist coating film excellent in heat resistance, flexibility, alkali developability, sensitivity, and resolution, a photosensitive composition containing the resin, and the photosensitive composition. And a coating film (resist coating film) using the resist material.
  • One package format for highly integrated semiconductor components is wafer level packaging.
  • wafer level packaging As the wiring density increases, for example, the electrochemical deposition method of electronic wiring described in Non-Patent Document 1 is used.
  • gold bumps, copper posts, and copper wires need to be redistributed to form the final metal structure, but to do this, a resist type that is later electroplated (Mold) is required.
  • This resist resist layer is much thicker than the resist used in the formation of critical layers in IC manufacturing.
  • the size of the figure and the resist thickness are typically as thick as 2 ⁇ m to 100 ⁇ m.
  • the photoresist with a high aspect ratio (resist thickness with respect to line size). And in order to pattern into a photoresist with a high aspect ratio, the resist composition from which the coating film which is excellent in a softness
  • a resist composition containing a novolak resin using an aliphatic polyaldehyde as a nodule of metacresol or paracresol is known (for example, Patent Documents). 3).
  • the problem to be solved by the present invention is a novolac type phenolic resin suitable for obtaining a coating film excellent in flexibility even in the case of a thick film and having excellent heat resistance, alkali developability, sensitivity, and resolution, It is providing the photosensitive composition containing resin, the resist material obtained using the said photosensitive composition, and the coating film (resist coating film) using the said resist material.
  • the present inventors use a phenolic trinuclear compound instead of metacresol or paracresol, and further use both monoaldehydes and polyaldehydes as nodules.
  • a novolac type phenol resin having excellent flexibility in the case of a thick film and having good heat resistance and alkali dissolution rate can be obtained, and the present invention has been completed.
  • R 1 , R 2 , and R 3 each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent. When a plurality of R 1 are present, they may be the same or different. When a plurality of R 2 are present, they may be the same or different. When a plurality of R 3 are present, May be the same or different. p and q are each independently an integer of 1 to 4, r is an integer of 0 to 4, and s is 1 or 2. However, the sum of r and s is 5 or less. ] And a compound represented by the following general formula (2)
  • the present invention also comprises a photosensitive composition comprising the novolak-type phenolic resin and a photosensitive agent, a resist material comprising the photosensitive composition, and the photosensitive composition. And a resist coating film comprising the resist material.
  • the novolac type phenolic resin and the photosensitive composition containing the resin according to the present invention provide a coating film that is excellent in flexibility even in the case of a thick film, and excellent in heat resistance, alkali developability, sensitivity, and resolution. Can do. For this reason, the said photosensitive composition can be used for a resist material.
  • FIG. 6 is a GPC chart of a novolac resin (1) obtained in Synthesis Example 2.
  • 6 is a GPC chart of a novolac resin (2) obtained in Synthesis Example 3.
  • 6 is a GPC chart of a novolac resin (3) obtained in Synthesis Example 4.
  • 3 is a GPC chart of a novolak resin (4) obtained in Comparative Synthesis Example 1.
  • 6 is a GPC chart of a novolak resin (5) obtained in Comparative Synthesis Example 2.
  • the novolak-type phenol resin according to the present invention is one or more phenolic trinuclear compounds selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). It is characterized by being obtained by reacting (A), a monoaldehyde (B) and a polyaldehyde (C) in the presence of an acid catalyst.
  • a compound represented by the general formula (1) (a trinuclear compound having a phenolic hydroxyl group in all three benzene rings) )
  • a compound represented by the general formula (2) (a trinuclear compound composed of two benzene rings having a phenolic hydroxyl group and a benzene ring not having a phenolic hydroxyl group) in an appropriate ratio
  • the amount of hydroxyl groups of the resulting novolak-type phenol resin can be controlled, and as a result, the alkali solubility can be easily controlled to a desired level.
  • p and q are each independently an integer of 1 to 4
  • r is an integer of 0 to 4
  • s is 1 or 2.
  • the sum of r and s is 5 or less.
  • t is an integer of 0 to 5.
  • R 1 , R 2 , and R 3 each independently represents an alkyl group having 1 to 8 carbon atoms that may have a substituent.
  • R 1 When a plurality of R 1 are present, they may be the same or different.
  • R 2 When a plurality of R 2 are present, they may be the same or different.
  • R 3 When a plurality of R 3 are present, May be the same or different.
  • the alkyl group may be linear, branched, or a group having a cyclic structure, but is preferably a linear group.
  • the alkyl group of R 1 , R 2 , or R 3 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and linear carbon More preferred is an alkyl group having 1 to 3 atoms.
  • the hydrogen atom in the alkyl group of R 1 , R 2 , or R 3 in the general formulas (1) and (2) may be substituted with a substituent.
  • the number of hydrogen atoms that can be substituted is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2.
  • each substituent may be the same as or different from each other.
  • substituents examples include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an aryl group which may have a substituent, and a halogen atom.
  • substituents of the alkyl group examples include a methoxy group, an ethoxy group, a propoxy group, an n-butyloxy group, a t-butyloxy group, a pentyloxy group, and an isoamyloxy group. Hexyloxy group, cyclohexyloxy group and the like.
  • examples of the aryl group which may have a substituent include a phenyl group, a naphthyl group, an indenyl group, and a biphenyl group.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
  • alkyl group represented by R 1 , R 2 , and R 3 in the general formulas (1) and (2) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
  • T-butyl group pentyl group, isoamyl group, hexyl group, cyclohexyl group, hydroxyethyl group, hydroxypropyl group, fluoromethyl group, methoxyethyl group, ethoxyethyl group, methoxypropyl group, phenylmethyl group, hydroxyphenyl Methyl group, dihydroxyphenylmethyl group, tolylmethyl group, xylylmethyl group, naphthylmethyl group, hydroxynaphthylmethyl group, dihydroxynaphthylmethyl group, phenylethyl group, hydroxyphenylethyl group, dihydroxyphenylethyl group, tolylethyl group, xylylethyl group, naphthylethyl group Group, hydro And naphthylethyl group and dihydroxynaphthylethyl group.
  • Methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, isoamyl group and hexyl group are preferable.
  • Group or ethyl group is more preferable, and methyl group is still more preferable.
  • R 1 and R 2 in general formulas (1) and (2) are preferably alkyl groups having the same number of carbon atoms. Further, each of R 1 and R 2 are, in the benzene ring of each R 1 and R 2 are bonded, attached to the carbon atom in the same position when viewed from the carbon atom to which phenolic hydroxyl group such as benzene ring has is attached It is preferable. A phenolic hydroxyl group is bonded to each of the benzene ring to which R 1 is bonded and the benzene ring to which R 2 is bonded. The position at which this phenolic hydroxyl group is bonded is also the same in each benzene ring. preferable. Furthermore, p and q are preferably the same number. As p and q, 2 is preferable.
  • R in the general formulas (1) and (2) is an integer of 0 to 4. Among these, r is preferably 0.
  • Examples of the compound represented by the general formula (1) include compounds represented by any one of the following general formulas (1-1) to (1-18).
  • R 1 , R 2 , and R 3 are the same as those in the general formula (1), r1 represents an integer of 0 to 4, and r2 is 0 Represents an integer of ⁇ 3.
  • the general formula (1-1) to the compound represented by the formula (1-18), Compound R 1 and R 2 are both methyl or ethyl group, and r1 and r2 is 0
  • R 1 R 2 and R 2 are both methyl groups, and r1 and r2 are 0.
  • the general formulas (1-1), (1-2), Compounds represented by (1-7), (1-8), (1-13), or (1-14) are preferred, and are represented by the general formulas (1-1), (1-7), or (1-
  • the compound represented by 13) is more preferred, and the compound represented by formula (1-1) is more preferred.
  • Examples of the compound represented by the general formula (2) include compounds represented by any one of the following general formulas (2-1) to (2-6).
  • R 1 , R 2 , R 3 , and t are the same as those in the general formula (2).
  • the general formula (2-1) to the compound represented by the formula (2-6) compound R 1 and R 2 are both methyl or ethyl group, and t is 0 are preferred, R 1 and R A compound in which both 2 are methyl groups and t is 0 is more preferable.
  • the compound represented by the general formula (2) a novolac type phenol resin capable of obtaining a coating film having heat resistance and high resolution can be obtained. Therefore, the compound represented by the general formula (2-1) or (2-2) The compound represented by Formula (2-1) is more preferable.
  • the compound represented by the general formula (1) includes, for example, an alkyl-substituted phenol (d1) and a hydroxyl group-containing aromatic aldehyde (d2), and a carbon atom on the aromatic hydrocarbon group of the alkyl-substituted phenol (d1). It can be obtained by carrying out the condensation under conditions where the difference in reaction activity energy can be utilized. Specifically, for example, the compound represented by the general formula (1) is obtained by polycondensing an alkyl-substituted phenol (d1) and a hydroxyl group-containing aromatic aldehyde (d2) in the presence of an acid catalyst. .
  • the compound represented by the general formula (2) is, for example, alkyl-substituted phenol (d1) and an aromatic aldehyde having no hydroxyl group (hydroxyl-free aromatic aldehyde) (d′ 2). It can be obtained by performing condensation under conditions that can utilize the difference in the reaction activity energy of carbon atoms on the aromatic hydrocarbon group of phenol (d1).
  • the compound represented by the general formula (1) is obtained by polycondensing an alkyl-substituted phenol (d1) and a hydroxyl group-free aromatic aldehyde (d′ 2) in the presence of an acid catalyst. Is obtained.
  • the alkyl-substituted phenol (d1) is a compound in which part or all of the hydrogen atoms bonded to the phenol benzene ring are substituted with an alkyl group.
  • alkyl group include alkyl groups having 1 to 8 carbon atoms, and a methyl group is particularly preferable.
  • alkyl-substituted phenol (d1) examples include o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, p-octylphenol, pt-butylphenol, o Monoalkylphenols such as cyclohexylphenol, m-cyclohexylphenol and p-cyclohexylphenol; dialkyl such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,4-xylenol, 2,6-xylenol Examples include alkylphenols; trialkylphenols such as 2,3,5-trimethylphenol and 2,3,6-trimethylphenol.
  • alkyl-substituted phenols those having a substitution number of alkyl groups on the benzene ring of phenol of 2 are preferable because of excellent balance between heat resistance and alkali solubility.
  • Specific examples include 2,5- Xylenol and 2,6-xylenol are preferred.
  • These alkyl-substituted phenols (d1) can be used alone or in combination of two or more, but preferably only one is used.
  • the hydroxyl group-containing aromatic aldehyde (d2) is a compound having at least one aldehyde group and at least one hydroxyl group in the aromatic ring.
  • the hydroxyl group-containing aromatic aldehyde (d2) include hydroxybenzaldehydes such as salicylaldehyde, m-hydroxybenzaldehyde and p-hydroxybenzaldehyde; dihydroxybenzaldehydes such as 2,4-dihydroxybenzaldehyde and 3,4-dihydroxybenzaldehyde; vanillin And vanillin compounds such as ortho vanillin, isovanillin and ethyl vanillin;
  • p-hydroxybenzaldehyde (4-hydroxybenzaldehyde) and 2,4-dihydroxybenzaldehyde are available because they are easily available industrially and have a good balance between heat resistance and alkali solubility.
  • the hydroxyl group-free aromatic aldehyde (d′ 2) is a compound having at least one aldehyde group in the aromatic ring and not having a phenolic hydroxyl group.
  • Examples of the hydroxyl group-free aromatic aldehyde (d′ 2) include benzaldehyde; alkylbenzaldehyde such as methylbenzaldehyde, ethylbenzaldehyde, dimethylbenzaldehyde, and diethylbenzaldehyde; alkoxybenzaldehyde such as methoxybenzaldehyde and ethoxybenzaldehyde; Among these hydroxyl group-free aromatic aldehydes (d′ 2), benzaldehyde is preferable.
  • the compound represented by the general formula (1) or (2) includes, for example, the alkyl-substituted phenol (d1), the hydroxyl group-containing aromatic aldehyde (d2) or the hydroxyl group-free aromatic aldehyde (d′ 2), Can be obtained by polycondensation in the presence of an acid catalyst.
  • an acid catalyst for example, by polycondensation of 2,5-xylenol and 4-hydroxybenzaldehyde in the presence of an acid catalyst, R 1 and R 2 in the general formula (1-1) are both methyl groups, and r A compound is obtained in which is 0.
  • R 1 and R 2 are both methyl groups, and r is 0 Is obtained.
  • the acid catalyst examples include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, manganese acetate and the like. These acid catalysts can be used alone or in combination of two or more. Of these acid catalysts, sulfuric acid and paratoluenesulfonic acid are preferred because of their excellent activity.
  • the acid catalyst may be added before the reaction or may be added during the reaction.
  • the polycondensation of the alkyl-substituted phenol (d1) and the hydroxyl group-containing aromatic aldehyde (d2) or the hydroxyl group-free aromatic aldehyde (d′ 2) may be performed in the presence of an organic solvent, if necessary. .
  • organic solvent examples include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin and other polyols; 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 ethers such as glycol ethyl methyl ether and ethylene glycol monophenyl ether
  • the reaction temperature for polycondensing the alkyl-substituted phenol (d1) with the hydroxyl group-containing aromatic aldehyde (d2) or the hydroxyl group-free aromatic aldehyde (d′ 2) is, for example, 60 to 140 ° C.
  • the reaction time is, for example, 0.5 to 100 hours.
  • the charge ratio [(d1) / (d2)] is excellent in the removal of unreacted alkyl-substituted phenol (d1), the yield of the product and the purity of the reaction product.
  • the ratio is preferably in the range of 1 / 0.2 to 1 / 0.5, more preferably in the range of 1 / 0.25 to 1 / 0.45.
  • the general formula (1 ) Or (2) and the unreacted substance may remain.
  • an unfavorable condensate other than the compound represented by the general formula (1) or (2) may be generated. Therefore, before being used as a raw material for the novolak-type phenol resin according to the present invention (phenolic trinuclear compound (A)), it is represented by the general formula (1) or (2) from the reaction solution after the polycondensation reaction. It is preferable to purify the compound.
  • the purity of the compound represented by the general formula (1) or (2) used as the phenol trinuclear compound (A) is preferably 85% or more, more preferably 90% or more, still more preferably 94% or more, 98% or more is particularly preferable.
  • the purity of the compound represented by the general formula (1) or (2) can be determined from the area ratio in the GPC chart.
  • the reaction solution after the polycondensation reaction is converted to the compound represented by the general formula (1) or (2).
  • the poor solvent (S1) which is insoluble or hardly soluble, and the resulting precipitate is dissolved in the compound represented by the general formula (1) or (2)
  • there is a method in which the precipitate generated by dissolving in the solvent (S2) that is also mixed with the poor solvent (S1) and throwing again into the poor solvent (S1) is filtered.
  • Examples of the poor solvent (S1) used in this case include water; monoalcohols such as methanol, ethanol, and propanol; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and cyclohyxane; toluene, xylene And aromatic hydrocarbons.
  • water and methanol are preferable because the acid catalyst can be efficiently removed at the same time.
  • examples of the solvent (S2) include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5- Polyols such as pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin; 2-ethoxyethanol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether Glycol ethers such as ethylene glycol ethyl methyl ether and ethylene glycol mono
  • one or more compounds represented by the general formula (1) may be used as the phenolic trinuclear compound (A).
  • Two or more kinds of compounds represented by the general formula (2) may be used, and one kind or two or more kinds of compounds represented by the general formula (1) and one kind or two or more kinds of the general formula (2). You may use the compound represented by these.
  • the phenolic trinuclear compound (A) by adjusting the ratio of the compound represented by the general formula (1) and the compound represented by the general formula (2), the resulting novolak-type phenol resin has a hydroxyl group. The amount can be adjusted.
  • R 4 represents a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent.
  • the monoaldehydes (B) used as a raw material may be a single compound or a combination of two or more compounds.
  • alkyl aldehydes such as acetaldehyde, propyl aldehyde, butyraldehyde, isobutyraldehyde, pentyl aldehyde, hexyl aldehyde; salicyl aldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde 2-hydroxy-4-methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde and the like; 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 4-hydroxy- 3-methoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-hydroxy-3,5-dimethoxybenzalde A benzaldehyde having both a hydroxy group and an alkoxy group such as alkoxide; an alkoxybenzaldeh
  • formaldehyde When formaldehyde is used as the monoaldehydes (B), formaldehyde and other aldehydes may be used in combination. When formaldehyde and other aldehydes are used in combination, the amount of other aldehydes used is preferably in the range of 0.05 to 1 mole per mole of formaldehyde.
  • the polyaldehyde (C) used as a raw material for the novolak type phenol resin according to the present invention is not particularly limited as long as it is a compound having two or more aldehyde groups in the molecule.
  • Specific examples of polyaldehydes (C) include aliphatic dialdehydes such as glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde and adipaldehyde; aromatic dialdehydes such as phthalaldehyde, isophthalaldehyde and terephthalaldehyde An aliphatic trialdehyde such as triformylmethane; an aromatic trialdehyde such as benzenetrialdehyde; Among them, terephthalaldehyde or glutaraldehyde is preferable as the polyaldehyde (C) because it is easily available and a higher heat-resistant novolak type phenol resin can be obtained.
  • the novolak-type phenol resin according to the present invention is obtained, for example, by condensing a phenol trinuclear compound (A), a monoaldehyde (B), and a polyaldehyde (C) in the presence of an acid catalyst. .
  • the charge ratio [(A) / (B)] of the phenolic trinuclear compound (A) and the monoaldehydes (B) can suppress excessive high molecular weight (gelation) and is suitable as a coating material. Since a molecular weight can be obtained, the molar ratio is preferably in the range of 1 / 0.5 to 1 / 1.2, and more preferably in the range of 1 / 0.6 to 1 / 0.9.
  • the charging ratio (amount used) [(B) / (C)] of the monoaldehydes (B) and polyaldehydes (C) to be reacted with the phenol trinuclear compound (A) is 1 / (mass ratio).
  • a range of 0.01 to 1 / 1.5 is preferable, and a range of 1 / 0.05 to 1 / 1.2 is more preferable.
  • Acid catalysts used in the reaction include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, hydrobromic acid, perchloric acid and phosphoric acid, sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and benzenesulfonic acid, and oxalic acid And organic acids such as succinic acid, malonic acid, monochloroacetic acid and dichloroacetic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride.
  • inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, hydrobromic acid, perchloric acid and phosphoric acid
  • sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and benzenesulfonic acid
  • oxalic acid and organic acids
  • organic acids such as succinic acid, malonic acid,
  • the condensation reaction of the phenolic trinuclear compound (A), the monoaldehydes (B) and the polyaldehydes (C) may be performed in the presence of an organic solvent as necessary.
  • the organic solvent include the same organic solvents that can be used in the polycondensation of the alkyl-substituted phenol (d1) and the hydroxyl group-containing aromatic aldehyde (d2).
  • the organic solvent can be used alone or in combination of two or more. Further, 2-ethoxyethanol is preferred as the organic solvent from the viewpoint of excellent solubility of the resulting novolak type phenol resin.
  • Examples of the novolak-type phenolic resin according to the present invention include, as repeating units, a structural unit (I-1) represented by the following general formula (I-1) and a structure represented by the following general formula (I-2). Group consisting of unit (I-2), structural unit (II-1) represented by the following general formula (II-1), and structural unit (II-2) represented by the following general formula (II-2) What has 1 or more types of structural site
  • R 1 and R 2 are the same as those in the general formula (1), and R 4 is It is the same as the general formula (3).
  • R 1 and R 2 are both the same group, and R 4 is preferably a hydrogen atom, R 1 and R 2 are both the same unsubstituted alkyl group having 1 to 3 carbon atoms, and R 4 is more preferably a hydrogen atom, and R 1 and More preferably, both R 2 are methyl groups and R 4 is a hydrogen atom.
  • the weight average molecular weight of the novolak type phenolic resin according to the present invention is preferably 1,000 to 100,000, more preferably 1,000 to 70,000, and still more preferably 1,000 to 35,000.
  • the molecular weight of the novolac type phenol resin having the structural unit represented by the general formula (I-1) or the structural unit represented by the general formula (II-1) as a repeating unit has a novolac having more excellent heat resistance.
  • Type phenol resin is obtained, the weight average molecular weight (Mw) is preferably 5,000 to 100,000, more preferably 5,000 to 70,000, still more preferably 5,000 to 35,000, 000 to 25,000 is particularly preferred.
  • the molecular weight of the novolac type phenol resin having the structural unit represented by the general formula (I-2) or the structural unit represented by the general formula (II-2) as a repeating unit has a novolak having more excellent heat resistance. Since a type phenol resin is obtained, the weight average molecular weight (Mw) is preferably 1,000 to 5,000, more preferably 2,000 to 4,000.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the novolak type phenol resin are measured by gel permeation chromatography (hereinafter abbreviated as “GPC”) as follows. It is measured under conditions.
  • the novolak type phenolic resin according to the present invention can be used for various electric and electronic member applications such as adhesives, paints, photoresists, printed wiring boards and the like.
  • the novolak type phenolic resin according to the present invention is excellent in balance among flexibility, heat resistance, and alkali solubility, and also has good substrate followability.
  • the novolak-type phenol resin according to the present invention is suitable as a resist material, particularly as a resist material for thick films.
  • a photosensitive composition suitable as a thick film resist having sensitivity, resolution, heat resistance, substrate followability and flexibility can be obtained.
  • the photosensitive composition according to the present invention is characterized by containing a photosensitive agent in addition to the novolac type phenol resin according to the present invention.
  • the photosensitive agent include compounds having a quinonediazide group when the photosensitive composition according to the present invention is used as a positive resist material.
  • a photo-acid generator etc. are mentioned.
  • the compound having a quinonediazide group include, for example, an aromatic (poly) hydroxy compound, naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, ortho Examples include complete ester compounds, partial ester compounds, amidated products, and partially amidated products with sulfonic acids having a quinonediazide group such as anthraquinone diazide sulfonic acid. These photosensitizers may be used alone or in combination of two or more.
  • aromatic (poly) hydroxy compound used here examples include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4, 6-trihydroxybenzophenone, 2,3,4-trihydroxy-2′-methylbenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2, 3 ′, 4,4 ′, 6-pentahydroxybenzophenone, 2,2 ′, 3,4,4′-pentahydroxybenzophenone, 2,2 ′, 3,4,5-pentahydroxybenzophenone, 2,3 ′, 4,4 ′, 5 ′, 6-hexahydroxybenzophenone, 2,3,3 ′, 4,4 ′, 5′-hexahydroxyben Polyhydroxy benzophenone compounds such phenone;
  • a tris (hydroxyphenyl) methane compound such as phenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, or a methyl-substituted product thereof;
  • the amount of the compound becomes a composition with excellent photosensitivity, so that the novolac type phenol resin according to the present invention (according to the present invention)
  • the photosensitive composition contains other resin components, the ratio is 5 to 50 parts by mass with respect to 100 parts by mass of the total resin component including the novolac type phenol resin according to the present invention.
  • the ratio is preferably 5 to 30 parts by mass.
  • Examples of the photoacid generator include onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds, and the like.
  • onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts.
  • preferred onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluorochlorosulfonate, Phenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenylpheny
  • halogen-containing compound examples include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds.
  • preferred halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, and phenyl-bis (trichloromethyl) -s-triazine.
  • S-triazine derivatives such as 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine, and the like.
  • sulfone compounds examples include ⁇ -ketosulfone compounds, ⁇ -sulfonylsulfone compounds, and ⁇ -diazo compounds of these compounds.
  • Specific examples of preferred sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenacylsulfonyl) methane.
  • sulfonic acid compound examples include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
  • Specific examples of preferred sulfonic acid compounds include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, and o-nitrobenzyl p-toluene sulfonate.
  • sulfonimide compound examples include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl).
  • diazomethane compound examples include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane.
  • the amount of the photoacid generator is a composition having excellent photosensitivity, and therefore the novolak-type phenolic resin according to the present invention
  • the ratio is 5 to 50 parts by mass with respect to 100 parts by mass of the total resin component including the novolac type phenol resin according to the present invention.
  • the proportion is preferably 5 to 30 parts by mass.
  • the photosensitive composition according to the present invention may contain an organic base compound for neutralizing the acid generated from the photoacid generator during exposure.
  • the addition of the organic base compound has an effect of preventing the dimensional variation of the resist pattern due to the movement of the acid generated from the photoacid generator.
  • Examples of the organic base compound used here include organic amine compounds selected from nitrogen-containing compounds.
  • Pyridine compounds such as pyridine, 4-dimethylaminopyridine, 2,6-dimethylpyridine;
  • Amine compounds substituted with a hydroxyalkyl group having 1 to 4 carbon atoms such as diethanolamine, triethanolamine, triisopropanolamine, tris (hydroxymethyl) aminomethane, bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane ;
  • Examples include aminophenol compounds such as 2-aminophenol, 3-aminophenol, and 4-aminophenol. These may be used alone or in combination of two or more. Among them, the pyrimidine compound, the pyridine compound, or the amine compound having a hydroxy group is preferable, and the amine compound having a hydroxy group is particularly preferable because of excellent dimensional stability of the resist pattern after exposure.
  • the addition amount is preferably in the range of 0.1 to 100 mol%, preferably in the range of 1 to 50 mol%, with respect to the content of the photoacid generator. Is more preferable.
  • the photosensitive composition according to the present invention may use other resins as the resin component in addition to the novolac type phenol resin according to the present invention.
  • Other resins are preferably those that are soluble in an alkali developer, or those that are soluble in an alkali developer when used in combination with an additive such as an acid generator (alkali-soluble resin).
  • resins used here include, for example, various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenolic compounds, modified novolaks of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds.
  • Resins phenol aralkyl resins (Zyloc resins), naphthol aralkyl resins, trimethylol methane resins, tetraphenylol ethane resins, biphenyl modified phenol resins, biphenyl modified naphthol resins, aminotriazine modified phenol resins, and various vinyl polymers It is done.
  • the various novolak resins include phenolphenol, cresol, xylenol and other alkylphenols, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, phenolic hydroxyl group-containing compounds such as naphthol and dihydroxynaphthalene. And a polymer obtained by reacting an aldehyde compound with acid catalyst conditions.
  • the various vinyl polymers include polyhydroxystyrene, polystyrene, polyvinyl naphthalene, polyvinyl anthracene, polyvinyl carbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, poly ( A homopolymer of a vinyl compound such as (meth) acrylate or a copolymer thereof may be mentioned.
  • the blending ratio of the novolac type phenol resin and the other resin according to the present invention can be arbitrarily adjusted depending on the desired application.
  • the novolac type phenol resin according to the present invention is 60% by mass with respect to the total of the novolac type phenol resin according to the present invention and other resins. It is preferable to use more, and it is more preferable to use 80% by mass or more.
  • the photosensitive composition according to the present invention may contain a surfactant for the purpose of improving the film forming property and pattern adhesion when used for resist applications, and reducing development defects.
  • a surfactant for the purpose of improving the film forming property and pattern adhesion when used for resist applications, and reducing development defects.
  • the surfactant used here include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ether compounds such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene Polyoxyethylene alkyl allyl ether compounds such as ethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid ester compounds such as poly
  • the amount of these surfactants to be added is 0.001 to 2 with respect to 100 parts by mass of the resin solid content (including the novolac type phenol resin according to the present invention as the resin solid content) in the photosensitive composition according to the present invention. It is preferable to use in the range of parts by mass.
  • the photosensitive composition according to the present invention may further contain a filler.
  • the filler can improve the hardness and thermal decomposition resistance of the coating film.
  • the filler contained in the photosensitive composition according to the present invention may be an organic filler, but is preferably an inorganic filler.
  • inorganic fillers include silica, mica, talc, clay, bentonite, montmorillonite, kaolinite, wollastonite, calcium carbonate, calcium hydroxide, magnesium carbonate, titanium oxide, alumina, aluminum hydroxide, barium sulfate, and titanium.
  • Examples thereof include barium acid, potassium titanate, zinc oxide, and glass fiber. Among them, it is preferable to use silica because the coefficient of thermal expansion can be lowered.
  • the photosensitive composition according to the present invention may further contain a curing agent.
  • a curing agent contained in the photosensitive composition according to the present invention for example, a melamine compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, a guanamine compound, a glycoluril compound, Examples include urea compounds, resol resins, epoxy compounds, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, acid anhydrides, and oxazoline compounds.
  • the melamine compound examples include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol melamine Examples thereof include compounds in which 1 to 6 methylol groups are acyloxymethylated.
  • guanamine compound examples include tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxymethylbenzoguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, tetramethoxyethylguanamine, tetraacyloxyguanamine, Examples thereof include compounds in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxymethylated.
  • glycoluril compound examples include 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6-tetrakis. (Hydroxymethyl) glycoluril and the like.
  • urea compound examples include 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea and 1,1,3,3-tetrakis (methoxymethyl) urea. Can be mentioned.
  • resole resins examples include phenols, alkylphenols such as cresol and xylenol, bisphenols such as phenylphenol, resorcinol, biphenyl, bisphenol A and bisphenol F, phenolic hydroxyl group-containing compounds such as naphthol and dihydroxynaphthalene, and aldehyde compounds.
  • alkylphenols such as cresol and xylenol
  • bisphenols such as phenylphenol, resorcinol, biphenyl, bisphenol A and bisphenol F
  • phenolic hydroxyl group-containing compounds such as naphthol and dihydroxynaphthalene
  • aldehyde compounds examples include polymers obtained by reacting under alkaline catalyst conditions.
  • epoxy compound examples include tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether, and the like.
  • isocyanate compound examples include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.
  • azide compound examples include 1,1′-biphenyl-4,4′-bisazide, 4,4′-methylidenebisazide, 4,4′-oxybisazide, and the like.
  • Examples of the compound containing a double bond such as an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, and tetramethylene glycol divinyl ether.
  • Vinyl ether neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane tri Examples include vinyl ether.
  • the acid anhydride examples include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4 , 4 ′-(isopropylidene) diphthalic anhydride, aromatic aromatic anhydrides such as 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydro anhydride Examples thereof include alicyclic carboxylic acid anhydrides such as phthalic acid, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride dodecenyl succinic anhydride, and trialkyltetrahydrophthalic anhydride.
  • a glycoluril compound, a urea compound, and a resole resin are preferable because the composition is excellent in curability and has excellent dry etching resistance and thermal decomposition resistance when used for resist underlayer film applications. Is particularly preferred.
  • the blending amount of the curing agent is the novolak according to the present invention in order to maintain the excellent sensitivity of the novolak type phenol resin according to the present invention. It is 50 mass parts or less with respect to 100 mass parts of type phenol resins. Since the compounding amount of the curing agent of the photosensitive composition according to the present invention is a composition from which a film excellent in curability, heat decomposability, and alkali developability is obtained, the novolak type phenol resin 100 according to the present invention is obtained.
  • the ratio is preferably 0.1 to 50 parts by mass with respect to part by mass, and further, the ratio is 0.1 to 30 parts by mass because a composition is obtained that provides a film with excellent photosensitivity. More preferably, the proportion is 0.5 to 20 parts by mass.
  • the photosensitive composition according to the present invention is preferably obtained by dissolving or dispersing various additives such as dyes, pigments, cross-linking agents, and dissolution accelerators in an organic solvent, if necessary.
  • a coating film can be formed by applying a material dissolved in an organic solvent to a substrate or the like.
  • Dyes, pigments, crosslinking agents, and dissolution accelerators can be appropriately selected from those commonly used as additives for resist materials in consideration of the intended use.
  • organic solvent examples include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether propylene glycol monomethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol diethylene ether.
  • alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether propylene glycol monomethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol diethylene ether.
  • Dialkylene glycol dialkyl ethers such as propyl 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 methyl, methyl ethyl ketone, cyclohexanone and methyl amyl ketone; cyclic ethers such as dioxane; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, Ester compounds such as ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl
  • the photosensitive composition according to the present invention can be prepared by blending the above components and mixing them using a stirrer or the like. Moreover, when a photosensitive composition contains a filler and a pigment, it can adjust by disperse
  • dispersers such as a dissolver, a homogenizer, and a 3 roll mill.
  • the photosensitive composition according to the present invention can be suitably used as a resist material.
  • the photosensitive composition according to the present invention may be used as a resist material as it is dissolved / dispersed in an organic solvent, or may be removed by applying a film dissolved / dispersed in an organic solvent.
  • a solvent may be used as a resist film.
  • the support film used as the resist film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate, and may be a single layer film or a plurality of laminated films.
  • the surface of the support film may be a corona-treated one or a release agent.
  • Photolithographic methods using the photosensitive composition according to the present invention include, for example, applying a photosensitive composition (resist material) dissolved and dispersed in an organic solvent onto an object to be subjected to silicon substrate photolithography, Pre-bake at a temperature of 60 to 150 ° C.
  • the coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating and the like.
  • Next is the creation of a resist pattern. If the photosensitive composition is positive, the target resist pattern is exposed through a predetermined mask, and the exposed portion is dissolved in an alkali developer. A resist pattern is formed. Since the photosensitive composition according to the present invention has high photosensitivity, it is possible to form a resist pattern with excellent resolution.
  • Examples of the exposure light source here include infrared light, visible light, ultraviolet light, far-ultraviolet light, X-rays, and electron beams.
  • Examples of ultraviolet light include g-line (wavelength 436 nm) and h-line (wavelength 436 nm) of a high-pressure mercury lamp. Examples include a wavelength 405 nm) i-line (wavelength 365 nm), a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), and an EUV laser (wavelength 13.5 nm). Since the photosensitive composition according to the present invention has high photosensitivity and alkali developability, a resist pattern can be formed with high resolution when any light source is used.
  • the film thickness of the coating film formed from the photosensitive composition (resist material) according to the present invention can be arbitrarily adjusted depending on the desired application. Even when a thick film is formed, the effect of the novolac-type phenolic resin according to the present invention that can form a coating film excellent in flexibility without sacrificing heat resistance or alkali solubility is sufficiently expressed.
  • the thickness of the coating film is preferably from 100 nm to 100 ⁇ m, more preferably from 500 nm to 100 ⁇ m, further preferably from 2 to 100 ⁇ m, still more preferably from 2 to 20 ⁇ m.
  • a GPC chart of the novolak resin (1) is shown in FIG.
  • the number average molecular weight (Mn) 2,051
  • the weight average molecular weight (Mw) 7,855
  • the polydispersity (Mw / Mn) 3.83. .
  • a GPC chart of the novolak resin (5) is shown in FIG.
  • the number average molecular weight (Mn) 2,150
  • the weight average molecular weight (Mw) 9,571
  • the polydispersity (Mw / Mn) 4.45. .
  • Examples 1 to 3, Comparative Examples 1 and 2 For the novolak resins (1) to (5) synthesized in Synthesis Examples 2 to 4 and Comparative Synthesis Examples 1 and 2, as shown in Table 1, novolak resins and photosensitizers (“P-200” manufactured by Toyo Gosei Co., Ltd.) 1 mol of 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1methylethyl] phenyl] ethylidene] bisphenol and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride And PGMEA were mixed and dissolved at 28/12/60 (parts by mass), followed by filtration using a 0.2 ⁇ m membrane filter to obtain a photosensitive composition. A coating film was prepared using these compositions, and alkali developability, sensitivity, resolution, heat resistance (Tg), substrate followability, and flexibility were evaluated according to the following. The evaluation results are shown in Table 1.
  • the photosensitive composition was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 ⁇ m and dried on a hot plate at 110 ° C. for 60 seconds to obtain a silicon wafer having a coating film.
  • the obtained wafer was immersed in an alkali developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and then dried on a 110 ° C. hot plate for 60 seconds.
  • the film thickness of the coating film of the photosensitive composition was measured before and after immersion in the developer, and the value obtained by dividing the difference by 60 was defined as the evaluation result of alkali developability (ADR ( ⁇ / sec)).
  • a wafer subjected to PEB Post Exposure Bake
  • PEB Post Exposure Bake
  • a ghi line lamp manufactured by USHIO INC., Multi-light
  • the ADR alkali developability was evaluated.
  • the film thickness of the coating film was measured using a film thickness meter (“f-20” manufactured by Filmetrics Co., Ltd.).
  • ⁇ Resolution evaluation> A photomask was placed on a 5-inch silicon wafer having a coating film on which the photosensitive composition had been applied and dried, and the film was exposed to 200 mJ / cm 2 with a ghi line lamp (manufactured by Ushio Inc., Multilight). The film after irradiation was developed and dried in the same manner as in ⁇ Alkali developability evaluation>.
  • the heat resistance was evaluated by the glass transition temperature (Tg) of the coating film.
  • Tg glass transition temperature
  • a photosensitive composition is applied onto a 5-inch silicon wafer with a spin coater to a thickness of about 1 ⁇ m, and dried on a hot plate at 110 ° C. for 60 seconds to form a silicon wafer having a coating film. Obtained.
  • the resin content was scraped from the obtained wafer and the glass transition temperature was measured.
  • the glass transition temperature was measured using a differential scanning calorimeter (DSC) (TA Instruments, product name: Q100) under a nitrogen atmosphere, temperature range: ⁇ 100 to 200 ° C., temperature rising temperature: 10 ° C. Scanning was performed under the conditions of / min, and the measurement result was taken as the glass transition temperature.
  • DSC differential scanning calorimeter
  • ⁇ Substrate following evaluation> The photosensitive composition was coated on a 5-inch silicon wafer with a spin coater to a thickness of about 50 ⁇ m and dried on a hot plate at 110 ° C. for 300 seconds. The presence or absence of cracks on the coating film surface of the obtained wafer was observed using a laser microscope (VK-X200) manufactured by Keyence Corporation. In the evaluation, “ ⁇ ” indicates that no crack was observed, and “X” indicates that a crack was observed.
  • the photosensitive composition was coated on a polyimide film having a thickness of 50 ⁇ m with a spin coater so as to have a thickness of about 5 ⁇ m, and dried on a hot plate at 110 ° C. for 300 seconds.
  • the obtained film-like coating film was bent at 180 degrees, and the state of the bent portion was observed using a laser microscope (VK-X200) manufactured by Keyence Corporation. In the evaluation, “ ⁇ ” indicates that no crack was observed, and “X” indicates that a crack was observed.
  • the coating films (Examples 1 to 3) of the photosensitive composition containing the novolak resins (1) to (3), which are novolak type phenol resins according to the present invention have an ADR of 1600 ⁇ / sec or more after exposure.
  • the alkali developability was good, the sensitivity and resolution were high, the glass transition temperature was sufficiently high at 160 ° C. or higher, the heat resistance was good, and the substrate followability and flexibility were excellent.
  • the coating film (Comparative Example 1) of the photosensitive composition containing the novolak resin (4) which is a novolak-type phenol resin synthesized using only monoaldehydes as the nodule, has an alkali developability and sensitivity.
  • the coating film (comparative example 2) of the photosensitive composition containing the novolak resin (5) which is a cresol novolak resin synthesized using polyaldehydes as a nodule is excellent in substrate followability and flexibility.
  • alkali developability, sensitivity, resolution, and heat resistance were all insufficient.

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Abstract

L'invention concerne : une résine phénolique de type novolaque qui est appropriée pour l'obtention d'un film de revêtement présentant une excellente flexibilité, même si ce dernier est épais, tout en présentant une excellente résistance à la chaleur, aptitude au développement alcalin, sensibilité et résolution ; et similaires. La présente invention concerne spécifiquement une résine phénolique de type novolaque qui est obtenue en faisant réagir (A) un ou plusieurs composés phénoliques trinucléaires choisis dans le groupe constitué des composés représentés par la formule générale (1) et des composés représentés par la formule générale (2), (B) un monoaldéhyde et (C) un polyaldéhyde en présence d'un catalyseur acide. (Dans les formules, chacun de R1, R2 et R3 représente indépendamment un groupe alkyle éventuellement substitué ayant 1 à 8 atomes de carbone ; R4 représente un atome d'hydrogène, un groupe alkyle éventuellement substitué ou un groupe aryle éventuellement substitué ; chacun de p et q représente indépendamment un nombre entier de 1 à 4 ; r représente un nombre entier de 0 à 4 ; et s représente 1 ou 2. Dans ce contexte, la somme de r et s est inférieure ou égale à 5. )
PCT/JP2015/078589 2014-12-24 2015-10-08 Résine phénolique de type novolaque, composition photosensible, matériau de réserve, film de revêtement et film de revêtement de réserve WO2016103850A1 (fr)

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WO2014017236A1 (fr) * 2012-07-25 2014-01-30 Dic株式会社 Composé durcissable par voie radicalaire, procédé pour la production du composé durcissable par voie radicalaire, composition durcissable par voie radicalaire, produit durci correspondant et composition pour produit de réserve
WO2014084097A1 (fr) * 2012-11-28 2014-06-05 Dic株式会社 Composé contenant un groupe hydroxyphénolique, composition contenant un groupe hydroxyphénolique, résine contenant un groupe (méth)acryloyle, composition durcissable et produit durci à base de celle-ci, et résine photosensible
WO2015141427A1 (fr) * 2014-03-20 2015-09-24 Dic株式会社 Résine phénolique de type novolaque contenant un groupe hydroxyle, son procédé de production, composition durcissable, composition de réserve et réserve colorée

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WO2018101058A1 (fr) * 2016-12-01 2018-06-07 Dic株式会社 Résine contenant un groupe hydroxy phénolique et matériau de réserve
JPWO2018101058A1 (ja) * 2016-12-01 2019-03-22 Dic株式会社 フェノール性水酸基含有樹脂及びレジスト材料
US20190339613A1 (en) * 2018-05-07 2019-11-07 Jeremy Golden Photosensitive Material For Lift-Off Applications

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