WO2016185865A1 - ノボラック型フェノール性水酸基含有樹脂及びレジスト膜 - Google Patents
ノボラック型フェノール性水酸基含有樹脂及びレジスト膜 Download PDFInfo
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- WO2016185865A1 WO2016185865A1 PCT/JP2016/062614 JP2016062614W WO2016185865A1 WO 2016185865 A1 WO2016185865 A1 WO 2016185865A1 JP 2016062614 W JP2016062614 W JP 2016062614W WO 2016185865 A1 WO2016185865 A1 WO 2016185865A1
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- hydroxyl group
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- PJJUZCVILYPGRA-UHFFFAOYSA-N CCCCSCNC Chemical compound CCCCSCNC PJJUZCVILYPGRA-UHFFFAOYSA-N 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
- C07C39/16—Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
-
- 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
-
- 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
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- 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
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- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Definitions
- the present invention relates to a novolac type phenolic hydroxyl group-containing resin excellent in developability, heat resistance and substrate followability, and a resist film using the same.
- phenolic hydroxyl group-containing resins are excellent in heat resistance and moisture resistance in cured products.
- a curable composition containing a phenolic hydroxyl group-containing resin itself as a main ingredient, or as a curing agent such as an epoxy resin it is widely used in the electrical and electronic fields such as semiconductor sealing materials and insulating materials for printed wiring boards.
- the phenolic hydroxyl group-containing resin most widely used for photoresist applications is of the cresol novolac type, but as mentioned above, it does not meet the demands of today's increasingly sophisticated and diversified markets, and is heat resistant. Also, developability was not sufficient (see Patent Document 1).
- the problem to be solved by the present invention is to provide a novolac type phenolic hydroxyl group-containing resin excellent in developability, heat resistance and substrate followability, a photosensitive composition and a curable composition containing the same, and a resist film.
- the present inventors have found that a triarylmethane type phenolic hydroxyl group-containing compound, a phenolic hydroxyl group-containing compound having an aliphatic hydrocarbon group having 4 to 20 carbon atoms, and The novolak-type phenolic hydroxyl group-containing resin obtained by novolak formation was found to be excellent in developability, heat resistance and substrate followability, and the present invention was completed.
- Ar represents the following structural formula (Ar-1) or (Ar-2)
- n is independently an integer of 0 to 2
- p is an integer of 0 to 5
- q is an integer of 0 to 7
- R 2 is independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, It is either an aralkyl group or a halogen atom.
- R 1 is each independently a hydrogen atom, alkyl group, alkoxy group, aryl group, aralkyl group, or halogen atom
- m is each independently an integer of 0-4. .
- R 3 is an aliphatic hydrocarbon group having 4 to 20 carbon atoms, and j is an integer of 1 to 3.
- R 4 is each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom, and k is an integer from 0 to (5-j).
- It is related with the novolak type phenolic hydroxyl group containing resin characterized by being a polycondensate which uses the phenolic hydroxyl group containing compound (B) and aldehyde compound (C) represented by these as an essential reaction component.
- the present invention further includes the following structural formula (3)
- Ar represents the following structural formula (Ar-3) or (Ar-4)
- n is independently an integer of 0 to 2
- p is an integer of 0 to 5
- q is an integer of 0 to 7
- R 2 is independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, It is any of the aralkyl group, the halogen atom, and the bonding point bonded to the structural site represented by the structural formula (3) or (4) via the carbon atom marked with *.
- R 1 is each independently a hydrogen atom, alkyl group, alkoxy group, aryl group, aralkyl group, or halogen atom
- m is each independently an integer of 0-4.
- R 5 is any one of a hydrogen atom, an alkyl group, and an aryl group.
- R 3 is an aliphatic hydrocarbon group having 4 to 20 carbon atoms
- j is an integer of 1 to 3.
- R 4 is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, a halogen atom, a structural site represented by the structural formula (3) or (4), and an asterisk (*). Any of the bonding points bonded through the attached carbon atoms, and k is an integer of 0 to (5-j).
- R 5 is any one of a hydrogen atom, an alkyl group, and an aryl group.
- a novolak-type phenolic hydroxyl group-containing resin having a structural unit (b) represented by
- the present invention further relates to a photosensitive composition containing the novolac type phenolic hydroxyl group-containing resin and a photosensitive agent.
- the present invention further relates to a resist film comprising the photosensitive composition.
- the present invention further relates to a curable composition containing the novolac type phenolic hydroxyl group-containing resin and a curing agent.
- the present invention further relates to a resist underlayer film comprising the curable composition.
- the present invention further relates to a resist permanent film comprising the curable composition.
- a novolac type phenolic hydroxyl group-containing resin excellent in developability, heat resistance and substrate followability, a photosensitive composition and a curable composition containing the resin, and a resist film.
- FIG. 1 is a GPC chart of the phenolic hydroxyl group-containing compound (A-1) obtained in Production Example 1.
- FIG. 2 is a 13 C-NMR chart of the phenolic hydroxyl group-containing compound (A-1) obtained in Production Example 1.
- FIG. 3 is a GPC chart of the novolak type phenolic hydroxyl group-containing resin (1) obtained in Example 1.
- FIG. 4 is a GPC chart of the novolak type phenolic hydroxyl group-containing resin (2) obtained in Example 2.
- FIG. 5 is a GPC chart of the novolac type phenolic hydroxyl group-containing resin (3) obtained in Example 3.
- FIG. 6 is a GPC chart of the novolac type phenolic hydroxyl group-containing resin (1 ′) obtained in Comparative Production Example 1.
- FIG. 7 is a GPC chart of the novolak-type phenolic hydroxyl group-containing resin (2 ′) obtained in Comparative Production Example 2.
- the novolac type phenolic hydroxyl group-containing resin of the present invention has the following structural formula (1).
- Ar represents the following structural formula (Ar-1) or (Ar-2)
- n is independently an integer of 0 to 2
- p is an integer of 0 to 5
- q is an integer of 0 to 7
- R 2 is independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, It is either an aralkyl group or a halogen atom.
- R 1 is each independently a hydrogen atom, alkyl group, alkoxy group, aryl group, aralkyl group, or halogen atom
- m is each independently an integer of 0-4. .
- R 3 is an aliphatic hydrocarbon group having 4 to 20 carbon atoms, and j is an integer of 1 to 3.
- R 4 is each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom, and k is an integer from 0 to (5-j).
- It is characterized by being a polycondensate comprising a phenolic hydroxyl group-containing compound (B) and an aldehyde compound (C) represented by
- the phenolic hydroxyl group-containing compound (A) has a highly symmetrical and rigid triarylmethane structure, and further has a phenolic hydroxyl group at a high density, so that it contains a novolac type phenolic hydroxyl group.
- the resin has characteristics of high heat resistance and excellent developability.
- this and the phenolic hydroxyl group-containing compound (B) novolak by making this and the phenolic hydroxyl group-containing compound (B) novolak, a novolak type having excellent toughness and flexibility while taking advantage of the characteristics of the phenolic hydroxyl group-containing compound (A).
- a phenolic hydroxyl group-containing resin is realized.
- the phenolic hydroxyl group-containing compound (A) has the following structural formula (1)
- Ar represents the following structural formula (Ar-1) or (Ar-2)
- n is each independently an integer of 0 to 2
- p is an integer of 0 to 5
- q is an integer of 0 to 7
- R 2 is independently an alkyl group, an alkoxy group, an aryl group, an aralkyl group, Any of halogen atoms.
- R 1 is each independently a hydrogen atom, alkyl group, alkoxy group, aryl group, aralkyl group, or halogen atom
- m is each independently an integer of 0-4.
- the phenolic hydroxyl group-containing compound (A) may be used alone as one of the compounds represented by the structural formula (1), Two or more types may be used in combination.
- R 1 in the structural formula (1) is independently an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom.
- the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.
- the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyloxy group.
- aryl group examples include a phenyl group, a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxyalkoxyphenyl group, an alkoxyphenyl group, a tolyl group, a xylyl group, a naphthyl group, a hydroxynaphthyl group, and a dihydroxynaphthyl group.
- the aralkyl group is, for example, phenylmethyl group, hydroxyphenylmethyl group, dihydroxyphenylmethyl group, tolylmethyl group, xylylmethyl group, naphthylmethyl group, hydroxynaphthylmethyl group, dihydroxynaphthylmethyl group, phenylethyl group, hydroxyphenylethyl group, Examples thereof include a dihydroxyphenylethyl group, a tolylethyl group, a xylylethyl group, a naphthylethyl group, a hydroxynaphthylethyl group, and a dihydroxynaphthylethyl group.
- the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
- R 1 is preferably an alkyl group because it becomes a novolac-type phenolic hydroxyl group-containing resin having an excellent balance between heat resistance and developability, and the effect of improving heat resistance by suppressing molecular motion and the aromatic nucleus.
- a methyl group is particularly preferred because of its excellent electron donating property and industrial availability.
- n in the structural formula (1) is each independently an integer of 0 to 4, and among them, a novolak type phenolic hydroxyl group-containing resin having an excellent balance between heat resistance and developability is obtained. It is preferable that
- the bonding position of the two phenolic hydroxyl groups in the structural formula (1) is a novolac type phenolic hydroxyl group-containing resin having excellent heat resistance, and is therefore in the para position with respect to the methine group connecting three aromatic rings. Is preferred.
- Ar in the structural formula (1) is a structural portion represented by the structural formula (Ar-1) or (Ar-2).
- a novolak type phenolic hydroxyl group-containing resin having better developability is preferable, and the structural site represented by the structural formula (Ar-1) is preferable.
- R 2 in the structural formulas (Ar-1) and (Ar-2) is each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom.
- alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.
- alkoxy group examples include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyloxy group.
- aryl group examples include a phenyl group, a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxyalkoxyphenyl group, an alkoxyphenyl group, a tolyl group, a xylyl group, a naphthyl group, a hydroxynaphthyl group, and a dihydroxynaphthyl group.
- the aralkyl group is, for example, phenylmethyl group, hydroxyphenylmethyl group, dihydroxyphenylmethyl group, tolylmethyl group, xylylmethyl group, naphthylmethyl group, hydroxynaphthylmethyl group, dihydroxynaphthylmethyl group, phenylethyl group, hydroxyphenylethyl group, Examples thereof include a dihydroxyphenylethyl group, a tolylethyl group, a xylylethyl group, a naphthylethyl group, a hydroxynaphthylethyl group, and a dihydroxynaphthylethyl group.
- the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
- R 2 is preferably a hydrogen atom or an alkyl group because it becomes a novolak-type phenolic hydroxyl group-containing resin having an excellent balance between heat resistance and developability, and the aromatic compound (A) can be easily produced. Therefore, a hydrogen atom is more preferable.
- the phenolic hydroxyl group-containing compound (A) represented by the structural formula (1) specifically has a molecular structure represented by any of the following structural formulas (1-1) to (1-16) Is mentioned.
- the phenolic hydroxyl group-containing compound (A) can be obtained, for example, by a method in which a phenol compound (a1) and an aromatic aldehyde (a2) are reacted in the presence of an acid catalyst.
- phenol compound (a1) part or all of hydrogen atoms bonded to phenol or the aromatic ring of phenol are substituted with any of an alkyl group, an alkoxy group, an aryl group, an aralkyl group, and a halogen atom.
- alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.
- alkoxy group examples include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyloxy group.
- aryl group examples include a phenyl group, a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxyalkoxyphenyl group, an alkoxyphenyl group, a tolyl group, a xylyl group, a naphthyl group, a hydroxynaphthyl group, and a dihydroxynaphthyl group.
- the aralkyl group is, for example, phenylmethyl group, hydroxyphenylmethyl group, dihydroxyphenylmethyl group, tolylmethyl group, xylylmethyl group, naphthylmethyl group, hydroxynaphthylmethyl group, dihydroxynaphthylmethyl group, phenylethyl group, hydroxyphenylethyl group, Examples thereof include a dihydroxyphenylethyl group, a tolylethyl group, a xylylethyl group, a naphthylethyl group, a hydroxynaphthylethyl group, and a dihydroxynaphthylethyl group.
- the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
- a phenol compound (a1) may be used individually by 1 type, and may use 2 or more types together.
- alkyl-substituted phenols are preferred because a novolac-type phenolic hydroxyl group-containing resin having an excellent balance between heat resistance and developability is obtained.
- 2,5-xylenol and 2,6-xylenol are particularly preferable because a modified novolac-type phenol resin can be obtained.
- aromatic aldehyde (a2) examples include benzaldehyde; hydroxybenzaldehyde compounds such as salicylaldehyde, m-hydroxybenzaldehyde, and p-hydroxybenzaldehyde; dihydroxybenzaldehyde such as 2,4-dihydroxybenzaldehyde and 3,4-dihydroxybenzaldehyde; vanillin And vanillin compounds such as ortho vanillin, isovanillin and ethyl vanillin; and hydroxy naphthaldehyde compounds such as 2-hydroxy-1-naphthaldehyde and 6-hydroxy-2-naphthaldehyde. These may be used alone or in combination of two or more.
- aromatic aldehydes (a2) a novolac-type phenolic hydroxyl group-containing resin having an excellent balance between heat resistance and developability is obtained, and therefore, a hydroxybenzaldehyde compound or a hydroxynaphthaldehyde compound is preferable, and p-hydroxybenzaldehyde is particularly preferable. preferable.
- the range is preferably 1 / 0.2 to 1 / 0.5, and more preferably 1 / 0.25 to 1 / 0.45.
- Examples of the acid catalyst used in the reaction between the phenol compound (a1) and the aromatic aldehyde (a2) include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, and manganese acetate. . These acid catalysts may be used alone or in combination of two or more. Among these, sulfuric acid and paratoluenesulfonic acid are preferable from the viewpoint of excellent catalytic activity.
- the reaction of the phenol compound (a1) and the aromatic aldehyde (a2) may be performed in an organic solvent as necessary.
- the solvent used here 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
- the reaction between the phenol compound (a1) and the aromatic aldehyde (a2) is performed, for example, in the temperature range of 60 to 140 ° C. for 0.5 to 100 hours.
- the reaction product After completion of the reaction, for example, the reaction product is put into a poor solvent (S1) of the phenolic hydroxyl group-containing compound (A), the precipitate is filtered off, and then the solubility of the phenolic hydroxyl group-containing compound (A) is increased.
- the reaction product By the method of redissolving the precipitate obtained in the solvent (S2) that is high and miscible with the poor solvent (S1), the reaction product from the unreacted phenol compound (a1) or aromatic aldehyde (a2), The used acid catalyst is removed, and a purified phenolic hydroxyl group-containing compound (A) can be obtained.
- the reaction product is heated to 80 ° C. or higher to produce the phenolic compound. Crystals of the phenolic hydroxyl group-containing compound (A) can be precipitated by dissolving the hydroxyl group-containing compound (A) in an aromatic hydrocarbon solvent and cooling as it is.
- the phenolic hydroxyl group-containing compound (A) preferably has a purity calculated from a GPC chart of 90% or more because a novolak-type phenolic hydroxyl group-containing resin excellent in both developability and heat resistance can be obtained. 94% or more is more preferable, and 98% or more is particularly preferable.
- the purity of the phenolic hydroxyl group-containing compound (A) can be determined from the area ratio in the chart of gel permeation chromatography (GPC).
- GPC measurement conditions are as follows.
- Measuring device “HLC-8220 GPC” manufactured by Tosoh Corporation
- the poor solvent (S1) used for purification of the phenolic hydroxyl group-containing compound (A) is, for example, water; monoalcohols such as methanol, ethanol, propanol, ethoxyethanol; n-hexane, n-heptane, n-octane, Aliphatic hydrocarbons such as cyclohixane; aromatic hydrocarbons such as toluene and xylene. These may be used alone or in combination of two or more. Of these, water, methanol, and ethoxyethanol are preferred because of the excellent solubility of the acid catalyst.
- the solvent (S2) is, for example, a monoalcohol such as methanol, ethanol, or propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentane.
- a monoalcohol such as methanol, ethanol, or propanol
- ethylene glycol 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentane.
- Polyols such as diol, 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 monophenyl ether; Cyclic ethers such as 1,3-dioxane and 1,4-dioxane; Glycol esters such as ethylene glycol acetate; Ketones such as acetone, methyl ethyl ketone and methyl isobutyl
- the phenolic hydroxyl group-containing compound (B) has the following structural formula (2)
- R 3 is an aliphatic hydrocarbon group having 4 to 20 carbon atoms, and j is an integer of 1 to 3.
- R 4 is each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom, and k is an integer from 0 to (5-j).
- the phenolic hydroxyl group-containing compound (B) may be used alone as one of the compounds represented by the structural formula (2), Two or more types may be used in combination.
- R 3 in the structural formula (2) is an aliphatic hydrocarbon group having 4 to 20 carbon atoms, and may be any of linear, branched, alicyclic and unsaturated bonds. Specifically, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group , Nonadecyl group, icosyl group, and structural isomers thereof.
- R 4 in the structural formula (2) is independently any one of an alkyl group having 1 to 3 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, and a halogen atom.
- the alkyl group include a methyl group, an ethyl group, and a propyl group.
- the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyloxy group.
- aryl group examples include a phenyl group, a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxyalkoxyphenyl group, an alkoxyphenyl group, a tolyl group, a xylyl group, a naphthyl group, a hydroxynaphthyl group, and a dihydroxynaphthyl group.
- the aralkyl group is, for example, phenylmethyl group, hydroxyphenylmethyl group, dihydroxyphenylmethyl group, tolylmethyl group, xylylmethyl group, naphthylmethyl group, hydroxynaphthylmethyl group, dihydroxynaphthylmethyl group, phenylethyl group, hydroxyphenylethyl group, Examples thereof include a dihydroxyphenylethyl group, a tolylethyl group, a xylylethyl group, a naphthylethyl group, a hydroxynaphthylethyl group, and a dihydroxynaphthylethyl group.
- the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
- R 4 is more preferably a hydrogen atom because it becomes a novolak type phenolic hydroxyl group-containing resin having an excellent balance of developability, heat resistance and substrate followability.
- the aldehyde compound (C) may be any compound capable of forming a novolac resin structure by causing a condensation reaction with the phenolic hydroxyl group-containing compound (A) or the phenolic hydroxyl group-containing compound (B). , Paraformaldehyde, 1,3,5-trioxane, acetaldehyde, propionaldehyde, tetraoxymethylene, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, crotonaldehyde, Examples include acrolein. These may be used alone or in combination of two or more.
- formaldehyde because of excellent reactivity.
- Formaldehyde may be used either as formalin in an aqueous solution or as paraformaldehyde in a solid state.
- formaldehyde and other aldehyde compounds are used in combination, it is preferable to use the other aldehyde compound in a ratio of 0.05 to 1 mol with respect to 1 mol of formaldehyde.
- the novolak type phenolic hydroxyl group-containing resin of the present invention is obtained by reacting the phenolic hydroxyl group-containing compound (A), the phenolic hydroxyl group-containing compound (B) and the aldehyde compound (C) as essential components.
- the ratio [(A) :( B)] is preferably in the range of 100: 0.1 to 100: 30, and more preferably in the range of 100: 0.5 to 100: 20.
- the novolak type phenolic hydroxyl group-containing resin of the present invention essentially comprises the phenolic hydroxyl group-containing compound (A) and the phenolic hydroxyl group-containing compound (B) as the phenolic hydroxyl group-containing compound component forming the novolak type resin structure.
- other phenolic hydroxyl group-containing compounds may be used in combination.
- Other phenolic hydroxyl group-containing compounds include phenol, alkylphenols such as cresol and xylenol, alkoxyphenols such as methoxyphenol and ethoxyphenol, resorcin, naphthol, and dihydroxynaphthalene. These may be used alone or in combination of two or more.
- the phenolic hydroxyl group-containing compound (A) and the phenol is preferably used in a proportion of 20% by mass or less based on the total mass of the polymerizable hydroxyl group-containing compound (B) and the other phenolic hydroxyl group-containing compound.
- the reaction molar ratio between the phenolic hydroxyl group-containing compound component and the aldehyde compound (C) can suppress excessive high molecular weight (gelation) and is suitable as a resist material. Since a novolak-type phenolic hydroxyl group-containing resin having an appropriate molecular weight is obtained, the aldehyde compound (C) is preferably in the range of 0.51.2 mol relative to 1 mol in total of the phenolic hydroxyl group-containing compound. A range of 6 to 0.9 mol is more preferable.
- Examples of the acid catalyst used in the reaction between the phenolic hydroxyl group-containing compound component and the aldehyde compound (C) include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, and manganese acetate. . These acid catalysts may be used alone or in combination of two or more. Among these, sulfuric acid and paratoluenesulfonic acid are preferable from the viewpoint of excellent catalytic activity.
- the reaction between the phenolic hydroxyl group-containing compound component and the aldehyde compound (C) may be performed in an organic solvent as necessary.
- the solvent used here 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 glyco
- the reaction between the phenolic hydroxyl group-containing compound component and the aldehyde compound (C) is performed, for example, in the temperature range of 60 to 140 ° C. for 0.5 to 100 hours.
- the target novolac type phenolic hydroxyl group-containing resin can be obtained by performing reprecipitation operation by adding water to the reaction product.
- the weight average molecular weight (Mw) of the novolak type phenolic hydroxyl group-containing resin thus obtained is excellent in balance of developability, heat resistance and substrate followability, and is suitable for resist materials. A range of 30,000 is preferred.
- the polydispersity (Mw / Mn) of the novolac type phenolic hydroxyl group-containing resin is preferably in the range of 3-10.
- the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) are values measured by GPC under the following conditions.
- the novolak type phenolic hydroxyl group-containing resin of the present invention is a polycondensate containing the phenolic hydroxyl group-containing compound (A), the phenolic hydroxyl group-containing compound (B) and the aldehyde compound (C) as essential reaction components
- the specific resin structure is not limited. For example, the following structural formula (3)
- Ar represents the following structural formula (Ar-3) or (Ar-4)
- n is independently an integer of 0 to 2
- p is an integer of 0 to 5
- q is an integer of 0 to 7
- R 2 is independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, It is any of the aralkyl group, the halogen atom, and the bonding point bonded to the structural site represented by the structural formula (3) or (4) via the carbon atom marked with *.
- R 1 is each independently a hydrogen atom, alkyl group, alkoxy group, aryl group, aralkyl group, or halogen atom
- m is each independently an integer of 0-4.
- R 5 is any one of a hydrogen atom, an alkyl group, and an aryl group.
- R 3 is an aliphatic hydrocarbon group having 4 to 20 carbon atoms
- j is an integer of 1 to 3.
- R 4 is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, a halogen atom, a structural site represented by the structural formula (3) or (4), and an asterisk (*). Any of the bonding points bonded through the attached carbon atoms, and k is an integer of 0 to (5-j).
- R 5 is any one of a hydrogen atom, an alkyl group, and an aryl group.
- a novolac-type phenolic hydroxyl group-containing resin having a structural unit (b) represented by the formula:
- R 1 is independently an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a halogen atom
- R 5 is a hydrogen atom, an alkyl group or an aryl group
- R 2 is each independently a hydrogen atom, or a bonding point bonded to the structural moiety represented by the structural formula (3-1) or (4-1) via a carbon atom marked with *.
- R 3 represents an aliphatic hydrocarbon group having 4 to 20 carbon atoms
- R 5 represents any one of a hydrogen atom, an alkyl group, and an aryl group.
- R 4 is a hydrogen atom, or any of the bonding points bonded to the structural moiety represented by the structural formula (3-1) or (4-1) via a carbon atom marked with *.
- a novolac type phenolic hydroxyl group-containing resin characterized by having as a repeating unit a structural moiety (b-1) represented by
- the molar ratio [(a-1) :( b-1)] between the structural part (a-1) and the structural part (b-1) present in the resin is determined depending on the developability, heat resistance and substrate. Since it is a novolac type phenolic hydroxyl group-containing resin having an excellent balance of followability, it is preferably in the range of 100: 0.1 to 100: 30, and preferably in the range of 100: 0.5 to 100: 20. More preferred.
- the novolac type phenolic hydroxyl group-containing resin of the present invention described in detail above is excellent in solubility in general-purpose organic solvents and thermal decomposition resistance, various electric and electronic materials such as adhesives, paints, photoresists, printed wiring boards, etc. It can be used for member applications. Since the novolac type phenolic hydroxyl group-containing resin of the present invention is excellent in alkali solubility, it is particularly suitable for resist applications and becomes a resist material excellent in photosensitivity and resolution. In addition, the novolak type phenolic hydroxyl group-containing resin of the present invention is excellent in heat resistance and flexibility in addition to developability, and exhibits high toughness even in a cured product reacted with a curing agent.
- resist underlayer films and resist permanent film applications can also be suitably used for resist underlayer films and resist permanent film applications.
- a sufficiently fine resist pattern can be formed as in the case of a normal resist film, and it has characteristics that it is highly flexible and does not easily crack.
- the substrate when used for a lower layer film or a permanent film, the substrate has excellent substrate followability and has a feature that deterioration or alteration due to a heat treatment process at the time of manufacturing a semiconductor hardly occurs.
- the photosensitive composition of the present invention contains the novolac type phenolic hydroxyl group-containing resin of the present invention and a photosensitive agent as essential components.
- other resins (X) may be used in combination.
- any resin can be used as long as it is soluble in an alkali developer or can be dissolved in an alkali developer by using it in combination with an additive such as an acid generator. .
- Examples of the other resin (X) used herein include other phenol resins (X-1) other than the novolak type phenolic hydroxyl group-containing resin, p-hydroxystyrene, and p- (1,1,1,3,3). , 3-Hexafluoro-2-hydroxypropyl) styrene-containing homopolymer or copolymer (X-2) of a styrene compound containing a hydroxy group, the hydroxyl group of (X-1) or (X-2) is t- Modified with an acid-decomposable group such as butoxycarbonyl group or benzyloxycarbonyl group (X-3), homopolymer or copolymer (X-4) of (meth) acrylic acid, norbornene compound or tetracyclododecene Examples thereof include an alternating polymer (X-5) of an alicyclic polymerizable monomer such as a compound and maleic anhydride or maleimide.
- Examples of the other phenol resin (X-1) include phenol novolak resin, cresol novolak resin, naphthol novolak resin, co-condensed novolak resin using various phenolic compounds, aromatic hydrocarbon formaldehyde resin-modified phenol resin, Cyclopentadiene phenol addition resin, phenol aralkyl resin (Zylok resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), Biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine-modified phenol resin (melamine, benzoguanamine, etc.
- phenol novolak resin cresol novolak resin
- naphthol novolak resin co-condensed novolak resin
- Nuclei include phenolic resins such as polyhydric phenol compound) and an alkoxy group-containing aromatic ring-modified novolac resins, which are linked (polyhydric phenol compound phenol nucleus and an alkoxy group-containing aromatic ring are connected by formaldehyde).
- phenolic resins such as polyhydric phenol compound
- alkoxy group-containing aromatic ring-modified novolac resins which are linked (polyhydric phenol compound phenol nucleus and an alkoxy group-containing aromatic ring are connected by formaldehyde).
- a cresol novolak resin or a co-condensed novolak resin of cresol and another phenolic compound is preferable because it is a photosensitive resin composition having high sensitivity and excellent heat resistance.
- the cresol novolak resin or the co-condensed novolak resin of cresol and other phenolic compound comprises at least one cresol selected from the group consisting of o-cresol, m-cresol and p-cresol and an aldehyde compound. It is a novolak resin obtained as an essential raw material and appropriately used in combination with other phenolic compounds.
- phenolic compounds other than the cresol include, for example, phenol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol Xylenol such as o-ethylphenol, m-ethylphenol, p-ethylphenol, etc .; butylphenol such as isopropylphenol, butylphenol, pt-butylphenol; p-pentylphenol, p-octylphenol, p-nonylphenol, alkylphenols such as p-cumylphenol; halogenated phenols such as fluorophenol, chlorophenol, bromophenol and iodophenol; p-phenylphenol, aminophenol, nitrophenol, 1-substituted phenols such as nitrophenol and trinitrophenol; condensed polycycl
- phenolic compounds may be used alone or in combination of two or more.
- the amount used is preferably such that the other phenolic compound is in the range of 0.05 to 1 mol with respect to a total of 1 mol of the cresol raw material.
- aldehyde compound examples include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, benzaldehyde, croton.
- formaldehyde is preferable because of its excellent reactivity, and formaldehyde and other aldehyde compounds may be used in combination.
- the amount of the other aldehyde compounds used is preferably in the range of 0.05 to 1 mole per mole of formaldehyde.
- the reaction ratio between the phenolic compound and the aldehyde compound in producing the novolak resin is such that a photosensitive resin composition having excellent sensitivity and heat resistance can be obtained.
- the range is preferably 1.6 mol, and more preferably in the range of 0.5 to 1.3.
- the reaction between the phenolic compound and the aldehyde compound is performed in the presence of an acid catalyst at a temperature of 60 to 140 ° C., and then water and residual monomers are removed under reduced pressure.
- an acid catalyst used here include oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, manganese acetate, etc., each of which may be used alone or in combination of two or more. May be. Of these, oxalic acid is preferred because of its excellent catalytic activity.
- cresol novolak resins using metacresol alone or cresol novolak resins using metacresol and paracresol in combination It is preferable that In the latter case, the reaction molar ratio of metacresol to paracresol [metacresol / paracresol] is a photosensitive resin composition having an excellent balance between sensitivity and heat resistance, so that the ratio is 10/0 to 2/8.
- the range is preferable, and the range of 7/3 to 2/8 is more preferable.
- the blending ratio of the novolac type phenolic hydroxyl group-containing resin of the present invention and the other resin (X) can be arbitrarily adjusted depending on the desired application.
- the novolak type phenolic hydroxyl group-containing resin of the present invention is excellent in light sensitivity, resolution and heat resistance when combined with a photosensitizer, a photosensitive composition containing this as the main component is optimal for resist applications.
- the ratio of the novolak type phenolic hydroxyl group-containing resin of the present invention in the total resin component is 60% by mass or more because it is a curable composition having high photosensitivity and excellent resolution and heat resistance. Preferably, it is 80 mass% or more.
- the mixing ratio of the novolac type phenolic hydroxyl group-containing resin to the other resin (X) is 3 to 80% of the novolac type phenolic hydroxyl group-containing resin of the present invention with respect to 100 parts by mass of the other resin (X). It is preferable that it is the range of a mass part.
- the photosensitive agent examples include compounds having a quinonediazide group.
- Specific examples of 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, orthoanthra Examples thereof include complete ester compounds, partial ester compounds, amidated products, and partially amidated products with sulfonic acids having a quinonediazide group such as quinonediazidesulfonic acid.
- 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 blending amount of the photosensitive agent in the photosensitive composition of the present invention is a photosensitive composition having excellent photosensitivity, and therefore 5 to 50 parts by mass with respect to 100 parts by mass in total of the resin solid content of the photosensitive composition. It is preferable that the ratio is
- the photosensitive composition of 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 polyoxy
- the compounding amount of these surfactants is preferably in the range of 0.001 to 2 parts by mass with respect to a total of 100 parts by mass of the resin solid content in the photosensitive composition of the present invention.
- a photosensitive agent in addition to the novolak type phenolic hydroxyl group-containing resin of the present invention, a photosensitive agent, and if necessary, other phenolic resin (X), a surfactant, Various additives such as dyes, fillers, crosslinking agents, and dissolution accelerators are added and dissolved in an organic solvent to obtain a resist composition.
- a resist composition This may be used as it is as a positive resist solution, or may be used as a positive resist film obtained by removing the solvent by applying the resist composition in a film form.
- the support film used as a resist film examples 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.
- the organic solvent used in the resist composition of the present invention is not particularly limited.
- alkylene glycol monoalkyl such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether propylene glycol monomethyl ether, etc.
- Dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; alkylene groups such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate Cole alkyl ether acetate; Ketone compounds such as acetone, 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, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate
- the resist composition of the present invention can be prepared by blending the above components and mixing them using a stirrer or the like. Moreover, when the resin composition for photoresists contains a filler or a pigment, it can be prepared by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three roll mill.
- a dispersing device such as a dissolver, a homogenizer, or a three roll mill.
- the resist composition is applied onto an object to be subjected to silicon substrate photolithography, and prebaked at a temperature of 60 to 150 ° C.
- the coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating and the like.
- a resist pattern is created. Since the resist composition of the present invention is a positive type, the target resist pattern is exposed through a predetermined mask, and the exposed portion is dissolved with an alkaline developer. Thus, a resist pattern is formed. Since the resist composition of the present invention has both high alkali solubility in the exposed area and high alkali resistance in the non-exposed area, it is possible to form a resist pattern with excellent resolution.
- the curable composition of the present invention contains the novolak type phenolic hydroxyl group-containing resin of the present invention and a curing agent as essential components.
- the curable composition of the present invention may use other resin (Y) in addition to the phenolic hydroxyl group-containing resin of the present invention.
- resins (Y) used here include, for example, various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, Modified novolak resin, phenol aralkyl resin (Xylok resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, biphenyl modified phenol resin, biphenyl modified naphthol resin, aminotriazine modified phenol resin, and various vinyl polymers Etc.
- various novolak resins such as dicyclopentadiene and phenol compounds, phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds
- Modified novolak resin phenol aralkyl resin (Xylok resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenyl
- 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 novolak type phenolic hydroxyl group-containing resin of the present invention and the other resin (Y) can be arbitrarily set according to the use, but the dry etching exhibited by the present invention Since the effect of excellent resistance and heat decomposability is more remarkably exhibited, the other resin (Y) is 0.5 to 100 parts by mass with respect to 100 parts by mass of the novolac type phenolic hydroxyl group-containing resin of the present invention. A ratio is preferred.
- the curing agent used in the present invention is, for example, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, a resole resin, an epoxy substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group.
- 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 methylol
- guanamine compound examples include tetramethylol guanamine, tetramethoxymethyl guanamine, tetramethoxymethyl benzoguanamine, a compound in which 1 to 4 methylol groups of tetramethylol guanamine are methoxymethylated, tetramethoxyethyl guanamine, tetraacyloxyguanamine, tetra Examples thereof include compounds in which 1 to 4 methylol groups of methylolguanamine 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. It is done.
- the resole resin may be, for example, an alkylphenol such as phenol, cresol or xylenol, a bisphenol such as phenylphenol, resorcinol, biphenyl, bisphenol A or bisphenol F, a phenolic hydroxyl group-containing compound such as naphthol or dihydroxynaphthalene, and an aldehyde compound.
- alkylphenol such as phenol, cresol or xylenol
- a bisphenol such as phenylphenol, resorcinol, biphenyl, bisphenol A or bisphenol F
- a phenolic hydroxyl group-containing compound such as naphthol or dihydroxynaphthalene
- aldehyde compound examples include polymers obtained by reacting under catalytic conditions.
- Examples of the epoxy compound include diglycidyloxynaphthalene, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane, naphthylene ether type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene- Examples include phenol addition reaction type epoxy resins, phosphorus atom-containing epoxy resins, polyglycidyl ethers of cocondensates of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, and the like. That.
- 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, tetramethylene glycol divinyl ether.
- Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4 Aromatic acid anhydrides such as '-(isopropylidene) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride And alicyclic carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, and trialkyltetrahydrophthalic anhydride.
- a glycoluril compound, a urea compound, and a resole resin are preferable, and a glycoluril compound is particularly preferable because it is a curable composition having excellent curability and heat resistance in a cured product.
- the compounding amount of the curing agent in the curable composition of the present invention is a composition having excellent curability, the total of 100 parts by mass of the novolac phenolic hydroxyl group-containing resin of the present invention and the other resin (Y).
- the ratio is preferably 0.5 to 50 parts by mass.
- the curable composition of the present invention is used for a resist underlayer film (BARC film), in addition to the novolak type phenolic hydroxyl group-containing resin of the present invention and a curing agent, other resins (Y) if necessary, Various additives such as a surfactant, a dye, a filler, a crosslinking agent, and a dissolution accelerator are added and dissolved in an organic solvent to obtain a resist underlayer film composition.
- the organic solvent used in the resist underlayer film composition is not particularly limited.
- alkylene glycol monoalkyl such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether propylene glycol monomethyl ether, etc.
- Dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; alkylene groups such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate Cole alkyl ether acetate; Ketone compounds such as acetone, 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, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate
- the resist underlayer film composition can be prepared by blending the above components and mixing them using a stirrer or the like.
- the resist underlayer film composition contains a filler or a pigment, it can be prepared by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three roll mill.
- the resist underlayer film composition is applied onto an object to be subjected to photolithography such as a silicon substrate, and is subjected to a temperature condition of 100 to 200 ° C. After drying, a resist underlayer film is formed by a method such as heat curing under a temperature condition of 250 to 400 ° C. Next, a resist pattern is formed on this lower layer film by performing a normal photolithography operation, and a resist pattern by a multilayer resist method can be formed by performing a dry etching process with a halogen-based plasma gas or the like.
- a resist permanent film composition can be obtained by adding various additives such as dyes, fillers, crosslinking agents and dissolution accelerators and dissolving them in an organic solvent.
- the organic solvent used here is the same as the organic solvent used in the resist underlayer film composition.
- a photolithography method using the resist permanent film composition includes, for example, dissolving and dispersing a resin component and an additive component in an organic solvent, and applying the solution on an object to be subjected to silicon substrate photolithography, and a temperature of 60 to 150 ° C. Pre-bake under the following temperature conditions.
- 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.
- the resist permanent film composition is positive, the target resist pattern is exposed through a predetermined mask, and the exposed portion is dissolved with an alkali developer. Thus, a resist pattern is formed.
- the permanent film made of the resist permanent film composition is, for example, a solder resist, a package material, an underfill material, a package adhesive layer such as a circuit element, an integrated circuit element-circuit board adhesive layer, an LCD, or an OELD for semiconductor devices.
- a solder resist for example, a solder resist, a package material, an underfill material, a package adhesive layer such as a circuit element, an integrated circuit element-circuit board adhesive layer, an LCD, or an OELD for semiconductor devices.
- a package adhesive layer such as a circuit element, an integrated circuit element-circuit board adhesive layer, an LCD, or an OELD for semiconductor devices.
- the number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity (Mw / Mn) of the synthesized resin are measured under the following GPC measurement conditions.
- GPC measurement conditions Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation Column: “Shodex KF802” (8.0 mm ⁇ ⁇ 300 mm) manufactured by Showa Denko KK + “Shodex KF802” (8.0 mm ⁇ ⁇ 300 mm) manufactured by Showa Denko KK + Showa Denko Co., Ltd.
- the 13 C-NMR spectrum was measured by analyzing the DMSO-d 6 solution of the sample using “AL-400” manufactured by JEOL Ltd. and performing structural analysis. The measurement conditions for 13 C-NMR spectrum are shown below. [ 13C -NMR spectrum measurement conditions] Measurement mode: SGNNE (1H complete decoupling method of NOE elimination) Pulse angle: 45 ° C pulse Sample concentration: 30 wt% Integration count: 10,000 times
- a GPC chart of the novolac type phenolic hydroxyl group-containing resin (1) is shown in FIG.
- the number average molecular weight (Mn) of the novolak type phenolic hydroxyl group-containing resin (1) was 2,909, the weight average molecular weight (Mw) was 14,426, and the polydispersity (Mw / Mn) was 4.96.
- FIG. 4 shows a GPC chart of the novolak type phenolic hydroxyl group-containing resin (2).
- the number average molecular weight (Mn) of the novolak type phenolic hydroxyl group-containing resin (2) was 3,200
- the weight average molecular weight (Mw) was 24,188
- the polydispersity (Mw / Mn) was 7.56.
- a GPC chart of the novolak type phenolic hydroxyl group-containing resin (3) is shown in FIG.
- the number average molecular weight (Mn) of the novolak type phenolic hydroxyl group-containing resin (3) was 3,221, the weight average molecular weight (Mw) was 18,778, and the polydispersity (Mw / Mn) was 5.83.
- FIG. 6 shows a GPC chart of the novolak type phenolic hydroxyl group-containing resin (1 ′).
- the novolak type phenolic hydroxyl group-containing resin (1 ′) had a number average molecular weight (Mn) of 1,792, a weight average molecular weight (Mw) of 11,701, and a polydispersity (Mw / Mn) of 6.53.
- the number average molecular weight (Mn) of the novolak type phenolic hydroxyl group-containing resin (2 ′) was 1,450, the weight average molecular weight (Mw) was 10,316, and the polydispersity (Mw / Mn) was 7.12.
- Photosensitive Composition 28 parts by mass of the novolak type phenolic hydroxyl group-containing resin was dissolved in 60 parts by mass of propylene glycol monomethyl ether acetate, and 12 parts by mass of a photosensitizing agent was added to the solution and dissolved. This was filtered through a 0.2 ⁇ m membrane filter to obtain a photosensitive composition.
- the photosensitizer was “P-200” (4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1methylethyl] phenyl] ethylidene] bisphenol, 1 mol 2-naphthoquinone-2-diazide-5-sulfonyl chloride condensate).
- composition for heat resistance test 28 parts by mass of the novolak type phenolic hydroxyl group-containing resin was dissolved in 60 parts by mass of propylene glycol monomethyl ether acetate, and this was filtered through a 0.2 ⁇ m membrane filter, and the composition for heat resistance test Got.
- the photosensitive composition obtained above was applied on a 5-inch silicon wafer with a spin coater so as to have a thickness of about 1 ⁇ m. Dried for 60 seconds. Two wafers were prepared, and one of the wafers was designated as “no exposure sample”. The other was used as an “exposed sample” and irradiated with 100 mJ / cm 2 of ghi line using a ghi line lamp (“Multi Light” manufactured by USHIO INC.), And then heat-treated at 140 ° C. for 60 seconds. .
- Both the “non-exposed sample” and the “exposed sample” were immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds and then dried on a hot plate at 110 ° C. for 60 seconds.
- the film thickness of each sample before and after immersion in the developer was measured, and the value obtained by dividing the difference by 60 was defined as alkali developability [ADR ( ⁇ / s)].
- the photosensitive composition obtained above was applied on a 5 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 60 seconds.
- a mask corresponding to a resist pattern with a line-and-space ratio of 1: 1 and a line width of 1 to 10 ⁇ m set every 1 ⁇ m is brought into close contact with this wafer, and then a ghi-line lamp (“Multi Light” manufactured by USHIO INC. )) was used for irradiation with ghi rays, and heat treatment was performed at 140 ° C. for 60 seconds.
- the film was immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and then dried on a hot plate at 110 ° C. for 60 seconds.
- the exposure amount (Eop exposure amount) capable of faithfully reproducing the line width of 3 ⁇ m when the ghi line exposure amount was increased from 30 mJ / cm 2 to 5 mJ / cm 2 was evaluated.
- the photosensitive composition obtained above 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.
- a photomask was placed on the obtained wafer, and an alkali development operation was performed by irradiating with 200 mJ / cm 2 of ghi line in the same manner as in the previous alkali developability evaluation.
- the composition for heat resistance test obtained above was applied on a 5-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 60 seconds.
- the resin content was scraped from the obtained wafer and its glass transition temperature (Tg) was measured.
- the glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC) (“Q100” manufactured by TA Instruments Co., Ltd.) under a nitrogen atmosphere, a temperature range of ⁇ 100 to 250 ° C., and a temperature rising temperature of 10 ° C. / Performed under the condition of minutes.
- DSC differential scanning calorimeter
- the photosensitive composition obtained above was applied on a 5-inch silicon wafer with a spin coater so as to have a thickness of about 50 ⁇ m, and dried on a hot plate at 110 ° C. for 300 seconds.
- the surface of the obtained wafer was observed using a laser microscope (Keyence Co., Ltd. “VK-X200”). The case where there was no crack was evaluated as ⁇ , and the case where there was a crack was evaluated as ⁇ .
- the photosensitive composition obtained above was applied onto 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 laminated 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). As evaluated.
- curable composition 16 parts by mass of the novolac type phenolic hydroxyl group-containing resin and 4 parts by mass of a curing agent (“1,3,4,6-tetrakis (methoxymethyl) glycoluril” manufactured by Tokyo Chemical Industry Co., Ltd.) This was dissolved in 30 parts by mass of glycol monomethyl ether acetate and filtered through a 0.2 ⁇ m membrane filter to obtain a curable composition.
- a curing agent 1,3,4,6-tetrakis (methoxymethyl) glycoluril
- composition for heat resistance test 28 parts by mass of the novolak type phenolic hydroxyl group-containing resin was dissolved in 60 parts by mass of propylene glycol monomethyl ether acetate, and this was filtered through a 0.2 ⁇ m membrane filter, and the composition for heat resistance test Got.
- the curable composition obtained above was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 ⁇ m, dried on a hot plate at 110 ° C. for 60 seconds, and then at 160 ° C., Heat treatment was performed for 60 seconds.
- the resin content was scraped from the obtained wafer and its glass transition temperature (Tg) was measured.
- the glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC) (“Q100” manufactured by TA Instruments Co., Ltd.) under a nitrogen atmosphere, a temperature range of ⁇ 100 to 250 ° C., and a temperature rising temperature of 10 ° C. / Performed under the condition of minutes.
- DSC differential scanning calorimeter
- Substrate following property The curable composition obtained above was applied on a 5-inch silicon wafer by a spin coater so as to have a thickness of about 50 ⁇ m, and dried on a hot plate at 110 ° C. for 300 seconds. The surface of the obtained wafer was observed using a laser microscope (Keyence Co., Ltd. “VK-X200”). The case where there was no crack was evaluated as ⁇ , and the case where there was a crack was evaluated as ⁇ .
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Abstract
Description
で表される構造部位であり、R1はそれぞれ独立に水素原子、アルキル基、アルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかであり、mはそれぞれ独立に0~4の整数である。]
で表されるフェノール性水酸基含有化合物(A)、下記構造式(2)
で表されるフェノール性水酸基含有化合物(B)及びアルデヒド化合物(C)を必須の反応成分とする重縮合物であることを特徴とするノボラック型フェノール性水酸基含有樹脂に関する。
で表される構造部位であり、R1はそれぞれ独立に水素原子、アルキル基、アルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかであり、mはそれぞれ独立に0~4の整数である。R5は水素原子、アルキル基又はアリール基の何れかである。]
で表される構造部位(a)と、下記構造式(4)
で表される構造部位(b)とを繰り返し単位として有することを特徴とするノボラック型フェノール性水酸基含有樹脂に関する。
本発明のノボラック型フェノール性水酸基含有樹脂は、下記構造式(1)
で表される構造部位であり、R1はそれぞれ独立に水素原子、アルキル基、アルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかであり、mはそれぞれ独立に0~4の整数である。]
で表されるフェノール性水酸基含有化合物(A)、下記構造式(2)
で表されるフェノール性水酸基含有化合物(B)及びアルデヒド化合物(C)を必須の反応成分とする重縮合物であることを特徴とする。
で表される構造部位であり、R1はそれぞれ独立に水素原子、アルキル基、アルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかであり、mはそれぞれ独立に0~4の整数である。]
で表される。本発明のノボラック型フェノール性水酸基含有樹脂を製造する際、前記フェノール性水酸基含有化合物(A)は、前記構造式(1)で表される化合物のうち1種類を単独で用いても良いし、2種類以上を併用しても良い。
[GPCの測定条件]
測定装置:東ソー株式会社製「HLC-8220 GPC」
カラム:昭和電工株式会社製「Shodex KF802」(8.0mmФ×300mm)
+昭和電工株式会社製「Shodex KF802」(8.0mmФ×300mm)
+昭和電工株式会社製「Shodex KF803」(8.0mmФ×300mm)
+昭和電工株式会社製「Shodex KF804」(8.0mmФ×300mm)
カラム温度:40℃
検出器: RI(示差屈折計)
データ処理:東ソー株式会社製「GPC-8020モデルIIバージョン4.30」
展開溶媒:テトラヒドロフラン
流速:1.0ml/分
試料:樹脂固形分換算で0.5質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの
注入量:0.1ml
標準試料:下記単分散ポリスチレン
(標準試料:単分散ポリスチレン)
東ソー株式会社製「A-500」
東ソー株式会社製「A-2500」
東ソー株式会社製「A-5000」
東ソー株式会社製「F-1」
東ソー株式会社製「F-2」
東ソー株式会社製「F-4」
東ソー株式会社製「F-10」
東ソー株式会社製「F-20」
で表される。本発明のノボラック型フェノール性水酸基含有樹脂を製造する際、前記フェノール性水酸基含有化合物(B)は、前記構造式(2)で表される化合物のうち1種類を単独で用いても良いし、2種類以上を併用しても良い。
[GPCの測定条件]
測定装置:東ソー株式会社製「HLC-8220 GPC」
カラム:昭和電工株式会社製「Shodex KF802」(8.0mmФ×300mm)+昭和電工株式会社製「Shodex KF802」(8.0mmФ×300mm)
+昭和電工株式会社製「Shodex KF803」(8.0mmФ×300mm)+昭和電工株式会社製「Shodex KF804」(8.0mmФ×300mm)
カラム温度:40℃
検出器: RI(示差屈折計)
データ処理:東ソー株式会社製「GPC-8020モデルIIバージョン4.30」
展開溶媒:テトラヒドロフラン
流速:1.0mL/分
試料:樹脂固形分換算で0.5質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(100μl)
標準試料:下記単分散ポリスチレン
(標準試料:単分散ポリスチレン)
東ソー株式会社製「A-500」
東ソー株式会社製「A-2500」
東ソー株式会社製「A-5000」
東ソー株式会社製「F-1」
東ソー株式会社製「F-2」
東ソー株式会社製「F-4」
東ソー株式会社製「F-10」
東ソー株式会社製「F-20」
で表される構造部位であり、R1はそれぞれ独立に水素原子、アルキル基、アルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかであり、mはそれぞれ独立に0~4の整数である。R5は水素原子、アルキル基又はアリール基の何れかである。]
で表される構造部位(a)と、下記構造式(4)
で表される構造部位(b)とを繰り返し単位として有することを特徴とするノボラック型フェノール性水酸基含有樹脂が挙げられる。
で表される構造部位(a-1)と、下記構造式(4-1)
で表される構造部位(b-1)とを繰り返し単位として有することを特徴とするノボラック型フェノール性水酸基含有樹脂がより好ましい。
[GPCの測定条件]
測定装置:東ソー株式会社製「HLC-8220 GPC」
カラム:昭和電工株式会社製「Shodex KF802」(8.0mmФ×300mm)+昭和電工株式会社製「Shodex KF802」(8.0mmФ×300mm)
+昭和電工株式会社製「Shodex KF803」(8.0mmФ×300mm)+昭和電工株式会社製「Shodex KF804」(8.0mmФ×300mm)
カラム温度:40℃
検出器: RI(示差屈折計)
データ処理:東ソー株式会社製「GPC-8020モデルIIバージョン4.30」
展開溶媒:テトラヒドロフラン
流速:1.0mL/分
試料:樹脂固形分換算で0.5質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの
注入量:0.1mL
標準試料:下記単分散ポリスチレン
(標準試料:単分散ポリスチレン)
東ソー株式会社製「A-500」
東ソー株式会社製「A-2500」
東ソー株式会社製「A-5000」
東ソー株式会社製「F-1」
東ソー株式会社製「F-2」
東ソー株式会社製「F-4」
東ソー株式会社製「F-10」
東ソー株式会社製「F-20」
[13C-NMRスペクトル測定条件]
測定モード:SGNNE(NOE消去の1H完全デカップリング法)
パルス角度:45℃パルス
試料濃度:30wt%
積算回数:10000回
冷却管を設置した2000mlの4口フラスコに、2,5-キシレノール293.2g(2.4mol)、4-ヒドロキシベンズアルデヒド122g(1mol)を仕込み、2-エトキシエタノール500mlに溶解させた。氷浴中で冷却しながら硫酸10mlを添加した後、マントルヒーターで100℃まで加熱し、2時間攪拌しながら反応させた。反応後、得られた溶液に水を加えて粗成生物を再沈殿させた。得られた粗生成物をアセトンに再溶解し、さらに水で再沈殿させた後、沈殿物を濾別して真空乾燥を行い、白色結晶のフェノール性水酸基含有化合物(A-1)213gを得た。13C-NMRにて下記構造式で表される化合物の生成を確認した。また、GPCチャート図から算出される純度は98.2%であった。フェノール性水酸基含有化合物(A-1)のGPCチャートを図1に、13C-NMRチャートを図2に示す。
冷却管を設置した300mlの4口フラスコに前記フェノール性水酸基含有化合物(A-1)34.8g(0.1mol)、3-ペンタデシルフェノール1.5g(0.005mol)を仕込んだ後、2-エトキシエタノール15ml、酢酸15mlに溶解させた。氷浴中で冷却しながら硫酸10mlを添加した後、92%パラホルムアルデヒド3.3g(0.1mol)を仕込んだ。オイルバスで80℃まで昇温し、10時間加熱、攪拌を継続し反応させた。反応後、得られた溶液に水を加えて粗生成物を再沈殿させた。得られた粗生成物をアセトンに再溶解し、さらに水で再沈殿させた後、沈殿物を濾別して真空乾燥し、赤色粉末のノボラック型フェノール性水酸基含有樹脂(1)33.6gを得た。ノボラック型フェノール性水酸基含有樹脂(1)のGPCチャートを図3に示す。ノボラック型フェノール性水酸基含有樹脂(1)の数平均分子量(Mn)は2,909、重量平均分子量(Mw)は14,426、多分散度(Mw/Mn)は4.96であった。
冷却管を設置した300mlの4口フラスコに前記フェノール性水酸基含有化合物(A-1)34.8g(0.1mol)、3-ペンタデシルフェノール6.1g(0.02mol)を仕込んだ後、2-エトキシエタノール15ml、酢酸15mlに溶解させた。氷浴中で冷却しながら硫酸10mlを添加した後、92%パラホルムアルデヒド3.3g(0.1mol)を仕込んだ。オイルバスで80℃まで昇温し、10時間加熱、攪拌を継続し反応させた。反応後、得られた溶液に水を加えて粗生成物を再沈殿させた。得られた粗生成物をアセトンに再溶解し、さらに水で再沈殿させた後、沈殿物を濾別して真空乾燥し、赤色粉末のノボラック型フェノール性水酸基含有樹脂(2)37.3gを得た。ノボラック型フェノール性水酸基含有樹脂(2)のGPCチャートを図4示す。ノボラック型フェノール性水酸基含有樹脂(2)の数平均分子量(Mn)は3,200、重量平均分子量(Mw)は24,188、多分散度(Mw/Mn)は7.56であった。
冷却管を設置した300mlの4口フラスコに前記フェノール性水酸基含有化合物(A-1)34.8g(0.1mol)、4-ノニルフェノール2.2g(0.01mol)を仕込んだ後、2-エトキシエタノール15ml、酢酸15mlに溶解させた。氷浴中で冷却しながら硫酸10mlを添加した後、92%パラホルムアルデヒド3.3g(0.1mol)を仕込んだ。オイルバスで80℃まで昇温し、10時間加熱、攪拌を継続し反応させた。反応後、得られた溶液に水を加えて粗生成物を再沈殿させた。得られた粗生成物をアセトンに再溶解し、さらに水で再沈させた後、沈殿物を濾別して真空乾燥し、赤色粉末のノボラック型フェノール性水酸基含有樹脂(3)35.1gを得た。ノボラック型フェノール性水酸基含有樹脂(3)のGPCチャートを図5に示す。ノボラック型フェノール性水酸基含有樹脂(3)の数平均分子量(Mn)は3,221、重量平均分子量(Mw)は18,778、多分散度(Mw/Mn)は5.83であった
冷却管を設置した300mlの4口フラスコにメタクレゾール13.0g(0.12mol)、パラクレゾール8.6g(0.08mol)、3-ペンタデシルフェノール6.1g(0.02mol)を仕込んだ後、2-エトキシエタノール15ml、酢酸15mlに溶解させた。氷浴中で冷却しながら硫酸10mlを添加した後、92%パラホルムアルデヒド6.5g(0.2mol)を仕込んだ。オイルバスで80℃まで昇温し、10時間加熱、攪拌を継続し反応させた。反応後、得られた溶液に水を加えて粗生成物を再沈殿させた。得られた粗生成物をアセトンに再溶解し、さらに水で再沈殿させた後、沈殿物を濾別して真空乾燥し、黄色粉末のノボラック型フェノール性水酸基含有樹脂(1’)24.6gを得た。ノボラック型フェノール性水酸基含有樹脂(1’)のGPCチャートを図6に示す。ノボラック型フェノール性水酸基含有樹脂(1’)の数平均分子量(Mn)は1,792、重量平均分子量(Mw)は11,701、多分散度(Mw/Mn)は6.53であった
攪拌機、温度計を備えた2Lの4つ口フラスコに、m-クレゾール648g(6mol)、p-クレゾール432g(4mol)、シュウ酸2.5g(0.2mol)、42%ホルムアルデヒド492gを仕込み、100℃まで昇温、反応させた。常圧で200℃まで加熱して脱水及び蒸留し、更に230℃で6時間減圧蒸留を行い、淡黄色固形のノボラック型フェノール性水酸基含有樹脂(2’)736gを得た。ノボラック型フェノール性水酸基含有樹脂(2’)の数平均分子量(Mn)は1,450、重量平均分子量(Mw)は10,316、多分散度(Mw/Mn)は7.12であった。
実施例1~3、比較製造例1、2で得たノボラック型フェノール性水酸基含有樹脂について、下記の要領で評価した。結果を表1に示す。
前記ノボラック型フェノール性水酸基含有樹脂28質量部をプロピレングリコールモノメチルエーテルアセテート60質量部に溶解させ、この溶液に感光剤12質量部を加えて溶解させた。これを0.2μmのメンブランフィルターで濾過し、感光性組成物を得た。
感光剤は東洋合成工業株式会社製「P-200」(4,4’-[1-[4-[1-(4-ヒドロキシフェニル)-1メチルエチル]フェニル]エチリデン]ビスフェノール1モルと1,2-ナフトキノン-2-ジアジド-5-スルホニルクロリド2モルとの縮合物)を用いた。
前記ノボラック型フェノール性水酸基含有樹脂28質量部をプロピレングリコールモノメチルエーテルアセテート60質量部に溶解させ、これを0.2μmのメンブランフィルターで濾過し、耐熱性試験用組成物を得た。
先で得た感光性組成物を5インチシリコンウェハー上に約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60秒乾燥させた。このウェハーを2枚用意し、一方を「露光なしサンプル」とした。他方を「露光有サンプル」としてghi線ランプ(ウシオ電機株式会社製「マルチライト」)を用いて100mJ/cm2のghi線を照射したのち、140℃、60秒間の条件で加熱処理を行った。
「露光なしサンプル」と「露光有サンプル」の両方をアルカリ現像液(2.38%水酸化テトラメチルアンモニウム水溶液)に60秒間浸漬した後、110℃のホットプレート上で60秒乾燥させた。各サンプルの現像液浸漬前後の膜厚を測定し、その差分を60で除した値をアルカリ現像性[ADR(Å/s)]とした。
先で得た感光性組成物を5インチシリコンウェハー上に約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60秒乾燥させた。このウェハー上にラインアンドスペースが1:1であり、ライン幅が1~10μmまで1μmごとに設定されたレジストパターン対応のマスクを密着させた後、ghi線ランプ(ウシオ電機株式会社製「マルチライト」)を用いてghi線を照射し、140℃、60秒間の条件で加熱処理を行った。次いで、アルカリ現像液(2.38%水酸化テトラメチルアンモニウム水溶液)に60秒間浸漬した後、110℃のホットプレート上で60秒乾燥させた。
ghi線露光量を30mJ/cm2から5mJ/cm2毎に増加させた場合の、ライン幅3μmを忠実に再現することのできる露光量(Eop露光量)を評価した。
先で得た感光性組成物を5インチシリコンウェハー上に約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60秒乾燥させた。得られたウェハー上にフォトマスクを乗せ、先のアルカリ現像性評価の場合と同様の方法でghi線200mJ/cm2を照射し、アルカリ現像操作を行った。レーザーマイクロスコープ(株式会社キーエンス製「VK-X200」)を用いてパターン状態を確認し、L/S=5μmで解像できているものを○、L/S=5μmで解像できていないものを×として評価した。
先で得た耐熱性試験用組成物を5インチシリコンウェハー上に約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60秒乾燥させた。得られたウェハーより樹脂分をかきとり、そのガラス転移温度(Tg)を測定した。ガラス転移温度(Tg)の測定は示差走査熱量計(DSC)(株式会社TAインスツルメント製「Q100」)を用いて、窒素雰囲気下、温度範囲-100~250℃、昇温温度10℃/分の条件で行った。
先で得た感光性組成物を5インチシリコンウェハー上に約50μm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300秒乾燥させた。得られたウェハーの表面をレーザーマイクロスコープ(株式会社キーエンス製「VK-X200」)を用いて観察し、クラックが無い場合を○、クラックがある場合を×として評価した。
先で得た感光性組成物を厚さ50μmのポリイミドフィルム上に約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300秒乾燥させた。得られた積層フィルムを180度に折り曲げて、折り曲げ箇所の状態をレーザーマイクロスコープ(株式会社キーエンス製「VK-X200」)を用いて観察し、クラックが無い場合を○、クラックがある場合を×として評価した。
実施例1~3、比較製造例1、2で得たノボラック型フェノール性水酸基含有樹脂について、下記の要領で評価した。結果を表2に示す。
前記ノボラック型フェノール性水酸基含有樹脂16質量部、硬化剤(東京化成工業株式会社製「1,3,4,6-テトラキス(メトキシメチル)グリコールウリル」)4質量部をプロピレングリコールモノメチルエーテルアセテート30質量部に溶解させ、これを0.2μmのメンブランフィルターで濾過し、硬化性組成物を得た。
前記ノボラック型フェノール性水酸基含有樹脂28質量部をプロピレングリコールモノメチルエーテルアセテート60質量部に溶解させ、これを0.2μmのメンブランフィルターで濾過し、耐熱性試験用組成物を得た。
先で得た硬化性組成物を5インチシリコンウェハー上に約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60秒乾燥させた。このウェハーを2枚用意し、一方を「未硬化サンプル」とした。他方を「硬化サンプル」として160℃、60秒間の条件で加熱処理を行った。
「未硬化サンプル」と「硬化サンプル」の両方をアルカリ現像液(2.38%水酸化テトラメチルアンモニウム水溶液)に60秒間浸漬した後、110℃のホットプレート上で60秒乾燥させた。各サンプルの現像液浸漬前後の膜厚を測定し、その差分を60で除した値をアルカリ現像性[ADR(Å/s)]とした。
先で得た硬化性組成物を5インチシリコンウェハー上に約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60秒乾燥させた後、160℃、60秒間の条件で加熱処理を行った。得られたウェハーより樹脂分をかきとり、そのガラス転移温度(Tg)を測定した。ガラス転移温度(Tg)の測定は示差走査熱量計(DSC)(株式会社TAインスツルメント製「Q100」)を用いて、窒素雰囲気下、温度範囲-100~250℃、昇温温度10℃/分の条件で行った。
先で得た硬化性組成物を5インチシリコンウェハー上に約50μm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300秒乾燥させた。得られたウェハーの表面をレーザーマイクロスコープ(株式会社キーエンス製「VK-X200」)を用いて観察し、クラックが無い場合を○、クラックがある場合を×として評価した。
Claims (10)
- 下記構造式(1)
で表される構造部位であり、R1はそれぞれ独立に水素原子、アルキル基、アルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかであり、mはそれぞれ独立に0~4の整数である。]
で表されるフェノール性水酸基含有化合物(A)、下記構造式(2)
で表されるフェノール性水酸基含有化合物(B)及びアルデヒド化合物(C)を必須の反応成分とする重縮合物であることを特徴とするノボラック型フェノール性水酸基含有樹脂。 - 前記フェノール性水酸基含有化合物(A)とフェノール性水酸基含有化合物(B)とのモル比[(A):(B)]が100:0.1~100:30の範囲である請求項1記載のノボラック型フェノール性水酸基含有樹脂。
- 下記構造式(3)
で表される構造部位であり、R1はそれぞれ独立に水素原子、アルキル基、アルコキシ基、アリール基、アラルキル基、ハロゲン原子の何れかであり、mはそれぞれ独立に0~4の整数である。R5は水素原子、アルキル基又はアリール基の何れかである。]
で表される構造部位(a)と、下記構造式(4)
で表される構造部位(b)とを繰り返し単位として有することを特徴とするノボラック型フェノール性水酸基含有樹脂。 - 樹脂中に存在する前記構造部位(a-1)と前記構造部位(b-1)とのモル比[(a-1):(b-1)]が100:0.1~100:30の範囲である請求項3記載のノボラック型フェノール性水酸基含有樹脂。
- 請求項1~4の何れか一つに記載のノボラック型フェノール性水酸基含有樹脂と感光剤とを含有する感光性組成物。
- 請求項5記載の感光性組成物からなるレジスト膜。
- 請求項1~4の何れか一つに記載のノボラック型フェノール性水酸基含有樹脂と硬化剤とを含有する硬化性組成物。
- 請求項7記載の硬化性組成物を硬化させてなる硬化物。
- 請求項7記載の硬化性組成物からなるレジスト下層膜。
- 請求項7記載の硬化性組成物からなるレジスト永久膜。
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