WO2015190233A1 - 永久膜用感光性組成物、レジスト材料、及び塗膜 - Google Patents
永久膜用感光性組成物、レジスト材料、及び塗膜 Download PDFInfo
- Publication number
- WO2015190233A1 WO2015190233A1 PCT/JP2015/064265 JP2015064265W WO2015190233A1 WO 2015190233 A1 WO2015190233 A1 WO 2015190233A1 JP 2015064265 W JP2015064265 W JP 2015064265W WO 2015190233 A1 WO2015190233 A1 WO 2015190233A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- photosensitive composition
- mass
- parts
- permanent film
- Prior art date
Links
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- 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
-
- 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
-
- 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
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
-
- 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
- C08G8/26—Condensation polymers of aldehydes or ketones with phenols only from mixtures of aldehydes and ketones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with 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
-
- 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
-
- 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
-
- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
-
- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
-
- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
Definitions
- the present invention relates to a photosensitive composition, a resist material, and a coating film thereof used as a permanent film forming material having high photosensitivity and resolution, excellent heat resistance and moisture absorption resistance, and hardly causing contamination even in a high temperature environment. .
- the phenolic hydroxyl group-containing compound is used in adhesives, molding materials, paints, photoresist materials, epoxy resin raw materials, epoxy resin curing agents, etc., it is excellent in heat resistance and moisture resistance in cured products, Widely used in the electrical and electronic fields such as semiconductor encapsulants and insulating materials for printed wiring boards, as curable resin compositions based on phenolic hydroxyl group-containing compounds themselves, or as curing agents such as epoxy resins .
- a coating film made of a photosensitive composition such as a photoresist material is also used as a member that is generically called a permanent film.
- a permanent film is a coating film made of a photosensitive composition formed on or between parts constituting a product, mainly in display devices such as semiconductor devices such as ICs and LSIs, and thin displays. It is what remains.
- Patent Document 1 discloses a chemical amplification type containing a reaction product of an alkali-soluble resin and a crosslinkable polyvinyl ether compound, a photoacid generator, and an epoxy resin as a material for a permanent film.
- a positive photosensitive thermosetting resin composition has been proposed.
- Patent Document 2 discloses that a positive photosensitive adhesive composition containing an alkali-soluble resin having a phenolic hydroxyl group or a carboxyl group, a compound having a quinonediazide group, and a crosslinking agent is used as a material for the permanent film. Is disclosed.
- the problem to be solved by the present invention is a photosensitive composition which is excellent in photosensitivity, resolution, heat resistance and moisture absorption resistance, and hardly contaminates in a high temperature environment and is suitable as a material for a permanent film. It is to provide a resist material and a coating film thereof.
- Hydroxynaphthalene novolak resin obtained by reacting in the system containing an amount of water in the presence of an acid catalyst is excellent in photosensitivity, resolution, heat resistance, and moisture absorption resistance, and unreacted. Since the residual amount of hydroxynaphthalenes is extremely small, it is difficult to cause contamination in a high-temperature environment, and the present invention has been completed by finding that it is suitable as a permanent film material.
- R 1 represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a halogen atom, R 1 present may be the same as or different from each other
- R 2 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent
- p represents 1 or 2
- q represents 4 or 5. However, the sum of p and q is 6.
- the hydroxy naphthalene (A) content represented by the formula (1) contains a hydroxy naphthalene novolak resin that is 2% by mass or less in terms of resin solid content and does not contain a curing agent, or 100 parts by mass of the hydroxy naphthalene novolak resin.
- the present invention relates to a photosensitive composition for a permanent film, which contains 50 parts by mass or less of a curing agent.
- the present invention further relates to a resist material comprising the photosensitive composition for permanent films and a coating film comprising the photosensitive composition for permanent films.
- the photosensitive composition for permanent film according to the present invention contains a hydroxy naphthalene novolak resin obtained from hydroxy naphthalenes and aldehydes, and therefore has excellent photosensitivity, resolution, heat resistance, and moisture absorption resistance.
- a hydroxy naphthalene novolak resin obtained from hydroxy naphthalenes and aldehydes, and therefore has excellent photosensitivity, resolution, heat resistance, and moisture absorption resistance.
- the amount of hydroxynaphthalenes mixed is very small, there is little risk of hydroxynaphthalene sublimating from the coating film even in a high temperature environment, and contamination of the surrounding area is unlikely to occur. For this reason, the permanent film excellent in heat resistance, moisture absorption resistance, and stain resistance can be provided by the photosensitive composition for permanent films according to the present invention.
- 6 is a GPC chart of a novolac resin (1) obtained in Synthesis Example 1.
- 6 is a GPC chart of a novolac resin (2) obtained in Synthesis Example 2.
- 6 is a GPC chart of a novolac resin (3) obtained in Synthesis Example 3.
- 6 is a GPC chart of a novolac resin (4) obtained in Synthesis Example 4.
- 6 is a GPC chart of a novolac resin (5) obtained in Synthesis Example 5.
- the photosensitive composition for a permanent film according to the present invention has a hydroxy naphthalene novolak resin having a structural site (I) represented by the following general formula (1) as a repeating unit (referred to as “hydroxy naphthalene novolak resin according to the present invention”). Contain).
- Photosensitivity capable of forming a resist coating film that has both photosensitivity, resolution, alkali developability, heat resistance, and moisture absorption resistance, which has been difficult in the past, by using a hydroxynaphthalene novolac resin structure as the main skeleton. A composition is obtained.
- p represents 1 or 2
- q represents 4 or 5.
- the sum of p and q is 6. That is, when p is 1, q is 5, and when p is 2, q is 4.
- the substitution position of the phenolic hydroxyl group on the naphthylene skeleton is arbitrary.
- the substitution position of the phenolic hydroxyl group is preferably the first position when p is 1, and the substitution position of the phenolic hydroxyl group when p is 2. Is preferably in the 2nd and 7th positions.
- R 1 represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a halogen atom.
- R 1 s there are 4 or 5 R 1 s , and these R 1 s may be the same as or different from each other.
- R 1 in the general formula (1) is an alkyl group
- the alkyl group may be linear, branched, or a group having a cyclic structure. It is preferably a linear group.
- R 1 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. More preferred are groups.
- examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isoamyl group, a hexyl group, and a cyclohexyl group.
- R 1 in the general formula (1) is an alkoxy group
- the alkyl group portion in the alkoxy group may be linear or branched, and may be a group having a cyclic structure. However, it is preferably a linear group.
- R 1 is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. More preferred are groups.
- alkoxy group for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, t-butyloxy group, pentyloxy group, isoamyloxy group, hexyl
- alkoxy group for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, t-butyloxy group, pentyloxy group, isoamyloxy group, hexyl
- Examples include oxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, methoxy group, ethoxy group, propyloxy group, butyloxy group, pentyloxy Group, hex
- R 1 in the general formula (1) is an aryl group which may have a substituent
- examples of the aryl group include a phenyl group, a naphthyl group, an indenyl group, and a biphenyl group.
- the hydrogen atom in the aryl group may be substituted with a substituent, and examples of the substituent include a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and the like.
- the number of substituents that the aryl group has 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.
- the aryl group which may have a substituent for example, phenyl group, hydroxyphenyl group, dihydroxyphenyl group, hydroxyalkoxyphenyl group, alkoxyphenyl group, tolyl group, xylyl group, naphthyl group, A hydroxy naphthyl group, a dihydroxy naphthyl group, etc. are mentioned, A phenyl group is preferable.
- R 1 in the general formula (1) is an aralkyl group which may have a substituent
- examples of the aryl group portion in the aralkyl group include a phenyl group, a naphthyl group, an indenyl group, a biphenyl group, and the like. And a phenyl group is preferable.
- the alkyl group portion in the aralkyl group may be linear, branched, or a group having a cyclic structure, but is a linear group Is more preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable.
- the hydrogen atom in the aryl group in the aralkyl group may be substituted with a substituent, and the type and number of the substituent are those exemplified as the substituent that the aryl group may have.
- the aralkyl group which may have a substituent includes phenylmethyl group, hydroxyphenylmethyl group, dihydroxyphenylmethyl group, tolylmethyl group, xylylmethyl group, naphthylmethyl group, hydroxynaphthylmethyl group, dihydroxynaphthyl group.
- Methyl group phenylethyl group, hydroxyphenylethyl group, dihydroxyphenylethyl group, tolylethyl group, xylylethyl group, naphthylethyl group, hydroxynaphthylethyl group, dihydroxynaphthylethyl group and the like, phenylmethyl group, hydroxyphenylmethyl group, A dihydroxyphenylmethyl group is preferred.
- R 1 in the general formula (1) is a halogen atom
- examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
- R 1 is preferably a hydrogen atom, an alkyl group, or an alkoxy group, and all of them are resins having excellent heat resistance and water absorption resistance.
- R 1 is more preferably a hydrogen atom or an alkyl group, and all R 1 are a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl More preferably a group, an isoamyl group, a hexyl group, or a cyclohexyl group, and all R 1 are hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, or t It is even more preferred that it is a butyl group, and it is particularly preferred that all R 1 are hydrogen atoms.
- R 2 represents a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent.
- R 2 in the general formula (1) is an alkyl group which may have a substituent
- the alkyl group may be linear or branched, and may have a cyclic structure. Although it may be a group having a linear group, it is preferably a linear group.
- R 2 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. More preferred are groups.
- R 2 in the general formula (1) is an alkyl group
- the hydrogen atom in the alkyl group may be substituted with a substituent.
- the substituent 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.
- the alkoxy group having 1 to 6 carbon atoms and the aryl group include those similar to the alkoxy group and aryl group that R 1 can take.
- the number of hydrogen atoms that can be substituted is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2. When one alkyl group has a plurality of substituents, each substituent may be the same as or different from each other.
- alkyl group for R 2 examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, isoamyl, hexyl, and cyclohexyl.
- R 2 in the general formula (1) is an aryl group which may have a substituent
- examples of the aryl group include a phenyl group, a naphthyl group, an indenyl group, and a biphenyl group.
- the hydrogen atom in the aryl group may be substituted with a substituent.
- the substituent include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an aryl group, a halogen atom, and the like.
- Examples of the alkoxy group having 1 to 6 carbon atoms and the aryl group include those similar to the alkoxy group and aryl group that R 1 can take.
- 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.
- Specific examples of the aryl group optionally having a substituent for R 2 include a phenyl group, a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxyalkoxyphenyl group, an alkoxyphenyl group, a tolyl group, a xylyl group, and a naphthyl group. , Hydroxy naphthyl group, dihydroxy naphthyl group, bromophenyl group and the like.
- R 2 is preferably an aryl group which may have a substituent, and is preferably a hydroxyl group-containing aryl group such as a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxyalkoxyphenyl group, a hydroxynaphthyl group, or a dihydroxynaphthyl group. More preferred.
- R 1 are a hydrogen atom, an alkyl group, or an alkoxy group
- R 2 is an aryl optionally having a hydrogen atom or a substituent.
- all R 1 are hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, or It is more preferably a cyclohexyl group and R 2 is a hydrogen atom or a hydroxyl group-containing aryl group, and all R 1 are a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or t- butyl group
- R 2 is a hydrogen atom, a hydroxypheny
- the hydroxy naphthalene novolak resin according to the present invention is obtained by reacting a hydroxy naphthalene (A) represented by the following general formula (2) with an aldehyde (B) represented by the following general formula (3).
- A hydroxy naphthalene
- B aldehyde
- R 1 , p, and q are the same as in general formula (1)
- R 2 is the same as in formula (1).
- the content of hydroxy naphthalene (A) is 2% by mass or less in terms of resin solid content. Unreacted hydroxy naphthalenes (A) are more easily sublimated than the resin component. For this reason, in a thin film such as a coating film formed from a resin in which the amount of hydroxy naphthalenes (A) is large, in a high temperature environment, Hydroxynaphthalenes (A) sublimated from the coating film are solidified on the coating film surface and the surrounding member surfaces and are contaminated.
- the coating film of the photosensitive composition mainly composed of the hydroxy naphthalene novolak resin according to the present invention is sublimated even in a high temperature environment because the amount of unreacted hydroxy naphthalene (A) is small. There is almost no hydroxy naphthalene (A), and contamination of the coating film surface and its surroundings hardly occurs.
- the content of hydroxynaphthalenes (A) in the hydroxynaphthalene novolak resin according to the present invention is preferably 1.5% by mass or less, more preferably 1.2% by mass or less in terms of resin solid content.
- content of the hydroxy naphthalene (A) in the hydroxy naphthalene novolak resin according to the present invention can be determined by gas chromatography (GC) analysis. Specifically, for each hydroxynaphthalene used as a raw material, the content is calculated from the area% of the GC peak based on a calibration curve created using a standard with a known concentration.
- GC gas chromatography
- the weight average molecular weight (Mw) of the hydroxy naphthalene novolak resin according to the present invention is preferably in the range of 1,000 to 8,000 because it has a high resolution and is excellent in heat resistance and moisture absorption resistance.
- the value of polydispersity (Mw / Mn) is preferably in the range of 1.2 to 2.3 because the resin has high resolution and is excellent in heat resistance and moisture absorption resistance.
- the weight average molecular weight (Mw) and polydispersity (Mw / Mn) of the hydroxy naphthalene novolak resin according to the present invention are values measured by GPC (gel permeation chromatographic analysis).
- GPC gel permeation chromatographic analysis
- the hydroxy naphthalene novolak resin according to the present invention includes, for example, a hydroxy naphthalene (A) represented by the general formula (2) and an aldehyde (B) represented by the general formula (3), which are hydrophobic. It can be obtained by reacting in a mixed solvent of an organic solvent and water under acid catalyst conditions.
- the hydroxy naphthalenes (A) are not particularly limited as long as they are represented by the general formula (2). Among them, 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthalene, 1 , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and aromatic nuclei thereof, alkyl group, alkoxy group, aryl group, aralkyl group, halogen atom is 1 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7- Dihydroxynaphthalene is preferred, 2,7-dihydroxynaphthalene Particularly preferred.
- a compound having an aromatic hydroxyl group other than the hydroxy naphthalenes (A) may be used in combination as long as the effects of the present invention are not impaired.
- the compound having an aromatic hydroxyl group include phenols.
- the phenols include phenol, cresol, xylenol, butylphenol, and phenylphenol.
- the amount used is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the hydroxynaphthalene (A).
- the aldehyde (B) is not particularly limited as long as it is represented by the general formula (3).
- formaldehyde (HCOH) formaldehyde
- pentyl Alkyl aldehydes such as aldehyde and hexyl aldehyde
- hydroxybenzaldehydes such as salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4-methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde
- aldehyde (B) used as the raw material is formaldehyde
- an aqueous formaldehyde solution (formalin), paraformaldehyde, and trioxane are also preferably used as the raw material.
- the reaction ratio between the hydroxy naphthalenes (A) and the aldehydes (B) is 0.5 to 1 in the molar ratio between them ((A) / (B)). It is preferable to carry out under the condition of .5.
- the amount of unreacted hydroxynaphthalene (A) remaining in the obtained hydroxynaphthalene novolak resin can be reduced by setting the reaction ratio of hydroxynaphthalene (A) and aldehyde (B) within the above range. it can.
- the reaction of hydroxynaphthalenes (A) and aldehydes (B) is performed in a mixed solvent of water and an organic solvent.
- organic solvent used in the reaction include alcohols such as propanol, butanol, octanol, ethylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether; methyl ethyl ketone, methyl isobutyl ketone, etc.
- Ketones esters such as butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like.
- the organic solvent used for the reaction may be composed of only one kind or two or more kinds of mixed solvents. Among these, it is preferable to use one or more selected from the group consisting of butanol, octanol, methyl ethyl ketone, and methyl isobutyl ketone, and it is more preferable to use methyl isobutyl ketone because of the separability between the aqueous layer and the organic layer.
- the proportion of the organic solvent in the mixed solvent used for the reaction is that the organic solvent is 50 to 500 parts by mass with respect to 100 parts by mass of the hydroxynaphthalene (A), and the reaction rate is sufficiently high and the hydroxynaphthalene novolak resin can be obtained efficiently.
- the solvent removal by distillation after the production of the hydroxynaphthalene novolak resin requires a relatively short time, and is preferably 100 to 500 parts by mass.
- a use ratio of water in the mixed solvent used for the reaction 30 to 300 parts by mass of water is used with respect to 100 parts by mass of the hydroxynaphthalene (A).
- the amount of water in the reaction system is more preferably 35 to 250 parts by mass with respect to 100 parts by mass of the hydroxynaphthalene (A).
- 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,
- p-toluenesulfonic acid is preferred because it exhibits strong acidity and promotes the reaction between the hydroxy naphthalenes (A) and the aldehydes (B) with high activity.
- the amount of these acid catalysts used is preferably in the range of 0.1 to 25% by mass relative to the total mass of the reaction raw materials.
- the temperature condition for reacting the hydroxy naphthalenes (A) and the aldehydes (B) is preferably in the range of 50 to 120 ° C. because the reaction efficiency is high. In particular, when 2,7-dihydroxynaphthalene and formaldehyde are reacted, it is preferable to react at 60 to 90 ° C.
- the reaction of hydroxynaphthalenes (A) and aldehydes (B) can be performed, for example, as follows. First, a hydroxynaphthalene (A), an organic solvent, an aldehyde (B), and water are charged into a flask equipped with a thermometer, a condenser tube, a fractionating tube, and a stirrer. Hydroxynaphthalenes (A), organic solvent, aldehydes (B) and water are charged and then stirred. The acid catalyst is added with stirring. The amount of the acid catalyst used is usually 0.01 to 5 parts by mass with respect to 100 parts by mass of the hydroxynaphthalene (A). Although it may be used more than that, a large amount of alkali and extra time are required for the neutralization step.
- hydroxynaphthalene (A) By adding hydroxynaphthalene (A), aldehyde (B), organic solvent and water to the reaction system, hydroxynaphthalene (A) is dissolved or dispersed in the organic solvent phase, and aldehyde (B) is Dissolve or disperse in the aqueous phase. Even if the organic solvent phase and the aqueous layer in the reaction system are stirred, they are not “uniformly” mixed (dissolved) but in a “non-uniform” state. As long as the two layers form a “non-uniform” state, a part of the organic layer may be mixed “uniformly” with the aqueous layer, and a part of the aqueous layer may be “uniform” with the organic layer. It may be mixed. Part of the hydroxy naphthalene (A) may be dissolved or dispersed in water, and part of the aldehyde (B) may be dissolved or dispersed in an
- the temperature of the reaction system is increased. After raising the temperature to the reaction temperature, the hydroxynaphthalenes (A) and aldehydes (B) are reacted with stirring. The reaction time is usually 0.5 to 10 hours. After completion of the reaction, the reaction system is transferred to a separatory funnel, and the aqueous layer is separated and removed from the organic layer. Thereafter, the organic layer is washed until the washing solution shows neutrality. After washing, the organic layer is allowed to stand under heating and reduced pressure, and the organic solvent is removed from the organic layer, whereby a hydroxynaphthalene novolak resin with a small amount of unreacted monomer (hydroxynaphthalene (A)) remaining can be obtained.
- the photosensitive composition for permanent films according to the present invention contains the hydroxy naphthalene novolak resin according to the present invention as an essential component, may not contain a curing agent, and may contain a curing agent as necessary. .
- Examples of the curing agent used in the present invention include 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, a urea compound, and a resole resin. , Epoxy compounds, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, acid anhydrides, oxazoline compounds, and the like.
- 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 excellent in dry etching resistance and thermal decomposition resistance when used for permanent film applications, and a glycoluril compound is particularly preferable. preferable.
- the blending amount of the curing agent maintains excellent alkali developability and sensitivity by the hydroxy naphthalene novolak resin according to the present invention. Therefore, it is 50 parts by mass or less with respect to 100 parts by mass of the hydroxy naphthalene novolac resin according to the present invention. Since the compounding amount of the curing agent of the photosensitive composition for permanent film according to the present invention is a composition excellent in curability, heat resistance, and alkali developability, 100 mass of the hydroxy naphthalene novolak resin according to the present invention.
- the ratio is preferably 0.1 to 50 parts by weight with respect to parts, and since the composition is further excellent in sensitivity, the ratio is more preferably 0.1 to 30 parts by weight. The ratio is more preferably 5 to 20 parts by mass.
- the photosensitive composition for permanent film according to the present invention preferably contains a photosensitizer in addition to the hydroxy naphthalene novolak resin according to the present invention.
- the photosensitive agent 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 photosensitizer in the photosensitive composition for a permanent film according to the present invention is a composition having excellent photosensitivity, so that it is 5 to 50 parts by mass with respect to 100 parts by mass of the hydroxynaphthalene novolac resin according to the present invention.
- the ratio is preferably
- the photosensitive composition for permanent film according to the present invention may be used in combination with a resin component.
- a resin component any resin can be used as long as it is soluble in an alkali developer or can be dissolved in an alkali developer when used in combination with an additive such as an acid generator.
- the blending ratio of the hydroxy naphthalene novolak resin according to the present invention and the other resin can be arbitrarily adjusted depending on the desired application.
- the hydroxy naphthalene novolac resin according to the present invention and other resins The hydroxy naphthalene novolak resin according to the present invention is preferably used in an amount of 60% by mass or more, and more preferably 80% by mass or more.
- the photosensitive composition for permanent film according to the present invention may contain a surfactant for the purpose of improving film-forming property and pattern adhesion when used for resist applications, and reducing development defects.
- a surfactant for the purpose of improving 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
- the amount of these surfactants to be used is preferably in the range of 0.001 to 2 parts by mass with respect to 100 parts by mass of the resin solid content in the photosensitive composition for permanent film according to the present invention.
- the photosensitive composition for permanent film according to the present invention may further contain a filler.
- the filler can improve the hardness and heat resistance of the coating film.
- the filler contained in the photosensitive composition for permanent film according to the present invention may be an organic filler, but an inorganic filler is preferred.
- 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 for permanent film according to the present invention if necessary, other resins, photosensitive agents, photoacid generators, organic base compounds, surfactants, filling It is preferable that various additives such as materials, dyes, pigments, crosslinking agents, and dissolution accelerators are dissolved or dispersed in an organic solvent.
- a coating film can be formed by applying a material dissolved in an organic solvent to a substrate or the like.
- the photoacid generator and the organic base compound can be appropriately selected from those widely used as additives for resist materials in consideration of the type of resin used.
- 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 for permanent film 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
- the photosensitive composition for permanent film according to the present invention may be used as a resist material.
- the photosensitive composition for permanent film according to the present invention may be used as a resist solution as it is in a state dissolved or dispersed in an organic solvent, or applied in the form of a film dissolved or dispersed in an organic solvent. Then, the solvent removed may be used as the 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.
- the method of photolithography using the photosensitive composition for permanent film according to the present invention includes, for example, applying a photosensitive composition for permanent film dissolved and dispersed in an organic solvent onto an object to be subjected to silicon substrate photolithography. And pre-baking 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.
- the permanent film photosensitive composition is positive, 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 photosensitive composition for permanent films according to the present invention has high photosensitivity, it is possible to form a resist pattern with excellent resolution.
- the thin film (coating film) obtained by applying the photosensitive composition for permanent film according to the present invention is suitable as a permanent film remaining in the final product after forming a resist pattern as necessary.
- permanent films include solder resists, package materials, underfill materials, package adhesive layers such as circuit elements, adhesive layers between integrated circuit elements and circuit boards, and thin displays such as LCD and OELD.
- Examples include a thin film transistor protective film, a liquid crystal color filter protective film, a black matrix, and a spacer.
- the permanent film made of the photosensitive composition for permanent film according to the present invention is excellent in heat resistance and moisture absorption, and has very little released hydroxynaphthalene (A), and has little contamination. It has a very good advantage.
- the photosensitive composition for permanent film according to the present invention is a positive resist material for permanent film having high sensitivity, high heat resistance, and moisture absorption reliability with little deterioration in image quality.
- the amount of residual monomer in the resin was determined by GC analysis under the following measurement conditions. For each hydroxy naphthalene used as a raw material, after preparing a calibration curve using a sample with a known concentration, the content of each hydroxy naphthalene is calculated from the area% of the GC peak of the sample based on the calibration curve. did.
- the amount of water in the reaction system was 69.9 parts by mass with respect to 100 parts by mass of 1-naphthol. Then, it heated up at 80 degreeC, stirring the solution in a system, and was made to react for 2 hours. During the reaction, the organic layer and the aqueous layer were not “uniform” which was completely compatible, but “non-uniform”. After completion of the reaction, the solution in the system was transferred to a separating funnel, and the aqueous layer was separated and removed from the organic layer. Subsequently, after washing with water until the washing water showed neutrality, the solvent was removed from the organic layer under heating and reduced pressure to obtain 152 g of novolak resin (3).
- the amount of water in the reaction system is 69.9 parts by mass with respect to 100 parts by mass of 1-naphthol. Then, it heated up at 60 degreeC, stirring the solution in a system, and was made to react for 2 hours. During the reaction, the organic layer and the aqueous layer were completely compatible and “uniform”. After completion of the reaction, 400 g of methyl isobutyl ketone was added, the solution in the system was transferred to a separatory funnel, and the aqueous layer was separated and removed from the organic layer. Subsequently, after washing with water until the washing water showed neutrality, the solvent was removed from the organic layer under heating and reduced pressure to obtain 149 g of novolak resin (4).
- Examples 1 to 3, Comparative Examples 1 and 2 For the novolak resins (1) to (5) synthesized in Synthesis Examples 1 to 5, as shown in Table 1, resin components and photosensitizers (P-200, manufactured by Toyo Gosei Co., Ltd.), propylene glycol monomethyl ether acetate (PGMEA) was mixed and dissolved at 16/4/80 (parts by mass), followed by filtration using a 0.2 ⁇ m membrane filter to obtain a photosensitive composition (positive resist composition). Each positive photosensitive composition obtained was evaluated for alkali developability, sensitivity, resolution, heat resistance, water absorption and stain resistance. The evaluation method was as follows.
- 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.
- the obtained wafer was immersed in a 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 alkali developability (ADR ( ⁇ / s)).
- PEB Post Exposure Bake
- PEB Post Exposure Bake
- Tg glass transition temperature
- 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.
- the obtained wafer was absorbed at 85 ° C. and a humidity of 85% for 24 hours, and the water absorption was calculated from the weight change.
- 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.
- Five pieces obtained by cutting the obtained wafer into 1 cm ⁇ 1 cm were sealed in a 10 mL transparent vial to prepare an evaluation sample.
- Each sample for evaluation was heated in an explosion-proof oven at 121 ° C. for 24 hours, and then cooled to room temperature. The cloudiness due to the sublimation component adhering to the vial glass surface was visually observed.
- a sample that was not clouded by visual inspection was marked with “ ⁇ ”, and a sample that was clouded was marked with “X”.
- the coating films (Examples 1 to 3) comprising the photosensitive composition containing the novolak resins (1) to (3), which are hydroxy naphthalene novolak resins according to the present invention, have an ADR after exposure of 1000 ⁇ / s.
- the sensitivity and resolution were high
- the hygroscopic property was low
- the Tg was sufficiently high as 200 ° C. or higher
- the heat resistance was also good.
- the contamination was low.
- the coating film (Comparative Example 1) comprising the photosensitive composition containing the novolak resin (4) having a residual monomer amount of 2.52% by mass in terms of resin solid content
- the hygroscopicity is slightly low.
- the ADR, sensitivity, and resolution after exposure were as good as those in Examples 1 to 3, but the antifouling property was poor.
- the coating film (Comparative Example 2) made of the photosensitive composition containing the novolak resin (5) having the cresol novolak resin structure as the main skeleton the residual monomer amount is as low as 0.12% by mass, so that it is contaminated.
- ADR, sensitivity, hygroscopicity, and heat resistance were all worse than those of Examples 1 to 3.
- Examples 4 to 8, Comparative Examples 3 to 5 For the novolak resins (1) to (5) synthesized in Synthesis Examples 1 to 5, as shown in Tables 2 and 3, a resin component, a photosensitizer (P-200, manufactured by Toyo Gosei Co., Ltd.), glycoluril, propylene glycol Monomethyl ether acetate (PGMEA) was mixed and dissolved in the proportions (parts by mass) shown in Tables 2 and 3, and then filtered using a 0.2 ⁇ m membrane filter to obtain a photosensitive composition (positive resist composition). It was. Each positive photosensitive composition obtained was evaluated for alkali developability, sensitivity, resolution, heat resistance, water absorption and stain resistance. The evaluation methods for alkali developability, sensitivity, resolution, and water absorption were performed in the same manner as in Example 1, and the heat resistance and stain resistance were evaluated as follows.
- a photosensitizer P-200, manufactured by Toyo Gosei Co., Ltd.
- glycoluril glycol Mono
- Tg glass transition temperature
- the photosensitive composition was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 ⁇ m, dried, and then cured by heating on a 230 ° C. hot plate for 60 seconds.
- Five pieces obtained by cutting the obtained wafer into 1 cm ⁇ 1 cm were sealed in a 10 mL transparent vial to prepare an evaluation sample.
- Each sample for evaluation was heated in an explosion-proof oven at 121 ° C. for 24 hours, then cooled to room temperature, and cloudiness due to adhesion of sublimation components to the vial glass surface was visually observed.
- a sample that was not clouded by visual inspection was marked with “ ⁇ ”, and a sample that was clouded was marked with “X”.
- the content of glycoluril as a curing agent with respect to 100 parts by mass of hydroxynaphthalene novolac resin is about 6 parts by mass, examples 4 to 6 are about 30 parts by mass, examples 7 are about 30 parts by mass, and examples 8 are about 50 parts by mass. From the result of Comparative Example 5 which is about 60 parts by mass, it was confirmed that the heat resistance was remarkably improved by adding a curing agent. On the other hand, as the blending amount of the curing agent increased, the ADR value after exposure decreased and the moisture absorption rate increased. In particular, in Comparative Example 5, the ADR value after exposure decreased rapidly to 180, and the moisture absorption rate increased to 1.8. That is, Comparative Example 5 had a problem in developability and was not suitable as a photosensitive material for a permanent film.
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Materials For Photolithography (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
また、これらの感光性組成物に含有される樹脂成分は、未反応のモノマー成分の混入量が多い。このため、高温環境下では、永久膜及びその周辺の部材に、永久膜から昇華したモノマー成分が付着して汚染されてしまうという問題がある。
R2は水素原子、置換基を有していてもよいアルキル基、又は置換基を有していてもよいアリール基を表し、
pは1又は2を表し、qは4又は5を表す。但し、pとqの和は6である。]
で表される構造部位(I)を繰り返し単位として有しており、下記一般式(2)
で表されるヒドロキシナフタレン類(A)の含有量が樹脂固形分換算で2質量%以下であるヒドロキシナフタレンノボラック樹脂を含有し、硬化剤を含有していない、又は前記ヒドロキシナフタレンノボラック樹脂100質量部に対して、50質量部以下の硬化剤を含有することを特徴とする、永久膜用感光性組成物に関する。
樹脂組成物の分子量分布は、GPCにより、ポリスチレン標準法において、以下の測定条件にて測定した。
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」(8.0mmφ×300mm)+昭和電工株式会社製「Shodex KF802」(8.0mmφ×300mm)+昭和電工株式会社製「Shodex KF803」(8.0mmφ×300mm)+昭和電工株式会社製「Shodex KF804」(8.0mmφ×300mm)
検出器:RI、
測定条件:カラム温度 40℃
展開溶媒 テトラヒドロフラン(THF)
流速 1.0mL/分
試料:樹脂固形分換算で1.0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(5μL)、
標準試料:分子量が既知の単分散ポリスチレンを用いた。
(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-1000」
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」
東ソー株式会社製「F-40」
東ソー株式会社製「F-80」
東ソー株式会社製「F-128」
東ソー株式会社製「F-288」
東ソー株式会社製「F-550」
樹脂中の残留モノマー量(未反応のヒドロキシナフタレン類の量)は、GC分析により、下記の測定条件により求めた。原料として用いた各ヒドロキシナフタレン類について、濃度既知の標品を用いて検量線を作成した後、当該検量線に基づいて、試料のGCピークの面積%から各ヒドロキシナフタレン類の含有量をそれぞれ算出した。
装置:島津製作所製 GC-14B、
カラム:キャピラリーカラムDB-1(25mmφ×60m)、
カラム温度:90℃で1分保持後、10℃/分で280℃まで昇温し、6分間保持
試料気化室温度:250℃、
検出器:FID、280℃、
キャリアガス:ヘリウム、
流速:1.4mL/分、
試料注入量:0.5μL、
温度計、冷却管、撹拌器を取り付けた1L容4つ口フラスコに、1-ナフトール144g(1.0モル)、メチルイソブチルケトン400g、水96g及び92%パラホルムアルデヒド27.7g(0.85モル)を仕込んだ。続いて、当該4つ口フラスコに、攪拌しながら、50%濃度に調整したパラトルエンスルホン酸の水溶液4.8gを添加した。反応系内の水の量は、1-ナフトール100質量部に対し、69.9質量部であった。その後、系内の溶液を攪拌しながら80℃に昇温し、2時間反応させた。反応中、有機層と水層は完全に相溶した「均一」とはなっておらず、「不均一」であった。反応終了後、系内の溶液を分液ロートに移し、水層を有機層から分離除去した。次いで、洗浄水が中性を示すまで水洗後、有機層から溶媒を加熱減圧下に除去し、ノボラック樹脂(1)147gを得た。ノボラック樹脂(1)について、GPC及びGCを行ったところ、数平均分子量(Mn)=1312、重量平均分子量(Mw)=2251、多分散度(Mw/Mn)=1.716、残留モノマー量=0.57質量%であった。ノボラック樹脂(1)のGPCチャートを図1に示す。
温度計、冷却管、撹拌器を取り付けた1L容4つ口フラスコに、1-ナフトール144g(1.0モル)、o-クレゾール2.2g(0.02モル)、1-ブタノール400g、水96g及び92%パラホルムアルデヒド27.7g(0.85モル)を仕込んだ。続いて、当該4つ口フラスコに、攪拌しながら50%濃度に調整したパラトルエンスルホン酸の水溶液4.8gを添加した。反応系内の水の量は、1-ナフトール100質量部に対し、69.9質量部であった。その後、系内の溶液を攪拌しながら80℃に昇温し、2時間反応させた。反応中、有機層と水層は完全に相溶した「均一」とはなっておらず、「不均一」であった。反応終了後、系内の溶液を分液ロートに移し、水層を有機層から分離除去した。次いで、洗浄水が中性を示すまで水洗後、有機層から溶媒を加熱減圧下に除去し、ノボラック樹脂(2)147g得た。ノボラック樹脂(2)について、GPC及びGCを行ったところ、数平均分子量(Mn)=1765、重量平均分子量(Mw)=3337、多分散度(Mw/Mn)=1.890、残留モノマー量=0.93質量%であった。ノボラック樹脂(2)のGPCチャートを図2に示す。
温度計、冷却管、撹拌器を取り付けた1L容4つ口フラスコに、1-ナフトール144g(1.0モル)、o-クレゾール2.2g(0.02モル)メチルイソブチルケトン400g、水96g及びパラアルデヒド37.5g(0.28モル)を仕込んだ。続いて、当該4つ口フラスコに、攪拌しながら50%濃度に調整したパラトルエンスルホン酸の水溶液4.8gを添加した。反応系内の水の量は、1-ナフトール100質量部に対し、69.9質量部であった。その後、系内の溶液を攪拌しながら80℃に昇温し、2時間反応させた。反応中、有機層と水層は完全に相溶した「均一」とはなっておらず、「不均一」であった。反応終了後、系内の溶液を分液ロートに移し、水層を有機層から分離除去した。次いで、洗浄水が中性を示すまで水洗後、有機層から溶媒を加熱減圧下に除去し、ノボラック樹脂(3)152g得た。ノボラック樹脂(3)について、GPC及びGCを行ったところ、数平均分子量(Mn)=1694、重量平均分子量(Mw)=2852、多分散度(Mw/Mn)=1.683、残留モノマー量=1.03質量%であった。ノボラック樹脂(3)のGPCチャートを図3に示す。
温度計、冷却管、撹拌器を取り付けた1L容4つ口フラスコに、1-ナフトール144g(1.0モル)、o-クレゾール2.2g(0.02モル)、メタノール400g、水96g及び92%パラホルムアルデヒド27.7g(0.85モル)を仕込んだ。続いて、当該4つ口フラスコに、攪拌しながら50%濃度に調整したパラトルエンスルホン酸の水溶液4.8gを添加した。反応系内の水の量は1-ナフトール100質量部に対し、69.9質量部である。その後、系内の溶液を攪拌しながら60℃に昇温し、2時間反応させた。反応中、有機層と水層は完全に相溶した「均一」であった。反応終了後、メチルイソブチルケトン400gを加え、系内の溶液を分液ロートに移し、水層を有機層から分離除去した。次いで、洗浄水が中性を示すまで水洗後、有機層から溶媒を加熱減圧下に除去し、ノボラック樹脂(4)149g得た。ノボラック樹脂(4)について、GPC及びGCを行ったところ、数平均分子量(Mn)=955、重量平均分子量(Mw)=1427、多分散度(Mw/Mn)=1.495、残留モノマー量=2.52質量%であった。ノボラック樹脂(4)のGPCチャートを図4に示す。
攪拌機、温度計を備えた2L容4つ口フラスコに、m-クレゾール648g(6モル)、p-クレゾール432g(4モル)、シュウ酸2.5g(0.2モル)、42%ホルムアルデヒド492gを仕込み、100℃まで昇温、反応させた。系内の溶液を常圧で200℃まで脱水、蒸留した後、230℃、6時間減圧蒸留を行い、ノボラック樹脂(5)736gを得た。ノボラック樹脂(5)について、GPC及びGCを行ったところ、数平均分子量(Mn)=1450、重量平均分子量(Mw)=10.316、多分散度(Mw/Mn)=7.116、残留モノマー量=0.12質量%であった。ノボラック樹脂(5)のGPCチャートを図5に示す。
合成例1~5で合成したノボラック樹脂(1)~(5)について、表1に示すように、樹脂成分と感光剤(東洋合成工業製、P-200)、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を16/4/80(質量部)で混合して溶解させた後、0.2μmメンブランフィルターを用いて濾過し、感光性組成物(ポジ型レジスト組成物)とした。
得られた各ポジ型感光性組成物について、アルカリ現像性、感度、解像度、耐熱性、吸水性及び汚染性を評価した。評価方法は下記の通りとした。
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秒間乾燥させた。得られたウェハーを、現像液(2.38%水酸化テトラメチルアンモニウム水溶液)に60秒間浸漬させた後、110℃のホットプレート上で60秒間乾燥させた。当該感光性組成物の塗膜の膜厚を、現像液浸漬前後で測定し、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。露光させる場合は、ghi線ランプ(ウシオ電機社製、マルチライト)で十分に露光される100mJ/cm2照射した後、140℃、60秒間の条件でPEB(Post Exposure Bake)を施したウェハーを用いてADR測定を実施した。
感光性組成物を約1μmの厚さで塗布して乾燥せしめたウェハー上に、ラインアンドスペースが1:1の1~10μmレジストパターン対応のマスクを密着させた後、ghi線ランプで3μmを忠実に再現することのできる露光量(Eop露光量)を求めた。
感光性組成物を塗布して乾燥したシリコンウェハー上にフォトマスクを乗せ、ghi線ランプ(ウシオ電機社製、マルチライト)で100mJ/cm2照射し感光せしめた。照射後の塗膜を、ADR測定と同様にして現像し乾燥させた。現像後のウェハー上のレジストパターンのパターン状態を、キーエンス社製レーザーマイクロスコープ(VK-8500)を用いて評価した。評価は、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秒間乾燥させた。得られたウェハーより樹脂分をかきとり、Tgを測定した。Tgの測定は、示差走査熱量計((株)TAインスツルメント製、示差走査熱量計(DSC)Q100)を用いて、窒素雰囲気下、温度範囲:-100~200℃、昇温温度:10℃/分の条件で走査を行い、測定結果をガラス転移温度(Tg)とした。
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秒間乾燥させた。得られたウェハーを85℃、湿度85%で24時間吸湿させ、重量変化により吸水率を算出した。
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秒間乾燥させた。得られたウェハーを1cm×1cmに切ったもの5片を10mL容の透明バイアル瓶に密封し、評価用サンプルとした。各評価用サンプルを防爆オーブン内で121℃、24時間加熱した後、室温に冷却し、バイアル瓶ガラス面への昇華成分付着による曇りを目視で観測した。目視により曇りがなかったものを「○」、曇りが有ったものを「×」とした。
合成例1~5で合成したノボラック樹脂(1)~(5)について、表2及び3に示すように、樹脂成分と、感光剤(東洋合成工業製、P-200)、グリコールウリル、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を表2及び3に記載の割合(質量部)で混合して溶解させた後、0.2μmメンブランフィルターを用いて濾過し、感光性組成物(ポジ型レジスト組成物)とした。
得られた各ポジ型感光性組成物について、アルカリ現像性、感度、解像度、耐熱性、吸水性及び汚染性を評価した。アルカリ現像性、感度、解像度、及び吸水性の評価方法は、実施例1と同様にして行い、耐熱性及び汚染性については下記の通り評価した。
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、乾燥させた後、230℃のホットプレート上で60秒間加熱することにより硬化させた。得られたウェハーより樹脂分をかきとり、Tgを測定した。Tgの測定は、示差走査熱量計((株)TAインスツルメント製、示差走査熱量計(DSC)Q100)を用いて、窒素雰囲気下、温度範囲:-100~200℃、昇温温度:10℃/分の条件で走査を行い、測定結果をガラス転移温度(Tg)とした。
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、乾燥させた後、230℃のホットプレート上で60秒間加熱することにより硬化させた。得られたウェハーを1cm×1cmに切ったもの5片を10mL容の透明バイアル瓶に密封し、評価用サンプルとした。各評価用サンプルを防爆オーブン内で121℃で24時間加熱した後、室温に冷却し、バイアル瓶ガラス面への昇華成分付着による曇りを目視で観測した。目視により曇りがなかったものを「○」、曇りが有ったものを「×」とした。
Claims (12)
- 下記一般式(1)
R2は水素原子、置換基を有していてもよいアルキル基、又は置換基を有していてもよいアリール基を表し、
pは1又は2を表し、qは4又は5を表す。但し、pとqの和は6である。]
で表される構造部位(I)を繰り返し単位として有しており、下記一般式(2)
で表されるヒドロキシナフタレン類(A)の含有量が、樹脂固形分換算で2質量%以下であるヒドロキシナフタレンノボラック樹脂を含有し、
硬化剤を含有していない、又は前記ヒドロキシナフタレンノボラック樹脂100質量部に対して、50質量部以下の硬化剤を含有することを特徴とする、永久膜用感光性組成物。 - さらに、前記ヒドロキシナフタレンノボラック樹脂100質量部に対して、0.1~50質量部の硬化剤を含有する、請求項1に記載の永久膜用感光性組成物。
- さらに、前記ヒドロキシナフタレンノボラック樹脂100質量部に対して、0.1~30質量部の硬化剤を含有する、請求項1に記載の永久膜用感光性組成物。
- 前記R2が水素原子である、請求項1~4のいずれか一項に記載の永久膜用感光性組成物。
- 前記R1が水素原子である、請求項1~5のいずれか一項に記載の永久膜用感光性組成物。
- 前記酸触媒が、p-トルエンスルホン酸である、請求項4~6のいずれか一項に記載の永久膜用感光性組成物。
- 前記有機溶剤が、ブタノール、オクタノール、メチルエチルケトン、及びメチルイソブチルケトンからなる群より選択される1種以上である、請求項4~7のいずれか一項に記載の永久膜用感光性組成物。
- さらに、感光剤を含有する、請求項1~8のいずれか一項に記載の永久膜用感光性組成物。
- 請求項9に記載の感光性組成物からなるレジスト材料。
- 請求項9に記載の感光性組成物からなる塗膜。
- 永久膜である、請求項11に記載の塗膜。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015543618A JP5907316B1 (ja) | 2014-06-12 | 2015-05-19 | 永久膜用感光性組成物、レジスト材料、塗膜、及び永久膜用感光性組成物の製造方法 |
CN201580031521.6A CN106462063A (zh) | 2014-06-12 | 2015-05-19 | 永久膜用感光性组合物、抗蚀材料及涂膜 |
US15/309,271 US20170082923A1 (en) | 2014-06-12 | 2015-05-19 | Photosensitive composition for permanent films, resist material and coating film |
KR1020167032857A KR102279987B1 (ko) | 2014-06-12 | 2015-05-19 | 영구막용 감광성 조성물, 레지스트 재료, 및 도막 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014121532 | 2014-06-12 | ||
JP2014-121532 | 2014-06-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015190233A1 true WO2015190233A1 (ja) | 2015-12-17 |
Family
ID=54833338
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/064265 WO2015190233A1 (ja) | 2014-06-12 | 2015-05-19 | 永久膜用感光性組成物、レジスト材料、及び塗膜 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20170082923A1 (ja) |
JP (2) | JP5907316B1 (ja) |
KR (1) | KR102279987B1 (ja) |
CN (1) | CN106462063A (ja) |
TW (1) | TWI673317B (ja) |
WO (1) | WO2015190233A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20180109707A (ko) * | 2017-03-27 | 2018-10-08 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 반도체 장치 및 그의 제조 방법, 및 적층체 |
WO2019050047A1 (ja) * | 2017-09-11 | 2019-03-14 | 明和化成株式会社 | フォトレジスト用フェノール樹脂組成物及びフォトレジスト組成物 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI675051B (zh) * | 2014-10-10 | 2019-10-21 | 日商迪愛生股份有限公司 | 萘酚型杯芳烴化合物及其製造方法、感光性組成物、光阻材料、及塗膜 |
WO2016114001A1 (ja) * | 2015-01-16 | 2016-07-21 | Dic株式会社 | フェノール性水酸基含有化合物、これを含む組成物及びその硬化膜 |
TWI715655B (zh) * | 2015-12-11 | 2021-01-11 | 日商迪愛生股份有限公司 | 酚醛清漆型樹脂及抗蝕劑膜 |
JP6952497B2 (ja) * | 2017-05-31 | 2021-10-20 | 日東電工株式会社 | 粘着剤組成物、表面保護シート、及び、光学部材 |
JP7067919B2 (ja) | 2017-12-26 | 2022-05-16 | 信越化学工業株式会社 | ジヒドロキシナフタレンの精製方法 |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4551409A (en) * | 1983-11-07 | 1985-11-05 | Shipley Company Inc. | Photoresist composition of cocondensed naphthol and phenol with formaldehyde in admixture with positive o-quinone diazide or negative azide |
JPS61130947A (ja) * | 1984-11-30 | 1986-06-18 | Japan Synthetic Rubber Co Ltd | ポジ型レジスト組成物 |
US5939511A (en) * | 1996-09-06 | 1999-08-17 | Shipley Company, L.L.C. | Resin purification process |
JP2000292919A (ja) * | 1999-04-02 | 2000-10-20 | Clariant (Japan) Kk | 感放射線性樹脂組成物 |
JP2003201324A (ja) * | 2001-12-28 | 2003-07-18 | Hitachi Ltd | 水性アルカリ可溶性樹脂、感光性樹脂組成物、フォトマスクおよび電子デバイスの製造方法 |
JP2005023210A (ja) * | 2003-07-03 | 2005-01-27 | Renesas Technology Corp | 水性アルカリ可溶性樹脂、感光性樹脂組成物およびそれを用いた半導体装置の製造方法 |
JP2006154403A (ja) * | 2004-11-30 | 2006-06-15 | Nippon Zeon Co Ltd | パターン形成方法 |
JP2007031527A (ja) * | 2005-07-26 | 2007-02-08 | Asahi Organic Chem Ind Co Ltd | ナフトール樹脂及びその製造方法 |
JP2008050513A (ja) * | 2006-08-28 | 2008-03-06 | Sumitomo Bakelite Co Ltd | ノボラック型フェノール樹脂の製造方法、ノボラック型フェノール樹脂及びフォトレジスト用フェノール樹脂組成物 |
JP2009227926A (ja) * | 2008-03-25 | 2009-10-08 | Sumitomo Bakelite Co Ltd | ノボラック型フェノール樹脂 |
JP2010248435A (ja) * | 2009-04-20 | 2010-11-04 | Dic Corp | ノボラック樹脂の製造方法 |
JP5613851B1 (ja) * | 2014-02-28 | 2014-10-29 | Jsr株式会社 | 表示又は照明装置 |
JP2015052770A (ja) * | 2013-08-08 | 2015-03-19 | Jsr株式会社 | 感放射線性樹脂組成物、絶縁膜及びその形成方法並びに有機el素子 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62212408A (ja) * | 1986-03-14 | 1987-09-18 | Matsushita Electric Works Ltd | 低分子量フエノ−ル樹脂の製造方法 |
JPH06118647A (ja) * | 1992-10-05 | 1994-04-28 | Mitsubishi Kasei Corp | ネガ型感光性組成物 |
JP3652071B2 (ja) * | 1997-07-25 | 2005-05-25 | 東京応化工業株式会社 | ノボラック樹脂前駆体およびノボラック樹脂の製造方法 |
US6936680B2 (en) * | 2000-12-12 | 2005-08-30 | Chang Chun Plastics Co., Ltd. | Method of producing novolak resin |
JP4131864B2 (ja) | 2003-11-25 | 2008-08-13 | 東京応化工業株式会社 | 化学増幅型ポジ型感光性熱硬化性樹脂組成物、硬化物の形成方法、及び機能素子の製造方法 |
JP5062714B2 (ja) * | 2006-01-19 | 2012-10-31 | 日本化薬株式会社 | 活性エネルギー線硬化型樹脂組成物、及びその用途 |
WO2007099670A1 (ja) * | 2006-02-28 | 2007-09-07 | Dic Corporation | フェノール樹脂の製造方法、およびエポキシ樹脂の製造方法 |
JP4778535B2 (ja) * | 2007-04-06 | 2011-09-21 | 大阪瓦斯株式会社 | フェノール樹脂およびその製造方法 |
JP5077023B2 (ja) | 2008-03-31 | 2012-11-21 | Jsr株式会社 | 接着方法およびそれに用いられるポジ型感光性接着剤組成物、並びに電子部品 |
JP5229044B2 (ja) | 2009-03-26 | 2013-07-03 | Jsr株式会社 | レジスト下層膜形成用組成物、レジスト下層膜、レジスト下層膜の形成方法、及びパターン形成方法 |
JP5439254B2 (ja) * | 2010-03-31 | 2014-03-12 | 太陽ホールディングス株式会社 | 感光性樹脂組成物 |
JP5485188B2 (ja) * | 2011-01-14 | 2014-05-07 | 信越化学工業株式会社 | レジスト下層膜材料及びこれを用いたパターン形成方法 |
-
2015
- 2015-05-19 US US15/309,271 patent/US20170082923A1/en not_active Abandoned
- 2015-05-19 WO PCT/JP2015/064265 patent/WO2015190233A1/ja active Application Filing
- 2015-05-19 KR KR1020167032857A patent/KR102279987B1/ko active IP Right Grant
- 2015-05-19 JP JP2015543618A patent/JP5907316B1/ja active Active
- 2015-05-19 CN CN201580031521.6A patent/CN106462063A/zh active Pending
- 2015-06-04 TW TW104118066A patent/TWI673317B/zh active
- 2015-12-04 JP JP2015237494A patent/JP5930114B2/ja active Active
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4551409A (en) * | 1983-11-07 | 1985-11-05 | Shipley Company Inc. | Photoresist composition of cocondensed naphthol and phenol with formaldehyde in admixture with positive o-quinone diazide or negative azide |
JPS61130947A (ja) * | 1984-11-30 | 1986-06-18 | Japan Synthetic Rubber Co Ltd | ポジ型レジスト組成物 |
US5939511A (en) * | 1996-09-06 | 1999-08-17 | Shipley Company, L.L.C. | Resin purification process |
JP2000292919A (ja) * | 1999-04-02 | 2000-10-20 | Clariant (Japan) Kk | 感放射線性樹脂組成物 |
JP2003201324A (ja) * | 2001-12-28 | 2003-07-18 | Hitachi Ltd | 水性アルカリ可溶性樹脂、感光性樹脂組成物、フォトマスクおよび電子デバイスの製造方法 |
JP2005023210A (ja) * | 2003-07-03 | 2005-01-27 | Renesas Technology Corp | 水性アルカリ可溶性樹脂、感光性樹脂組成物およびそれを用いた半導体装置の製造方法 |
JP2006154403A (ja) * | 2004-11-30 | 2006-06-15 | Nippon Zeon Co Ltd | パターン形成方法 |
JP2007031527A (ja) * | 2005-07-26 | 2007-02-08 | Asahi Organic Chem Ind Co Ltd | ナフトール樹脂及びその製造方法 |
JP2008050513A (ja) * | 2006-08-28 | 2008-03-06 | Sumitomo Bakelite Co Ltd | ノボラック型フェノール樹脂の製造方法、ノボラック型フェノール樹脂及びフォトレジスト用フェノール樹脂組成物 |
JP2009227926A (ja) * | 2008-03-25 | 2009-10-08 | Sumitomo Bakelite Co Ltd | ノボラック型フェノール樹脂 |
JP2010248435A (ja) * | 2009-04-20 | 2010-11-04 | Dic Corp | ノボラック樹脂の製造方法 |
JP2015052770A (ja) * | 2013-08-08 | 2015-03-19 | Jsr株式会社 | 感放射線性樹脂組成物、絶縁膜及びその形成方法並びに有機el素子 |
JP5613851B1 (ja) * | 2014-02-28 | 2014-10-29 | Jsr株式会社 | 表示又は照明装置 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20180109707A (ko) * | 2017-03-27 | 2018-10-08 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 반도체 장치 및 그의 제조 방법, 및 적층체 |
JP2018164002A (ja) * | 2017-03-27 | 2018-10-18 | 信越化学工業株式会社 | 半導体装置及びその製造方法、並びに積層体 |
KR102506002B1 (ko) * | 2017-03-27 | 2023-03-06 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 반도체 장치 및 그의 제조 방법, 및 적층체 |
WO2019050047A1 (ja) * | 2017-09-11 | 2019-03-14 | 明和化成株式会社 | フォトレジスト用フェノール樹脂組成物及びフォトレジスト組成物 |
KR20200051748A (ko) * | 2017-09-11 | 2020-05-13 | 메이와가세이가부시키가이샤 | 포토레지스트용 페놀 수지 조성물 및 포토레지스트 조성물 |
JPWO2019050047A1 (ja) * | 2017-09-11 | 2020-10-29 | 明和化成株式会社 | フォトレジスト用フェノール樹脂組成物及びフォトレジスト組成物 |
JP7147768B2 (ja) | 2017-09-11 | 2022-10-05 | Ube株式会社 | フォトレジスト用フェノール樹脂組成物及びフォトレジスト組成物 |
KR102515382B1 (ko) | 2017-09-11 | 2023-03-30 | 유비이 가부시키가이샤 | 포토레지스트용 페놀 수지 조성물 및 포토레지스트 조성물 |
Also Published As
Publication number | Publication date |
---|---|
US20170082923A1 (en) | 2017-03-23 |
CN106462063A (zh) | 2017-02-22 |
TWI673317B (zh) | 2019-10-01 |
KR20170019346A (ko) | 2017-02-21 |
TW201602218A (zh) | 2016-01-16 |
JP5930114B2 (ja) | 2016-06-08 |
JPWO2015190233A1 (ja) | 2017-04-20 |
JP2016075937A (ja) | 2016-05-12 |
KR102279987B1 (ko) | 2021-07-22 |
JP5907316B1 (ja) | 2016-04-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5930114B2 (ja) | 永久膜用感光性組成物、レジスト材料、及び塗膜 | |
JP5988122B1 (ja) | ナフトール型カリックスアレーン化合物及びその製造方法、感光性組成物、レジスト材料、並びに塗膜 | |
JP6025011B1 (ja) | フェノール性水酸基含有化合物、これを含む組成物及びその硬化膜 | |
CN107531858B (zh) | 酚醛清漆型含酚性羟基树脂以及抗蚀膜 | |
CN107848926B (zh) | 酚醛清漆型含酚性羟基树脂以及抗蚀膜 | |
JP5939450B1 (ja) | フェノール性水酸基含有樹脂、その製造方法、感光性組成物、レジスト材料、塗膜、硬化性組成物とその硬化物、及びレジスト下層膜 | |
JP6028883B1 (ja) | レジスト永久膜用硬化性組成物及びレジスト永久膜 | |
TWI722135B (zh) | 酚醛清漆型樹脂及抗蝕劑材料 | |
JP6140506B2 (ja) | ポジ型レジスト組成物及びレジストパターン形成方法 | |
JP6269904B1 (ja) | ノボラック型樹脂の製造方法 | |
JP6590084B2 (ja) | フェノール性水酸基含有樹脂及びレジスト材料 | |
JPWO2017175589A1 (ja) | ノボラック型樹脂及びレジスト材料 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2015543618 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15806044 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15309271 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20167032857 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15806044 Country of ref document: EP Kind code of ref document: A1 |