US4299911A
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High energy radiation curable resist material and method of using the same
Assignee: Somar Corp
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Filing: 1978-08-09
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Granted: 1981-11-10
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Expires: 1998-08-09
Abstract
Abstract A resist material curable by irradiation with high energy radiation such as electron beams, X-rays, ion beams, neutron beams, gamma -rays or deep ultraviolet light but substantially non-curable by irradiation with light having a wavelength of about 300 nm or more, the resist material comprising, as a main component, a solvent-soluble polymer containing an ethylenically unsaturated double bond, the polymer being obtained by reacting (a) a polymer having a plurality of oxirane rings therein and (b) a monomer containing (i) at least one ethylenically unsaturated double bond and (ii) one functional group capable of opening the oxirane rings, and then opening the unreacted oxirane rings.
Inventors
- 👤 Hideo Ochi
- 👤 Yumi Shibata
- 👤 Kohtaro Nagasawa
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 13:14
CPC Classifications
G; G03; G03F; G03F7/00; G03F7/004; G03F7/038; G03F7/0388; C; C08; C08F; C08F8/00; C08G; C08G59/00; C08G59/14; C08G59/1433; H; H01; H01R; H01R43/00; H01R43/005; Y; Y10; Y10S; Y10S430/00; Y10S430/167; Y10S430/168
Claims Analysis
Total Claims: 33
Claim 1
Independent Claim
107 words
A resist material curable by irradiation with high energy radiation but substantially non-curable by irradiation with light having a wavelength of about 300 nm or more, the resist material comprising, as a main component, a solvent-soluble polymer containing ethylenically unsaturated double bonds, the polymer being obtained by reacting (a) a polymer having a plurality of oxirane rings therein and (b) a monomer containing (i) at least one ethylenically unsaturated double bond and (ii) one functional group capable of opening the oxirane rings, and then opening unreacted oxirane rings with an oxirane ring-opening agent selected from the group consisting of a hydrogen halide, hydrogen sulfide and hydrogen cyanide.
Claim 2
Dependent Claim
107 words
A resist material curable by irradiation with high energy radiation but substantially non-curable by irradiation with light having a wavelength of about 300 nm or more, the resist material comprising, as a main component, a solvent-soluble polymer containing ethylenically unsaturated double bonds, the polymer being obtained by reacting (a) a polymer having a plurality of oxirane rings therein and (b) a monomer containing (i) at least one ethylenically unsaturated double bond and (ii) one functional group capable of opening the oxirane rings, and then opening unreacted oxirane rings with an oxirane ring-opening agent selected from the group consisting of a hydrogen halide, hydrogen sulfide and hydrogen cyanide.
Claim 3
Dependent Claim
93 words
The resist material of claim 1, wherein the polymer having a plurality of oxirane rings is a homopolymer of a monomer containing an ethylenically unsaturated double bond and an oxirane ring, a copolymer of two or more monomers containing an ethylenically unsaturated double bond and an oxirane ring, or a copolymer of at least one monomer containing an ethylenically unsaturated double bond and an oxirane ring with at least one other monomer containing an ethylenically unsaturated double bond and free of oxirane rings and free of a substituent group reactive with oxirane rings.
Claim 4
Dependent Claim
40 words
The resist material of claim 1 or 2, wherein said polymer containing a plurality of oxirane rings is a polymer of monomer units in which at least 10 mol% of the monomer units are monomer units containing an oxirane ring.
Claim 5
Dependent Claim
49 words
The resist material of claim 1, wherein the polymer having a plurality of oxirane rings is a homopolymer of a monomer containing an ethylenically unsaturated double bond and an oxirane ring or a copolymer of two or more monomers containing an ethylenically unsaturated double bond and an oxirane ring.
Claim 6
Dependent Claim
60 words
The resist material of claim 1, wherein the polymer having a plurality of oxirane rings is a copolymer of at least one monomer containing an ethylenically unsaturated double bond and an oxirane ring with at least one other monomer containing an ethylenically unsaturated double bond and free of oxirane rings and free of a substituent group reactive with oxirane rings.
Claim 7
Dependent Claim
50 words
The resist material of claim 2, wherein said monomer containing an ethylenically unsaturated double bond and an oxirane ring is glycidyl acrylate, glycidyl methacrylate, 2-vinylthioglycidyl ether, allyl glycidyl ether, glycidyl vinylacetate, glycidyl allylacetate, 4-glycidyl styrene, 2-allylphenyl glycidyl ether, 4-allylphenyl glycidyl ether, glycidyl 4-vinylbenzoate, 3,4-epoxybutene, 3,4-epoxy-2-methylbutene, 4-vinylcyclohexene oxide or p-divinylstyrene monooxide.
Claim 8
Dependent Claim
72 words
The resist material of claim 2, wherein said at least one other monomer containing an ethylenically unsaturated double bond and free from an oxirane ring and a substituent group reactive with oxirane rings is a vinyl monomer, an alkylacrylate or methacrylate, a cycloalkylacrylate or methacrylate, an arylacrylate or methacrylate, an aralkylacrylate or methacrylate, an acrylic or methacrylic acid derivative, a vinyl halide, a vinyl ketone, vinyl acetic acid or allyl acetic acid.
Claim 9
Dependent Claim
29 words
The resist material of claim 1, wherein said polymer having a plurality of oxirane rings has a number average molecular weight of about 10 2 to 10 6 .
Claim 10
Dependent Claim
48 words
The resist material of claim 1, wherein said monomer containing at least one ethylenically unsaturated double bond and one functional group capable of opening oxirane rings is a monomer containing a carboxyl group, an acyl halide group, a hydroxyl group, a thiol group or a secondary amino group.
Claim 11
Dependent Claim
23 words
The resist material of claim 9, wherein said monomer containing a carboxyl group is an unsaturated aliphatic monocarboxylic acid or dicarboxylic acid monoester.
Claim 12
Dependent Claim
52 words
The resist material of claim 10, wherein said unsaturated aliphatic monocarboxylic acid or dicarboxylic acid monoester is a monoester of maleic acid, a monoester of fumaric acid, a monoester of itaconic acid, acrylic acid, methacrylic acid, a monoester of cis-4-cyclohexene-1,2-dicarboxylic acid, a monoester of 5-norbornene-2,2-dicarboxylic acid, or a monoester of hexachloro[2,2,1]-bicyclohept-5-ene-2,3-dicarboxylic acid.
Claim 13
Dependent Claim
50 words
The resist material of claim 9, wherein said monomer containing an acyl halide group is acryloyl chloride, methacryloyl chloride, methylvinylacetyl chloride, 3-allylpropionyl chloride, allylphenylacetyl chloride, allylbenzylacetyl chloride, monomethylmaleoyl chloride, monoethylmaleoyl chloride, monoisopropylmaleoyl chloride, monomethylfumaroyl chloride, monoethylfumaroyl chloride, monoisopropylfumaroyl chloride, monomethylitaconoyl chloride or the corresponding acid bromides to these acid chlorides.
Claim 14
Dependent Claim
29 words
The resist material of claim 9, wherein said monomer containing a hydroxyl group is a monomer containing an alcoholic hydroxyl group or a monomer containing a phenolic hydroxyl group.
Claim 15
Dependent Claim
69 words
The resist material of claim 13, wherein said monomer containing a hydroxyl group is allyl alcohol, ethylene glycol monoacrylate, ethylene glycol monomethacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-vinylbenzyl alcohol, 4-allylbenzyl alcohol, 4-hydroxystyrene, 2-hydroxystyrene, 3-hydroxystyrene, 2-allyl phenol, 2-methyl-6-allyl phenol, 2-allyl-4-methylphenol, 1-allyl-2-naphthol, eugenol, 4-allyl anisole, 3-allyl anisole, 2,6-diallyl phenol, 2,6-diallyl p-cresol or 2,4,5-triallyl phenol.
Claim 16
Dependent Claim
23 words
The resist material of claim 9, wherein said monomer containing a thiol group is allyl mercaptan, mercapto-butene-2, mercaptobutene-3, mercaptopentene-4, mercaptopentene-1, 2-vinylthiophenol or 2-allylthiophenol.
Claim 17
Dependent Claim
34 words
The resist material of claim 9, wherein said monomer containing a secondary amino group is N-methylallylamine, diallylamine, N-methylaminoethyl acrylate, N-methylaminoethyl methacrylate, N-propylaminomethyl acrylate, N-propylaminomethyl methacrylate, N-propylaminoethyl acrylate, N-propylaminoethyl methacrylate, N-benzylallylamine, N-allyl aniline, or N-allyl-2-toluidine.
Claim 18
Dependent Claim
67 words
A method of forming a resist comprising irradiating an element comprising a substrate having thereon a thin film of the resist material of claim 1, with high energy radiation, and removing the unexposed, uncured portions of the resist film by dissolving the uncured portions in a solvent, thereby forming a pattern of the cured, exposed portions of the resist material film on the surface of the substrate.
Claim 19
Dependent Claim
96 words
The method of forming a resist of claim 17, wherein the polymer having a plurality of oxirane rings is a homopolymer of a monomer containing an ethylenically unsaturated double bond and an oxirane ring, a copolymer of two or more monomers containing an ethylenically unsaturated double bond and an oxirane ring, or a copolymer of at least one monomer containing an ethylenically unsaturated double bond and an oxirane ring with at least one other monomer containing an ethylenically unsaturated double bond and free of oxirane rings and free of a substituent group reactive with oxirane rings.
Claim 20
Dependent Claim
43 words
The method of forming a resist of claim 17 or 18, wherein said polymer containing a plurality of oxirane rings is a polymer of monomer units in which at least 10 mol% of the monomer units are monomer units containing an oxirane ring.
Claim 21
Dependent Claim
52 words
The method of forming a resist of claim 17, wherein the polymer having a plurality of oxirane rings is a homopolymer of a monomer containing an ethylenically unsaturated double bond and an oxirane ring or a copolymer of two or more monomers containing an ethylenically unsaturated double bond and an oxirane ring.
Claim 22
Dependent Claim
63 words
The method of forming a resist of claim 17, wherein the polymer having a plurality of oxirane rings is a copolymer of at least one monomer containing an ethylenically unsaturated double bond and an oxirane ring with at least one other monomer containing an ethylenically unsaturated double bond and free of oxirane rings and free of a substituent group reactive with oxirane rings.
Claim 23
Dependent Claim
53 words
The method of forming a resist of claim 18, wherein said monomer containing an ethylenically unsaturated double bond and an oxirane ring is glycidyl acrylate, glycidyl methacrylate, 2-vinylthioglycidyl ether, allyl glycidyl ether, glycidyl vinylacetate, glycidyl allylacetate, 4-glycidyl styrene, 2-allylphenyl glycidyl ether, 4-allylphenyl glycidyl ether, glycidyl 4-vinylbenzoate, 3,4-epoxybutene, 3,4-epoxy-2-methylbutene, 4-vinylcyclohexene oxide or p-divinylstyrene monooxide.
Claim 24
Dependent Claim
75 words
The method of forming a resist of claim 18, wherein said at least one other monomer containing an ethylenically unsaturated double bond and free from an oxirane ring and a substituent group reactive with oxirane rings is a vinyl monomer, an alkylacrylate or methacrylate, a cycloalkylacrylate or methacrylate, an arylacrylate or methacrylate, an aralkylacrylate or methacrylate, an acrylic or methacrylic acid derivative, a vinyl halide, a vinyl ketone, vinyl acetic acid or allyl acetic acid.
Claim 25
Dependent Claim
32 words
The method of forming a resist of claim 17, wherein said polymer having a plurality of oxirane rings has a number average molecular weight of about 10 2 to 10 6 .
Claim 26
Dependent Claim
51 words
The method of forming a resist of claim 17, wherein said monomer containing at least one ethylenically unsaturated double bond and one functional group capable of opening oxirane rings is a monomer containing a carboxyl group, an acyl halide group, a hydroxyl group, a thiol group or a secondary amino group.
Claim 27
Dependent Claim
26 words
The method of forming a resist of claim 25, wherein said monomer containing a carboxyl group is an unsaturated aliphatic monocarboxylic acid or dicarboxylic acid monoester.
Claim 28
Dependent Claim
55 words
The method of forming a resist of claim 26, wherein said unsaturated aliphatic monocarboxylic acid or dicarboxylic acid monoester is a monoester of maleic acid, a monoester of fumaric acid, a monoester of itaconic acid, acrylic acid, methacrylic acid, a monoester of cis-4-cyclohexene-1,2-dicarboxylic acid, a monoester of 5-norbornene-2,2-dicarboxylic acid, or a monoester of hexachloro-[2,2,1]-bicyclohept-5-ene-2,3-dicarboxylic acid.
Claim 29
Dependent Claim
53 words
The method of forming a resist of claim 25, wherein said monomer containing an acyl halide group is acryloyl chloride, methacryloyl chloride, methylvinylacetyl chloride, 3allylpropionyl chloride, allylphenylacetyl chloride, allylbenzylacetyl chloride, monomethylmaleoyl chloride, monoethylmaleoyl chloride, monoisopropylmaleoyl chloride, monomethylfumaroyl chloride, monoethylfumaroyl chloride, monoisopropylfumaroyl chloride, monomethylitaconoyl chloride or the corresponding acid bromides to these acid chlorides.
Claim 30
Dependent Claim
32 words
The method of forming a resist of claim 25, wherein said monomer containing a hydroxyl group is a monomer containing an alcoholic hydroxyl group or a monomer containing a phenolic hydroxyl group.
Claim 31
Dependent Claim
72 words
The method of forming a resist of claim 29, wherein said monomer containing a hydroxyl group is allyl alcohol, ethylene glycol monoacrylate, ethylene glycol monomethacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-vinylbenzyl alcohol, 4-allylbenzyl alcohol, 4-hydroxystyrene, 2-hydroxystyrene, 3-hydroxystyrene, 2-allyl phenol, 2-methyl-6-allyl phenol, 2-allyl-4-methylphenol, 1-allyl-2-naphthol, eugenol, 4-allyl anisole, 3-allyl anisole, 2,6-diallyl phenol, 2,6-diallyl p-cresol or 2,4,5-triallyl phenol.
Claim 32
Dependent Claim
26 words
The method of forming a resist of claim 25, wherein said monomer containing a thiol group is allyl mercaptan, mercaptobutene-2, mercaptobutene-3, mercaptopentene-4, mercaptopentene-1, 2-vinylthiophenol, or 2-allylthiophenol.
Claim 33
Dependent Claim
37 words
The method of forming a resist of claim 25, wherein said monomer containing a secondary amino group is N-methylallylamine, diallylamine, N-methylaminoethyl acrylate, N-methylaminoethyl methacrylate, N-propylaminomethyl acrylate, N-propylaminomethyl methacrylate, N-propylaminoethyl acrylate, N-propylaminoethyl methacrylate, N-benzylallylamine, N-allyl aniline, or N-allyl-2-toluidine.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-11-09 | 1985-05-11 | 1985-11-10 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-11-09 | 1989-05-11 | 1989-11-10 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-11-09 | 1993-05-11 | 1993-11-10 | $7700.00 | Window Closed / Lapsed |