JP2008248209A - Thinner composition for removing cyclic olefin polymer-containing composition - Google Patents

Abstract

An object of the present invention is to provide a thinner composition that exhibits excellent removability with respect to a composition containing a cyclic olefin polymer and can sufficiently clean an insulating substrate.
A thinner composition for removing a cyclic olefin polymer-containing composition comprising at least one selected from the group consisting of 1-methoxy-2-propanol and N, N-dimethylacetamide.
[Selection figure] None

Description

  The present invention relates to a thinner composition suitably used for removing a composition comprising a cyclic olefin polymer.

  In a photolithography process in the manufacturing process of a semiconductor device, a photoresist film formed on an insulating substrate is irradiated with actinic radiation to form a latent image pattern in the film, and then a latent image pattern is brought into contact with a developer. The film is patterned by revealing an image pattern.

  The photoresist film is usually formed by evaporating the solvent from the photoresist by applying heat treatment (prebaking) after applying the photoresist on the insulating substrate, but after the prebaking and before the irradiation with active radiation, the edge of the insulating substrate is formed. Unnecessary photoresist adhering to the portion and the back surface (surface where the photoresist film is not present) is removed. The removal of the photoresist is effective in preventing the occurrence of various defects in post-etching and ion implantation due to the presence of unnecessary photoresist, resulting in a decrease in productivity of the semiconductor device.

  Conventionally, unnecessary photoresist existing on an insulating substrate can be removed by, for example, installing injection nozzles above and below the edge portion of the insulating substrate, and through this nozzle, a thinner composed of a predetermined organic solvent component on the edge portion and back surface of the insulating substrate. This is done by spraying the composition and cleaning the insulating substrate.

  The thinner composition is selected from the group consisting of propylene glycol ether acetate, ethyl lactate, and ethyl-3-ethoxypropionate, for example, as a composition having excellent solubility in various photoresists. A thinner composition containing at least one ester compound and methyl-2-hydroxy-2-methylpropionate is disclosed (Patent Document 1). Moreover, a thinner composition for removing a photoresist containing a) an alkylamide and b) an alkylethanolate is disclosed as a composition capable of safely and efficiently removing the photoresist (Patent Document 2).

These thinner compositions appeal for the removal properties of generally used photoresists regardless of the resin component contained in the photoresist.
JP 2005-227770 A JP 2005-338825 A

  However, when a conventional thinner composition was applied to a photoresist containing a cyclic olefin polymer, it was found that the solubility of the polymer was low and the insulating substrate could not be washed sufficiently.

  Therefore, the present invention exhibits excellent removability for a composition comprising a cyclic olefin polymer, particularly a radiation-sensitive resin composition such as the photoresist, and sufficiently cleans the insulating substrate. It is an object to provide a thinner composition that can be used.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that 1-methoxy-2-propanol and N, N-dimethylacetamide are suitable for removing a composition containing a cyclic olefin polymer. The inventors have found that a composition comprising at least any of the above is effective and have completed the present invention.

That is, the present invention
[1] A thinner composition for removing a cyclic olefin polymer-containing composition, comprising at least one selected from the group consisting of 1-methoxy-2-propanol and N, N-dimethylacetamide,
[2] The above-mentioned [1] wherein the weight ratio of 1-methoxy-2-propanol to N, N-dimethylacetamide (1-methoxy-2-propanol / N, N-dimethylacetamide) is 1/9 to 9/1 A thinner composition as described above,
[3] The thinner composition according to the above [1] or [2], wherein the total content of 1-methoxy-2-propanol and N, N-dimethylacetamide is 50% by weight or more,
[4] The thinner composition according to any one of [1] to [3], further comprising a surfactant,
[5] The thinner composition according to the above [4], wherein the surfactant is at least one surfactant selected from the group consisting of a silicone surfactant and a fluorosurfactant, and [6] the above [ 1) to [5] Using the thinner composition according to any one of the above, a method for manufacturing a semiconductor device or a flat display device, which includes a step of cleaning an object to be cleaned to which the cyclic olefin polymer-containing composition is attached,
I will provide a.

  According to the thinner composition of the present invention, for example, when manufacturing a semiconductor device, an insulating substrate to which an unnecessary cyclic olefin polymer-containing photoresist is attached is a process such as etching or ion implantation, which is a subsequent process of the photolithography process. Can be sufficiently washed to such an extent that no defects occur.

  The thinner composition for removing a cyclic olefin polymer-containing composition of the present invention (hereinafter simply referred to as a thinner composition) is at least one selected from the group consisting of 1-methoxy-2-propanol and N, N-dimethylacetamide. One of the characteristics is that it contains.

  The thinner composition of the present invention is typically used as a cleaning composition for removing a radiation-sensitive resin composition containing a cyclic olefin polymer attached to an insulating substrate for a semiconductor device. Is done.

  1-Methoxy-2-propanol (boiling point: about 120 ° C.) and N, N-dimethylacetamide (boiling point: about 165 ° C.), which are active ingredients of the thinner composition of the present invention, are colorless liquids at room temperature. Methoxy-2-propanol is easier to dry. Both components are available as commercially available solvents.

  The thinner composition of the present invention contains at least one selected from the group consisting of 1-methoxy-2-propanol and N, N-dimethylacetamide, but has better removability of the cyclic olefin polymer-containing composition. Therefore, it is preferable to include N, N-dimethylacetamide, and from the viewpoint of maintaining a good balance between removability and drying property, it is preferable to include 1-methoxy-2-propanol and N, N-dimethylacetamide. .

  When 1-methoxy-2-propanol and N, N-dimethylacetamide are contained in the thinner composition of the present invention, the weight ratio of both components (1-methoxy-2-propanol / N, N-dimethylacetamide) , Preferably 1/9 to 9/1, more preferably 2/8 to 8/2. If the weight ratio is within such a range, the thinner composition is excellent in drying properties.

  In the thinner composition of the present invention, the total content of 1-methoxy-2-propanol and N, N-dimethylacetamide is preferably 50% by weight or more, more preferably 70% by weight or more. If the total content is within such a range, the removability of the cyclic olefin polymer-containing composition is excellent. The total content includes the case where the content of any one component is 0% by weight.

  From the viewpoint of improving the removability of the cyclic olefin-based polymer-containing composition, the thinner composition of the present invention preferably further contains a surfactant.

  The surfactant is not particularly limited, but is excellent in the ability to improve the removability of the cyclic olefin polymer-containing composition, so that it is at least selected from the group consisting of silicone surfactants and fluorosurfactants. One surfactant is preferred.

Examples of the silicone-based surfactant include polyether-modified polydimethylsiloxane, polyether-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, and polyether ester-modified hydroxyl group-containing polydimethylsiloxane. Is mentioned. Of these, polyether-modified polydimethylsiloxane and polyether-modified polymethylalkylsiloxane are preferable.
Examples of the fluorosurfactant include perfluoroalkyl ethylene oxide adducts, perfluorobutyl sulfone, perfluoroalkyl group-containing carboxylates, and perfluoroalkyl group-containing phosphate esters. Of these, perfluoroalkylethylene oxide adducts are preferred.
These silicone-based surfactants and fluorine-based surfactants are commercially available. Examples of the silicone surfactant include BYK series manufactured by Big Chemie Japan Co., Ltd., KP series manufactured by Shin-Etsu Chemical Co., Ltd., and EMALEX series manufactured by Nippon Emulsion Co., Ltd., and examples of the fluorine-based surfactant include Sumitomo 3M. Examples include the Novec series manufactured by Neoc, the aftergent series manufactured by Neos, and the MegaFuck series manufactured by Dainippon Ink and Chemicals.

  The content of the surfactant in the thinner composition is usually 0.01 to 10% by weight.

  The thinner composition of the present invention is used as an active ingredient in known thinner compositions as long as expression of the desired effect of the present invention is not inhibited, such as cellosolve, cellosolve acetate, ethylene glycol dimethyl ether, Ethers and ether acetates such as ethylene glycol diethyl ether, ethylene glycol di-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, Ketones such as 3-pentanone, 2-hexanone, cyclohexanone; butyl formate, isobutyl formate, pentyl formate Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, may contain other components such as esters such as γ- butyrolactone.

  The thinner composition of the present invention can be produced by appropriately mixing the above components according to a known method.

  The thinner composition of the present invention exhibits excellent removability with respect to a composition containing a cyclic olefin polymer, typically a radiation-sensitive resin composition containing a cyclic olefin polymer. It is considered that this is because the thinner composition is excellent in the solubility of the cyclic olefin polymer.

In this specification, the cyclic olefin polymer is a homopolymer or copolymer of a cyclic olefin monomer having a cyclic structure (alicyclic ring or aromatic ring) and a carbon-carbon double bond. The cyclic olefin polymer may have a monomer unit other than the cyclic olefin monomer. The ratio of the cyclic olefin monomer unit in all the structural units of the cyclic olefin polymer is usually 30 to 100% by weight, preferably 50 to 100% by weight, and more preferably 70 to 100% by weight.
The cyclic olefin monomer is not particularly limited, and examples thereof include a cyclic olefin monomer (ac), a vinyl alicyclic hydrocarbon monomer (d), and a vinyl aromatic hydrocarbon described later. A monomer (e) is mentioned. On the other hand, the monomer other than the cyclic olefin monomer is not particularly limited, and examples thereof include a chain olefin (f) described later.
The cyclic olefin polymer can be formed by polymerizing these monomers in any combination. Moreover, when the cyclic structure of the obtained polymer has an unsaturated bond, it may be a saturated cyclic structure by hydrogenation.

Examples of the first group of cyclic olefin monomers include cyclic olefin monomers (a) having no polar group. Specific examples thereof include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [ 2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] hept-2-ene, 5- Vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene), tetracyclo [8.4 .0.1 ^11,14 . 0 ^3,7 ] pentadeca-3,5,7,12,11-pentaene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dec-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, cyclopentene, cyclopentadiene, 1,4-methano -1,4,4a, 5,10,10a hexa hydro anthracene, 8-phenyl - tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as “1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene”), pentacyclo [7.4.0 ^.1,3,6 . 110,13.0 ^2,7] pentadeca-4,11-diene, pentacyclo [9.2.1.1 ^4,7. 0 ^2,10 . 0 ^3,8 ] pentadeca-5,12-diene and the like.
These cyclic olefin monomers may be used alone or in combination of two or more.

  The second group of cyclic olefin monomers can include cyclic olefin monomers having a polar group. The cyclic olefin monomer having a polar group may be used alone or in combination of two or more.

  The polar group can be divided into a protic polar group and another polar group. Therefore, the cyclic olefin monomer having a polar group includes a cyclic olefin monomer (b) having a protic polar group and a cyclic olefin monomer having a polar group other than the protic polar group (aprotic polar group). It can be shown separately from the body (c).

  In this specification, the protic polar group refers to an atomic group in which a hydrogen atom is directly bonded to an atom other than a carbon atom. Here, the atoms other than carbon atoms are preferably atoms belonging to Groups 15 and 16 of the periodic table, more preferably atoms belonging to the first and second periods of Groups 15 and 16 of the Periodic Table, More preferred are an oxygen atom, a nitrogen atom and a sulfur atom, and particularly preferred is an oxygen atom.

  Specific examples of the protic polar group include polar groups having an oxygen atom such as carboxyl group (hydroxycarbonyl group), sulfonic acid group, phosphoric acid group, hydroxyl group; primary amino group, secondary amino group, A polar group having a nitrogen atom such as a primary amide group or a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group; Among these, those having an oxygen atom are preferable, and a carboxyl group is more preferable.

Specific examples of the cyclic olefin monomer (b) having a protic polar group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene and 5-methyl-5-hydroxycarbonylbicyclo [2. 2.1] Hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] ] Hept-2-ene, 8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-exo-9-endo-dihydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . Cyclic olefin having a carboxyl group such as 1 ^7,10 ] dodec-3-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4- Hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . And a cyclic olefin having a hydroxy group such as ^{17, 10} ] dodec-3-ene, among which a cyclic olefin having a carboxyl group is preferable.

  Specific examples of aprotic polar groups include ester groups (collectively referring to alkoxycarbonyl groups and aryloxycarbonyl groups), N-substituted imide groups, epoxy groups, halogen atoms, cyano groups, carbonyloxycarbonyl groups (dicarboxylic acid). Acid anhydride residues), alkoxy groups, carbonyl groups, tertiary amino groups, sulfone groups, halogen atoms, acryloyl groups and the like. Of these, an ester group, an N-substituted imide group, a cyano group, and a halogen atom are preferred, and an ester group and an N-substituted imide group are more preferred. In particular, an N-substituted imide group is preferable.

  Specific examples of the cyclic olefin monomer (c) having an aprotic polar group include the following.

Examples of the cyclic olefin having an ester group include 5-acetoxybicyclo [2.
2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 8-acetoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

  Examples of the cyclic olefin having an N-substituted imide group include N- (4-phenyl)-(5-norbornene-2,3-dicarboximide).

Examples of the cyclic olefin having a cyano group include 8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5-cyanobicyclo [2.2.1] hept-2-ene, and the like.

Examples of the cyclic olefin having a halogen atom include 8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

  Examples of the vinyl alicyclic hydrocarbon monomer (d) include vinyl cycloalkanes such as vinyl cyclopropane, vinyl cyclobutane, vinyl cyclopentane, vinyl cyclohexane and vinyl cycloheptane; 3-methyl-1-vinyl And vinylcycloalkanes having substituents such as cyclohexane, 4-methyl-1-vinylcyclohexane, 1-phenyl-2-vinylcyclopropane, 1,1-diphenyl-2-vinylcyclopropane, and the like.

  Examples of the vinyl aromatic hydrocarbon monomer (e) include vinyl aromatics such as styrene, 1-vinylnaphthalene, 2-vinylnaphthalene and 3-vinylnaphthalene; 3-methylstyrene, 4-propylstyrene, Vinyl aromatics having a substituent such as 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene; m-divinylbenzene, p-divinylbenzene, bis (4 -Polyfunctional vinyl aromatics such as vinylphenyl) methane;

Examples of the chain olefin (f) include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl-1- Pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl- 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like α-olefins having 2 to 20 carbon atoms; 1,4-hexadiene, 4 Non-conjugated dienes such as -methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene and the like can be mentioned.
These monomers can be used alone or in combination of two or more.

  The polymerization method of each monomer may be in accordance with a conventional method, for example, a ring-opening polymerization method or an addition polymerization method is employed. As the polymerization catalyst, for example, metal complexes such as molybdenum, ruthenium and osmium are preferably used. These polymerization catalysts can be used alone or in combination of two or more. For example, a ring-opening polymer of a cyclic olefin monomer and a ring-opening copolymer of a cyclic olefin monomer (hereinafter referred to as “a ring-opening (co) polymer of a cyclic olefin monomer” together) are obtained. In this case, the amount of the polymerization catalyst is usually 1: 100 to 1: 2,000,000, preferably 1: 500 to 1: 1,000 in terms of a molar ratio of the metal compound to the cyclic olefin monomer in the polymerization catalyst. 1,000, more preferably in the range of 1: 1,000 to 1: 500,000.

  The cyclic olefin polymer obtained by the above polymerization can be hydrogenated as desired. Hydrogenation is usually performed using a hydrogenation catalyst. As the hydrogenation catalyst, for example, those generally used for hydrogenation of olefin compounds can be used. Specifically, Ziegler type homogeneous catalysts, noble metal complex catalysts, supported noble metal catalysts and the like can be used. The hydrogenation rate of the cyclic olefin polymer is preferably 80% or more, more preferably 90% or more.

The cyclic olefin polymer according to the present invention is not particularly limited, but is preferably a ring-opening (co) polymer of a cyclic olefin monomer and a hydrogenated product thereof; a cyclic olefin monomer and a vinyl alicyclic carbonization. An addition copolymer of a hydrogen monomer and a hydrogenated product thereof; and an addition copolymer of a cyclic olefin monomer and a vinyl aromatic hydrocarbon monomer and a hydrogenated product thereof; It is at least one, and more preferably a hydrogenated product of a ring-opening (co) polymer of a cyclic olefin monomer.
In the present invention, the cyclic olefin polymers may be different from each other in composition or the like alone or in combination of two or more.

  The thinner composition of the present invention is particularly excellent in removability of a cyclic olefin polymer having a polar group. The number of polar groups contained in the cyclic olefin polymer having a polar group is not particularly limited, and the polar groups may include the same or different types. The polar group may be bonded to the cyclic olefin monomer unit or may be bonded to a monomer unit other than the cyclic olefin monomer. As the cyclic olefin polymer having a polar group, those having a protic polar group are particularly preferred.

  As the protic polar group-containing cyclic olefin polymer according to the present invention, those having a structural unit represented by the formula (I) as shown below are preferable, and the structure represented by the formula (I) What has a unit and the structural unit represented by Formula (II) is more suitable. The structural unit represented by formula (I) and the structural unit represented by formula (II) are both cyclic olefin monomer units.

[In the formula (I), R ^{1 to} R ⁴ each independently represents a hydrogen atom or a —X _n —R ′ group (X is a divalent organic group, n is 0 or 1, R ′ Is an alkyl group which may have a substituent, an aromatic group which may have a substituent, or a protic polar group), and at least one of R ^{1 to} R ⁴ is , R ′ is a —X _n —R ′ group, which is a protic polar group, and m is an integer of 0-2. ]

[In the formula (II), R ⁵ and R ⁶ together with the two carbon atoms to which they are bonded contain an oxygen atom or a nitrogen atom which may have a substituent. It forms a membered heterocyclic structure, and k is an integer of 0-2. ]

  In the general formula (I), examples of the divalent organic group represented by X include a methylene group, an ethylene group, and a carbonyl group. The alkyl group which may have a substituent for R ′ is usually a linear or branched alkyl group having 1 to 7 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, and isopropyl. Groups and the like. The aromatic group that may have a substituent is usually an aromatic group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a benzyl group. Examples of substituents for alkyl groups and aromatic groups include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group; phenyl group, xylyl group, And aryl groups having 6 to 12 carbon atoms such as a tolyl group and a naphthyl group. Examples of the protic polar group include the groups described above.

In the general formula (II), R ⁵ and R ⁶ are formed together with two carbon atoms to which they are bonded to each other and include an oxygen atom or a nitrogen atom which may have a substituent 3 Examples of the membered heterocyclic structure include an epoxy structure. In addition, as a 5-membered heterocyclic structure formed by including an oxygen atom or a nitrogen atom, R ⁵ and R ⁶ together with two carbon atoms to which they are bonded may have a substituent, Examples thereof include a dicarboxylic anhydride structure [—C (O) —O—C (O) —] and a dicarboximide structure [—C (O) —N—C (O) —]. Examples of the substituent for the oxygen atom or nitrogen atom include a phenyl group, a naphthyl group, and an anthracenyl group.

  In the protic polar group-containing cyclic olefin polymer, the ratio of the monomer unit having a protic polar group to the other monomer unit (monomer unit having a protic polar group / the other monomer) The body unit) is usually in the range of 100/0 to 10/90, preferably 90/10 to 20/80, and more preferably 80/20 to 30/70 by weight.

  The weight average molecular weight (Mw) of the cyclic olefin polymer according to the present invention is usually 1,000 to 1,000,000, preferably 1,500 to 100,000, more preferably 2,000 to 10,000. Range. On the other hand, the molecular weight distribution of the cyclic olefin polymer is usually 4 or less, preferably 3 or less, and more preferably 2.5 or less in terms of a weight average molecular weight / number average molecular weight (Mw / Mn) ratio. Moreover, the iodine value of the said cyclic olefin polymer is 200 or less normally, Preferably it is 50 or less, More preferably, it is 10 or less.

  The radiation-sensitive resin composition containing the cyclic olefin polymer according to the present invention is not particularly limited, but usually a cyclic olefin polymer having a polar group, a cross-linking agent, a sensitivity. It contains a radiation compound and a solvent.

  Examples of the cyclic olefin polymer having a polar group include a cyclic olefin polymer having a structural unit represented by the formula (I) and / or a structural unit represented by the formula (II). Examples of the crosslinking agent include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, polyphenol type having two or more epoxy groups, preferably three or more epoxy groups. Examples thereof include polyfunctional epoxy compounds such as epoxy resins, cycloaliphatic epoxy resins, aliphatic glycidyl ethers, and epoxy acrylate polymers. Examples of radiation-sensitive compounds (compounds that can cause a chemical reaction upon irradiation with radiation such as ultraviolet rays and electron beams) include 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1,2-naphthoquinonediazide-4. Quinonediazidesulfonic acid halides such as sulfonic acid chloride, 1,2-benzoquinonediazide-5-sulfonic acid chloride, and 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane; Photoacid generators such as ester compounds with compounds having a phenolic hydroxyl group such as 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol Can be mentioned. Such a composition may contain, for example, colloidal silica as inorganic fine particles in addition to other components commonly used in known radiation-sensitive resin compositions. Examples of the solvent include a monoalkylene glycol solvent; a polyalkylene glycol solvent; a monoalkylene glycol alkyl ester solvent; a polyalkylene glycol alkyl ester solvent; a monoalkylene glycol diester solvent; a polyalkylene glycol diester solvent;

  The above radiation sensitive resin composition is a positive type example, but may be a negative type. Such compositions can be prepared according to known methods.

  According to the thinner composition of the present invention, for example, in a manufacturing process of a flat panel display device such as a semiconductor device or a liquid crystal display device or an organic electroluminescence display device, the composition is attached to the cyclic olefin polymer-containing composition. The unnecessary photoresist is removed by dripping or spraying through a nozzle on an insulating substrate on which unnecessary photoresist adheres to the object to be cleaned, for example, the edge portion or the back surface, and the substrate. Can be washed. Further, the substrate can be similarly cleaned by immersing the insulating substrate in the thinner composition. Here, the material of the insulating substrate is not particularly limited, and examples thereof include glass and a silicon wafer.

  The dripping amount or the spraying amount of the thinner composition of the present invention may be appropriately adjusted according to the amount of the deposited photoresist, etc., but is usually selected in the range of 5 to 100 mL / min. When the object to be cleaned is immersed and cleaned, the thinner composition is put in a container so that at least a portion requiring cleaning is immersed in the thinner composition, and the object to be cleaned is usually immersed in the container for 1 to 5 minutes. Good. Although the temperature at the time of contact of the thinner composition of this invention and a to-be-cleaned object does not have limitation in particular, What is necessary is just to be 15-50 degreeC normally. After washing, if desired, a step of drying the thinner composition may be employed. By the above operation, for example, the insulating substrate is sufficiently cleaned, so that a fine circuit pattern can be formed on the substrate without causing a defect in a subsequent process of the photolithography process.

  In the manufacturing process of a semiconductor device or a flat display device, the object to be cleaned includes an insulating substrate, a slit nozzle for photoresist injection, and a substrate on which a defective photoresist pattern has occurred. Removing the adhesion of the photoresist by washing the former can contribute to an improvement in production efficiency of a semiconductor device or the like. On the other hand, if the photoresist pattern is removed by washing the latter, the substrate can be reused.

Therefore, as one aspect of the present invention, there is provided a method for manufacturing a semiconductor device or a flat display device, which includes a step of cleaning an object to be cleaned to which a cyclic olefin polymer-containing composition is attached using the thinner composition of the present invention. The According to this method, the manufacturing process of the semiconductor device or the flat display device can be made efficient and the production efficiency thereof can be improved.
In addition, in the method for manufacturing a semiconductor device or a flat display device of the present invention, those skilled in the art can perform processes other than the cleaning process of the object to be cleaned with the thinner composition of the present invention, for example, Japanese Patent Laid-Open No. 6-324499. It can be appropriately implemented with reference to JP-A-2006-085140 or the like.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, unless otherwise indicated, the part and% in each example are a basis of weight.

Reference Example 1 Synthesis of Cyclic Olefin Polymer 8-Hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 62.5 parts, N-phenyl- (5-norbornene-2,3-dicarboximide) 37.5 parts, 1-hexene 1.3 parts, 1,3-dimethyl Imidazolidine-2-ylidene (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 part and 400 parts of tetrahydrofuran were charged into a nitrogen-substituted glass pressure-resistant reactor and reacted at 70 ° C. for 2 hours with stirring. Solution A (solid content concentration: about 20%) was obtained.

  A part of this polymer solution A is transferred to an autoclave equipped with a stirrer, and hydrogen is dissolved at a pressure of 4 MPa at 150 ° C. and reacted for 5 hours, and a polymer solution B containing a hydrogenated polymer (hydrogenation rate 100%). (Solid content concentration: about 20%) was obtained.

  A heat-resistant container containing a mixed solution of 100 parts of the polymer solution B and 1 part of activated carbon powder was placed in an autoclave, and hydrogen was dissolved at 150 ° C. under a pressure of 4 MPa for 3 hours while stirring. Next, the solution was taken out and filtered through a fluororesin filter having a pore size of 0.2 μm to separate the activated carbon to obtain a polymer solution. Filtration was performed without any delay. The polymer solution was poured into ethyl alcohol to solidify, and the produced crumb was dried to obtain a polymer. When the obtained polymer (cyclic olefin polymer) was measured by gel permeation chromatography (GPC) method using tetrahydrofuran (THF) as an eluent, the weight average molecular weight (Mw) in terms of polyisoprene was 5,500. Yes, the number average molecular weight (Mn) was 3,200.

Reference Example 2 Preparation of Cyclic Olefin Polymer-Containing Radiation Sensitive Resin Composition 100 Parts of Cyclic Olefin Polymer of Reference Example 1, 25 Parts of Epoxy Compound (trade name: EHPE3150, manufactured by Daicel Chemical Industries, Ltd.), Sensitivity 1,1,3-Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol) as radiation compounds 25 parts of condensate, 4 parts of anti-aging agent (product name: Irganox 1010, manufactured by Ciba Specialty Chemicals), 5 parts of γ-glycidoxypropyltrimethoxysilane as an adhesion assistant, and silicone-based interface Mixing 0.05 parts of an activator (Shin-Etsu Chemical Co., Ltd., trade name: KP341) and mixing it with diethylene glycol ethyl methyl solvent. After dissolving in 450 parts of ruether, it was filtered through a polytetrafluoroethylene filter having a pore diameter of 0.45 μm to prepare a cyclic olefin polymer-containing radiation sensitive resin composition.

Examples 1 to 6 Evaluation of Thinner Composition (1) Preparation of Washed Object (Contaminated Glass Substrate) Reference was made using a spinner (Mikasa Corp.) on a glass substrate (Corning Corp., 1737 material; 100 × 100 mm). After the radiation sensitive resin composition of Example 2 was applied, it was dried on a hot plate at 90 ° C. for 120 seconds and measured to 2 μm with a stylus type film thickness meter P-10 (manufactured by Tencor). The film was formed as follows.
(2) Preparation of thinner composition and evaluation of cleaning performance Each component was mixed according to the composition of Table 1 to prepare a thinner composition (Examples 1 to 7). The article to be cleaned (contaminated glass substrate) prepared in (1) was immersed in the obtained thinner composition at 23 ° C. for 20 seconds or 40 seconds. After immersion, the degree of removal of the radiation-sensitive resin composition was visually confirmed, and the cleaning performance of the thinner composition was evaluated according to the following evaluation criteria. The results are shown in Table 2.
〔Evaluation criteria〕
Excellent: Completely removed Good: Almost removed, but remains a little OK: Removed a little, but much remains Impossible: Not removed at all

Comparative Examples 1 to 3 Evaluation of Thinner Composition In the same manner as in the Examples, each component was mixed according to the formulation shown in Table 1 to prepare a thinner composition (Comparative Examples 1 to 3), and the resulting thinner composition was washed. Performance was evaluated. The results are shown in Table 2.

  According to the thinner composition of Examples 1-7, the thinner composition of Comparative Examples 1 to 3 which does not contain an active ingredient used in the present invention could not clean the object to be cleaned (contaminated glass substrate). It can be seen that a sufficient cleaning effect can be obtained. In Examples 1 to 7, the more 1-methoxy-2-propanol was contained, the easier it was to dry.

Claims (6)

  A thinner composition for removing a cyclic olefin polymer-containing composition, comprising at least one selected from the group consisting of 1-methoxy-2-propanol and N, N-dimethylacetamide.   The thinner according to claim 1, wherein the weight ratio of 1-methoxy-2-propanol to N, N-dimethylacetamide (1-methoxy-2-propanol / N, N-dimethylacetamide) is 1/9 to 9/1. Composition.   The thinner composition according to claim 1 or 2, wherein the total content of 1-methoxy-2-propanol and N, N-dimethylacetamide is 50% by weight or more.   The thinner composition according to any one of claims 1 to 3, further comprising a surfactant.   The thinner composition according to claim 4, wherein the surfactant is at least one surfactant selected from the group consisting of a silicone surfactant and a fluorosurfactant.   A method for producing a semiconductor device or a flat display device, comprising: using the thinner composition according to any one of claims 1 to 5 to wash an object to be cleaned to which the cyclic olefin polymer-containing composition is attached.