JP2008250221A - Methods for manufacturing thinner composition, semiconductor device, and the like - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide methods for manufacturing a thinner composition that has superior solubility with respect to a composition containing cyclic olefin polymers and is superior in drying characteristics, and a semiconductor device or a flat display device having a process for cleaning an object to be cleaned, to which a composition containing cyclic olefin polymers is attached, using a thinner composition. <P>SOLUTION: The methods manufacture a thinner composition for removing a composition containing cyclic olefin polymers containing two kinds of alcohol ether and two kinds of alcohol ester, and a semiconductor device or a flat display device, and have a process for cleaning an object to be cleaned to which a composition containing cyclic olefin polymers is attached, using the thinner composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thinner composition suitably used for removing a composition containing a cyclic olefin polymer, and a method for manufacturing a semiconductor device or a flat display device.

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

  The photoresist film is usually formed by applying a resist composition (photosensitive resin composition) onto an insulating substrate to form a coating film of the resist composition, and then heat-treating (pre-baking) the coating film. It is formed by evaporating the solvent from the film.

  Further, after pre-baking and before irradiation with actinic radiation, an unnecessary resist composition adhering to the edge portion or the back surface of the insulating substrate (the non-existing surface of the photoresist film) is removed. The removal of the resist composition means that the presence of an unnecessary resist composition causes various defects in the subsequent etching process, ion implantation process, and the like, resulting in a decrease in productivity of the semiconductor device. It is effective to prevent.

  As a method of removing an unnecessary resist composition present on the insulating substrate, for example, an injection nozzle is installed above and below the edge portion of the insulating substrate, and a predetermined organic solvent component is formed on the edge portion and back surface of the insulating substrate through this nozzle. There is a method of cleaning an insulating substrate by spraying a thinner composition.

  Conventionally, as a thinner composition used in the above method, (i) photoresist stripping mainly composed of propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and γ-butyrolactone disclosed in Patent Document 1 Thinner composition, (ii) at least one ester compound selected from the group consisting of propylene glycol ether acetate, ethyl lactate and ethyl-3-ethoxypropionate disclosed in Patent Document 2, and methyl- A thinner composition containing 2-hydroxy-2-methylpropionate, (iii) a thinner composition for removing a photoresist containing an alkylamide and an alkylethanolate disclosed in Patent Document 3, and the like are known.

JP 2004-139209 A JP 2005-227770 A JP 2005-338825 A

  The present applicant has proposed a photosensitive resin composition containing a cyclic olefin polymer in JP-A No. 2002-296780. According to this resin composition, it is excellent in flatness, heat resistance, transparency, chemical resistance, etc., has good degassing properties, excellent in low dielectric properties, and can efficiently form a fine patterned cured film. Is possible.

  When the present inventors tried to remove a photosensitive resin composition containing a cyclic olefin polymer attached to an insulating substrate using a conventionally used thinner composition, the resin composition was sufficient. It was found that the insulating substrate could not be sufficiently washed. Moreover, some existing thinner compositions have solubility in the cyclic olefin polymer, but this is inferior in dryness (volatility). When a thinner composition having poor drying properties is used, the tact down of the apparatus occurs and the productivity is lowered.

  Then, this invention aims at providing the thinner composition which has the outstanding solubility with respect to the composition (cyclic olefin type polymer containing composition) containing a cyclic olefin type polymer, and is excellent also in drying property. And

  As a result of intensive studies to solve the above problems, the inventors of the present invention have a thinner composition containing two kinds of alcohol ethers and two kinds of alcohol esters, which has excellent solubility in a cyclic olefin polymer-containing composition. In addition, the present inventors have found that it has excellent drying properties and has completed the present invention.

Thus, according to the first aspect of the present invention, the following thinner compositions (1) to (7) are provided.
(1) A thinner composition for removing a cyclic olefin polymer-containing composition, comprising two kinds of alcohol ethers and two kinds of alcohol esters.
(2) The thinner composition according to (1), wherein the two alcohol ethers are ethylene glycol monoether and propylene glycol monoether, and the two alcohol esters are propylene glycol monoether ester and primary alcohol ester. .
(3) The content of ethylene ether monoether is 40 to 70% by weight based on the whole composition, and the total content of propylene glycol monoether and propylene glycol monoether ester is based on the whole composition. The thinner composition according to (2), which is 20 to 40% by weight, and the content of the primary alcohol ester is 10 to 30% by weight based on the entire composition.
(4) The weight ratio of propylene glycol monoether to propylene glycol monoether ester (propylene glycol monoether / propylene glycol monoether ester) is 6/4 to 8/2. Thinner composition.

(5) Ethylene glycol monoether is 2-methoxyethanol, propylene glycol monoether is propylene glycol monomethyl ether, propylene glycol monoether ester is propylene glycol monomethyl ether acetate, and primary alcohol ester is acetic acid The thinner composition according to any one of (1) to (4), which is n-butyl.
(6) The thinner composition according to any one of (1) to (5), further containing a surfactant.
(7) The thinner composition according to (6), wherein the surfactant is at least one selected from the group consisting of a silicone surfactant and a fluorosurfactant.

According to a second aspect of the present invention, there is provided the following method (8) for manufacturing a semiconductor device or a flat display device.
(8) A semiconductor device or a flat display device having a step of cleaning an object to be cleaned, to which a cyclic olefin polymer-containing composition is attached, using the thinner composition according to any one of (1) to (7). Production method.

The thinner composition of the present invention has excellent solubility with respect to the cyclic olefin polymer-containing composition, and also has excellent drying properties. Therefore, by using the thinner composition of the present invention, the unnecessary cyclic olefin polymer-containing composition attached to the object to be cleaned can be efficiently cleaned and removed.
According to the manufacturing method of the present invention, the manufacturing process of a semiconductor device or a flat display device can be made efficient, and the production efficiency thereof can be improved.

  Hereinafter, the present invention will be described in detail by dividing into 1) a thinner composition for removing a cyclic olefin polymer-containing composition, and 2) a method for producing a semiconductor device or a flat display device.

1) Thinner composition for removing cyclic olefin-based polymer-containing composition The thinner composition for removing cyclic olefin-based polymer-containing composition of the present invention (hereinafter referred to as “thinner composition”) is composed of two alcohol ethers and It contains two kinds of alcohol esters.

(1) Cyclic olefin polymer-containing composition The thinner composition of the present invention is a cleaning composition for removing (dissolving and removing) a cyclic olefin polymer-containing composition.

The cyclic olefin polymer-containing composition is a composition containing at least a cyclic olefin polymer and a solvent.
In the cyclic olefin polymer-containing composition that is the subject of the present invention, the content of the cyclic olefin polymer in the cyclic olefin polymer-containing composition is usually 1 to 50% by weight, preferably 5 to 20% by weight. %.

  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 ratio of the cyclic olefin monomer unit in the repeating unit 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 having no polar group (hereinafter referred to as “cyclic olefin monomer (a)”) and a protic polar group. A cyclic olefin monomer (hereinafter referred to as “cyclic olefin monomer (b)”), a cyclic olefin monomer having a polar group (aprotic polar group) other than a protic polar group (hereinafter referred to as “cyclic olefin”). Monomer (c) "), vinyl alicyclic hydrocarbon monomer (hereinafter referred to as" vinyl alicyclic hydrocarbon monomer (d) "), and vinyl aromatic hydrocarbon monomer. (Hereinafter referred to as “vinyl aromatic hydrocarbon monomer (e)”) and the like.

  The cyclic olefin monomer (a) is a cyclic olefin monomer having no polar group. Here, the polar group refers to a polar group other than a protic polar group described later and an aprotic polar group described later (the same applies hereinafter).

Specific examples of the cyclic olefin monomer (a) 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: dicyclo pentadiene), 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.

  The cyclic olefin monomer (b) is a cyclic olefin monomer having a protic polar group. Here, the protic polar group means an atomic group in which a hydrogen atom is directly bonded to an atom other than a carbon atom (the same applies hereinafter). 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 preferably An oxygen atom, a nitrogen atom and a sulfur atom, particularly preferably an oxygen atom.

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

Specific examples of the cyclic olefin monomer (b) include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 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 cyclic olefins having a hydroxy group such as ^{17, 10} ] dodec-3-ene. Among these, a cyclic olefin having a carboxyl group is preferable.

  The cyclic olefin monomer (c) is a cyclic olefin monomer having an aprotic polar group which is a polar group other than the protic polar group.

  Specific examples of the aprotic polar group include an ester group (referred to generically as an alkoxycarbonyl group and an aryloxycarbonyl group), an N-substituted imide group, an epoxy group, a halogen atom, a cyano group, a carbonyloxycarbonyl group (dicarboxylic group). Acid anhydride residues), alkoxy groups, carbonyl groups, tertiary amino groups, sulfone groups, halogen atoms, acryloyl groups and the like. Among these, an ester group, an N-substituted imide group, a cyano group, and a halogen atom are preferable, an ester group and an N-substituted imide group are more preferable, and an N-substituted imide group is particularly preferable.

Specific examples of the cyclic olefin monomer (c) 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 ] cyclic olefin having an ester group such as dodec-3-ene;

Cyclic olefin monomers having an N-substituted imide group such as N- (4-phenyl)-(5-norbornene-2,3-dicarboximide);
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, cyclic olefin having a cyano group such as 5-cyanobicyclo [2.2.1] hept-2-ene;
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 ] cyclic olefin having a halogen atom such as dodec-3-ene;

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

Specific 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; and the like.
These monomers can be used alone or in combination of two or more.

  The cyclic olefin polymer may have a monomer unit other than the cyclic olefin monomer. Although there is no limitation in particular as monomers other than a cyclic olefin monomer, For example, a chain olefin is mentioned.

  Specific examples of the chain olefin include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 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-methyl- Non-conjugated dienes such as 1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene; and the like.

  The cyclic olefin polymer can be obtained by polymerizing these monomers in any combination.

The polymerization 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.
Examples of the polymerization catalyst used in the ring-opening polymerization method and the addition polymerization method include metal complexes such as molybdenum, ruthenium, and osmium. 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 used is usually 1: 100 to 1: 2,000,000, preferably 1: 500 to 1: 1, in the molar ratio of the metal compound to the cyclic olefin monomer in the polymerization catalyst. It is in the range of 1,000,000, more preferably 1: 1,000 to 1: 500,000.

  Further, as the cyclic olefin polymer, for example, when the cyclic structure in the polymer has an unsaturated bond, a saturated cyclic structure may be formed by hydrogenating the unsaturated structure.

  Hydrogenation is usually performed using a hydrogenation catalyst. As a hydrogenation catalyst, what is generally used as a hydrogenation catalyst of an olefin compound 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.

  Specific examples of cyclic olefin polymers include ring-opening (co) polymers of cyclic olefin monomers (ac) and their hydrides; cyclic olefin monomers (ac) and vinyl alicyclics. Addition copolymer of hydrocarbon monomer (d) and hydride thereof; and addition copolymer of cyclic olefin monomer (ac) and vinyl aromatic hydrocarbon monomer (e) and the same Preferred examples include at least one selected from the group consisting of hydrides. Among these, it is more preferable that it is a hydride of a ring-opening (co) polymer of cyclic olefin monomers (ac), and the thinner composition of the present invention is a cyclic olefin polymer having a polar group. A cyclic olefin polymer having a polar group is particularly preferred because of its excellent solubility.

The number of polar groups contained in the cyclic olefin polymer having a polar group is not particularly limited, and when having a plurality of polar groups, the plurality of polar groups may be the same or different.
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.

The cyclic olefin polymer having a polar group is preferably a cyclic olefin polymer having a protic polar group (hereinafter referred to as “protic polar group-containing cyclic olefin polymer”).
Examples of the cyclic olefin polymer having a protic polar group include those represented by the formula (I)

[Wherein, R ^{1 to} R ⁴ each independently represents a hydrogen atom or a formula: —X _n —R ′ (X is a divalent organic group, n is 0 or 1, and R ′ is An alkyl group which may have a substituent, an aromatic group which may have a substituent, or a protic polar group), and R ^{1 to} R ⁴ . At least one of them is a group represented by the formula: —X _n —R ′, wherein R ′ is a protic polar group, and m is an integer of 0-2. And a repeating unit represented by the formula (I), and a compound represented by the formula (II)

(Wherein R ⁵ and R ⁶ together with the two carbon atoms to which they are attached, a 3-membered or 5-membered heterocyclic ring containing an oxygen atom or a nitrogen atom which may have a substituent) It is more preferable to form a structure, and k is an integer of 0 to 2). The repeating units represented by the formulas (I) and (II) are both cyclic olefin monomer units.

In the formula (I), examples of the divalent organic group represented by X include alkylene groups such as a methylene group and an ethylene group; carbonyl groups;
Examples of the alkyl group which may have a substituent for R ′ include linear or branched alkyl groups having 1 to 7 carbon atoms such as a methyl group, an ethyl group, an n-propyl group and an isopropyl group. . Examples of the aromatic group which may have a substituent include aromatic groups having 6 to 10 carbon atoms such as a phenyl group and a benzyl group.

Examples of the substituent for the alkyl group represented by R ′ include an aryl group having 6 to 12 carbon atoms such as a phenyl group, a xylyl group, a tolyl group, and a naphthyl group. In addition, examples of the substituent of the aromatic group include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group; phenyl group, xylyl group, and tolyl Group, aryl groups having 6 to 12 carbon atoms such as naphthyl group; and the like.
Examples of the protic polar group include the same groups as those exemplified above.

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

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

  The cyclic olefin polymer has a weight average molecular weight (Mw) of usually 1,000 to 1,000,000, preferably 1,500 to 100,000, more preferably 2,000 to 10,000. is there. The molecular weight distribution of the cyclic olefin-based polymer is usually 4 or less, preferably 3 or less, more preferably 2.5 or less, as a weight average molecular weight / number average molecular weight (Mw / Mn) ratio.

  The iodine value of the cyclic olefin polymer is usually 200 or less, preferably 50 or less, more preferably 10 or less.

  The cyclic olefin polymer-containing composition that is the subject of the present invention preferably contains at least one cyclic olefin polymer as an essential component, and further contains a solvent.

  Such a solvent is not particularly limited as long as it dissolves a cyclic olefin polymer, and examples thereof include a monoalkylene glycol solvent; a polyalkylene glycol solvent; a monoalkylene glycol alkyl ester solvent; a polyalkylene glycol alkyl ester solvent; Glycol diester solvent; polyalkylene glycol diester solvent; and the like.

  The cyclic olefin polymer-containing composition may contain other components commonly used in known resin compositions.

The cyclic olefin polymer-containing composition that is the subject of the present invention is preferably a radiation-sensitive resin composition containing a cyclic olefin polymer.
Here, the radiation sensitivity means a property that can cause a chemical reaction by irradiation with radiation such as ultraviolet rays and electron beams.

  The radiation-sensitive resin composition is not particularly limited as long as it contains at least one cyclic olefin polymer and has radiation sensitivity, but the cyclic olefin heavy polymer having the polar group is not limited. A composition comprising a coalescence, the solvent, a crosslinking agent, and a radiation sensitive compound is preferred.

  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 the radiation sensitive compound include a photoacid generator such as an ester compound obtained from a quinonediazide sulfonic acid halide and a compound having a phenolic hydroxyl group. Here, examples of the quinonediazide sulfonic acid halide include 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-benzoquinonediazide-5-sulfonic acid chloride, and the like. Can be mentioned. Examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like.

The radiation-sensitive resin composition containing the cyclic olefin polymer may contain other components commonly used in known radiation-sensitive resin compositions or inorganic fine particles such as colloidal silica. Good.
In addition, although the radiation sensitive resin composition illustrated above is a positive type, a negative type may be sufficient.
The cyclic olefin polymer-containing composition that is the subject of the present invention can be prepared according to a known method.

(2) Thinner composition The thinner composition of the present invention is characterized by containing two alcohol ethers and two alcohol esters.
As the two alcohol ethers, ethylene glycol monoether and propylene glycol monoether are suitable, and as the two alcohol esters, propylene glycol monoether ester and primary alcohol ester are suitable.

  In the thinner composition of the present invention, the content of monoether of ethylene glycol is 40 to 70% by weight with respect to the whole composition, and the total content of monoether of propylene glycol and monoether ester of propylene glycol is It is preferable that it is 20 to 40 weight% with respect to the whole composition, and content of primary alcohol ester is 10 to 30 weight% with respect to the whole composition. When each content is within such a range, the solubility of the cyclic olefin polymer-containing composition is excellent.

  Further, the weight ratio of propylene glycol monoether to propylene glycol monoether ester (propylene glycol monoether / propylene glycol monoether ester) is preferably 6/4 to 8/2. By adjusting the weight ratio of the propylene glycol monoether and the propylene glycol monoether ester to such a range, a thinner composition having excellent drying properties can be obtained.

The ethylene glycol monoether, propylene glycol monoether, propylene glycol monoether ester, and primary alcohol ester used in the present invention are not particularly limited. Among them, ethylene glycol monoether is 2-methoxyethanol. Preferably, the monoether of propylene glycol is propylene glycol monomethyl ether, the monoether ester of propylene glycol is propylene glycol monomethyl ether acetate, and the primary alcohol ester is n-butyl acetate.
2-methoxyethanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and n-butyl acetate used in the thinner composition of the present invention are commercially available.

  The thinner composition of the present invention preferably further contains a surfactant in order to improve the solubility of the cyclic olefin polymer-containing composition.

  The surfactant to be used is not particularly limited, but it is excellent in the ability to improve the solubility of the cyclic olefin polymer-containing composition, so that it is at least one selected from the group consisting of a silicone surfactant and a fluorine 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. Examples include the Novec series manufactured by Neoc, the aftergent series manufactured by Neos, and the MegaFuck series manufactured by Dainippon Ink and Chemicals.

These surfactants can be used alone or in combination of two or more.
The content of the surfactant is usually 0.01 to 10% by weight with respect to the entire composition.

The thinner composition of the present invention may contain other components as long as the effects of the present invention are not impaired.
Other components are not particularly limited, and include those used as active ingredients in known thinner compositions. For example, cellosolve, cellosolve acetate, ethylene glycol dimethyl ether, 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, and ether acetates; acetone Ketones such as methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, cyclohexanone; n-butyl formate, isobutyl formate, n-pentyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, Esters such as n-propyl acetate, n-butyl acetate, isobutyl acetate, γ-butyrolactone; etc. And the like.

  In the thinner composition of the present invention, for example, 2-methoxyethanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, n-butyl acetate, and optionally a surfactant and other components are appropriately mixed according to a known method. Can be prepared.

  The thinner composition of the present invention has excellent solubility in the above-mentioned cyclic olefin polymer-containing composition, particularly a radiation-sensitive resin composition containing the cyclic olefin polymer.

  The thinner composition of the present invention is excellent in solubility in the cyclic olefin polymer-containing composition. For example, the cyclic olefin polymer-containing composition is coated on a glass substrate and dried. The glass substrate on which the containing composition is formed is immersed in the thinner composition of the present invention, and then confirmed by visually confirming the presence or absence of a residue (undissolved residue) of the cyclic olefin polymer-containing composition. Can do. The thinner composition of the present invention has very little residue of the cyclic olefin polymer-containing composition as compared with the conventional thinner composition.

  The thinner composition of the present invention is excellent in drying properties. Therefore, the tact down of the apparatus to be used does not occur, and the drying time is short, so that productivity is improved.

  The thinner composition of the present invention is excellent in drying property because the glass substrate having the cyclic olefin polymer-containing composition formed on the surface thereof is immersed in the thinner composition of the present invention, and then spin-dried. It can be confirmed by measuring the time required for drying. The thinner composition of the present invention has quick drying properties.

  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. .

2) Manufacturing method of semiconductor device or flat display device The manufacturing method of the semiconductor device or flat display device of the present invention cleans the object to be cleaned to which the cyclic olefin polymer-containing composition is attached, using the thinner composition of the present invention. The process of carrying out.
Examples of the flat display device include a liquid crystal display device and an organic electroluminescence display device.

As an object to be cleaned, an insulating substrate in which an unnecessary photoresist containing a cyclic olefin polymer (hereinafter simply referred to as “photoresist”) is attached to the edge portion or the back surface; For example, a slit nozzle for spraying a photoresist to which a resist is attached; a substrate having a defective photoresist pattern;
The material of the insulating substrate is not particularly limited, and examples thereof include glass and a silicon wafer.

  Examples of the cleaning method include a method of dripping the thinner composition of the present invention onto the object to be cleaned, a method of spraying through a nozzle by a spray method, a method of immersing the object of cleaning in the thinner composition of the present invention, and the like.

The dripping amount or the spraying amount of the thinner composition of the present invention may be appropriately adjusted according to the adhesion amount of the photoresist to be removed, etc., but it 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, and the object to be cleaned is immersed in the container. The immersion time is not particularly limited, but is usually 1 to 5 minutes.

  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, Usually, it is 15-50 degreeC. After washing, if desired, a step of drying the thinner composition may be employed.

According to the production method of the present invention, unnecessary photoresist (cyclic olefin polymer-containing composition) can be sufficiently removed from the insulating substrate by washing, so that etching, ion implantation, etc., which are subsequent steps of the photolithography process, can be performed. In the process, a fine circuit pattern can be formed on the substrate without causing defects.
Further, the production efficiency of a semiconductor device or the like can be further improved by cleaning the photoresist injection slit nozzle to eliminate adhesion of the photoresist.
If the photoresist pattern is removed by washing the substrate on which the photoresist pattern defect has occurred, the substrate can be reused.

According to the manufacturing method of the present invention, the manufacturing process of a semiconductor device or a 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.

Production 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 to give a polymer. 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. The polymer solution was poured into ethyl alcohol to solidify, and the produced crumb was dried to obtain a polymer.

  Using the tetrahydrofuran (THF) of the obtained polymer (cyclic olefin polymer) as an eluent, the weight average molecular weight (Mw) and the number average molecular weight (MPC) were measured by gel permeation chromatography (GPC) method. Mn) was determined. As a result, the weight average molecular weight (Mw) in terms of polyisoprene was 5,500, and the number average molecular weight (Mn) was 3,200.

Production Example 2 Preparation of Cyclic Olefin Polymer-Containing Radiation Sensitive Resin Composition 100 Parts of Cyclic Olefin Polymer Obtained in Production Example 1 and Epoxy Compound as a Crosslinking Agent (trade name: EHPE3150, manufactured by Daicel Chemical Industries, Ltd.) 25 parts, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1 mol) as radiation sensitive compounds 2.5 parts) of a condensate, 4 parts of an antioxidant (Ciba Specialty Chemicals, trade name: Irganox 1010), 5 parts of γ-glycidoxypropyltrimethoxysilane as an adhesion assistant, In addition, 0.05 part of silicone surfactant (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KP341) is mixed with diethylene glycol as a solvent. After dissolving in 450 parts of ethyl methyl ether, the mixture was filtered through a polytetrafluoroethylene filter having a pore diameter of 0.45 μm to obtain a cyclic olefin polymer-containing radiation-sensitive resin composition.

(Examples 1-5, Comparative Examples 1-6)
(1) Preparation of object to be cleaned (contaminated glass substrate) Radiation-sensitive resin obtained in Production Example 2 using a spinner (Mikasa) on a glass substrate (Corning, 1737 material; 100 × 100 mm) After applying the composition, it was dried at 90 ° C. for 120 seconds on a hot plate, and formed into a film having a thickness of 2 μm when measured with a stylus type film thickness meter (P-10, manufactured by Tencor).

(2) Preparation of thinner composition Each component was mixed by the compounding quantity (weight%) shown in the following Table 1, and the thinner composition of Examples 1-5 and Comparative Examples 1-6 was prepared.

(3) Evaluation of solubility of thinner composition The object to be cleaned (contaminated glass substrate) prepared in (1) above was immersed in each of the thinner compositions obtained in (2) above at 23 ° C for 40 seconds. . After immersion, the residue of the radiation sensitive resin composition adhering to the article to be cleaned was visually confirmed, and the solubility of the thinner composition was evaluated according to the following evaluation criteria. The results are shown in Table 1 below.

〔Evaluation criteria〕
A: No residue and excellent solubility B: A small amount of residue and slightly excellent solubility C: Residue and slightly poor solubility D: Not dissolved Poor solubility

(3) Evaluation of drying property of thinner composition The object to be cleaned (contaminated glass substrate) prepared in (1) was immersed in each of the thinner compositions obtained in (2) above at 23 ° C for 40 seconds. . After immersion, 1200 rpm spin drying was performed, the time required for complete drying was measured, and the drying property of the thinner composition was evaluated according to the following evaluation criteria. The results are shown in Table 1 below.

〔Evaluation criteria〕
A: Less than 12 seconds B: 12 seconds to less than 14 seconds C: 14 seconds to less than 20 seconds D: 20 seconds or more

In Table 1, the abbreviations have the following meanings.
ME: 2-methoxyethanol PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl acetate nBA: n-butyl acetate MIBK: methyl isobutyl ketone DMA: N, N-dimethylacetamide

From Table 1, the thinner compositions of Examples 1 to 5 were excellent in both solubility and drying property.
The thinner compositions of Comparative Examples 1 and 3 were excellent in solubility but inferior in drying properties. The thinner composition of Comparative Example 2 was excellent in drying property but poor in solubility. None of the thinner compositions of Comparative Examples 4 to 6 was excellent in solubility or drying.

Claims (8)

  A thinner composition for removing a cyclic olefin polymer-containing composition, comprising two alcohol ethers and two alcohol esters.   The thinner composition according to claim 1, wherein the two alcohol ethers are ethylene glycol monoether and propylene glycol monoether, and the two alcohol esters are propylene glycol monoether ester and primary alcohol ester.   The content of monoether of ethylene glycol is 40 to 70% by weight with respect to the whole composition, and the total content of monoether of propylene glycol and monoether ester of propylene glycol is 20 to 40 with respect to the whole composition. The thinner composition according to claim 2, wherein the thinner composition is 10% by weight and the content of the primary alcohol ester is 10 to 30% by weight based on the whole composition.   The thinner composition according to claim 3, wherein a weight ratio of the monoether of propylene glycol to the monoether ester of propylene glycol (monoether of propylene glycol / monoether ester of propylene glycol) is 6/4 to 8/2. .   The monoether of ethylene glycol is 2-methoxyethanol, the monoether of propylene glycol is propylene glycol monomethyl ether, the monoether ester of propylene glycol is propylene glycol monomethyl ether acetate, and the primary alcohol ester is n-butyl acetate The thinner composition according to any one of claims 1 to 4, wherein   The thinner composition according to any one of claims 1 to 5, further comprising a surfactant.   The thinner composition according to claim 6, wherein the surfactant is at least one selected from the group consisting of a silicone surfactant and a fluorine surfactant.   A method for manufacturing a semiconductor device or a flat display device, comprising: using the thinner composition according to any one of claims 1 to 7 to clean an object to be cleaned to which the cyclic olefin polymer-containing composition is attached.