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WO2006016648A1 - Polymère en étoile, composition de résine décomposable avec de l’acide, pour réserve et composition et composé di(meth)acrylate - Google Patents

Polymère en étoile, composition de résine décomposable avec de l’acide, pour réserve et composition et composé di(meth)acrylate Download PDF

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Publication number
WO2006016648A1
WO2006016648A1 PCT/JP2005/014740 JP2005014740W WO2006016648A1 WO 2006016648 A1 WO2006016648 A1 WO 2006016648A1 JP 2005014740 W JP2005014740 W JP 2005014740W WO 2006016648 A1 WO2006016648 A1 WO 2006016648A1
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group
formula
star polymer
independently
carbon atoms
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Japanese (ja)
Inventor
Shinji Marumo
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Nippon Soda Co Ltd
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Nippon Soda Co Ltd
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Priority to JP2006531726A priority Critical patent/JP4421614B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters

Definitions

  • the present invention has a structure that can be easily cleaved by an acid and is suitable for a resist material and the like, a novel star polymer, an acid-decomposable resin composition and a resist composition containing the star polymer, and a star
  • the present invention relates to a compound of di (meth) attateroi toy useful as a raw material for polymer production.
  • Patent Document 1 US Pat. No. 6,323, 360
  • the present invention has been made in view of the above-mentioned problems of the prior art, and is derived from a poly (meth) atrelate toy compound having an acetal structure that is considered to be thermally stable and easy to mass-produce.
  • This new star polymer which is derived and has the property of being easily cleaved by acid It is an object of the present invention to provide an acid-decomposable resin composition and resist composition containing a mer, and a novel di (meth) ataretoy compound useful as a raw material for producing a star polymer.
  • star polymers (1) to (14) are provided.
  • R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • ⁇ represents a divalent or higher valent organic linking group not containing an acetal structure
  • B represents an acetal structure.
  • nl to! ⁇ 4 each independently represents an integer of 1 or more, nl when but 2 or more, when Yogu n2 be R 1 each other have the same or different are 2 or more, when Yogu n3 be the or different in each of R 1 each other and a with each other the same is 2 or more, R 2 may be the same or different.
  • R 2 and B may be the same or different, respectively.
  • A is an alkylene group having 2 or more carbon atoms (1) or (1) 2) Star polymer.
  • R 11 and R 12 each independently represents a hydrogen atom or an organic group, and A 1 represents a divalent or higher organic linking group
  • R U to R 14 each independently represents a hydrogen atom or an organic group
  • a 1 and A 2 each independently represent a divalent or higher valent organic linking group
  • ml represents an integer greater than or equal to 1.
  • R 13 , R 14 and A 2 may be the same or different from each other.
  • V which is a star polymer, characterized in that it is a functional group having a functional group represented by) in a partial structure.
  • a 1 and A 2 are each independently a chain alkylene group, a cycloalkylene group, or a cycloalkylalkylene group.
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 21 to R 24 each independently represents a hydrogen atom or an organic group
  • a 11 and A 13 are each independently a divalent organic linking group having 2 or more carbon atoms.
  • a 11 and A 13 are each independently a divalent hydrocarbon group having 2 or more carbon atoms.
  • a 12 is a chain alkylene group, a cycloalkylene group or a cycloalkylalkylene group.
  • the following acid-decomposable rosin compositions (15) and (16) are provided.
  • An acid-decomposable resin composition comprising any one of the above (1) to (14).
  • a resist composition comprising the star polymer of any one of the above (1) to (14) and a compound that generates an acid in response to an external stimulus.
  • a compound that generates an acid in response to an external stimulus Provided.
  • a 21 and A 23 each independently represents a divalent organic linking group
  • a 22 represents a divalent organic linking group having an alicyclic skeleton.
  • a 21 and A 23 are each independently a divalent organic linking group having 2 or more carbon atoms. .
  • a 21 and A 23 are each independently a divalent hydrocarbon group having 2 or more carbon atoms, Atarylate compound.
  • a 21 and A 23 are each independently an alkylene group having 2 or more carbon atoms,
  • the star polymer of the present invention is obtained by polymerizing a poly (meth) atreatoi compound having a thermally stable structure, and has a structure that can be easily cleaved by an acid. It is useful as a resist material.
  • the acid-decomposable resin composition and the resist composition of the present invention contain the star polymer of the present invention having a structure that can be easily cleaved by an acid, and are useful as a highly sensitive resist resin composition. is there.
  • monomers are also derived from the monomers.
  • the derived polymer can also be improved in thermal stability while maintaining the property of being easily cleaved by an acid, and can be industrially produced in large quantities.
  • the star polymer of the present invention is characterized by having a core part induced by the compound force represented by the formula (D). That is, the compound represented by the formula (I) is a core of the star polymer of the present invention. It is a monomer for constituting the part.
  • R 1 and R 2 are each independently a hydrogen atom; or carbon such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, etc. Represents an alkyl group of 1 to 4;
  • A represents a divalent or higher valent organic linking group that does not include an acetal structure.
  • A is not particularly limited as long as it is a divalent or higher valent organic group that does not contain an acetal structure and connects an ester oxygen atom and B, and is stable under polymerization reaction conditions. It is preferably a divalent or higher valent hydrocarbon group.
  • the hydrocarbon group having 2 or more carbon atoms and 2 or more valences of A includes (a) an alkylene group having 2 or more carbon atoms, (b) an alkyleneoxy group having 2 or more carbon atoms, (c) an arylene. (D) an aryleneoxy group, (e) an aryl atom which may have an oxygen atom, (f) a carbon atom having a trivalent or higher carbon number of 2 or more, which may have an oxygen atom.
  • a hydrogen group etc. are mentioned.
  • these groups may have an unsaturated bond in a part thereof.
  • alkylene group having 2 or more carbon atoms examples include a chain alkylene group having 2 or more carbon atoms, a cycloalkylene group, and a cycloalkylalkylene group.
  • a chain alkylene group having 2 or more carbon atoms is represented by the following chemical formula (7).
  • Ra and Rb each independently represent a hydrogen atom; or an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and an isopropyl group, and p is an integer of 2 or more, preferably Represents an integer of 2 to 10, more preferably an integer of 2, 3, or 4.
  • the repeating units: —C (Ra) (Rb) — may be the same as or different from each other.
  • chain alkylene group having 2 or more carbon atoms include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
  • the cycloalkylene group may be a monocyclic cycloalkylene group or a polycyclic cycloalkylene group as long as the group has two bonds extending from the carbon atom of the cycloalkyl ring. May be.
  • Examples of the cycloalkyl ring include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, an adamantane ring, and a norbornane ring.
  • Preferred examples of the cycloalkylene group include the following groups.
  • the cycloalkylalkylene group is not particularly limited as long as it has a structure in which an alkylene group is bonded to a carbon atom of a cycloalkyl ring.
  • Examples of the cycloalkyl ring include those described above.
  • cycloalkylalkylene group examples include the following groups.
  • alkyleneoxy group having 2 or more carbon atoms examples include (i) chain alkyleneoxy group, GO cycloalkyleneoxy group, () cycloalkylalkyleneoxy group, and the like.
  • chain alkyleneoxy group (i) examples include the following groups.
  • q represents an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1, 2, or 3.
  • q is 2 or more, the formula: —CH 2 CH 2 O
  • the groups represented by — are identical to each other.
  • Examples of the cycloalkyleneoxy group of (ii) include the following groups.
  • the arylene group is not particularly limited as long as it has a divalent or higher valent aromatic group.
  • Specific examples of the arylene group include the following groups.
  • aryleneoxy group examples include the following groups.
  • arylalkylene group which may have an oxygen atom include the following. [0048] [Chemical 15]
  • Examples of the trivalent or higher hydrocarbon group having 2 or more carbon atoms which may have an oxygen atom include a group having a chain structure shown in Chemical Formula 16 below, a chain structure and an aromatic group shown in Chemical Formula 17 and Chemical Formula 18 below. Examples include groups in which group groups are combined.
  • These hydrocarbon groups having 2 or more carbon atoms and 2 or more carbon atoms may have a substituent at an arbitrary position.
  • substituents include an alkyl group such as a methyl group, an ethyl group, a propyl group, and an isopropyl group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a t-butoxy group; a halogen atom such as a fluorine atom and a chlorine atom; Can be mentioned.
  • the A is more preferably a divalent chain alkylene group having 2 or more carbon atoms, which is preferably an alkylene group having 2 or more carbon atoms of (a). Particularly preferred is a divalent chain alkylene group having 2 to 10 carbon atoms! /.
  • B represents a divalent or higher-valent organic linking group having an acetal structure.
  • the acetal structure is obtained by reacting a dialkoxy compound obtained by reacting an aldehyde and an alcohol in the presence of an acid catalyst, or reacting a ketone and an alcohol in the presence of an acid catalyst. The structure of the resulting dialkoxy compound!
  • B is not particularly limited as long as it has at least acetal structure and is a divalent or higher-valent organic group that links the ester oxygen atom and A.
  • B may be an organic linking group that forms an acetal structure with an ester oxygen atom.
  • Formula (III) is preferably a functional group possessed by the structure
  • R U to R 14 each independently represents a hydrogen atom or an organic group.
  • the organic group may have, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, or an isopropyl group; a substituent such as a phenyl group, a 4-chlorophenyl group, or a 4-methylphenol group.
  • an alkyl group such as a methyl group, an ethyl group, a propyl group, or an isopropyl group
  • a substituent such as a phenyl group, a 4-chlorophenyl group, or a 4-methylphenol group.
  • R U to R 14 are preferably each independently an alkyl group.
  • a 1 and A 2 each independently represent a divalent or higher valent organic linking group, but in the present invention, A 1 and A 2 each independently represent a divalent or higher valent hydrocarbon.
  • a group is preferably each independently and more preferably a chain alkylene group, a cycloalkylene group or a cycloalkylalkylene group.
  • ml represents an integer of 1 or more, preferably represents an integer of 1 to 5, and more preferably represents an integer of 1, 2, or 3.
  • the groups represented by the formula: OC (R 13 ) (R 14 ) O—A 2 ) — may be the same or different.
  • nl to n4 each independently represents an integer of 1 or more, and nl is 2 or more.
  • R 1 may be the same or different.
  • R 1 and A may be the same or different.
  • R 2 are May be the same or different.
  • n4 is 2 or more, R 2 and B may be the same or different.
  • the compound represented by the formula (I) is particularly preferably a compound represented by the formula (IV).
  • R 1 and R 2 represent the same meaning as described above, and 1 to R 24 each independently represent a hydrogen atom or an organic group.
  • Specific examples of the organic group of R 21 to R 24 include the same as those listed as specific examples of the organic group of R U to R 14 .
  • a 11 , A 12 and A 13 each independently represent a divalent organic linking group.
  • Specific examples of the divalent organic linking group of A 11 , A 12 and A 13 include the same as those listed as specific examples of the divalent organic linking group of AA 2 .
  • a 11 and A 13 are each independently a divalent organic linking group having 2 or more carbon atoms, and each independently is a divalent having 2 or more carbon atoms.
  • the hydrocarbon group is more preferably an alkylene group having 2 or more carbon atoms, more preferably each independently.
  • a 12 is more preferably a chain alkylene group, a cycloalkylene group, or a cycloalkylalkylene group, preferably a divalent hydrocarbon group.
  • n represents an arbitrary natural number.
  • the formula (I) does not include a partial structure in which the ester oxygen atom is a part of the acetal structure.
  • the compound represented by [0075] is a novel compound.
  • the compound represented by the formula (V) is thermally stable, easily purified, and easily industrially mass-produced.
  • the compound represented by the formula (V) is particularly useful as a raw material for producing the star polymer of the present invention.
  • R 1 and R 2 represent the same meaning as described above.
  • R 31 to 4 each independently represent a hydrogen atom or an organic group. 1 to 4 of the organic group Specific examples of these include those listed as specific examples of the organic groups of R U to R 14 .
  • a 21 and A 23 each independently represent a divalent organic linking group, and A 22 represents a divalent organic linking group having an alicyclic skeleton.
  • divalent organic linking group of A 21 and A 23 include the same as those listed as specific examples of the divalent organic linking group of AA 2 .
  • a 21 and A 23 are each independently a divalent organic linking group having 2 or more carbon atoms. More preferably, it is a divalent hydrocarbon group having 2 or more carbon atoms, more preferably each independently a divalent alkylene group having 2 or more carbon atoms.
  • alkylene group having 2 or more carbon atoms of A 21 and A 23 include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.
  • Examples of the divalent organic linking group having an alicyclic skeleton of A 22 include a cycloalkylene group, a cycloanolenoanolylene group, a cycloanolylene xylene group, and a cycloanolequinolenoylene xylene group. Etc. Specific examples thereof are the same as those listed as specific examples of the cycloalkylene group, cycloalkylalkylene group, cycloalkyleneoxy group and cycloalkylalkyleneoxy group of A.
  • a 22 is preferably a cycloalkylene group or a cycloalkylanolylene group.
  • the star polymer of the present invention has a core part derived from the compound represented by the formula (I) (hereinafter abbreviated as “compound (1)”).
  • the repeating unit constituting the arm part is not particularly limited.
  • repeating unit constituting the arm part include addition-polymerizable unsaturated groups such as (meth) acrylic acid esters, (meth) acrylamides, butyl ethers, butyl esters, and styrenes.
  • a compound (monomer) having one bond can be obtained.
  • Examples of the monomer include the following. Methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethyl hexyl acrylate, octyl acrylate, t-octyl acrylate, chlorethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylol propane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofluor Furyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropylenomethacrylate, aminoremethacrylate, hexyl methacrylate, cyclohexyl methacrylate
  • Q represents any of the following groups (al) to (a6).
  • R ′′ to R b & are independently a carbon number such as methyl group, ethyl group, n-propyl group, isopropyl group, n butyl group, isobutyl group, sec butyl group, t butyl group, etc. Represents an alkyl group of 6; or an alicyclic hydrocarbon group.
  • R 66 represents a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec butyl group, or a t-butyl group; .
  • Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom.
  • R 67 is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec butyl group, or a t-butyl group; or an alicyclic carbonization Represents a hydrogen group.
  • Examples of the alicyclic hydrocarbon group of 1 to R ea include an adamantyl group, a noradamantyl group, a decalin group, a tricyclodeoxy group, a tetracyclodecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, and a cyclooctyl group.
  • N-alkylacrylamide alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohexyl group, hydroxy group
  • N, N-dialkyl acrylamide the alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group
  • N-Hydroxychetyl-N-Methylacrylamide N-2-Acetamidoethyl-N-Acetylacrylamide
  • Methacrylamide, N-Alkylmethacrylamide the alkyl group has 1 to L carbon atoms
  • Alkyl butyl ether for example, hexyl vinyl ether, octyl vinyl ethere, decenorevinino reetenore, ethino hexeno vinino reetenole, methoxy ethino revino ethenore, ethoxy ethino levino reetenole, chrono Reethino Levinino Reethenole, 1 Methinole 2, 2-Dimethylpropyl Vinyl Ether, 2-Ethyl Butyl Vinyl Ether, Hydroxetyl Vinyl Ether, Diethylene Glycol Vinyl Ether, Dimethylamino Ethyl Butyl Ether, Jetyl Amino Ethyl Butyl Ether, Butino Reamino Butyl ethers such as chinole butyl ether, benzyl butyl ether, tetrahydrofurfuryl butyl ether;
  • Itaconic acid esters such as dimethyl itaconate, decyl itaconate, dibutyl itaconate; dialkyl or monoalkyl esters of fumaric acid; dialkyl itaconates such as dibutyl fumarate;
  • R 72 , R 74 and R 77 are each independently an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an isopropyl group or a t-propyl group; or a halogen atom such as a fluorine atom or a chlorine atom; Represents.
  • r, s, t, and u each independently represent an integer of 0 to 2.
  • R 72 , R 74 , R 77, and R 78 are These may be the same or different.
  • R 75 represents an acid-decomposable 'leaving group.
  • the acid-decomposable leaving group means a group that is decomposed and Z or eliminated by an acid.
  • R 78 examples include groups represented by the following formula (X).
  • R represents an unsubstituted or alkoxy-substituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an unsubstituted or alkoxy group having 6 to 20 carbon atoms.
  • R 82 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 83 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Represents.
  • Specific examples of the group represented by the formula (X) include 1-methoxyethyl group, 1-ethyloxy group, 1-methoxypropyl group, 1-methyl-1-methoxyethyl group, and 1- (isopropoxy) ethyl.
  • the substitution position of the hydroxyl group (OH group) and the group represented by the formula: OR 75 is not particularly limited. The position or meta position is preferred.
  • the arm portion of the star polymer of the present invention may be a homopolymer made of one of these monomers or a copolymer of two or more kinds, but is preferably a copolymer. .
  • the ratio of each repeating unit in the arm portion of the star polymer of the present invention is determined by, for example, resist dry etching resistance, standard stock solution suitability, substrate adhesion, resist file, and general resist performance. It can be set as appropriate in consideration of certain resolution, heat resistance, sensitivity, and the like.
  • the ratio of each repeating unit in the arm portion of the star polymer of the present invention can be arbitrarily selected by the ratio of the monomer used for the reaction, for example, a repeating unit having a rataton ring.
  • the content of the unit is 30 to 70 mol%, preferably 35 to 65 mol%, more preferably 40 to 60 mol%, based on all the repeating units of the arm part.
  • the content of the repetition unit having an alicyclic skeleton, in the arm portion all repeating units is usually 20 to 75 mol%, preferable properly 25 to 70 mole 0/0, more preferably at 30 to 66 mole% is there.
  • the content of the repeating unit having a Rataton rings and structure other than the alicyclic skeleton is usually total monomer in 0 to 70 mol%, preferably from 2 to 40 mol 0/0, more preferably 5 to 30 mol 0/0.
  • the number average molecular weight (Mn) of the arm part measured by gel 'permeation' chromatography is preferably 1,000 to 1,000,000, more preferably 1,500 to 500, in terms of polystyrene. , 000, more preferred ⁇ or 2,000-200, 000, specially preferred ⁇ or 2,500 to 100, 000.
  • the ratio (MwZMn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the arm is in the range force S of 1.01 to 3.00, preferably in the range of 1.01 to 2.00 More preferred is S, and the range of 1.01 to L50 is more preferred.
  • a method for producing the star polymer of the present invention (a) in the presence of a cation polymerization initiator, (meth) acrylate or the like having an alicyclic skeleton, a rataton ring, or the like is polymerized.
  • a method of synthesizing an arm polymer and then reacting a poly (meth) attaleito compound (b) In the presence of a polymerization initiator, a poly (meth) atalyte toy compound is reacted to form a polyfunctional core, and then (meth) acrylate and the like having an alicyclic skeleton and a rataton ring are used.
  • Etc. can be illustrated.
  • the methods (a) and (c) are preferable for producing a star polymer with easy reaction control and a controlled structure.
  • Examples of the key-on polymerization initiator used in the above-mentioned key-on polymerization include alkali metals and organic alkali metals.
  • Examples of the alkali metal include lithium, sodium, potassium, cesium and the like
  • examples of the organic alkali metal include the above-mentioned alkali metal alkylates, arylates and arylides. Specific examples include ethynolethium, n-butynolethium, sec-butynolethium, tertbutylenolithium, ethylsodium, lithium biphenyl, lithium naphthalene, lithium triphenyl, sodium naphthalene, ⁇ -methylstyrene. Examples include sodium dione, 1,1-diphenylhexyllithium, 1,1-diphenyl-3-methylpentyllithium, and the like.
  • the polymerization reaction for synthesizing the arm polymer in the above method (a) or (c) includes a method of dropping a monomer polymerization initiator into a monomer (mixed) liquid, a monomer polymerization initiator,
  • the method of dropping the monomer (mixed) solution into the solution containing can also be performed by a deviation method.
  • a method of dropping a monomer (mixed) solution into a solution containing a polymerization initiator is preferred.
  • the synthesis reaction of the arm polymer is usually carried out in an organic solvent under an inert gas atmosphere such as nitrogen gas or argon gas, in the range of ⁇ 100 + 50 ° C, preferably ⁇ 100 + 40 ° C. Done under temperature,
  • Examples of the organic solvent used in the synthesis reaction of the arm polymer include aliphatic hydrocarbons such as n-xane and n-heptane; alicyclic hydrocarbons such as cyclohexane and cyclopentane; benzene and toluene Aromatic hydrocarbons such as: ethers such as jetyl ether, tetrahydrofuran (THF), dioxane, and azole; amides such as hexamethylphosphoramide; The organic solvent used can be used. This These solvents can be used alone or in combination of two or more.
  • Examples of the polymerized form of the arm polymer include random copolymerization, partial block copolymerization, and complete block copolymerization. These can be synthesized by selecting the method of adding (meth) acrylates to be used.
  • the above-mentioned poly (meth) alkyl relay toy compound is added to the reaction solution after the end of the arm polymer synthesis reaction. This can be done.
  • This reaction is usually performed at 100 ° C to + 50 ° C, preferably 70 ° C to + 40 ° C in an organic solvent under an inert gas atmosphere such as nitrogen gas or argon gas.
  • an inert gas atmosphere such as nitrogen gas or argon gas.
  • the star polymer formation reaction can be performed continuously in the solvent used to form the arm polymer, but the solvent composition is changed by adding a solvent, or the solvent is separated. It can also be carried out by substituting the solvent.
  • the powerful solvent the same solvents as those used in the arm polymer synthesis reaction can be used.
  • an alicyclic skeleton and a poly (meth) acrylate compound (P) and a cation polymerization method using a cation polymerization initiator as a polymerization initiator are used. It is preferable that the molar ratio [(P) / (D)] of the active terminal (D) of the polymer chain obtained by polymerizing the (meth) atarylate having a bilatonic ring is 0.1 to 10! /, .
  • the reaction between an arm polymer chain and a poly (meth) atari toy compound is a method of adding a poly (meth) atta relay toy compound to an arm polymer chain having an active end. Any method of adding an arm polymer chain having an active end to the rate compound can be employed.
  • the number of arms of the star polymer is determined by the addition amount of poly (meth) atalylate compound, the reaction temperature, and the reaction time, but usually the end of the living polymer and the poly (meth) atalytoy compound, etc. Multiple star block copolymers with different numbers of arms are produced at the same time due to the difference in reactivity with vinyl groups and steric hindrance.
  • the ratio (MwZMn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the star polymer to be produced is preferably in the range of 1.00 to L50 (weight average molecular weight ( Mw) ⁇ or 3,000 powers, 300, 000 powers! / ⁇ .
  • the active terminal present in the central core can be reacted with a directly polymerizable monomer, but after reacting with a compound such as diphenylethylene or stilbene, or with lithium chloride or the like. After adding an alkali metal or alkaline earth metal mineral salt, the monomer is reacted more highly, like an acrylic acid derivative, and when the monomer is reacted, the polymerization reaction proceeds slowly. And may be advantageous in controlling the overall structure of the polymer produced.
  • the above reaction can also be carried out continuously in the solvent used to form the central nucleus having an active end, but the solvent composition is changed by adding a solvent, or the solvent is replaced with another solvent. It is also possible to replace it with.
  • the powerful solvent include the same solvents as those used for the synthesis of the arm polymer.
  • two types of monomers are used as an arm polymer chain newly introduced to the active terminal existing in the central core in the method (c) or as an arm polymer chain in the method (b).
  • By mixing and reacting it is possible to make a polymer chain randomly copolymerized, or it can be made a block polymer chain by adding two kinds of monomers sequentially.
  • the star polymer of the present invention has a structure that can be easily cleaved by an acid, and can be suitably used for a resist material or the like.
  • the star polymer of the present invention is converted into a photoacid generator and, if necessary, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a surfactant, a photosensitizer, an organic basic compound, and a developer.
  • An acid-decomposable rosin composition can be prepared by dissolving it in a suitable organic solvent together with a compound that promotes solubility in water. This composition is useful as a resist composition.
  • the photoacid generator is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays or radiation.
  • known light 400-200 nm
  • photoinitiators for photopower thione polymerization photoinitiators for photoradical polymerization
  • photodecolorants for dyes photochromic agents
  • microresists for example, known light (400-200 nm) used in photoinitiators for photopower thione polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, or microresists.
  • Ultraviolet rays, deep ultraviolet rays, particularly preferably g-line, h-line, i-line, KrF excimer laser beam), ArF excimer laser beam, electron beam, X-ray, molecular beam or ion beam and compounds that generate acids Mixtures and the like can be used.
  • the addition amount of these photoacid generators is generally used in the range of 0.001 to 30% by weight, preferably 0.3 to 20% by weight, more preferably based on the solid content in the composition. Is in the range of 0.5 to 10% by weight.
  • the organic solvent used in the preparation of the acid-decomposable rosin composition includes ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, ⁇ -butyrolatatane, methinoreethinoleketone, ethylene glycol monomono. Methinoleethenore, Ethylene Glycole Monomethinoleetenore
  • 2-methoxyethyl acetate ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, Examples include methyl pyruvate, ethyl pyruvate, propyl pyruvate, ⁇ , ⁇ -dimethylformamide, dimethyl sulfoxide, ⁇ ⁇ ⁇ -methylpyrrolidone, and tetrahydrofuran.
  • the obtained acid-decomposable resin composition is applied onto a substrate by an appropriate application method such as a spinner or a coater, then exposed through a predetermined mask, subjected to beta, and using a developer.
  • a good resist pattern can be obtained by imaging.
  • the exposure light is preferably 150 ⁇ ! Light with a wavelength of ⁇ 250nm.
  • Developers include inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine.
  • Secondary amines such as jetylamine, di-n-butylamine, Tertiary amines such as triethylamine, methyljetylamine, alcohol amines such as dimethylethanolamine, triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, Alkaline aqueous solutions such as cyclic amines such as pyrrole and pyrrolidine can be used. Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline aqueous solution.
  • GCJ gas chromatography
  • TLC thin layer chromatography
  • the target product (colorless transparent oil) was quantitatively obtained in the same manner as in Example 1, except that 1,4-cyclohexanedimethanol dibule ether was used in place of ethylene glycol dibule ether. It was.
  • the structure of the crude product was determined by measuring 1 H-NMR spectrum and confirmed to be of sufficient purity.
  • the target product (colorless transparent oil) was quantitatively obtained in the same manner as in Example 1 except that 1,6 hexanediol dibule ether was used in place of ethylene glycol dibule ether.
  • the structure of the crude product was determined by measuring 1 H-NMR spectrum and confirmed to be of sufficient purity.
  • THF tetrahydrofuran
  • SBL sec-butyllithium
  • tBMA t-butylmetatalylate
  • the acid decomposability and thermal stability of star polymers containing acetal bonds in the core portion were tested according to the following procedure. That is, for a 5.0 wt% THF solution of star polymer 1, a sample containing 2 parts of camphorsulfonic acid (hereinafter abbreviated as “CS”) and a sample not containing CS are prepared for the polymer, This was done by analyzing the GPC chart of the sample after heating at 130 ° C for 5 minutes.
  • CS camphorsulfonic acid
  • Star polymer 1 is decomposed into an arm polymer in the stage before heating due to the presence of CS, and is well decomposed into an arm polymer after 5 minutes of heating, including high molecular weight polymer partially generated by acid. It was confirmed.
  • the above behavior is stable during heating operations (baking, etc.), and rapidly decomposes the core due to acid generation during exposure (degradation of molecular weight). When it happens, it is said that it is an excellent characteristic.
  • Star Polymer 2 also shows exactly the same tendency as Star Polymer 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)

Abstract

L’invention exposée ici traite d’un polymère en étoile possédant une portion de noyau dérivée depuis un composé représenté par la formule suivante (1) : (1) (où R1 et R2 représentent respectivement un atome d’hydrogène ou un groupe d’alkyles ayant 1-4 atomes de carbone ; où A représente un divalent ou groupe de liaisons organiques de valence supérieure n’ayant pas de structure d’acétal ; où B représente un divalent ou un groupe de liaisons organiques de valence supérieure ayant une structure d’acétal ou de cétal ; et où n1-n4 représentent respectivement un nombre entier non inférieur à 1). Le polymère en étoile possède une structure d’acétal qui est thermiquement stable et qui peut aisément être produite en masse, et est facilement fissible avec un acide.
PCT/JP2005/014740 2004-08-13 2005-08-11 Polymère en étoile, composition de résine décomposable avec de l’acide, pour réserve et composition et composé di(meth)acrylate Ceased WO2006016648A1 (fr)

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Cited By (9)

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JP2007045924A (ja) * 2005-08-09 2007-02-22 Mitsubishi Rayon Co Ltd （メタ）アクリル酸エステル、重合体、レジスト組成物、およびパターンが形成された基板の製造方法
KR100870855B1 (ko) 2006-05-29 2008-11-27 도오꾜오까고오교 가부시끼가이샤 분해성 조성물 및 그 사용 방법
WO2009028212A1 (fr) * 2007-08-31 2009-03-05 Nippon Soda Co., Ltd. Procédé de production de polymère en étoile
WO2009147823A1 (fr) * 2008-06-06 2009-12-10 ダイセル化学工業株式会社 Polymère destiné à des fins lithographiques et son procédé de fabrication
US20100055606A1 (en) * 2008-08-27 2010-03-04 Tokyo Ohka Kogyo Co., Ltd. Positive resist composition and method of forming resist pattern
JP2010250278A (ja) * 2009-03-26 2010-11-04 Tokyo Ohka Kogyo Co Ltd ポジ型レジスト組成物、レジストパターン形成方法
JP2012003075A (ja) * 2010-06-17 2012-01-05 Tokyo Ohka Kogyo Co Ltd ポジ型レジスト組成物、レジストパターン形成方法
JP2017110191A (ja) * 2015-12-18 2017-06-22 ダウ グローバル テクノロジーズ エルエルシー 酸に不安定な超分岐コポリマー、及び関連するフォトレジスト組成物、及び電子デバイスを形成する方法
CN112125998A (zh) * 2020-09-30 2020-12-25 中国科学院宁波材料技术与工程研究所 一种缩醛型动态共价网络材料及其制备方法

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JP2004091757A (ja) * 2002-09-04 2004-03-25 Nippon Shokubai Co Ltd （メタ）アクリレート化合物を含む水系組成物
WO2005022260A1 (fr) * 2003-08-28 2005-03-10 Hitachi Chemical Co., Ltd. Composition de resine photosensible, element photosensible faisant appel a cette composition, methode de formation d'un motif de resist, methode pour produire un tableau de connexions imprime, et une methode de suppression du produit photodurci

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007045924A (ja) * 2005-08-09 2007-02-22 Mitsubishi Rayon Co Ltd （メタ）アクリル酸エステル、重合体、レジスト組成物、およびパターンが形成された基板の製造方法
KR100870855B1 (ko) 2006-05-29 2008-11-27 도오꾜오까고오교 가부시끼가이샤 분해성 조성물 및 그 사용 방법
KR101176813B1 (ko) * 2007-08-31 2012-08-24 닛뽕소다 가부시키가이샤 스타 폴리머의 제조 방법
WO2009028212A1 (fr) * 2007-08-31 2009-03-05 Nippon Soda Co., Ltd. Procédé de production de polymère en étoile
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JP2009292982A (ja) * 2008-06-06 2009-12-17 Daicel Chem Ind Ltd リソグラフィー用重合体並びにその製造方法
WO2009147823A1 (fr) * 2008-06-06 2009-12-10 ダイセル化学工業株式会社 Polymère destiné à des fins lithographiques et son procédé de fabrication
US20100055606A1 (en) * 2008-08-27 2010-03-04 Tokyo Ohka Kogyo Co., Ltd. Positive resist composition and method of forming resist pattern
US8574809B2 (en) * 2008-08-27 2013-11-05 Tokyo Ohka Kogyo Co., Ltd. Positive resist composition and method of forming resist pattern
JP2010250278A (ja) * 2009-03-26 2010-11-04 Tokyo Ohka Kogyo Co Ltd ポジ型レジスト組成物、レジストパターン形成方法
JP2012003075A (ja) * 2010-06-17 2012-01-05 Tokyo Ohka Kogyo Co Ltd ポジ型レジスト組成物、レジストパターン形成方法
JP2017110191A (ja) * 2015-12-18 2017-06-22 ダウ グローバル テクノロジーズ エルエルシー 酸に不安定な超分岐コポリマー、及び関連するフォトレジスト組成物、及び電子デバイスを形成する方法
CN112125998A (zh) * 2020-09-30 2020-12-25 中国科学院宁波材料技术与工程研究所 一种缩醛型动态共价网络材料及其制备方法

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