WO2001018084A1 - Copolymere alcenylphenolique de type a-b-a - Google Patents

Copolymere alcenylphenolique de type a-b-a Download PDF

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Publication number
WO2001018084A1
WO2001018084A1 PCT/JP2000/006085 JP0006085W WO0118084A1 WO 2001018084 A1 WO2001018084 A1 WO 2001018084A1 JP 0006085 W JP0006085 W JP 0006085W WO 0118084 A1 WO0118084 A1 WO 0118084A1
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general formula
represented
repeating unit
group
alkenylphenol
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PCT/JP2000/006085
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English (en)
Japanese (ja)
Inventor
Yukikazu Nobuhara
Asami Kobayashi
Hitoshi Matsumoto
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Nippon Soda Co., Ltd.
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Publication of WO2001018084A1 publication Critical patent/WO2001018084A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof

Definitions

  • the present invention relates to an alkenylfuninol-based copolymer having a novel skeleton useful as an electronic material, particularly a resist material, and a method for producing the same. More specifically, the present invention relates to various kinds of radiation, particularly ultraviolet rays, far ultraviolet rays, X Alkenyl phenol having a novel skeleton that can be suitably used as a resin constituting a chemically amplified resist for fabricating highly integrated circuits used in microfabrication using radiation such as electron beams or charged particle beams The present invention relates to a copolymer and a method for producing the copolymer. Background technology:
  • R 14 is a methyl group
  • R 15 and R 16 are a hydrogen atom or a methyl group
  • R 17 is a tertiary alcohol residue or an aryl group
  • m is any of 0, 1
  • X is a positive number from 0.6 to 0.9
  • a chemically amplified resist containing a resin component of an alkenyl phenol copolymer represented by the following formula.
  • the alkenyl phenol copolymer for resists reported so far has a polymerized segment [b] of a styrene derivative and a polymerized segment [ a ] of an acrylic acid derivative bonded to an ab type. Many are related to such copolymers.
  • Japanese Patent Application Laid-Open No. 63-245410 discloses that a dianion type living telomer obtained by reacting a styrene derivative with an alkali metal is used as an anion polymerization initiator, and an acrylic acid derivative is used. It describes a method for producing a copolymer in which a polymerized segment [b] of a styrene derivative and a polymerized segment [a] of an acrylic acid derivative are bonded in an a-ba type by polymerizing.
  • Japanese Patent Application Laid-Open No. H13-84122 discloses a diabetic type living telomer obtained by reacting a styrene derivative with an organic alkali metal as an anion polymerization initiator. A method for producing an a-type copolymer is described.
  • Japanese Patent Publication No. 7-432326 discloses an alkali metal salt of a mineral acid such as lithium chloride or alkaline earth metal. It describes a method of conducting anionic polymerization in the presence of an additive composed of a metal salt.
  • the resist material containing a copolymer in which the styrene polymer segment [b] and the acrylic acid derivative polymer segment [a] are bonded in an ab type has been reported.
  • the a-b-a-type copolymer using Alkyri metal described in the above-mentioned Japanese Patent Application Laid-Open No. 63-245410 is not capable of being cross-linked into a polymer chain. It is a polymer related to a highly solidified base resin for paint, which has a large number of functional groups that can be formed.It does not describe the usefulness as a resist material. The process of manufacturing the segment had to be performed in a separate reactor, which had the disadvantage that the manufacturing process was complicated.
  • copolymer obtained by the method for producing an a-b-a-type copolymer using an organic alkali metal described in JP-A-H13-80412 It is described in the examples that it has bimodality, and there was a problem as a resist material having high resolution.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the polymer segment [B] made of a styrene derivative and the polymer segment [A] made of an acrylic acid derivative are bonded in an A_B_A type. It has been found that by using such a copolymer, the disadvantages of the conventional resist material can be improved, and the present invention has been completed.
  • the present invention provides a compound represented by the general formula (I):
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents a hydrogen atom, a C 1 -C 12 alkyl group, a hydrocarbon group having a C 3 or more alicyclic skeleton, or a heterocyclic ring
  • An alkenyl phenol copolymer characterized by the fact that component (A) containing a repeating unit represented by the formula (A) is block-bonded to the A—B—A type, and the molecular weight distribution is narrow and monomodal.
  • the component (B) containing the repeating unit (Claim 1) or the repeating unit (B 1) represented by the general formula (I) comprises the repeating unit (B 1) represented by the general formula (1) and the general formula ( III)
  • R 5 represents a hydrogen atom or a methyl group
  • R 6 represents a C 1 -C 6 alkyl group, or 0R 18 (R 18 represents a group capable of leaving and decomposing under acidic conditions.
  • n represents 0, 1 or 2, and when n is 2, R 6 may be the same or different.
  • the component (B) containing the repeating unit (B 2) has a repeating unit (B 1) represented by the general formula (I) and a repeating unit (B 2) represented by the general formula (III) (B 1 ) — (B 2) an alkenyl phenol copolymer according to claim 2 (claim 3), wherein the alkenyl phenol copolymer is a block bond to the (B 1) type, or a repeat
  • the ratio (MwZMn) of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of the vinyl copolymer is from 1.00 to 1.50, wherein the ratio is from 1.00 to 1.50.
  • the present invention relates to an alkenyl fuanol copolymer (claim 5).
  • R represents a hydrogen atom or a methyl group
  • R 12 does not react with alkali metals or organic ⁇ alkali metal, represents a leaving-group capable of decomposing under acidic conditions
  • R 13 is C Represents an alkyl group of 1 to C6, p represents 0, 1 or 2, and when p is 2, R 13 may be the same or different.
  • R 7 represents a hydrogen atom or a methyl group
  • R 8 is a C 1 to C 12 alkyl group, a hydrocarbon group having a C 3 or more alicyclic skeleton which may have a substituent, Or a step of copolymerizing with one or more (meth) acrylic ester derivatives represented by the following formulas: and a step of bringing into contact with an acidic compound.
  • the method for producing an alkenyl phenol copolymer according to claim 7, wherein a sodium-potassium alloy is used as the alkali metal, and the step of synthesizing dianion are the following. Equation (V)
  • R 9 represents a hydrogen atom or a methyl group, R t . Is a C 1 -C 6 alkyl group Where q represents 0, 1 or 2, and when q is 2, May be the same or different.
  • a dianion synthesis step in which a styrene derivative represented by the general formula (VI) is polymerized into a dianion, and then a styrene derivative represented by the general formula (VI) is added and copolymerized.
  • the method comprises polymerizing a styrene derivative represented by the general formula (V) to form dianion.
  • the present invention also relates to the above-mentioned method for producing an alkenyl phenol copolymer (claim 11).
  • Ri represents a hydrogen atom or a methyl group.
  • R 2 represents a C 1 to C 5 alkyl group, and examples of the C 1 to C 5 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a t_butyl group. And the like can be specifically exemplified.
  • m represents 0, 1 or 2, and when m is 2, R 2 may be the same or different.
  • the substitution position of the hydroxyl group (OH group) and R 2 is not particularly limited, but the hydroxyl group is preferably a para-position to a meta-position of the alkenyl group.
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents a hydrogen atom, a C 1 to C 12 alkyl group
  • It represents a hydrocarbon group having an alicyclic skeleton or a heterocyclic group as described above, and in particular, a group having a t-butyl group which can be eliminated and decomposed by an acid is preferable, and specifically, a methyl group, Ethyl group, n-propyl group, isopropyl group, n_butyl group, t-butyl group, and the following formula CH,
  • the constituent unit in the repeating unit represented by the general formula (II) may be a single unit or a mixture of two or more types. In the case of a mixture of two or more types, the structure is not particularly limited, and may be random or They may be connected by a block.
  • the “component (B) containing the repeating unit (B 1) represented by the general formula (I)” is represented by the repeating unit (B 1) represented by the general formula (I) and the general formula (III):
  • the component (B) containing the repeating unit (B 2) represented can be exemplified.
  • R 5 represents a hydrogen atom or a methyl group
  • R 6 is C 1 ⁇ alkyl group or OR i 8 groups C 6 (1 18 Haji 1 Ji 6, under acidic conditions represents a leaving-group capable of decomposing) it represents, n represents 0, 1 or 2, n When R is 2, R 6 may be the same or different.
  • R 6 include a C 1 to C 6 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n_butyl group, a t-butyl group, a methoxymethoxy group, 2-methoxyethoxy, bis (2-chloroethoxy) methoxy, tetrahydrobiranyloxy, 4-methoxytetrahydrobiranyloxy, tetrahydrofuranyloxy, triphenylenyl, trimethylsilyl Oxy, 2_ (trimethylsilyl) ethoxy methoxy, t-butyldimethylsilyloxy, t-butyldimethylsilyloxy, trimethylsilylmethoxy, t-butoxy, t-butoxycarbonyloxy, t— Butoxycarbonyl methoxy, 2-methyl-1-t-butoxy carbonyl methoxy, 1-methoxy
  • the substitution position is not particularly limited.
  • the molar ratio of the repeating unit (B1) to the repeating unit (B2) in the component (B) is not particularly limited, but is in the range of 99.5 / 0.5 to 5050, preferably 98Z2 to 6040. Can be exemplified.
  • the repeating unit represented by the general formula (I) A component (B) formed by block bonding to the unit (B 1) and the repeating unit (B 2) represented by the general formula (III) (B 1)-(B 2)-(B 1)
  • a component (B3) consisting of a random combination of the repeating unit (B1) represented by the formula (I) and the repeating unit (B2) represented by the general formula ( ⁇ ), and a component represented by the general formula (III) Component (B) in which a repeating unit (B2) is block-bonded to the (B3)-(B2)-(B3) type.
  • the repeating units may be the same or different.
  • the molar ratio of the repeating unit (B 3) to the repeating unit (B 2) in the component (B) formed by (B 3)-(B 2) -one (B 3) is not particularly limited. . 5/0. 5 ⁇
  • the range of 50 50, preferably 98 2 to 80 20 can be exemplified.
  • the molar ratio of the repeating unit (B1) to the repeating unit (B2) in the component (B3) is not particularly limited, but is, for example, in the range of 99 ⁇ 1 to 50/50, preferably 95/5 to 60/40. be able to.
  • polymer of the present invention may contain a repeating unit other than the general formulas (I) to (III) as necessary.
  • the repeating unit is represented by the general formula (I)
  • the repeating unit is not particularly limited as long as it is a repeating unit obtained from a compound having a double bond copolymerizable with the monomer corresponding to the general formula (in), and is an acidic substituent such as a sulfonic acid group, a carboxyl group, or a fuynol hydroxyl group.
  • a repeating unit having no repeating unit is preferable, and examples of the monomer corresponding to the repeating unit include a vinyl group-containing compound and a (meth) acryloyl group-containing compound.
  • vinyl group-containing compound examples include p-t-butoxystyrene, p-t-butoxy-1- ⁇ -methylstyrene, m-t_butoxystyrene, m-t-butoxy- ⁇ -methylstyrene, ⁇ - (1-ethoxyethoxy) styrene, ⁇ - (1-ethoxyethoxy) mono- ⁇ -methylstyrene, ⁇ - (tetrahydropyranyloxy) styrene, ⁇ — (tetrahydropyranyloxy) monomethylstyrene, Aromatic vinyl compounds such as 1,1,1-diphenylethylene and stilbene; Heteroatom-containing aromatic vinyl compounds such as vinylpyridine; vinyl ketone compounds such as methyl vinyl ketone and ethyl vinyl ketone; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether Heteroatom-containing fats such as compounds, vinylpyrrolidone and vinyll
  • repeating units obtained from the vinyl group-containing compound include a repeating unit represented by the general formula (0 or a repeating unit represented by the general formula ( ⁇ ), or a repeating unit represented by the general formulas (I) to (III);
  • the alkenyl phenol copolymer of the present invention can be contained in the alkenyl phenol copolymer of the present invention by random or block copolymerization.
  • the alkenyl phenol copolymer of the present invention comprises a component ( ⁇ ) containing a repeating unit (B 1) represented by the general formula (I) and a component ( ⁇ ) containing a repeating unit represented by the general formula (II). ) And ( ⁇ )-( ⁇ )-( ⁇ ) type.
  • the component ( ⁇ ) is a repeating unit represented by the general formula (III).
  • (B 2) and the repeating unit (B 1) represented by the general formula (0) are of the (B 1) — (B 2) — (B 1) type.
  • Block copolymerization is preferred, and the repeating units (B 3) and (B 2) in which (B 1) and (B 2) are randomly bonded are represented by (B 3)-(B 2) 3) It is preferable that the block copolymer is formed in the mold.
  • the molar ratio of the components (A) and (B) [(A) / (B)] is not particularly limited.
  • the range of 4Z6 is preferred.
  • the number average molecular weight of the alkenylphenol copolymer of the present invention is preferably in the range of 1,000 to 100,000, particularly preferably in the range of 5,000 to 20,000.
  • the ratio (MwZMn) between the molecular weight (Mw) and the number average molecular weight (Mn) is preferably in the range of 1.00 to 1.50, and preferably in the range of 1.00 to 1.20.
  • alkenyl phenol copolymer of the present invention examples include the following copolymers.
  • R u represents a hydrogen atom or a methyl group
  • R i 2 is without reacting with Al force Li metals or organic Al force Li metal, leaving Decomposes under acidic conditions
  • Compounds represented by the general formula (VI) include pt-butoxystyrene, pt-butoxy- ⁇ -methylstyrene, m-t-butoxystyrene, m_t-butoxy ⁇ -methylstyrene, ⁇ - (tetrahydrobilanyloxy) styrene, ⁇ - (tetrahydrobilanyloxy) - ⁇ -methylstyrene, ⁇ - (1-ethoxyethoxy) styrene, ⁇ - (1-ethoxyethoxy) - ⁇ -methyl Styrene and the like can be exemplified, and these can be used alone or as a mixture of two or more.
  • R 9 represents a hydrogen atom or a methyl group
  • Specific examples of the compound represented by the general formula (V) include styrene, o-methylstyrene, m-methylstyrene, and p-meth Styrene, p-t_butylstyrene, 3,5-dimethylstyrene, 3,5-dibutylstyrene, 1,1-diphenylethylene, stilbene and the like. These may be used alone or in combination of two or more. Used as a mixture.
  • R 7 represents a hydrogen atom or a methyl group
  • R 8 represents a C 1 to C 12 alkyl.
  • R 8 corresponds to R 4 in the general formula (II), and specific examples are as described above.
  • Specific examples of the compound represented by the general formula (IV) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and t-butyl acrylate.
  • the method for producing the alkenylphenol copolymer of the present invention is represented by the general formula (VI) by anionic polymerization using a metal or organic metal such as sodium metal as a polymerization initiator.
  • a metal or organic metal such as sodium metal as a polymerization initiator.
  • dianion is synthesized from a component containing a styrene derivative as a monomer.
  • a styrene derivative represented by the general formula (V) is polymerized to form a dianion-type telomer, and then a hydroxyl group of a fuynol residue represented by the general formula (VI) is synthesized.
  • a dianion is synthesized by adding and copolymerizing a styrene derivative protected by a protecting group, or by polymerizing a styrene derivative represented by the general formula (V) to form a dianion, and then preparing a dianion by the general formula (V). And a styrene derivative represented by the general formula (VI) are added and copolymerized to synthesize dianion.
  • the styrene derivative represented by the general formula (V) used for the synthesis of the dianion type telomer and the styrene derivative represented by the general formula (V) used for further copolymerizing the dianion are used.
  • the styrene derivatives may be the same or different.
  • an alkali metal salt of a mineral acid and Z or an alkaline earth metal salt such as lithium chloride are added, and the compound represented by the general formula (IV) is successively added.
  • the alkenylphenol copolymer of the present invention can be produced by adding, copolymerizing, and contacting with an acidic compound.
  • the reaction between the dianion and the compound represented by the general formula (IV) is usually performed in an organic solvent under an atmosphere of an inert gas such as nitrogen or argon in a temperature range of 100 ° C to 50 ° C. And preferably at a temperature of ⁇ 100 to 0 ° C., more preferably at a temperature of ⁇ 100 to 120 ° C.
  • alkali metal used for the polymerization initiator examples include, for example, sodium, potassium, cesium, and the like.
  • Sodium is particularly preferred in terms of ease of handling and reactivity. Sodium can be used in bulk, but its activity is higher when it is used as a fine particle dispersion in higher hydrocarbons such as kerosene, and the reaction proceeds more quickly than when bulk sodium is used. Above gold It is preferable to use a sodium-potassium alloy as the metal because the activity can be further increased. In the sodium-potassium alloy, the ratio of potassium can be set arbitrarily, particularly when it is set to 40 to 90% by weight, it is preferable because it becomes a liquid at room temperature and is easy to handle.
  • organic alkali metal compound used for the polymerization initiator examples include lithium naphthalene, sodium naphthalene, potassium naphthalene, calcium naphthalene, cesium naphthalene, and the like.
  • reaction solvent used examples include aliphatic hydrocarbons such as n-hexane and n-pentane; alicyclic hydrocarbons such as cyclohexane and cyclopentane; aromatic hydrocarbons such as benzene and toluene;
  • aliphatic hydrocarbons such as n-hexane and n-pentane
  • alicyclic hydrocarbons such as cyclohexane and cyclopentane
  • aromatic hydrocarbons such as benzene and toluene
  • One or a mixture of two or more organic solvents commonly used in anionic polymerization, such as ether, tetrahydrofuran (THF) and dioxane can be used.
  • THF tetrahydrofuran
  • dioxane dioxane
  • a mixed system of THF and THF-hexane is preferable.
  • the mixing ratio is not particularly limited, but the volume ratio of THF he
  • the alkali metal salt and / or alkaline earth metal salt of a mineral acid added before the addition of the acrylic acid derivative of the general formula (II) is not particularly limited, but lithium chloride is particularly preferred in terms of controlling the reaction.
  • the addition of a mineral acid salt of a mineral acid and an alkali metal salt or a mineral acid salt can control the polymerization reaction of an acrylic acid derivative to obtain a target monodispersed polymer.
  • an acrylic acid derivative is used as the acrylic acid derivative, a remarkable effect is obtained. Even if the compound represented by the general formula (II) coexists in the system from the start of the polymerization, the effect is hardly observed, and the polymerization reaction is inhibited. It is desirable to do.
  • the amount of the metal salt used is usually in the range of 5 to 20 equivalents, preferably in the range of 5 to 15 equivalents, more preferably in the range of 8 to 12 equivalents, based on the amount of the initiator.
  • the reaction for removing the protecting group for the phenolic hydroxyl group from the obtained copolymer to form an alkenylphenol skeleton is carried out in addition to the solvents exemplified in the above polymerization reaction, alcohols such as methanol and ethanol, acetone, and methyl alcohol.
  • the reaction can be carried out in ketones such as tyl ketone, cellosolves such as ethyl cellulose solvent, and halogenated hydrocarbons such as carbon tetrachloride.
  • the acidic compound to be used is not particularly limited.
  • hydrochloric acid hydrogen chloride gas
  • sulfuric acid hydrobromic acid
  • 1,1,1-trifluoroacetic acid 1,1,1-trifluoroacetic acid
  • p-toluenesulfonic acid methanesulfonic acid
  • trifluoromethane Methanesulfonic acid and the like.
  • the amount of the acidic compound used may be a catalytic amount, but it is usually in the range of 0.01 to 0.8 mol, preferably 0.02 mol, per mol of the alkoxy group of the polymer before the deprotecting group. It is in the range of ⁇ 0.5 mol.
  • the reaction can be performed at a temperature ranging from room temperature to 150 ° C.
  • room temperature to less than 70 ° C preferably room temperature to less than 60 ° C, Preferably, it is carried out in the range of 30 ° C to 50 ° C.
  • the ester may be reacted at 60 ° C. or more even if the reaction is carried out at 60 ° C. or more.
  • the alkenyl phenol-based copolymer of the present invention having a narrow dispersion and a controlled structure can be produced.
  • the copolymer of the present invention may be obtained by removing all the protecting groups for the phenolic hydroxyl group and / or hydrolyzing all or one part of the (meth) acrylate portion, and Can also be synthesized by a method of re-introducing.
  • r represents the total number of repeating units (B 1) of the styrene derivative represented by the general formula 0), and s represents the total number of repeating units (B 2) of the styrene derivative represented by the general formula ( ⁇ ). And t represents the total number of repeating units (A) obtained by polymerizing (meth) acrylates represented by the general formula ( ⁇ ).
  • THF tetrahydrofuran
  • SD sodium dispersion
  • ⁇ -methylstyrene 3 88 g (32.8 mmol, abbreviated as aMeSt) was added, cooled to 160 ° C after 15 minutes, aged for 15 minutes, and then 40 g of p-t-butoxymethylstyrene (226.9
  • GC gas chromatography
  • LiC1 a 3% lithium chloride (hereinafter abbreviated as LiC1) 3% THF solution was added to the reaction system, the reaction was continued for 30 minutes, and methacrylic acid was further added.
  • t-Butyl ester hereinafter abbreviated as tBMA
  • tBMA t-Butyl ester
  • IR infrared absorption spectrum
  • NMR 13 CNMR
  • the acid value of the produced polymer was measured and found to be 2.80 KOHmg / g, which was almost the same value as that of the poly (p-hydroxystyrene) homopolymer.
  • the copolymerization ratio (molar ratio) measured by NMR rZt 85/15 Met.
  • the peak derived from the t-butyl group of poly PTB ST at around 29 ppm disappears after the reaction, whereas the peak derived from the t-butyl group of poly tBA near 27 ppm is represented by a benzene ring.
  • the area ratio to the number of carbon atoms did not change before and after the reaction.
  • the absorption derived from the t-butyl group of poly PTB ST at 890 cm-1 disappears after the reaction, and a new broad absorption derived from the hydroxyl group is observed around 3300 cm- 1 was done.
  • the peak derived from the t-butyl group of poly PTB ST at around 29 ppm disappears after the reaction, while the peak derived from the t-butyl group of poly t BMA at around 27 ppm is represented by benzene.
  • the area ratio to ring carbon did not change before and after the reaction.
  • Example 1 when LiC1 was added before adding SD, the polymerization reaction did not start even if aMeSt was added.
  • Example 1 After the polymerization of PTB ST was completed, when tBA was added without adding the LiClZTHF solution, the polymerization system gelled, and the desired polymer was not obtained.
  • the unimodal, narrow molecular weight distribution, and structure-controlled copolymer of alkenyl phenol and (meth) acrylate obtained by the present invention is a novel compound and is useful for electronic materials, especially for resists. It is an A-B-A-type alkenyl phenol copolymer expected to be used in materials.
  • a salt such as lithium chloride.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un nouveau copolymère d'ester alcénylphénolique/(méth)acrylique pouvant être utilisé comme matériau électronique, notamment comme matériau de réserve, et présentant une répartition de poids moléculaire étroite et unimodale, ainsi qu'un poids moléculaire et une structure régulés. L'invention concerne également un procédé de production de ce copolymère alcénylphénolique. Un dianion dont un composant comprend des unités itératives représentées par la formule générale (I) est synthétisé par polymérisation anionique à l'aide d'un composé de métal alcalin ou de métal alcalin organique, tel qu'un initiateur de polymérisation. Ce dianion est copolymérisé au moyen d'un dérivé d'ester (méth)acrylique représenté par la formule générale (IV) en présence de chlorure de lithium. Le copolymère résultant est mis au contact d'un composé acide, d'où l'obtention d'un copolymère alcénylphénolique dans lequel un segment polymérique [B] provenant d'un dérivé de styrène et deux segments polymériques [A] provenant d'un dérivé d'acide acrylique sont liés ensemble de manière à former un bloc de type A-B-A.
PCT/JP2000/006085 1999-09-08 2000-09-07 Copolymere alcenylphenolique de type a-b-a WO2001018084A1 (fr)

Applications Claiming Priority (4)

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JP25482999 1999-09-08
JP11/254829 1999-09-08
JP2000/157290 2000-05-26
JP2000157290 2000-05-26

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011021392A1 (fr) * 2009-08-21 2011-02-24 日本曹達株式会社 Procédé de production de composé polysiloxane modifié
US8729187B2 (en) 2009-08-04 2014-05-20 Nippon Soda Co., Ltd. High-molecular-weight copolymer

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10168132A (ja) * 1996-12-09 1998-06-23 Nippon Soda Co Ltd 狭分散アルケニルフェノール系共重合体及びその製造方法
JPH10265524A (ja) * 1997-01-24 1998-10-06 Shin Etsu Chem Co Ltd 高分子化合物及び化学増幅ポジ型レジスト材料
EP0898201A1 (fr) * 1997-08-18 1999-02-24 JSR Corporation Composition à base de résine sensible aux radiations

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10168132A (ja) * 1996-12-09 1998-06-23 Nippon Soda Co Ltd 狭分散アルケニルフェノール系共重合体及びその製造方法
JPH10265524A (ja) * 1997-01-24 1998-10-06 Shin Etsu Chem Co Ltd 高分子化合物及び化学増幅ポジ型レジスト材料
EP0898201A1 (fr) * 1997-08-18 1999-02-24 JSR Corporation Composition à base de résine sensible aux radiations

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8729187B2 (en) 2009-08-04 2014-05-20 Nippon Soda Co., Ltd. High-molecular-weight copolymer
WO2011021392A1 (fr) * 2009-08-21 2011-02-24 日本曹達株式会社 Procédé de production de composé polysiloxane modifié
US8420744B2 (en) 2009-08-21 2013-04-16 Nippon Soda Co., Ltd. Process for the production of modified polysiloxanes
JP5503654B2 (ja) * 2009-08-21 2014-05-28 日本曹達株式会社 変性ポリシロキサン化合物の製造方法

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