WO2020166580A1 - ポリマーの製造方法 - Google Patents
ポリマーの製造方法 Download PDFInfo
- Publication number
- WO2020166580A1 WO2020166580A1 PCT/JP2020/005232 JP2020005232W WO2020166580A1 WO 2020166580 A1 WO2020166580 A1 WO 2020166580A1 JP 2020005232 W JP2020005232 W JP 2020005232W WO 2020166580 A1 WO2020166580 A1 WO 2020166580A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- component
- methyl
- carbon atoms
- producing
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3236—Heterocylic compounds
- C08G59/3245—Heterocylic compounds containing only nitrogen as a heteroatom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4207—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/423—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof containing an atom other than oxygen belonging to a functional groups to C08G59/42, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/094—Multilayer resist systems, e.g. planarising layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
Definitions
- the present invention relates to a method for producing a polymer by reacting an epoxy compound having two or more epoxy groups in the molecule with a reactive compound having two or more functional groups that react with the epoxy group in the molecule.
- the molecular weight of a polymer greatly affects the physical properties, so controlling the molecular weight can be said to be a common issue in polymer production.
- a method as described in Non-Patent Document 1 is used as a general method.
- a method for suppressing the increase in the molecular weight there is generally a method of greatly shifting the equivalent ratio of the diepoxy monomer and the reactive monomer from 1:1 (for example, 1:1.2 etc.).
- the increase in the molecular weight can be suppressed, it cannot be stabilized at the desired molecular weight, and since the monomer charged in excess remains in the system, a purification step for removing the residual monomer is essential, and from the viewpoint of productivity. Not preferable.
- the present invention has been made in view of the above circumstances, and a reaction between an epoxy compound having two or more epoxy groups in the molecule and a reactive compound having two or more functional groups that react with the epoxy groups in the molecule. It is an object of the present invention to provide a method for producing a polymer, which can be accurately controlled to a target molecular weight without being continuously increased in the system and can be stabilized at the molecular weight.
- the present inventors have found that an epoxy compound having two or more epoxy groups in the molecule and a reaction having two or more functional groups reactive with the epoxy group in the molecule.
- the molecular weight of the reaction system does not increase continuously.
- the present invention has been completed by finding a method capable of controlling the target molecular weight with high precision and stabilizing the molecular weight.
- the present invention provides the following method for producing a polymer.
- A an epoxy compound having two or more epoxy groups in the molecule
- B a reactive compound having two or more functional groups that react with the epoxy group in the molecule
- C a polymerization catalyst
- D A method for producing a polymer, which comprises reacting in the presence of a cocatalyst.
- the method for producing a polymer according to 2 wherein the Group 15 element of the component (C) is nitrogen or phosphorus. 4.
- the substituent in the Group 15 element structure of the component (C) is at least one selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aralkyl group having 7 to 20 carbon atoms 2 Alternatively, the method for producing the polymer according to 3). 5.
- the counter anion in the onium salt has a halide ion, a nitrate ion, a sulfate ion, an acetate ion, a formate ion, a hydroxide ion, and a sulfonic acid having an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.
- the substituent in the Group 15 element structure of the component (D) is at least one selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
- the method for producing a polymer according to any one of 8 to 8. 10. The method for producing a polymer according to any one of 1 to 9, wherein the component (A) is one kind or two or more kinds selected from a diepoxy compound, a triepoxy compound, a tetraepoxy compound and a polymer having an epoxy group. 11.
- the functional group of the component (B) is a hydroxyl group, formyl group, carboxy group, amino group, imino group, azo group, azido group, thiol group, sulfo group, amide group, imide group, thiocarboxy group, dithiocarboxy group, phosphorus.
- the mixing ratio (molar ratio) of the component (C) and the component (D) is 0.1:1.0 to 1.0:0.1, and the total amount of the component (C) and the component (D) is The method for producing a polymer according to any one of 1 to 12, which is 0.0001 to 0.5 mol per 1 mol of the component (A). 14.
- ethylene glycol monomethyl ether ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, 2-hydroxyiso Ethyl butyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-me
- the weight average molecular weight of a target polymer can be easily controlled, and a polymer having a desired weight average molecular weight can be produced with good reproducibility.
- the method for producing a polymer according to the present invention comprises (A) an epoxy compound having two or more epoxy groups in a molecule, and (B) a reactive compound having two or more functional groups that react with an epoxy group in a molecule. , (C) polymerization catalyst and (D) cocatalyst are allowed to react in the coexistence.
- the epoxy compound having two or more epoxy groups in the molecule (A) is a diepoxy compound, a triepoxy compound, a tetraepoxy compound and an epoxy compound in view of controlling the weight average molecular weight of the obtained polymer with high accuracy.
- Polymers having groups are preferred, diepoxy compounds and triespoxy compounds are more preferred, diepoxy compounds are even more preferred.
- a weight average molecular weight is a polystyrene conversion value by gel permeation chromatography (GPC) measurement.
- Preferred compounds as the diepoxy compound, the triepoxy compound and the tetraepoxy compound as the component (A) include, for example, compounds represented by the following formulas (A1) to (A9).
- E 1 is a group represented by the following formula (a-1).
- m1 is an integer of 0 to 4
- m2 is 0 or 1
- m3 is 0 or 1
- m4 is 1 or 2.
- m3 is 1, m1 and m2 are not 0 at the same time.
- R 1a and R 2a each independently represent a hydrogen atom, an oxygen atom or an alkyl group having 1 to 10 carbon atoms which may be interrupted by a sulfur atom, an oxygen atom or sulfur.
- R 3a is a hydrogen atom, an oxygen atom, or an alkyl group having 1 to 10 carbon atoms which may be interrupted by a sulfur atom, and an alkyl group having 2 to 12 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom.
- It may be substituted with at least one monovalent group selected from a group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms.
- alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group.
- Cyclobutyl group 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group Group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl -Cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl- Cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group,
- alkenyl group having 2 to 10 carbon atoms examples include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2- Methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3 -Pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2 -Propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-buten
- alkynyl group having 2 to 10 carbon atoms examples include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 4-methyl-1-pentynyl group, and 3 -Methyl-1-pentynyl group and the like.
- the phrase "may be interrupted by an oxygen atom or a sulfur atom” means, for example, that the carbon atom in the saturated carbon chain of the above alkyl group, alkenyl group and alkynyl group is replaced by an oxygen atom or a sulfur atom. Point to.
- an alkyl group, an alkenyl group and an alkynyl group when any carbon atom is replaced by an oxygen atom, it means that it contains an ether bond, and when any carbon atom is replaced by a sulfur atom, it is a thioether bond. Will be included.
- the halogen atom includes fluorine, chlorine, bromine, and iodine atoms.
- alkoxy group having 1 to 6 carbon atoms examples include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group and n-pentoxy group.
- alkylthio group having 1 to 6 carbon atoms examples include ethylthio group, butylthio group, and hexylthio group.
- R 4a's each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and —W— is a single bond, It represents —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CO—, —O—, —S— or —SO 2 —.
- n1 represents an integer of 2 to 4.
- n2 represents an integer of 2 to 4.
- n3 and n4 each independently represent an integer of 0 to 4, and n3+n4 is 2 to 4.
- n5 represents an integer of 2 to 4.
- n6 and n7 each independently represent an integer of 0 to 4, and n6+n7 is 2 to 4.
- n8 to n11 each independently represent an integer of 0 to 4, and n8+n9+n10+n11 is 2 to 4.
- E 2 is a group represented by the following formula (a-2).
- m5 is an integer of 0 to 4, m6 is 0 or 1, m7 is 0 or 1, and m8 is 1 or 2.
- alkyl group having 1 to 10 carbon atoms and the alkenyl group having 2 to 10 carbon atoms include the same ones as described above.
- the epoxy compounds represented by the formulas (A3) and (A4) are preferable from the viewpoint of accurately controlling the molecular weight of the obtained polymer, and the epoxy compounds represented by the following are more preferable. It can be preferably used.
- R 3a′ is a hydrogen atom, an oxygen atom or an alkyl group having 1 to 10 carbon atoms which may be interrupted by a sulfur atom, an oxygen atom or a sulfur atom.
- epoxy compounds represented by the above formulas (A1) to (A9) include, but are not limited to, the following compounds.
- Examples of the polymer having an epoxy group include polymers having repeating units represented by the following formulas (A10-1) to (A10-12).
- component (A) examples include epoxy compounds represented by the following formulas (A11-1) to (A11-2).
- the reactive compound having two or more functional groups capable of reacting with an epoxy group in the molecule is a functional group capable of reacting with an epoxy group in the molecule in view of controlling the weight average molecular weight of the obtained polymer with high accuracy.
- a compound having two or more groups is preferable, and a compound having two to three groups is more preferable.
- Examples of the functional group include a hydroxyl group, a formyl group, a carboxy group, an amino group, an imino group, an azo group, an azyl group, a thiol group, a sulfo group, an amide group, an imide group, a thiocarboxy group, a dithiocarboxy group, and a phosphoric acid.
- a hydroxyl group, a carboxy group, an amino group, an imide group and an amide group are preferred.
- component (B) include the following compounds, but are not limited to these.
- the blending amount of the component (B) is set as an equivalent ratio between the epoxy group of the component (A) and the functional group of the component (B).
- the (C) polymerization catalyst is a component added as a catalyst for the reaction between the above-mentioned (A) component and (B) component.
- the component (C) in combination with the below-mentioned (D) cocatalyst the molecular weight of the polymer in the reaction system can be controlled and stabilized to an appropriate molecular weight without continuously increasing. ..
- the component (C) is preferably an onium salt having one or more quaternary Group 15 element structure in consideration of controlling the weight average molecular weight of the obtained polymer with high accuracy.
- the number of quaternary group 15 element structures is preferably 1 or 2, and more preferably 1.
- the Group 15 element includes nitrogen, phosphorus, arsenic, antimony and bismuth, with nitrogen and phosphorus being preferred.
- Examples of the substituent in the Group 15 element structure include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
- alkyl group having 1 to 20 carbon atoms examples include n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl and n-hexadecyl, in addition to the groups exemplified as the alkyl group having 1 to 10 carbon atoms. , N-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosanyl group and the like. In the present invention, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable.
- aryl group having 6 to 20 carbon atoms examples include phenyl group, tolyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group and 2-phenanthryl group. Group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like. In the present invention, a phenyl group is preferred.
- Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, p-methylphenylmethyl group, m-methylphenylmethyl group, o-ethylphenylmethyl group, m-ethylphenylmethyl group, p-ethylphenylmethyl group, 2 -Propylphenylmethyl group, 4-isopropylphenylmethyl group, 4-isobutylphenylmethyl group, ⁇ -naphthylmethyl group and the like can be mentioned.
- a benzyl group is preferred.
- the counter anion in the onium salt has a halide ion, a nitrate ion, a sulfate ion, an acetate ion, a formate ion, a hydroxide ion, and an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Examples thereof include sulfonate ion.
- the halide ion include fluoride ion, chloride ion, bromide ion and iodide ion. In the present invention, halide ions are preferred.
- the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms are the same as above.
- sulfonate ion examples include methanesulfonic acid, p-toluenesulfonic acid and benzenesulfonic acid.
- Suitable examples of the component (C) include onium salts represented by the following formula (C1).
- G represents a Group 15 element
- R 1c independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
- X c ⁇ represents a halide ion, a nitrate ion, a sulfate ion, an acetate ion, a formate ion, a hydroxide ion, or a sulfone having an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Represents an acid ion.
- the Group 15 element, the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the aralkyl group having 7 to 20 carbon atoms, the halide ion and the sulfonate ion are the same as above.
- the component (C) is preferably a quaternary ammonium salt or a quaternary phosphonium salt, more preferably a quaternary phosphonium salt.
- Examples of the quaternary ammonium salt include tetramethylammonium fluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium nitrate, tetramethylammonium sulfate, tetramethylammonium acetate, tetraethylammonium chloride, tetraethylammonium bromide.
- Examples of the quaternary phosphonium salt include methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, hexyltriphenylphosphonium bromide, tetrabutylphosphonium bromide, benzyltriphenylphosphonium bromide, methyltriphenylphosphonium chloride.
- ethyltriphenylphosphonium bromide and tetrabutylphosphonium bromide can be preferably used.
- the blending amount of the component (C) is not particularly limited as long as it is an amount that allows the reaction to proceed, but in consideration of appropriately controlling the polymerization reaction of the polymer, with respect to 1 mol of the component (A),
- the amount is preferably 0.0001 to 0.5 mol, more preferably 0.0005 to 0.1 mol, still more preferably 0.001 to 0.05 mol.
- the co-catalyst (D) is a component used in combination with the component (C), and when used in combination with the component (C), the molecular weight of the polymer in the reaction system does not increase continuously, and the co-catalyst has an appropriate molecular weight. It can be controlled and stabilized.
- the component (D) is a compound having a primary to tertiary group 15 element structure and a group 15 element in the aromatic ring in view of controlling the weight average molecular weight of the obtained polymer with high accuracy.
- a heteroaryl compound containing the compound is preferable, and a compound having a tertiary Group 15 element structure and a heteroaryl compound containing a Group 15 element in the aromatic ring are more preferable.
- the Group 15 element include nitrogen, phosphorus, arsenic, antimony, and bismuth, and nitrogen and phosphorus are preferable.
- the substituent in the Group 15 element structure include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
- alkyl group having 1 to 20 carbon atoms the same groups as those exemplified above can be mentioned.
- an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.
- aryl group having 6 to 20 carbon atoms the same as those exemplified above can be mentioned.
- a phenyl group is preferred.
- aralkyl group having 7 to 20 carbon atoms the same groups as those exemplified above can be mentioned.
- a benzyl group is preferred.
- component (D) include compounds represented by the following formula (D1) or (D2).
- G 1d represents a Group 15 element
- R 1d independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
- R 2d represents a hydrogen atom or a dialkylamino group in which each alkyl group is independently an alkyl group having 1 to 12 carbon atoms.
- examples of the alkyl group having 1 to 20 carbon atoms include the same groups as those exemplified above.
- an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
- Examples of the aryl group having 6 to 20 carbon atoms are the same as those exemplified above.
- a phenyl group is preferred.
- Examples of the aralkyl group having 7 to 20 carbon atoms include the same groups as those exemplified above.
- a benzyl group is preferred.
- examples of the alkyl group having 1 to 12 carbon atoms include those similar to the alkyl group having 1 to 12 carbon atoms presented for the above alkyl group having 1 to 20 carbon atoms.
- an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.
- Preferred embodiments of the compound represented by the formula (D2) include those represented by the following formula (D2').
- component (D) examples include pyridine, N,N-dimethyl-4-aminopyridine, tributylphosphine and triphenylphosphine.
- the blending amount of the component (D) is not particularly limited as long as it is an amount that allows the reaction to proceed, but in consideration of appropriately controlling the polymerization reaction of the polymer, with respect to 1 mol of the component (A),
- the amount is preferably 0.0001 to 0.5 mol, more preferably 0.0005 to 0.2 mol, still more preferably 0.001 to 0.1 mol.
- the total amount of the component (C) and the component (D) is preferably 0.0002 to 0.5 mol, and more preferably 0.001 to 0.2 mol, relative to 1 mol of the component (A).
- the compounding ratio (molar ratio) of the (C) polymerization catalyst and the (D) cocatalyst is 0.1:1.0 to 1.0: considering that the weight average molecular weight of the obtained polymer is accurately controlled. 0.1 is preferable, and 0.3:1.0 to 1.0:0.3 is more preferable.
- a known organic solvent can be used.
- any solvent can be used without particular limitation as long as it can dissolve the above compound or a reaction product thereof and does not affect the polymerization reaction.
- Specific examples thereof include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxy
- propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferable, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are more preferable.
- These solvents may be used alone or in combination of two or more.
- the amount of the organic solvent used is preferably 0.1 to 100 times the mass of the component (A), preferably 0.5 to 20 mass, in view of controlling the weight average molecular weight of the obtained polymer with high accuracy. Double is more preferable.
- the reaction temperature is preferably 25 to 200° C., more preferably 50 to 150° C., and 80 in view of allowing the reaction to proceed efficiently and controlling the weight average molecular weight of the obtained polymer with high accuracy. Even more preferably, the temperature is 150°C. In addition, reflux may be performed during heating.
- the reaction time cannot be specified unconditionally because it depends on the reaction temperature and the reactivity of the raw materials, but it is usually about 1 to 30 hours, and when the reaction temperature is 100 to 130°C, it is about 1 to 15 hours. is there.
- the weight average molecular weight Mw of the polymer obtained by the method for producing a polymer of the present invention is 500 to 100,000. However, the increase in the molecular weight reaches a peak after a lapse of a certain time from the start of the reaction, and thereafter, the purpose is increased. It stabilizes near the molecular weight (generally within ⁇ 300).
- the weight average molecular weight Mw is a polystyrene conversion value measured by gel permeation chromatography (GPC).
- the weight average molecular weight of the obtained polymer can be accurately controlled, and a polymer having a target weight average molecular weight can be produced with good reproducibility.
- the polymer obtained by the production method of the present invention is, for example, an antireflection film forming composition for lithography, a resist lower layer film forming composition, a resist upper layer film forming composition, a photocurable resin composition, a thermosetting resin composition.
- the present invention can be applied to materials, flattening film forming compositions, adhesive compositions, and other compositions.
- the polymer solution after the reaction may be appropriately mixed with components such as a crosslinking agent and a crosslinking catalyst.
- B Reactive compound (b1) adipic acid: molecular weight 79.10 (B2) 3,3-dithiopropionic acid: molecular weight 210.26 (B3) barbital: molecular weight 184.20 (B4) Bisphenol A: molecular weight 228.29
- Example 1 In a 200 mL reaction flask, (A) 12.6 g of monoallyl diglycidyl isocyanuric acid, (B) adipic acid of 6.6 g, and (C) 0.84 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) pyridine as a cocatalyst. A raw material solution was prepared by charging 0.18 g and 60 g of propylene glycol monomethyl ether. The molar ratio of the component (C) and the component (D) is 1:1 and the equivalent ratio of the component (A) and the component (B) is 1:1.01. Next, this solution was heated under reflux at 121° C.
- Example 2 In a 200 mL reaction flask, (A) 12.6 g of monoallyl diglycidyl isocyanuric acid, (B) adipic acid of 6.6 g, and (C) 0.84 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) pyridine as a cocatalyst. 0.26 g and 60 g of propylene glycol monomethyl ether were charged to prepare a raw material solution. The molar ratio of the component (C) and the component (D) is 1:1.5, and the equivalent ratio of the component (A) and the component (B) is 1:1.01. Next, this solution was heated under reflux at 121° C.
- Mw 6,500 at 1 hour after reaching the reflux temperature
- Mw 8,100 at 2 hours
- Mw 8,100 at 4 hours
- Example 3 In a 200 mL reaction flask, (A) 12.6 g of monoallyl diglycidyl isocyanuric acid, (B) adipic acid of 6.6 g, and (C) 0.84 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) pyridine as a cocatalyst. A raw material solution was prepared by charging 0.09 g and 60 g of propylene glycol monomethyl ether. The molar ratio of the component (C) and the component (D) is 1:0.5, and the equivalent ratio of the component (A) and the component (B) is 1:1.01. Next, this solution was heated under reflux at 121° C.
- Example 4 In a 200 mL reaction flask, (A) monoallyl diglycidyl isocyanuric acid 12.6 g, (B) adipic acid 6.6 g, and (C) ethyltriphenylphosphonium bromide 0.42 g as a polymerization catalyst, (D) pyridine as a cocatalyst. A raw material solution was prepared by charging 0.09 g and 60 g of propylene glycol monomethyl ether. The molar ratio of the component (C) and the component (D) is 1.0:1.0, and the equivalent ratio of the component (A) and the component (B) is 1:1.01. Next, this solution was heated under reflux at 121° C.
- Example 5 In a 500 mL reaction flask, (A) monoallyl diglycidyl isocyanuric acid 31.5 g, (B) adipic acid 16.4 g, and (C) ethyltriphenylphosphonium bromide 1.68 g as a polymerization catalyst, and (D) pyridine as a cocatalyst. A raw material solution was prepared by charging 0.09 g and 60 g of propylene glycol monomethyl ether. The molar ratio of the component (C) and the component (D) is 1:0.25, and the equivalent ratio of the component (A) and the component (B) is 1:1.01. Next, this solution was heated under reflux at 121° C.
- Example 6 In a 500 mL reaction flask, (A) monoallyl diglycidyl isocyanuric acid 31.5 g, (B) adipic acid 16.4 g, and (C) ethyltriphenylphosphonium bromide 1.26 g as a polymerization catalyst, and (D) pyridine as a cocatalyst.
- a raw material solution was prepared by charging 0.18 g and 60 g of propylene glycol monomethyl ether. The molar ratio of the component (C) and the component (D) is 1:0.67, and the equivalent ratio of the component (A) and the component (B) is 1:1.01. Next, this solution was heated under reflux at 121° C.
- Example 7 In a 500 mL reaction flask, (A) monoallyl diglycidyl isocyanuric acid 31.5 g, (B) adipic acid 16.4 g, and (C) ethyltriphenylphosphonium bromide 0.84 g as a polymerization catalyst, (D) pyridine as a cocatalyst. 0.26 g and 60 g of propylene glycol monomethyl ether were charged to prepare a raw material solution. The molar ratio of the component (C) and the component (D) is 0.67:1, and the equivalent ratio of the component (A) and the component (B) is 1:1.01. Next, this solution was heated under reflux at 121° C.
- Example 8 In a 500 mL reaction flask, (A) monoallyl diglycidyl isocyanuric acid 31.5 g, (B) adipic acid 16.4 g, and (C) ethyltriphenylphosphonium bromide 0.42 g as a polymerization catalyst, and (D) pyridine as a cocatalyst. 0.35 g and 60 g of propylene glycol monomethyl ether were charged to prepare a raw material solution. The molar ratio of the component (C) and the component (D) is 0.25:1, and the equivalent ratio of the component (A) and the component (B) is 1:1.01. Next, this solution was heated under reflux at 121° C.
- Example 9 In a 200 mL reaction flask, (A) monoallyl diglycidyl isocyanuric acid 12.6 g, (B) adipic acid 6.6 g, and (C) ethyltriphenylphosphonium bromide 0.84 g as a polymerization catalyst, and (D) tricatalyst as a cocatalyst. 0.58 g of phenylphosphine and 60 g of propylene glycol monomethyl ether were charged to prepare a raw material solution. The molar ratio of the component (C) and the component (D) is 1:1 and the equivalent ratio of the component (A) and the component (B) is 1:1.01.
- this solution was heated under reflux at 121° C. and reacted for 1 to 7 hours to synthesize a polymer.
- Mw of the first hour after reaching the reflux temperature was 7,700
- Mw of the second hour was 12,500
- Mw of the fourth hour was 13,200
- Mw of the fifth hour 13,200
- Mw at 6th hour 13,200
- Mw at 7th hour 13,200
- the weight average molecular weight Mw was stabilized after 4 hours after reaching the reflux temperature.
- Example 10 In a 200 mL reaction flask, (A) monoallyl diglycidyl isocyanuric acid 12.6 g, (B) adipic acid 6.6 g, and (C) ethyltriphenylphosphonium bromide 0.84 g as a polymerization catalyst, and (D) tributyl as a cocatalyst. 0.45 g of phosphine and 60 g of propylene glycol monomethyl ether were charged to prepare a raw material solution. The molar ratio of the component (C) and the component (D) is 1:1 and the equivalent ratio of the component (A) and the component (B) is 1:1.01. Next, this solution was heated under reflux at 121° C.
- Example 11 In a 200 mL reaction flask, (A) 11.0 g of monoallyl diglycidyl isocyanuric acid, (B) 8.3 g of 3,3-dithiopropionic acid, and (C) 0.73 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D ) 0.15 g of pyridine and 60 g of propylene glycol monomethyl ether were charged as a cocatalyst to prepare a raw material solution. The molar ratio of the component (C) and the component (D) is 1:1 and the equivalent ratio of the component (A) and the component (B) is 1:1.01. Next, this solution was heated under reflux at 121° C.
- Example 11 The results of Example 11 and Comparative Example 3 are summarized in Table 4.
- Example 12 In a 200 mL reaction flask, (A) 12.8 g of monoallyl diglycidyl isocyanuric acid, (B) 10.4 g of bisphenol A, and (C) 0.85 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) pyridine as a cocatalyst.
- a raw material solution was prepared by charging 0.05 g and 56 g of propylene glycol monomethyl ether. The molar ratio between the component (C) and the component (D) is 1:0.3, and the equivalent ratio between the component (A) and the component (B) is 1:1.005. Next, this solution was heated under reflux at 121° C.
- Example 12 The results of Example 12 and Comparative Example 4 are summarized in Table 5.
- Example 13 In a 500 mL reaction flask, (A) monoallyldiglycidyl isocyanuric acid 34.2 g, (B) barbital 23.5 g, and (C) ethyltriphenylphosphonium bromide 2.3 g as a polymerization catalyst, (D) pyridine 0 as a cocatalyst. .29 g and 240 g of propylene glycol monomethyl ether were charged to prepare a raw material solution. The molar ratio of the component (C) and the component (D) is 1:0.6, and the equivalent ratio of the component (A) and the component (B) is 1:1.04. Next, this solution was heated under reflux at 121° C.
- Example 14 In a 500 mL reaction flask, (A) monoallyl diglycidyl isocyanuric acid 34.1 g, (B) barbital 23.4 g, and (C) tetrabutylphosphonium bromide 2.1 g as a polymerization catalyst, and (D) pyridine 0. A raw material solution was prepared by charging 48 g and 240 g of propylene glycol monomethyl ether. The molar ratio of the component (C) and the component (D) is 1:1 and the equivalent ratio of the component (A) and the component (B) is 1:1.04. Next, this solution was heated under reflux at 121° C. and reacted for 1 to 8 hours to synthesize a polymer.
- Example 15 In a 500 mL reaction flask, (A) monoallyl diglycidyl isocyanuric acid 34.0 g, (B) barbital 23.3 g, and (C) tetrabutylphosphonium bromide 2.1 g as a polymerization catalyst, and (D) N,N as a cocatalyst. -Dimethyl-4-aminopyridine 0.74 g and propylene glycol monomethyl ether 240 g were charged to prepare a raw material solution. The molar ratio of the component (C) and the component (D) is 1:1 and the equivalent ratio of the component (A) and the component (B) is 1:1.04. Next, this solution was heated under reflux at 121° C.
- Example 16 In a 200 mL reaction flask, (A) terephthalic acid diglycidyl ester 15.3 g, (B) adipic acid 7.7 g, and ethyltriphenylphosphonium bromide 1.0 g as a polymerization catalyst, (D) pyridine 0.21 g as a cocatalyst, 56 g of propylene glycol monomethyl ether was charged to prepare a raw material solution. The molar ratio of the component (C) and the component (D) is 1:1 and the equivalent ratio of the component (A) and the component (B) is 1:1.001. Next, this solution was heated under reflux at 105° C.
- Example 16 The results of Example 16 and Comparative Example 7 are summarized in Table 7.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Structural Engineering (AREA)
- Architecture (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Epoxy Resins (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
1. (A)分子内にエポキシ基を2つ以上有するエポキシ化合物と、(B)分子内にエポキシ基と反応する官能基を2つ以上有する反応性化合物とを、(C)重合触媒および(D)共触媒の存在下で反応させることを特徴とするポリマーの製造方法。
2. (C)成分が、4級の第15族元素構造を1つ以上有するオニウム塩である1のポリマーの製造方法。
3. (C)成分の第15族元素が、窒素またはリンである2のポリマーの製造方法。
4. (C)成分の第15族元素構造における置換基が、炭素数1~20のアルキル基、炭素数6~20のアリール基および炭素数7~20のアラルキル基から選ばれる少なくとも1種である2または3のポリマーの製造方法。
5. オニウム塩におけるカウンターアニオンが、ハロゲン化物イオン、硝酸イオン、硫酸イオン、酢酸イオン、ギ酸イオン、水酸化物イオン、および炭素数1~20のアルキル基または炭素数6~20のアリール基を有するスルホン酸イオンから選ばれる2~4のいずれかのポリマーの製造方法。
6. (D)成分が、1~3級の第15族元素構造を有する化合物、または芳香環に第15族元素を含むヘテロアリール化合物である1~5のいずれかのポリマーの製造方法。
7. (D)成分の第15族元素が、窒素またはリンである6のポリマーの製造方法。
8. (D)成分が、3級の第15族元素構造を有する化合物、または芳香環に第15族元素を含むヘテロアリール化合物である6または7のポリマーの製造方法。
9. (D)成分の第15族元素構造における置換基が、炭素数1~20のアルキル基、炭素数6~20のアリール基および炭素数7~20のアラルキル基から選ばれる少なくとも1種である6~8のいずれかのポリマーの製造方法。
10. (A)成分が、ジエポキシ化合物、トリエポキシ化合物、テトラエポキシ化合物およびエポキシ基を有するポリマーから選ばれる1種または2種以上である1~9のいずれかのポリマーの製造方法。
11. (B)成分の官能基が、水酸基、ホルミル基、カルボキシ基、アミノ基、イミノ基、アゾ基、アジ基、チオール基、スルホ基、アミド基、イミド基、チオカルボキシ基、ジチオカルボキシ基、リン酸基、亜リン酸基、ホスホン酸基、亜ホスホン酸基、ホスフィン酸基、亜ホスフィン酸基、ホスフィン基、酸無水物または酸クロリドである1~10のいずれかのポリマーの製造方法。
12. (A)成分が有するエポキシ基と(B)成分が有する官能基との当量比が、(A):(B)=0.1:1.0~1.0:0.1である1~11のいずれかのポリマーの製造方法。
13. (C)成分と(D)成分の配合比(モル比)が、0.1:1.0~1.0:0.1であり、かつ(C)成分と(D)成分の合計量が(A)成分1モルに対して、0.0001~0.5モルである1~12のいずれかのポリマーの製造方法。
14. 更に、有機溶媒として、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン、シクロヘプタノン、4-メチル-2-ペンタノール、2-ヒドロキシイソ酪酸メチル、2-ヒドロキシイソ酪酸エチル、エトキシ酢酸エチル、酢酸2-ヒドロキシエチル、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、2-ヘプタノン、メトキシシクロペンタン、アニソール、γ-ブチロラクトン、N-メチルピロリドン、N,N-ジメチルホルムアミド、およびN,N-ジメチルアセトアミドから選ばれる1種以上を用いる1~13のいずれかのポリマーの製造方法。
15. 有機溶媒の使用量が、(A)成分の質量に対して、0.1~100質量倍である14のポリマーの製造方法。
16. 反応温度が、25~200℃である1~15のいずれかのポリマーの製造方法。
17. 1~16のいずれかの製造方法により得られたポリマーと、有機溶媒とを混合するレジスト下層膜形成組成物の製造方法。
なお、本発明において、重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)測定によるポリスチレン換算値である。
4級の第15族元素構造の数は、1つまたは2つが好ましく、1つがより好ましい。
第15族元素としては、窒素、リン、ヒ素、アンチモンおよびビスマスが挙げられるが、窒素およびリンが好ましい。
第15族元素構造における置換基としては、炭素数1~20のアルキル基、炭素数6~20のアリール基および炭素数7~20のアラルキル基が挙げられる。
上記第15族元素としては、窒素、リン、ヒ素、アンチモンおよびビスマス等が挙げられるが、窒素およびリンが好ましい。
第15族元素構造における置換基としては、炭素数1~20のアルキル基、炭素数6~20のアリール基および炭素数7~20のアラルキル基が挙げられる。
炭素数6~20のアリール基としては、上記で例示したものと同様のものが挙げられる。本発明においては、フェニル基が好ましい。
炭素数7~20のアラルキル基としては、上記で例示したものと同様のものが挙げられる。本発明においては、ベンジル基が好ましい。
有機溶媒としては、上記化合物またはその反応生成物を溶解でき、重合反応に影響を及ぼさない溶媒であれば、特に制限なく使用することができる。その具体例としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン、シクロヘプタノン、4-メチル-2-ペンタノール、2-ヒドロキシイソ酪酸メチル、2-ヒドロキシイソ酪酸エチル、エトキシ酢酸エチル、酢酸2-ヒドロキシエチル、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、2-ヘプタノン、メトキシシクロペンタン、アニソール、γ-ブチロラクトン、N-メチルピロリドン、N,N-ジメチルホルムアミド、およびN,N-ジメチルアセトアミドが挙げられる。本発明では、これらの溶媒の中でも、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、乳酸エチル、乳酸ブチル、およびシクロヘキサノンが好ましく、プロピレングリコールモノメチルエーテル、およびプロピレングリコールモノメチルエーテルアセテートがより好ましい。これらの溶剤は、1種を単独で、または2種以上を組み合わせて用いることができる。
本発明において、重量平均分子量Mwは、ゲルパーミエーションクロマトグラフィー(GPC)測定によるポリスチレン換算値である。
ポリマーの重量平均分子量Mwおよび多分散度Mw/Mnは、ゲルパーミエーションクロマトグラフィー(GPC)による測定で得られたクロマトグラムの各ピークから、検量線に基づいて算出した。測定条件は、以下のとおりである。
〈測定条件〉
装置:HLC-8320GPC(東ソー(株)製)
カラム:Shodex〔登録商標〕(昭和電工(株))
溶離液:10mM 臭化リチウム/DMF
流量:0.6mL/min
カラム温度:40℃
検出器:RI
標準試料:ポリスチレン
(b1)アジピン酸:分子量79.10
(b2)3,3-ジチオプロピオン酸:分子量210.26
(b3)バルビタール:分子量184.20
(b4)ビスフェノールA:分子量228.29
(d1)ピリジン:分子量79.10
(d2)N,N-ジメチル-4-アミノピリジン:分子量122.17
(d3)トリブチルホスフィン:Bu3P、分子量202.32
(d4)トリフェニルホスフィン:Ph3P、分子量262.29
200mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸12.6g、(B)アジピン酸6.6g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド0.84g、(D)共触媒としてピリジン0.18g、プロピレングリコールモノメチルエーテル60gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:1、(A)成分と(B)成分との当量比は1:1.01である。
次いで、この溶液を121℃にて加熱還流を行い1~6時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=6,400、2時間目のMw=10,100、4時間目のMw=10,500、5時間目のMw=10,400、6時間目のMw=10,400であり、還流温度到達後4時間目以降、重量平均分子量Mwが安定化した。
200mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸12.6g、(B)アジピン酸6.6g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド0.84g、(D)共触媒としてピリジン0.26g、プロピレングリコールモノメチルエーテル60gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:1.5、(A)成分と(B)成分との当量比は1:1.01である。
次いで、この溶液を121℃にて加熱還流を行い1~7時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=6,500、2時間目のMw=8,100、4時間目のMw=8,100、5時間目のMw=8,000、6時間目のMw=7,900、7時間目のMw=7,800であり、還流温度到達後2時間目以降、重量平均分子量Mwが安定化した。
200mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸12.6g、(B)アジピン酸6.6g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド0.84g、(D)共触媒としてピリジン0.09g、プロピレングリコールモノメチルエーテル60gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:0.5、(A)成分と(B)成分との当量比は1:1.01である。
次いで、この溶液を121℃にて加熱還流を行い1~7時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=8,500、2時間目のMw=13,200、4時間目のMw=15,000、5時間目のMw=14,900、6時間目のMw=14,800、7時間目のMw=14,600であり、還流温度到達後4時間目以降、重量平均分子量Mwが安定化した。
200mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸12.6g、(B)アジピン酸6.6g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド0.42g、(D)共触媒としてピリジン0.09g、プロピレングリコールモノメチルエーテル60gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1.0:1.0、(A)成分と(B)成分との当量比は1:1.01である。
次いで、この溶液を121℃にて加熱還流を行い1~8時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=3,800、2時間目のMw=9,900、4時間目のMw=13,900、5時間目のMw=14,000、6時間目のMw=14,000、7時間目のMw=13,900、8時間目のMw=13,900であり、還流温度到達後4時間目以降、重量平均分子量Mwが安定化した。
500mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸31.5g、(B)アジピン酸16.4g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド1.68g、(D)共触媒としてピリジン0.09g、プロピレングリコールモノメチルエーテル60gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:0.25、(A)成分と(B)成分との当量比は1:1.01である。
次いで、この溶液を121℃にて加熱還流を行い1~8時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=7,000、2時間目のMw=14,600、4時間目のMw=21,200、5時間目のMw=25,600、6時間目のMw=26,400、7時間目のMw=27,300、8時間目のMw=27,900であり、還流温度到達後6時間目以降、重量平均分子量Mwが安定化した。
500mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸31.5g、(B)アジピン酸16.4g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド1.26g、(D)共触媒としてピリジン0.18g、プロピレングリコールモノメチルエーテル60gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:0.67、(A)成分と(B)成分との当量比は1:1.01である。
次いで、この溶液を121℃にて加熱還流を行い1~8時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=5,200、2時間目のMw=10,800、4時間目のMw=15,900、5時間目のMw=16,300、6時間目のMw=16,300、7時間目のMw=16,100、8時間目のMw=16,100であり、還流温度到達後4時間目以降、重量平均分子量Mwが安定化した。
500mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸31.5g、(B)アジピン酸16.4g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド0.84g、(D)共触媒としてピリジン0.26g、プロピレングリコールモノメチルエーテル60gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は0.67:1、(A)成分と(B)成分との当量比は1:1.01である。
次いで、この溶液を121℃にて加熱還流を行い1~8時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=3,000、2時間目のMw=7,400、4時間目のMw=12,500、5時間目のMw=12,900、6時間目のMw=12,800、7時間目のMw=12,800、8時間目のMw=12,800であり、還流温度到達後4時間目以降、重量平均分子量Mwが安定化した。
500mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸31.5g、(B)アジピン酸16.4g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド0.42g、(D)共触媒としてピリジン0.35g、プロピレングリコールモノメチルエーテル60gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は0.25:1、(A)成分と(B)成分との当量比は1:1.01である。
次いで、この溶液を121℃にて加熱還流を行い1~8時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=1,900、2時間目のMw=4,800、4時間目のMw=9,400、5時間目のMw=9,800、6時間目のMw=10,000、7時間目のMw=10,000、8時間目のMw=10,000であり、還流温度到達後4時間目以降、重量平均分子量Mwが安定化した。
200mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸12.6g、(B)アジピン酸6.6g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド0.84g、プロピレングリコールモノメチルエーテル60gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:0、(A)成分と(B)成分との当量比は1:1.01である。
次いで、この溶液を121℃にて加熱還流を行い1~6時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=8,800、2時間目のMw=19,400、4時間目のMw=40,000、5時間目のMw=50,900、6時間目のMw=68,600であり、重量平均分子量Mwは安定化することなく、増大し続けた。
200mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸12.6g、(B)アジピン酸6.6g、(D)共触媒としてピリジン0.18g、プロピレングリコールモノメチルエーテル60gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は0:1、(A)成分と(B)成分との当量比は1:1.01である。
次いで、この溶液を121℃にて加熱還流を行い1~8時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=1,300、2時間目のMw=7,300、4時間目のMw=9,600、5時間目のMw=8,700、6時間目のMw=7,900、7時間目のMw=7,500、8時間目のMw=7,200であり、還流温度到達後4時間目に最大値を示した後、重量平均分子量Mwが低下し続けた。
200mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸12.6g、(B)アジピン酸6.6g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド0.84g、(D)共触媒としてトリフェニルホスフィン0.58g、プロピレングリコールモノメチルエーテル60gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:1、(A)成分と(B)成分との当量比は1:1.01である。
次いで、この溶液を121℃にて加熱還流を行い1~7時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=7,700、2時間目のMw=12,500、4時間目のMw=13,200、5時間目のMw=13,200、6時間目のMw=13,200、7時間目のMw=13,200であり、還流温度到達後4時間目以降、重量平均分子量Mwが安定化した。
200mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸12.6g、(B)アジピン酸6.6g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド0.84g、(D)共触媒としてトリブチルホスフィン0.45g、プロピレングリコールモノメチルエーテル60gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:1、(A)成分と(B)成分との当量比は1:1.01である。
次いで、この溶液を121℃にて加熱還流を行い1~6時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=6,800、2時間目のMw=10,300、4時間目のMw=10,900、5時間目のMw=10,900、6時間目のMw=10,800であり、還流温度到達後4時間目以降、重量平均分子量Mwが安定化した。
200mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸11.0g、(B)3,3-ジチオプロピオン酸8.3g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド0.73g、(D)共触媒としてピリジン0.15g、プロピレングリコールモノメチルエーテル60gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:1、(A)成分と(B)成分との当量比は1:1.01である。
次いで、この溶液を121℃にて加熱還流を行い1~7時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=1,800、2時間目のMw=1,800、4時間目のMw=1,800、5時間目のMw=1,800、6時間目のMw=1,700、7時間目のMw=1,800であり、還流温度到達後1時間目以降、重量平均分子量Mwが安定化した。
200mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸11.0g、(B)3,3-ジチオプロピオン酸8.3g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド0.73g、プロピレングリコールモノメチルエーテル60gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:0、(A)成分と(B)成分との当量比は1:1.01である。
次いで、この溶液を121℃にて加熱還流を行い1~7時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=2,000、2時間目のMw=2,900、4時間目のMw=3,500、5時間目のMw=3,700、6時間目のMw=3,800、7時間目のMw=4,000であり、重量平均分子量Mwは安定化することなく、増大し続けた。
200mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸12.8g、(B)ビスフェノールA 10.4g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド0.85g、(D)共触媒としてピリジン0.05g、プロピレングリコールモノメチルエーテル56gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:0.3、(A)成分と(B)成分との当量比は1:1.005である。
次いで、この溶液を121℃にて加熱還流を行い1~7時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=4,400、2時間目のMw=5,600、5時間目のMw=5,600、6時間目のMw=5,600、7時間目のMw=5,500であり、還流温度到達後2時間目以降、重量平均分子量Mwが安定化した。
200mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸12.8g、(B)ビスフェノールA 10.4g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド0.85g、プロピレングリコールモノメチルエーテル56gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:0、(A)成分と(B)成分との当量比は1:1.005である。
次いで、この溶液を121℃にて加熱還流を行い1~7時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=2,100、2時間目のMw=3,800、4時間目のMw=5,300、5時間目のMw=5,700、6時間目のMw=6,000、7時間目のMw=6,300であり、重量平均分子量Mwは安定化することなく、増大し続けた。
500mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸34.2g、(B)バルビタール23.5g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド2.3g、(D)共触媒としてピリジン0.29g、プロピレングリコールモノメチルエーテル240gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:0.6、(A)成分と(B)成分との当量比は1:1.04である。
次いで、この溶液を121℃にて加熱還流を行い1~6時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=7,600、2時間目のMw=10,400、4時間目のMw=11,300、6時間目のMw=11,400であり、還流温度到達後4時間目以降、重量平均分子量Mwが安定化した。
500mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸34.2g、(B)バルビタール23.5g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド2.3g、プロピレングリコールモノメチルエーテル240gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:0、(A)成分と(B)成分との当量比は1:1.04である。
次いで、この溶液を121℃にて加熱還流を行い1~8時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=5,400、2時間目のMw=8,900、4時間目のMw=12,100、6時間目のMw=14,100、8時間目のMw=15,800であり、重量平均分子量Mwは安定化することなく、増大し続けた。
500mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸34.1g、(B)バルビタール23.4g、および(C)重合触媒としてテトラブチルホスホニウムブロミド2.1g、(D)共触媒としてピリジン0.48g、プロピレングリコールモノメチルエーテル240gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:1、(A)成分と(B)成分との当量比は1:1.04である。
次いで、この溶液を121℃にて加熱還流を行い1~8時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=4,700、2時間目のMw=7,000、4時間目のMw=7,900、6時間目のMw=7,900、8時間目のMw=7,900であり、還流温度到達後4時間目以降、重量平均分子量Mwが安定化した。
500mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸34.0g、(B)バルビタール23.3g、および(C)重合触媒としてテトラブチルホスホニウムブロミド2.1g、(D)共触媒としてN,N-ジメチル-4-アミノピリジン0.74g、プロピレングリコールモノメチルエーテル240gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:1、(A)成分と(B)成分との当量比は1:1.04である。
次いで、この溶液を121℃にて加熱還流を行い1~8時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=5,700、2時間目のMw=5,800、4時間目のMw=5,900、6時間目のMw=5,900、8時間目のMw=5,900であり、還流温度到達後2時間目以降、重量平均分子量Mwが安定化した。
500mL反応フラスコに、(A)モノアリルジグリシジルイソシアヌル酸34.2g、(B)バルビタール23.5g、および(C)重合触媒としてテトラブチルホスホニウムブロミド2.1g、プロピレングリコールモノメチルエーテル240gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:0、(A)成分と(B)成分との当量比は1:1.04である。
次いで、この溶液を121℃にて加熱還流を行い1~8時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=2,900、2時間目のMw=5,600、4時間目のMw=8,300、6時間目のMw=10,300、8時間目のMw=11,900であり、重量平均分子量Mwは安定化することなく、増大し続けた。
200mL反応フラスコに、(A)テレフタル酸ジグリシジルエステル15.3g、(B)アジピン酸7.7g、および重合触媒としてエチルトリフェニルホスホニウムブロミド1.0g、(D)共触媒としてピリジン0.21g、プロピレングリコールモノメチルエーテル56gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:1、(A)成分と(B)成分との当量比は1:1.001である。
次いで、この溶液を105℃にて加熱還流を行い1~6時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=5,500、2時間目のMw=11,100、4時間目のMw=13,000、5時間目のMw=13,000、6時間目のMw=13,000であり、還流温度到達後4時間目以降、重量平均分子量Mwが安定化した。
200mL反応フラスコに、(A)テレフタル酸ジグリシジルエステル15.3g、(B)アジピン酸7.7g、および(C)重合触媒としてエチルトリフェニルホスホニウムブロミド1.0g、プロピレングリコールモノメチルエーテル56gを仕込み、原料溶液を調製した。(C)成分と(D)成分とのモル比は1:0、(A)成分と(B)成分との当量比は1:1.001である。
次いで、この溶液を105℃にて加熱還流を行い1~6時間反応させ、ポリマーを合成した。生成するポリマーのGPC分析を行ったところ、還流温度到達後1時間目のMw=5,100、2時間目のMw=14,700、4時間目のMw=19,900、5時間目のMw=20,400、6時間目のMw=20,500であり、重量平均分子量Mwは安定化することなく、増大し続けた。
Claims (17)
- (A)分子内にエポキシ基を2つ以上有するエポキシ化合物と、(B)分子内にエポキシ基と反応する官能基を2つ以上有する反応性化合物とを、(C)重合触媒および(D)共触媒の存在下で反応させることを特徴とするポリマーの製造方法。
- (C)成分が、4級の第15族元素構造を1つ以上有するオニウム塩である請求項1記載のポリマーの製造方法。
- (C)成分の第15族元素が、窒素またはリンである請求項2記載のポリマーの製造方法。
- (C)成分の第15族元素構造における置換基が、炭素数1~20のアルキル基、炭素数6~20のアリール基および炭素数7~20のアラルキル基から選ばれる少なくとも1種である請求項2または3記載のポリマーの製造方法。
- オニウム塩におけるカウンターアニオンが、ハロゲン化物イオン、硝酸イオン、硫酸イオン、酢酸イオン、ギ酸イオン、水酸化物イオン、および炭素数1~20のアルキル基または炭素数6~20のアリール基を有するスルホン酸イオンから選ばれる請求項2~4のいずれか1項記載のポリマーの製造方法。
- (D)成分が、1~3級の第15族元素構造を有する化合物、または芳香環に第15族元素を含むヘテロアリール化合物である請求項1~5のいずれか1項記載のポリマーの製造方法。
- (D)成分の第15族元素が、窒素またはリンである請求項6記載のポリマーの製造方法。
- (D)成分が、3級の第15族元素構造を有する化合物、または芳香環に第15族元素を含むヘテロアリール化合物である請求項6または7記載のポリマーの製造方法。
- (D)成分の第15族元素構造における置換基が、炭素数1~20のアルキル基、炭素数6~20のアリール基および炭素数7~20のアラルキル基から選ばれる少なくとも1種である請求項6~8のいずれか1項記載のポリマーの製造方法。
- (A)成分が、ジエポキシ化合物、トリエポキシ化合物、テトラエポキシ化合物およびエポキシ基を有するポリマーから選ばれる1種または2種以上である請求項1~9のいずれか1項記載のポリマーの製造方法。
- (B)成分の官能基が、水酸基、ホルミル基、カルボキシ基、アミノ基、イミノ基、アゾ基、アジ基、チオール基、スルホ基、アミド基、イミド基、チオカルボキシ基、ジチオカルボキシ基、リン酸基、亜リン酸基、ホスホン酸基、亜ホスホン酸基、ホスフィン酸基、亜ホスフィン酸基、ホスフィン基、酸無水物または酸クロリドである請求項1~10のいずれか1項記載のポリマーの製造方法。
- (A)成分が有するエポキシ基と(B)成分が有する官能基との当量比が、(A):(B)=0.1:1.0~1.0:0.1である請求項1~11のいずれか1項記載のポリマーの製造方法。
- (C)成分と(D)成分の配合比(モル比)が、0.1:1.0~1.0:0.1であり、かつ(C)成分と(D)成分の合計量が(A)成分1モルに対して、0.0001~0.5モルである請求項1~12のいずれか1項記載のポリマーの製造方法。
- 更に、有機溶媒として、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン、シクロヘプタノン、4-メチル-2-ペンタノール、2-ヒドロキシイソ酪酸メチル、2-ヒドロキシイソ酪酸エチル、エトキシ酢酸エチル、酢酸2-ヒドロキシエチル、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、2-ヘプタノン、メトキシシクロペンタン、アニソール、γ-ブチロラクトン、N-メチルピロリドン、N,N-ジメチルホルムアミド、およびN,N-ジメチルアセトアミドから選ばれる1種以上を用いる請求項1~13のいずれか1項記載のポリマーの製造方法。
- 有機溶媒の使用量が、(A)成分の質量に対して、0.1~100質量倍である請求項14記載のポリマーの製造方法。
- 反応温度が、25~200℃である請求項1~15のいずれか1項記載のポリマーの製造方法。
- 請求項1~16のいずれか1項記載の製造方法により得られたポリマーと、有機溶媒とを混合するレジスト下層膜形成組成物の製造方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020572256A JP7476807B2 (ja) | 2019-02-14 | 2020-02-12 | ポリマーの製造方法 |
US17/430,833 US20220153920A1 (en) | 2019-02-14 | 2020-02-12 | Method for producing polymer |
KR1020217028510A KR20210127715A (ko) | 2019-02-14 | 2020-02-12 | 폴리머의 제조 방법 |
CN202080014431.7A CN113454138A (zh) | 2019-02-14 | 2020-02-12 | 聚合物的制造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019-024362 | 2019-02-14 | ||
JP2019024362 | 2019-02-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020166580A1 true WO2020166580A1 (ja) | 2020-08-20 |
Family
ID=72044927
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2020/005232 WO2020166580A1 (ja) | 2019-02-14 | 2020-02-12 | ポリマーの製造方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20220153920A1 (ja) |
JP (1) | JP7476807B2 (ja) |
KR (1) | KR20210127715A (ja) |
CN (1) | CN113454138A (ja) |
WO (1) | WO2020166580A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023181960A1 (ja) * | 2022-03-24 | 2023-09-28 | 日産化学株式会社 | 保護膜形成用組成物 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60123527A (ja) * | 1983-12-07 | 1985-07-02 | Toto Kasei Kk | エポキシ樹脂の製造法 |
JPS6433117A (en) * | 1987-07-14 | 1989-02-03 | Bayer Ag | Manufacture of phenacrylate resin |
JPH0616838A (ja) * | 1992-07-02 | 1994-01-25 | Nippon Oil Co Ltd | プリプレグ用樹脂組成物および複合材 |
JP2000017150A (ja) * | 1998-06-29 | 2000-01-18 | Shin Etsu Chem Co Ltd | 半導体封止用エポキシ樹脂組成物及び半導体装置 |
JP2006306923A (ja) * | 2005-04-26 | 2006-11-09 | Dainippon Ink & Chem Inc | 水性エポキシ樹脂組成物 |
JP2009253213A (ja) * | 2008-04-10 | 2009-10-29 | Hitachi Kasei Polymer Co Ltd | フレキシブルプリント配線板用接着剤組成物およびそれを用いたフレキシブルプリント配線板用接着フィルム、及びフレキシブルプリント配線板用カバーレイフィルム |
JP2013234313A (ja) * | 2011-11-02 | 2013-11-21 | Hitachi Chemical Co Ltd | エポキシ樹脂組成物、その半硬化体および硬化体、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板、プリント配線板、およびパワー半導体装置 |
JP2016079273A (ja) * | 2014-10-15 | 2016-05-16 | 三菱化学株式会社 | エポキシ樹脂及びその製造方法、エポキシ樹脂含有組成物並びに硬化物 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011093474A1 (ja) | 2010-01-29 | 2011-08-04 | 日本化薬株式会社 | フェノール化合物、エポキシ樹脂、エポキシ樹脂組成物、プリプレグおよびそれらの硬化物 |
JP6008598B2 (ja) | 2012-06-11 | 2016-10-19 | キヤノン株式会社 | 吐出口形成部材及び液体吐出ヘッドの製造方法 |
US10113083B2 (en) * | 2013-08-08 | 2018-10-30 | Nissan Chemical Industries, Ltd. | Resist underlayer film-forming composition containing polymer which contains nitrogen-containing ring compound |
KR102273332B1 (ko) | 2015-03-31 | 2021-07-06 | 닛산 가가쿠 가부시키가이샤 | 양이온 중합성 레지스트 하층막 형성 조성물 |
-
2020
- 2020-02-12 WO PCT/JP2020/005232 patent/WO2020166580A1/ja active Application Filing
- 2020-02-12 KR KR1020217028510A patent/KR20210127715A/ko unknown
- 2020-02-12 US US17/430,833 patent/US20220153920A1/en active Pending
- 2020-02-12 CN CN202080014431.7A patent/CN113454138A/zh active Pending
- 2020-02-12 JP JP2020572256A patent/JP7476807B2/ja active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60123527A (ja) * | 1983-12-07 | 1985-07-02 | Toto Kasei Kk | エポキシ樹脂の製造法 |
JPS6433117A (en) * | 1987-07-14 | 1989-02-03 | Bayer Ag | Manufacture of phenacrylate resin |
JPH0616838A (ja) * | 1992-07-02 | 1994-01-25 | Nippon Oil Co Ltd | プリプレグ用樹脂組成物および複合材 |
JP2000017150A (ja) * | 1998-06-29 | 2000-01-18 | Shin Etsu Chem Co Ltd | 半導体封止用エポキシ樹脂組成物及び半導体装置 |
JP2006306923A (ja) * | 2005-04-26 | 2006-11-09 | Dainippon Ink & Chem Inc | 水性エポキシ樹脂組成物 |
JP2009253213A (ja) * | 2008-04-10 | 2009-10-29 | Hitachi Kasei Polymer Co Ltd | フレキシブルプリント配線板用接着剤組成物およびそれを用いたフレキシブルプリント配線板用接着フィルム、及びフレキシブルプリント配線板用カバーレイフィルム |
JP2013234313A (ja) * | 2011-11-02 | 2013-11-21 | Hitachi Chemical Co Ltd | エポキシ樹脂組成物、その半硬化体および硬化体、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板、プリント配線板、およびパワー半導体装置 |
JP2016079273A (ja) * | 2014-10-15 | 2016-05-16 | 三菱化学株式会社 | エポキシ樹脂及びその製造方法、エポキシ樹脂含有組成物並びに硬化物 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023181960A1 (ja) * | 2022-03-24 | 2023-09-28 | 日産化学株式会社 | 保護膜形成用組成物 |
Also Published As
Publication number | Publication date |
---|---|
CN113454138A (zh) | 2021-09-28 |
JPWO2020166580A1 (ja) | 2021-12-09 |
JP7476807B2 (ja) | 2024-05-01 |
KR20210127715A (ko) | 2021-10-22 |
US20220153920A1 (en) | 2022-05-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11392037B2 (en) | Resist underlayer film forming composition containing silicone having cyclic amino group | |
CN105027005B (zh) | 含有具有羟基的芳基磺酸盐的抗蚀剂下层膜形成用组合物 | |
EP2881794A1 (en) | Composition for forming underlayer film for silicon-containing euv resist and containing onium sulfonate | |
JP7476807B2 (ja) | ポリマーの製造方法 | |
JP7101353B2 (ja) | Iii族窒化物系化合物層を有する半導体基板の製造方法 | |
JP7355012B2 (ja) | グリシジルエステル化合物との反応生成物を含むレジスト下層膜形成組成物 | |
WO2021251482A1 (ja) | ジオール構造を含むレジスト下層膜形成用組成物 | |
WO2022196606A1 (ja) | 酸触媒担持型ポリマーを含むレジスト下層膜形成組成物 | |
KR20220161272A (ko) | 가교제의 변성이 억제된 레지스트 하층막 형성 조성물 | |
KR20210135252A (ko) | 디올구조를 말단에 갖는 중합생성물을 포함하는 약액내성 보호막형성 조성물 | |
JP2021105703A (ja) | イオン液体を含むレジスト下層膜形成組成物 | |
US11965059B2 (en) | Chemical-resistant protective film forming composition containing hydroxyaryl-terminated polymer | |
TWI846857B (zh) | 包含羥芳基末端之聚合物之耐藥液性保護膜形成組成物 | |
JPWO2020166635A1 (ja) | ラジカルトラップ剤を含むレジスト下層膜形成組成物 | |
WO2024122488A1 (ja) | 保護膜形成用組成物 | |
WO2021070919A1 (ja) | 複素環化合物を含むレジスト下層膜形成組成物 | |
WO2023145703A1 (ja) | 末端封止ポリマーを含むレジスト下層膜形成組成物 | |
TW202036163A (zh) | 含有離子液體之阻劑下層膜形成組成物 | |
US20230152700A1 (en) | Film-forming composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20754884 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2020572256 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20217028510 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 20754884 Country of ref document: EP Kind code of ref document: A1 |