Method for producing polymer

Abstract

Provided is a method for producing a polymer, characterized in that (A) an epoxy compound having two or more epoxy groups in its molecule and (B) a reactive compound having two or more functional groups reactive with epoxy groups in its molecule are reacted in the presence of (C) a polymerization catalyst and (D) a co-catalyst.

Description

Technical Field

[0001] The present invention relates to a method for producing a polymer by reacting an epoxy compound having two or more epoxy groups in its molecule with a reactive compound having two or more functional groups reactive with epoxy groups in its molecule. Background Art

[0002] Generally, the molecular weight of polymer has a great influence on physical property, so the control of molecular weight can be said to be a common topic in the manufacture of polymer. In the manufacture of polymers reacting at least one diepoxide with a compound (reactive compound) with more than two reactive functional groups, as a general method, the method described in known non-patent literature 1. So far, in order to control the molecular weight of polymer to the range of target, the following technique has been adopted: by strictly managing the reaction time, cooling at the stage of reaching the molecular weight of target, thereby forcibly stopping the polymerization reaction. However, this technique requires time for cooling when the scale of manufacturing is expanded, and it is difficult to reproducibly control the molecular weight of target well. In addition, for example, when the scale is too large, a fault is generated in the cooling device and cooling is delayed, because the molecular weight is excessively increased, there is a risk of high viscosity of the reaction solution and damage to the stirring paddle of the reactor.

[0003] On the other hand, as a method for suppressing the increase in molecular weight, there is generally a method of significantly shifting the equivalent ratio of diepoxy monomer to reactive monomer from 1:1 (for example, 1:1.2, etc.). Although this method can suppress a significant increase in molecular weight, it cannot stabilize the target molecular weight. In addition, since the excessively charged monomer remains in the system, a purification step is required to remove the residual monomer, which is not preferred from the perspective of productivity.

[0004] Prior art literature

[0005] Non-patent literature

[0006] Non-patent document 1: Polymer Papers (Polymer Papers), Vol. 53, No. 9, pp. 522-529 (1996) Summary of the Invention

[0007] Problems to be solved by the invention

[0008] The present invention has been completed in view of the above-mentioned actual situation, and its object is to provide a method for producing a polymer, wherein, in a reaction system of an epoxy compound having two or more epoxy groups in its molecule and a reactive compound having two or more functional groups reactive with the epoxy groups in its molecule, the molecular weight does not continue to increase, and the molecular weight can be controlled with high precision to a target molecular weight and stabilized at that molecular weight.

[0009] Means for solving problems

[0010] The present inventors have conducted repeated and in-depth studies to achieve the above-mentioned objectives, and as a result, have discovered the following method: when an epoxy compound having two or more epoxy groups in its molecule is reacted with a reactive compound having two or more functional groups reactive with the epoxy groups in its molecule, by adding two or more catalysts including a polymerization catalyst and a catalyst different from the polymerization catalyst (co-catalyst), the molecular weight in the reaction system does not continue to increase, the target molecular weight can be controlled with high precision, and the target molecular weight can be stabilized; thus, the present invention has been completed.

[0011] That is, the present invention provides the following method for producing a polymer.

[0012] 1. A method for producing a polymer, characterized in that (A) an epoxy compound having two or more epoxy groups in its molecule and (B) a reactive compound having two or more functional groups reactive with epoxy groups in its molecule are reacted in the presence of (C) a polymerization catalyst and (D) a co-catalyst.

[0013] 2. The method for producing a polymer according to 1, wherein the component (C) is an onium salt having a quaternary structure of one or more Group 15 elements.

[0014] 3. The method for producing a polymer according to 2, wherein the Group 15 element of the component (C) is nitrogen or phosphorus.

[0015] 4. The method for producing a polymer according to 2 or 3, wherein the substituent in the Group 15 element structure of 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.

[0016] 5. The method for producing a polymer according to any one of 2 to 4, wherein the counter anion in the onium salt is selected from halide ion, nitrate ion, sulfate ion, acetate ion, formate ion, hydroxide ion, and sulfonate ion having an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

[0017] 6. The method for producing a polymer according to any one of 1 to 5, wherein the component (D) is a compound having a primary or tertiary Group 15 element structure, or a heteroaryl compound containing a Group 15 element in an aromatic ring.

[0018] 7. The method for producing a polymer according to 6, wherein the Group 15 element of the component (D) is nitrogen or phosphorus.

[0019] 8. The method for producing a polymer according to 6 or 7, wherein the component (D) is a compound having a tertiary Group 15 element structure, or a heteroaryl compound containing a Group 15 element in an aromatic ring.

[0020] 9. The method for producing a polymer according to any one of 6 to 8, wherein the substituent in the Group 15 element structure of 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.

[0021] 10. The method for producing a polymer according to any one of 1 to 9, wherein the component (A) is one or more selected from diepoxy compounds, triepoxy compounds, tetraepoxy compounds, and polymers having an epoxy group.

[0022] 11. The method for producing a polymer according to any one of 1 to 10, wherein the functional group of component (B) is a hydroxyl group, a formyl group, a carboxyl group, an amino group, an imino group, an azo group, an azido group, a thiol group, a sulfo group, an amide group, an imide group, a thiocarboxyl group, a dithiocarboxyl group, a phosphoric acid group, a phosphite group, a phosphonic acid group, a phosphite group, a subhoshonic acid group, a phosphinic acid group, a trivalent phosphonic acid group, a phosphine group, an acid anhydride, or an acid chloride.

[0023] 12. The method for producing a polymer according to any one of 1 to 11, wherein the equivalent ratio of the epoxy group of the component (A) to the functional group of the component (B) is (A):(B)=0.1:1.0 to 1.0:0.1.

[0024] 13. The method for producing a polymer according to any one of 1 to 12, wherein the mixing ratio (molar ratio) of the component (C) to 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 0.0001 to 0.5 mol per 1 mol of the component (A).

[0025] 14. The method for producing a polymer according to any one of 1 to 13, wherein the organic solvent is selected from 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-pentanone, One or more of alcohol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0026] 15. The method for producing a polymer according to 14, wherein the amount of the organic solvent used is 0.1 to 100 times by mass relative to the mass of the component (A).

[0027] 16. The method for producing a polymer according to any one of 1 to 15, wherein the reaction temperature is 25 to 200°C.

[0028] 17. A method for producing a resist underlayer film-forming composition, comprising mixing a polymer obtained by the production method according to any one of 1 to 16 and an organic solvent.

[0029] Effects of the Invention

[0030] According to the method for producing a polymer according to the present invention, 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. DETAILED DESCRIPTION

[0031] The method for producing a polymer according to the present invention is characterized in that (A) an epoxy compound having two or more epoxy groups in its molecule and (B) a reactive compound having two or more functional groups reactive with epoxy groups in its molecule are reacted in the presence of (C) a polymerization catalyst and (D) a co-catalyst.

[0032] As for (A) the epoxy compound having two or more epoxy groups in the molecule, in the present invention, in view of the high-precision control of the weight-average molecular weight of the obtained polymer, diepoxy compounds, triepoxy compounds, tetraepoxy compounds and polymers having epoxy groups are preferred, diepoxy compounds and triepoxy compounds are more preferred, and diepoxy compounds are still more preferred.

[0033] In the present invention, the weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0034] (A) As a compound preferable as a diepoxy compound, a triepoxy compound, and a tetraepoxy compound of a component, the compound represented by following formula (A1) - (A9) is mentioned, for example.

[0035] [Chemistry 1]

[0036]

[0037] In formulas (A1) to (A3), E 1 It is a group represented by the following formula (a-1).

[0038] [Chemistry 2]

[0039]

[0040] (In the formula, m1 is an integer from 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is 1 or 2. When m3 is 1, m1 and m2 cannot be 0 at the same time.)

[0041] In formulas (A1) and (A2), R 1a and R 2a Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted by at least one monovalent group selected from an alkyl group having 1 to 6 carbon atoms, 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.

[0042] In formula (A3), R 3a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, a phenyl group, or the above-mentioned E 1 The phenyl group may be substituted with at least one monovalent group selected from an alkyl group having 1 to 10 carbon atoms, 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.

[0043] Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methylcyclobutyl, 2-methyl Cyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl n-Butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl cyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, and 2-ethyl-3-methylcyclopropyl, etc.

[0044] Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, and 2-methyl-3-butenyl. , 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3-dimethyl- methyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-tert-butylvinyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-2-cyclopentenyl , 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl, etc. ,

[0045] Examples of the alkynyl group having 2 to 10 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 4-methyl-1-pentynyl, and 3-methyl-1-pentynyl.

[0046] The phrase "interrupted by an oxygen atom or a sulfur atom" means, for example, that a carbon atom in the middle of a saturated carbon chain of the alkyl, alkenyl, and alkynyl groups is replaced by an oxygen atom or a sulfur atom. For example, in an alkyl, alkenyl, or alkynyl group, if any carbon atom is replaced by an oxygen atom, the group contains an ether bond, and if any carbon atom is replaced by a sulfur atom, the group contains a thioether bond.

[0047] Examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms.

[0048] Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-pentoxy, oxy, 4-methyl-n-pentoxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy, etc.

[0049] Examples of the alkylthio group having 1 to 6 carbon atoms include ethylthio, butylthio, and hexylthio.

[0050] In formulas (A4) to (A9), R 4a Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms; -W- represents a single bond, -CH2-, -C(CH3)2-, -C(CF3)2-, -CO-, -O-, -S-, or -SO2-. 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.

[0051] In formulas (A4) to (A9), E 2 It is a group represented by the following formula (a-2).

[0052] [Chemistry 3]

[0053]

[0054] (Wherein, m5 is an integer from 0 to 4, m6 is 0 or 1, m7 is 0 or 1, and m8 is 1 or 2.)

[0055] Examples of the alkyl group having 1 to 10 carbon atoms and the alkenyl group having 2 to 10 carbon atoms include the same groups as those mentioned above.

[0056] In the present invention, among these epoxy compounds, epoxy compounds represented by formulae (A3) and (A4) are preferred from the viewpoint of accurately controlling the molecular weight of the obtained polymer. In particular, epoxy compounds of the following forms are more preferably used.

[0057] [Chemistry 4]

[0058]

[0059] Where, E 1 and E 2 Same as above, R 3a’ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted by at least one monovalent group selected from an alkyl group having 1 to 6 carbon atoms, 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.

[0060] Specific examples of the epoxy compounds represented by the above formulae (A1) to (A9) include the following compounds, but are not limited thereto.

[0061] [Chemistry 5]

[0062]

[0063] [Chemistry 6]

[0064]

[0065] [Chemistry 7]

[0066]

[0067] [Chemistry 8]

[0068]

[0069] [Chemistry 9]

[0070]

[0071] [Chemistry 10]

[0072]

[0073] [Chemistry 11]

[0074]

[0075] [Chemistry 12]

[0076]

[0077] [Chemistry 13]

[0078]

[0079] [Chemistry 14]

[0080]

[0081] [Chemistry 15]

[0082]

[0083] Examples of the polymer having an epoxy group include polymers having repeating units represented by the following formulae (A10-1) to (A10-12).

[0084] [Chemistry 16]

[0085]

[0086] Moreover, in this invention, as a specific example of (A) component, the epoxy compound represented by following formula (A11-1) - (A11-2) can also be mentioned.

[0087] [Chemistry 17]

[0088]

[0089] In formula (A11-1), f, g, h, and i are each 0 or 1, and f+g+h+i=1.

[0090] As the reactive compound (B) having two or more functional groups reactive with epoxy groups in its molecule, if the weight average molecular weight of the obtained polymer is to be controlled with high precision, a compound having two or more functional groups reactive with epoxy groups in its molecule is preferred, and a compound having 2 to 3 functional groups reactive with epoxy groups is more preferred.

[0091] Examples of the functional group include a hydroxyl group, a formyl group, a carboxyl group, an amino group, an imino group, an azo group, an azido group, a thiol group, a sulfo group, an amide group, an imide group, a thiocarboxyl group, a dithiocarboxyl group, a phosphoric acid group, a phosphite group, a phosphonic acid group, a phosphinate group, a trivalent phosphonic acid group, a phosphine group, an acid anhydride, and an acid chloride. In the present invention, a hydroxyl group, a carboxyl group, an amino group, an imide group, and an amide group are preferred.

[0092] Specific examples of the component (B) include the following compounds, but are not limited to these.

[0093] [Chemistry 18]

[0094]

[0095] [Chemistry 19]

[0096]

[0097] [Chemistry 20]

[0098]

[0099] [Chemistry 21]

[0100]

[0101] [Chemistry 22]

[0102]

[0103] The amount of component (B) is determined by the equivalent ratio of the epoxy groups in component (A) to the functional groups in component (B). In the present invention, the equivalent ratio is preferably (A):(B) = 0.1:1.0 to 1.0:0.1, and more preferably (A):(B) = 0.5:1.0 to 1.0:0.5, in order to accurately control the weight-average molecular weight of the resulting polymer.

[0104] The polymerization catalyst (C) is a component incorporated as a catalyst for the reaction between the components (A) and (B). In the present invention, by using the component (C) in combination with the co-catalyst (D) described later, the molecular weight of the polymer in the reaction system does not continue to increase, but can be controlled to an appropriate molecular weight and stabilized.

[0105] In the present invention, the component (C) is preferably an onium salt having one or more quaternary Group 15 element structures in order to accurately control the weight average molecular weight of the obtained polymer.

[0106] The number of the quaternary Group 15 element structure is preferably 1 or 2, more preferably 1.

[0107] Examples of Group 15 elements include nitrogen, phosphorus, arsenic, antimony, and bismuth, with nitrogen and phosphorus being preferred.

[0108] Examples of the substituent in the structure of the Group 15 element 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.

[0109] Examples of the alkyl group having 1 to 20 carbon atoms include, in addition to the groups exemplified in the alkyl group having 1 to 10 carbon atoms, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-eicosyl. In the present invention, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 8 carbon atoms is more preferred.

[0110] Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, and 9-phenanthrenyl. In the present invention, phenyl is preferred.

[0111] Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, and α-naphthylmethyl. In the present invention, benzyl is preferred.

[0112] Examples of the counter anion in the onium salt include halide ions, nitrate ions, sulfate ions, acetate ions, formate ions, hydroxide ions, and sulfonate ions having an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Examples of halide ions include fluoride ions, chloride ions, bromide ions, and iodide ions. In the present invention, halide ions are preferred.

[0113] In the above-mentioned sulfonic acid ions, the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms are the same as those described above.

[0114] Specific examples of the sulfonate ion include methanesulfonic acid, p-toluenesulfonic acid, and benzenesulfonic acid.

[0115] As a preferred embodiment of the component (C), an onium salt represented by the following formula (C1) can be mentioned, for example.

[0116] [Chemistry 23]

[0117]

[0118] (wherein, G represents a Group 15 element, R 1c Each 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, and X c - represents a halide ion, a nitrate ion, a sulfate ion, an acetate ion, a formate ion, a hydroxide ion, or a sulfonate ion having an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

[0119] 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 those described above.

[0120] In the present invention, as the component (C), quaternary ammonium salts and quaternary phosphonium salts are preferred, and quaternary phosphonium salts are more preferred.

[0121] Examples of the quaternary ammonium salt include tetramethylammonium fluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium nitrate, tetramethylammonium sulfate, tetramethylammonium acetate, tetraethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltrimethylammonium chloride, phenyltrimethylammonium chloride, benzyltriethylammonium chloride, methyltributylammonium chloride, benzyltributylammonium chloride, and methyltrioctylammonium chloride.

[0122] Examples of the quaternary phosphonium salt include methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, hexyltriphenylphosphonium bromide, tetrabutylphosphonium bromide, benzyltriphenylphosphonium bromide, methyltriphenylphosphonium chloride, ethyltriphenylphosphonium chloride, butyltriphenylphosphonium chloride, hexyltriphenylphosphonium chloride, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride, methyltriphenylphosphonium iodide, ethyltriphenylphosphonium iodide, butyltriphenylphosphonium iodide, hexyltriphenylphosphonium iodide, tetrabutylphosphonium iodide, and benzyltriphenylphosphonium iodide. In the present invention, ethyltriphenylphosphonium bromide and tetrabutylphosphonium bromide can be preferably used.

[0123] The amount of component (C) to be added is not particularly limited as long as it is an amount that allows the reaction to proceed. However, in order to appropriately control the polymerization reaction of the polymer, the amount is preferably 0.0001 to 0.5 mol, more preferably 0.0005 to 0.1 mol, and even more preferably 0.001 to 0.05 mol relative to 1 mol of component (A).

[0124] The co-catalyst (D) is used in combination with the component (C). By using the co-catalyst with the component (C), the molecular weight of the polymer in the reaction system does not continue to increase, but can be controlled to an appropriate molecular weight and stabilized.

[0125] In the present invention, as for the above-mentioned component (D), if it is taken into account to control the weight average molecular weight of the obtained polymer with high precision, compounds having a primary to tertiary Group 15 element structure and heteroaryl compounds containing a Group 15 element in the aromatic ring are preferred, and compounds having a tertiary Group 15 element structure and heteroaryl compounds containing a Group 15 element in the aromatic ring are more preferred.

[0126] Examples of the Group 15 element include nitrogen, phosphorus, arsenic, antimony, and bismuth, with nitrogen and phosphorus being preferred.

[0127] Examples of the substituent in the structure of the Group 15 element 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.

[0128] Examples of the alkyl group having 1 to 20 carbon atoms include the same groups as those exemplified above. In the present invention, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred.

[0129] Examples of the aryl group having 6 to 20 carbon atoms include the same groups as those exemplified above. In the present invention, a phenyl group is preferred.

[0130] Examples of the aralkyl group having 7 to 20 carbon atoms include the same groups as those exemplified above. In the present invention, a benzyl group is preferred.

[0131] Preferred specific examples of the component (D) include compounds represented by the following formula (D1) or (D2).

[0132] [Chemistry 24]

[0133]

[0134] (Where G 1d Represents Group 15 elements, R 1d Each 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, and R 2drepresents a hydrogen atom, or a dialkylamino group in which each alkyl group is independently an alkyl group having 1 to 12 carbon atoms.

[0135] In (D1), examples of the alkyl group having 1 to 20 carbon atoms include the same groups as exemplified above. In the present invention, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred.

[0136] Examples of the aryl group having 6 to 20 carbon atoms include the same groups as exemplified above. In the present invention, a phenyl group is preferred.

[0137] Examples of the aralkyl group having 7 to 20 carbon atoms include the same groups as those exemplified above. In the present invention, a benzyl group is preferred.

[0138] In formula (D2), examples of the alkyl group having 1 to 12 carbon atoms include the same groups as those mentioned above for the alkyl group having 1 to 20 carbon atoms. In the present invention, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred.

[0139] Preferred embodiments of the compound represented by formula (D2) include those represented by the following formula (D2′).

[0140] [Chemistry 25]

[0141]

[0142] (Where G 1d and R 2d Means the same as above.)

[0143] Preferred specific examples of the component (D) include pyridine, N,N-dimethyl-4-aminopyridine, tributylphosphine, and triphenylphosphine.

[0144] The amount of component (D) to be added is not particularly limited as long as it is an amount that allows the reaction to proceed. However, in order to appropriately control the polymerization reaction of the polymer, the amount is preferably 0.0001 to 0.5 mol, more preferably 0.0005 to 0.2 mol, and even more preferably 0.001 to 0.1 mol relative to 1 mol of component (A).

[0145] The total amount of the component (C) and the component (D) is preferably 0.0002 to 0.5 mol, more preferably 0.001 to 0.2 mol, relative to 1 mol of the component (A).

[0146] The mixing ratio (molar ratio) of (C) polymerization catalyst and (D) cocatalyst is preferably 0.1:1.0 to 1.0:0.1, and more preferably 0.3:1.0 to 1.0:0.3, in order to precisely control the weight-average molecular weight of the obtained polymer.

[0147] In the production method of the present invention, a known organic solvent can be used.

[0148] As the organic solvent, any solvent that can dissolve the above-mentioned compound or its reaction product and does not affect the polymerization reaction can be used without particular limitation. Specific examples thereof include 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, and methyl 2-hydroxyisobutyrate. , ethyl 2-hydroxyisobutyrate, ethyl ethoxylate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, gamma-butyrolactone, N-Methyl pyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide. In the present invention, among these solvents, preferred propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate and cyclohexanone, more preferably propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. These solvents can be used alone or in combination of two or more.

[0149] The amount of the organic solvent used is preferably 0.1 to 100 times, more preferably 0.5 to 20 times the mass of the component (A) in order to accurately control the weight average molecular weight of the obtained polymer.

[0150] The reaction temperature (internal temperature) is preferably 25 to 200° C., more preferably 50 to 150° C., and even more preferably 80 to 150° C., in order to efficiently proceed the reaction and accurately control the weight-average molecular weight of the resulting polymer. Reflux may be performed during heating.

[0151] The reaction time cannot be generally specified because it depends on the reaction temperature and the reactivity of the starting materials, but is usually about 1 to 30 hours, and when the reaction temperature is 100 to 130°C, about 1 to 15 hours.

[0152] The weight average molecular weight Mw of the polymer obtained by the method for producing the polymer of the present invention is 500 to 100,000. The molecular weight increases to a certain extent after a certain period of time after the start of the reaction and then stabilizes near the target molecular weight (within about ±300).

[0153] In the present invention, the weight average molecular weight Mw is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0154] Thus, by adopting the method for producing a polymer according to the present invention, the weight average molecular weight of the obtained polymer can be controlled with high precision, and a polymer having a target weight average molecular weight can be produced with good reproducibility.

[0155] In addition, the polymer obtained by the production method of the present invention can be applied to, for example, antireflection film-forming compositions for lithography, resist underlayer film-forming compositions, resist upperlayer film-forming compositions, photocurable resin compositions, thermosetting resin compositions, planarization film-forming compositions, adhesive compositions, and other compositions.

[0156] For example, when the obtained polymer is used in a resist underlayer film-forming composition, the polymer solution after the reaction may be appropriately mixed with components such as a crosslinking agent and a crosslinking catalyst.

[0157] Example

[0158] The present invention is described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The abbreviations and structures of the measuring devices and raw materials used in the Examples are as follows.

[0159] [Determination of Weight Average Molecular Weight Mw and Polydispersity Mw / Mn]

[0160] The weight average molecular weight Mw and polydispersity Mw / Mn of the polymer were calculated from each peak of a chromatogram obtained by measurement using gel permeation chromatography (GPC) based on a calibration curve. The measurement conditions are as follows.

[0161] <Measurement conditions>

[0162] Equipment: HLC-8320GPC (manufactured by Tosoh Corporation)

[0163] Column: Shodex [registered trademark] (Showa Denko K.K.)

[0164] Eluent: 10 mM lithium bromide / DMF

[0165] Flow rate: 0.6mL / min

[0166] Column temperature: 40°C

[0167] Detector: RI

[0168] Standard sample: polystyrene

[0169] (A) Epoxy compounds

[0170] (a1) Monoallyl diglycidyl isocyanuric acid: molecular weight 269.26

[0171] (a2) diglycidyl terephthalate: molecular weight 278.26

[0172] [Chemistry 26]

[0173]

[0174] (B) Reactive compounds

[0175] (b1) Adipic acid: molecular weight 79.10

[0176] (b2) 3,3-dithiopropionic acid: molecular weight 210.26

[0177] (b3) Barbiturate: molecular weight 184.20

[0178] (b4) Bisphenol A: molecular weight 228.29

[0179] [Chemistry 27]

[0180]

[0181] (C) Polymerization catalyst

[0182] (c1) Ethyltriphenylphosphonium bromide: molecular weight 371.26

[0183] (c2) Tetrabutylphosphonium bromide: molecular weight 339.34

[0184] [Chemistry 28]

[0185]

[0186] (D) Co-catalyst

[0187] (d1) Pyridine: molecular weight 79.10

[0188] (d2) N,N-dimethyl-4-aminopyridine: molecular weight 122.17

[0189] (d3) Tributylphosphine: Bu3P, molecular weight 202.32

[0190] (d4) Triphenylphosphine: Ph3P, molecular weight 262.29

[0191] [Chemistry 29]

[0192]

[0193] [Example 1]

[0194] A raw material solution was prepared by placing (A) 12.6 g of monoallyl diglycidyl isocyanuric acid, (B) 6.6 g of adipic acid, (C) 0.84 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) 0.18 g of pyridine as a co-catalyst, and 60 g of propylene glycol monomethyl ether into a 200 mL reaction flask. The molar ratio of component (C) to component (D) was 1:1, and the equivalent ratio of component (A) to component (B) was 1:1.01.

[0195] Next, the solution was heated under reflux at 121°C and reacted for 1 to 6 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 6400 one hour after reaching reflux temperature, Mw = 10100 two hours after reaching reflux temperature, Mw = 10500 four hours after reaching reflux temperature, Mw = 10400 five hours after reaching reflux temperature, and Mw = 10400 six hours after reaching reflux temperature. The weight-average molecular weight (Mw) stabilized after four hours after reaching reflux temperature.

[0196] [Example 2]

[0197] A raw material solution was prepared by placing (A) 12.6 g of monoallyl diglycidyl isocyanuric acid, (B) 6.6 g of adipic acid, (C) 0.84 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) 0.26 g of pyridine as a co-catalyst, and 60 g of propylene glycol monomethyl ether into a 200 mL reaction flask. The molar ratio of component (C) to component (D) was 1:1.5, and the equivalent ratio of component (A) to component (B) was 1:1.01.

[0198] Next, the solution was heated under reflux at 121°C and reacted for 1 to 7 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 6500 one hour after reaching reflux temperature, Mw = 8100 at two hours, Mw = 8100 at four hours, Mw = 8000 at five hours, Mw = 7900 at six hours, and Mw = 7800 at seven hours. The weight-average molecular weight (Mw) stabilized after two hours after reaching reflux temperature.

[0199] [Example 3]

[0200] A raw material solution was prepared by placing (A) 12.6 g of monoallyl diglycidyl isocyanuric acid, (B) 6.6 g of adipic acid, (C) 0.84 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) 0.09 g of pyridine as a co-catalyst, and 60 g of propylene glycol monomethyl ether into a 200 mL reaction flask. The molar ratio of component (C) to component (D) was 1:0.5, and the equivalent ratio of component (A) to component (B) was 1:1.01.

[0201] Next, the solution was heated under reflux at 121°C and reacted for 1 to 7 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 8,500 one hour after reaching reflux temperature, Mw = 13,200 at two hours, Mw = 15,000 at four hours, Mw = 14,900 at five hours, Mw = 14,800 at six hours, and Mw = 14,600 at seven hours. The weight-average molecular weight (Mw) stabilized after four hours after reaching reflux temperature.

[0202] [Example 4]

[0203] A raw material solution was prepared by placing (A) 12.6 g of monoallyl diglycidyl isocyanuric acid, (B) 6.6 g of adipic acid, (C) 0.42 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) 0.09 g of pyridine as a co-catalyst, and 60 g of propylene glycol monomethyl ether into a 200 mL reaction flask. The molar ratio of component (C) to component (D) was 1.0:1.0, and the equivalent ratio of component (A) to component (B) was 1:1.01.

[0204] Next, the solution was heated under reflux at 121°C and reacted for 1 to 8 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 3800 one hour after reaching reflux temperature, Mw = 9900 two hours after reaching reflux temperature, Mw = 13900 four hours after reaching reflux temperature, Mw = 14000 five hours after reaching reflux temperature, Mw = 14000 six hours after reaching reflux temperature, Mw = 13900 seven hours after reaching reflux temperature, and Mw = 13900 eight hours after reaching reflux temperature. The weight average molecular weight Mw stabilized after four hours after reaching reflux temperature.

[0205] [Example 5]

[0206] A raw material solution was prepared by placing (A) 31.5 g of monoallyl diglycidyl isocyanuric acid, (B) 16.4 g of adipic acid, (C) 1.68 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) 0.09 g of pyridine as a co-catalyst, and 60 g of propylene glycol monomethyl ether into a 500 mL reaction flask. The molar ratio of component (C) to component (D) was 1:0.25, and the equivalent ratio of component (A) to component (B) was 1:1.01.

[0207] Next, the solution was heated under reflux at 121°C and reacted for 1 to 8 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 7,000 one hour after reaching reflux temperature, Mw = 14,600 at two hours, Mw = 21,200 at four hours, Mw = 25,600 at five hours, Mw = 26,400 at six hours, Mw = 27,300 at seven hours, and Mw = 27,900 at eight hours. The weight-average molecular weight (Mw) stabilized after six hours after reaching reflux temperature.

[0208] [Example 6]

[0209] A raw material solution was prepared by placing (A) 31.5 g of monoallyl diglycidyl isocyanuric acid, (B) 16.4 g of adipic acid, (C) 1.26 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) 0.18 g of pyridine as a co-catalyst, and 60 g of propylene glycol monomethyl ether into a 500 mL reaction flask. The molar ratio of component (C) to component (D) was 1:0.67, and the equivalent ratio of component (A) to component (B) was 1:1.01.

[0210] Next, the solution was heated under reflux at 121°C and reacted for 1 to 8 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 5200 one hour after reaching reflux temperature, Mw = 10800 two hours after reaching reflux temperature, Mw = 15900 four hours after reaching reflux temperature, Mw = 16300 five hours after reaching reflux temperature, Mw = 16300 six hours after reaching reflux temperature, Mw = 16100 seven hours after reaching reflux temperature, and Mw = 16100 eight hours after reaching reflux temperature. The weight-average molecular weight Mw stabilized after four hours after reaching reflux temperature.

[0211] [Example 7]

[0212] A raw material solution was prepared by placing (A) 31.5 g of monoallyl diglycidyl isocyanuric acid, (B) 16.4 g of adipic acid, (C) 0.84 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) 0.26 g of pyridine as a co-catalyst, and 60 g of propylene glycol monomethyl ether into a 500 mL reaction flask. The molar ratio of component (C) to component (D) was 0.67:1, and the equivalent ratio of component (A) to component (B) was 1:1.01.

[0213] Next, the solution was heated under reflux at 121°C and reacted for 1 to 8 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 3000 one hour after reaching reflux temperature, Mw = 7400 two hours after reaching reflux temperature, Mw = 12500 four hours after reaching reflux temperature, Mw = 12900 five hours after reaching reflux temperature, Mw = 12800 six hours after reaching reflux temperature, Mw = 12800 seven hours after reaching reflux temperature, and Mw = 12800 eight hours after reaching reflux temperature. The weight-average molecular weight Mw stabilized after four hours after reaching reflux temperature.

[0214] [Example 8]

[0215] A raw material solution was prepared by placing (A) 31.5 g of monoallyl diglycidyl isocyanuric acid, (B) 16.4 g of adipic acid, (C) 0.42 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) 0.35 g of pyridine as a co-catalyst, and 60 g of propylene glycol monomethyl ether into a 500 mL reaction flask. The molar ratio of component (C) to component (D) was 0.25:1, and the equivalent ratio of component (A) to component (B) was 1:1.01.

[0216] Next, the solution was heated under reflux at 121°C and reacted for 1 to 8 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 1900 one hour after reaching reflux temperature, Mw = 4800 two hours after reaching reflux temperature, Mw = 9400 four hours after reaching reflux temperature, Mw = 9800 five hours after reaching reflux temperature, Mw = 10000 six hours after reaching reflux temperature, Mw = 10000 seven hours after reaching reflux temperature, and Mw = 10000 eight hours after reaching reflux temperature. The weight average molecular weight Mw stabilized after four hours after reaching reflux temperature.

[0217] [Comparative Example 1]

[0218] A raw material solution was prepared by placing (A) 12.6 g of monoallyl diglycidyl isocyanuric acid, (B) 6.6 g of adipic acid, (C) 0.84 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, and 60 g of propylene glycol monomethyl ether into a 200 mL reaction flask. The molar ratio of component (C) to component (D) was 1:0, and the equivalent ratio of component (A) to component (B) was 1:1.01.

[0219] Next, the solution was heated under reflux at 121°C and reacted for 1 to 6 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 8,800 one hour after reaching reflux temperature, Mw = 19,400 two hours later, Mw = 40,000 four hours later, Mw = 50,900 five hours later, and Mw = 68,600 six hours later, indicating that the weight-average molecular weight (Mw) continued to increase without stabilizing.

[0220] [Comparative Example 2]

[0221] A raw material solution was prepared by charging (A) 12.6 g of monoallyl diglycidyl isocyanuric acid, (B) 6.6 g of adipic acid, (D) 0.18 g of pyridine as a co-catalyst, and 60 g of propylene glycol monomethyl ether into a 200 mL reaction flask. The molar ratio of component (C) to component (D) was 0:1, and the equivalent ratio of component (A) to component (B) was 1:1.01.

[0222] Next, the solution was heated under reflux at 121°C and reacted for 1 to 8 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 1300 one hour after reaching reflux temperature, Mw = 7300 two hours after reaching reflux temperature, Mw = 9600 four hours after reaching reflux temperature, Mw = 8700 five hours after reaching reflux temperature, Mw = 7900 six hours after reaching reflux temperature, Mw = 7500 seven hours after reaching reflux temperature, and Mw = 7200 eight hours after reaching reflux temperature. The weight average molecular weight Mw continued to decrease after reaching a maximum value four hours after reaching reflux temperature.

[0223] The results of Examples 1 to 8 and Comparative Examples 1 and 2 are summarized in Tables 1 and 2.

[0224] [Table 1]

[0225]

[0226] [Table 2]

[0227]

[0228] [Example 9]

[0229] A raw material solution was prepared by placing (A) 12.6 g of monoallyl diglycidyl isocyanuric acid, (B) 6.6 g of adipic acid, (C) 0.84 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) 0.58 g of triphenylphosphine as a co-catalyst, and 60 g of propylene glycol monomethyl ether into a 200 mL reaction flask. The molar ratio of component (C) to component (D) was 1:1, and the equivalent ratio of component (A) to component (B) was 1:1.01.

[0230] Next, the solution was heated under reflux at 121°C and reacted for 1 to 7 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 7700 one hour after reaching reflux temperature, Mw = 12500 at two hours, Mw = 13200 at four hours, Mw = 13200 at five hours, Mw = 13200 at six hours, and Mw = 13200 at seven hours. The weight-average molecular weight (Mw) stabilized after four hours after reaching reflux temperature.

[0231] [Example 10]

[0232] A raw material solution was prepared by charging (A) 12.6 g of monoallyl diglycidyl isocyanuric acid, (B) 6.6 g of adipic acid, (C) 0.84 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) 0.45 g of tributylphosphine as a co-catalyst, and 60 g of propylene glycol monomethyl ether into a 200 mL reaction flask. The molar ratio of component (C) to component (D) was 1:1, and the equivalent ratio of component (A) to component (B) was 1:1.01.

[0233] Next, the solution was heated under reflux at 121°C and reacted for 1 to 6 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 6800 one hour after reaching reflux temperature, Mw = 10300 at two hours, Mw = 10900 at four hours, Mw = 10900 at five hours, and Mw = 10800 at six hours. The weight-average molecular weight (Mw) stabilized after four hours after reaching reflux temperature.

[0234] The results of Examples 9 and 10 are summarized in Table 3.

[0235] [Table 3]

[0236]

[0237] [Example 11]

[0238] A raw material solution was prepared by placing (A) 11.0 g of monoallyl diglycidyl isocyanuric acid, (B) 8.3 g of 3,3-dithiopropionic acid, (C) 0.73 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) 0.15 g of pyridine as a co-catalyst, and 60 g of propylene glycol monomethyl ether into a 200 mL reaction flask. The molar ratio of component (C) to component (D) was 1:1, and the equivalent ratio of component (A) to component (B) was 1:1.01.

[0239] Next, the solution was heated under reflux at 121°C and reacted for 1 to 7 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 1800 one hour after reaching reflux temperature, Mw = 1800 two hours after reaching reflux temperature, Mw = 1800 four hours after reaching reflux temperature, Mw = 1800 five hours after reaching reflux temperature, Mw = 1700 six hours after reaching reflux temperature, and Mw = 1800 seven hours after reaching reflux temperature. The weight-average molecular weight Mw stabilized after one hour after reaching reflux temperature.

[0240] [Comparative Example 3]

[0241] A raw material solution was prepared by placing (A) 11.0 g of monoallyl diglycidyl isocyanuric acid, (B) 8.3 g of 3,3-dithiopropionic acid, (C) 0.73 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, and 60 g of propylene glycol monomethyl ether into a 200 mL reaction flask. The molar ratio of component (C) to component (D) was 1:0, and the equivalent ratio of component (A) to component (B) was 1:1.01.

[0242] Next, the solution was heated under reflux at 121°C and reacted for 1 to 7 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 2000 one hour after reaching reflux temperature, Mw = 2900 two hours later, Mw = 3500 four hours later, Mw = 3700 five hours later, Mw = 3800 six hours later, and Mw = 4000 seven hours later, indicating that the weight-average molecular weight (Mw) continued to increase without stabilizing.

[0243] The results of Example 11 and Comparative Example 3 are summarized in Table 4.

[0244] [Table 4]

[0245]

[0246] [Example 12]

[0247] A raw material solution was prepared by placing (A) 12.8 g of monoallyl diglycidyl isocyanuric acid, (B) 10.4 g of bisphenol A, (C) 0.85 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) 0.05 g of pyridine as a co-catalyst, and 56 g of propylene glycol monomethyl ether into a 200 mL reaction flask. The molar ratio of component (C) to component (D) was 1:0.3, and the equivalent ratio of component (A) to component (B) was 1:1.005.

[0248] Next, the solution was heated under reflux at 121°C and reacted for 1 to 7 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 4400 one hour after reaching reflux temperature, Mw = 5600 two hours after reaching reflux temperature, Mw = 5600 five hours after reaching reflux temperature, Mw = 5600 six hours after reaching reflux temperature, and Mw = 5500 seven hours after reaching reflux temperature. The weight-average molecular weight (Mw) stabilized after two hours after reaching reflux temperature.

[0249] [Comparative Example 4]

[0250] A raw material solution was prepared by placing (A) 12.8 g of monoallyl diglycidyl isocyanuric acid, (B) 10.4 g of bisphenol A, (C) 0.85 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, and 56 g of propylene glycol monomethyl ether into a 200 mL reaction flask. The molar ratio of component (C) to component (D) was 1:0, and the equivalent ratio of component (A) to component (B) was 1:1.005.

[0251] Next, the solution was heated under reflux at 121°C and reacted for 1 to 7 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 2100 one hour after reaching reflux temperature, Mw = 3800 two hours later, Mw = 5300 four hours later, Mw = 5700 five hours later, Mw = 6000 six hours later, and Mw = 6300 seven hours later, indicating that the weight-average molecular weight (Mw) continued to increase without stabilizing.

[0252] The results of Example 12 and Comparative Example 4 are summarized in Table 5.

[0253] [Table 5]

[0254]

[0255] [Example 13]

[0256] A raw material solution was prepared by placing (A) 34.2 g of monoallyl diglycidyl isocyanuric acid, (B) 23.5 g of barbiturate, (C) 2.3 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) 0.29 g of pyridine as a co-catalyst, and 240 g of propylene glycol monomethyl ether into a 500 mL reaction flask. The molar ratio of component (C) to component (D) was 1:0.6, and the equivalent ratio of component (A) to component (B) was 1:1.04.

[0257] Next, the solution was heated under reflux at 121°C and reacted for 1 to 6 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 7600 one hour after reaching reflux temperature, Mw = 10400 two hours after reaching reflux temperature, Mw = 11300 four hours after reaching reflux temperature, and Mw = 11400 six hours after reaching reflux temperature. The weight-average molecular weight (Mw) stabilized after four hours after reaching reflux temperature.

[0258] [Comparative Example 5]

[0259] A raw material solution was prepared by placing (A) 34.2 g of monoallyl diglycidyl isocyanuric acid, (B) 23.5 g of barbiturate, (C) 2.3 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, and 240 g of propylene glycol monomethyl ether into a 500 mL reaction flask. The molar ratio of component (C) to component (D) was 1:0, and the equivalent ratio of component (A) to component (B) was 1:1.04.

[0260] Next, the solution was heated under reflux at 121°C and reacted for 1 to 8 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 5400 one hour after reaching reflux temperature, Mw = 8900 two hours later, Mw = 12100 four hours later, Mw = 14100 six hours later, and Mw = 15800 eight hours later, indicating that the weight-average molecular weight (Mw) continued to increase without stabilizing.

[0261] [Example 14]

[0262] A raw material solution was prepared by placing (A) 34.1 g of monoallyl diglycidyl isocyanuric acid, (B) 23.4 g of barbiturate, (C) 2.1 g of tetrabutylphosphonium bromide as a polymerization catalyst, (D) 0.48 g of pyridine as a co-catalyst, and 240 g of propylene glycol monomethyl ether into a 500 mL reaction flask. The molar ratio of component (C) to component (D) was 1:1, and the equivalent ratio of component (A) to component (B) was 1:1.04.

[0263] Next, the solution was heated under reflux at 121°C and reacted for 1 to 8 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 4700 one hour after reaching reflux temperature, Mw = 7000 two hours after reaching reflux temperature, Mw = 7900 four hours after reaching reflux temperature, Mw = 7900 six hours after reaching reflux temperature, and Mw = 7900 eight hours after reaching reflux temperature. The weight-average molecular weight (Mw) stabilized after four hours after reaching reflux temperature.

[0264] [Example 15]

[0265] A raw material solution was prepared by charging (A) 34.0 g of monoallyl diglycidyl isocyanuric acid, (B) 23.3 g of barbiturate, (C) 2.1 g of tetrabutylphosphonium bromide as a polymerization catalyst, (D) 0.74 g of N,N-dimethyl-4-aminopyridine as a co-catalyst, and 240 g of propylene glycol monomethyl ether into a 500 mL reaction flask. The molar ratio of component (C) to component (D) was 1:1, and the equivalent ratio of component (A) to component (B) was 1:1.04.

[0266] Next, the solution was heated under reflux at 121°C and reacted for 1 to 8 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 5700 one hour after reaching reflux temperature, Mw = 5800 two hours after reaching reflux temperature, Mw = 5900 four hours after reaching reflux temperature, Mw = 5900 six hours after reaching reflux temperature, and Mw = 5900 eight hours after reaching reflux temperature. The weight-average molecular weight (Mw) stabilized after two hours after reaching reflux temperature.

[0267] [Comparative Example 6]

[0268] A raw material solution was prepared by placing (A) 34.2 g of monoallyl diglycidyl isocyanuric acid, (B) 23.5 g of barbiturate, (C) 2.1 g of tetrabutylphosphonium bromide (polymerization catalyst), and 240 g of propylene glycol monomethyl ether into a 500 mL reaction flask. The molar ratio of component (C) to component (D) was 1:0, and the equivalent ratio of component (A) to component (B) was 1:1.04.

[0269] Next, the solution was heated under reflux at 121°C and reacted for 1 to 8 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 2900 one hour after reaching reflux temperature, Mw = 5600 two hours later, Mw = 8300 four hours later, Mw = 10300 six hours later, and Mw = 11900 eight hours later, indicating that the weight-average molecular weight (Mw) continued to increase without stabilizing.

[0270] The results of Examples 13 to 15 and Comparative Examples 5 to 6 are summarized in Table 6.

[0271] [Table 6]

[0272]

[0273] [Example 16]

[0274] A raw material solution was prepared by placing (A) 15.3 g of diglycidyl terephthalate, (B) 7.7 g of adipic acid, 1.0 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, (D) 0.21 g of pyridine as a co-catalyst, and 56 g of propylene glycol monomethyl ether into a 200 mL reaction flask. The molar ratio of component (C) to component (D) was 1:1, and the equivalent ratio of component (A) to component (B) was 1:1.001.

[0275] Next, the solution was heated under reflux at 105°C and reacted for 1 to 6 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 5500 one hour after reaching reflux temperature, Mw = 11100 at two hours, Mw = 13000 at four hours, Mw = 13000 at five hours, and Mw = 13000 at six hours. The weight-average molecular weight (Mw) stabilized after four hours after reaching reflux temperature.

[0276] [Comparative Example 7]

[0277] A raw material solution was prepared by placing (A) 15.3 g of diglycidyl terephthalate, (B) 7.7 g of adipic acid, (C) 1.0 g of ethyltriphenylphosphonium bromide as a polymerization catalyst, and 56 g of propylene glycol monomethyl ether into a 200 mL reaction flask. The molar ratio of component (C) to component (D) was 1:0, and the equivalent ratio of component (A) to component (B) was 1:1.001.

[0278] Next, the solution was heated under reflux at 105°C and reacted for 1 to 6 hours to synthesize a polymer. GPC analysis of the resulting polymer revealed Mw = 5100 one hour after reaching reflux temperature, Mw = 14700 two hours later, Mw = 19900 four hours later, Mw = 20400 five hours later, and Mw = 20500 six hours later, indicating that the weight-average molecular weight (Mw) continued to increase without stabilizing.

[0279] The results of Example 16 and Comparative Example 7 are summarized in Table 7.

[0280] [Table 7]

[0281]

Claims

1. A method for producing a polymer, characterized in that: (A) an epoxy compound having two or more epoxy groups in its molecule and (B) a reactive compound having two or more functional groups reactive with epoxy groups in its molecule are reacted in a solution containing the components (A) to (D) and an organic solvent at 50 to 150° C. in the presence of (C) a polymerization catalyst, (D) a co-catalyst, and an organic solvent. The co-catalyst (D) is pyridine or N,N-dimethyl-4-aminopyridine, Among them, the component (C) is an onium salt having a quaternary structure of a Group 15 element of one or more groups. The Group 15 element of the component (C) is nitrogen or phosphorus.

2. The method for producing a polymer according to claim 1, wherein 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.

3. The method for producing a polymer according to claim 1, wherein The counter anion in the onium salt is selected from halide ion, nitrate ion, sulfate ion, acetate ion, formate ion, hydroxide ion, and sulfonate ion having an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

4. The method for producing a polymer according to claim 1, wherein The component (D) is a compound having a primary to tertiary structure of a Group 15 element, or a heteroaryl compound containing a Group 15 element in an aromatic ring.

5. The method for producing a polymer according to claim 4, wherein The Group 15 element of the component (D) is nitrogen or phosphorus.

6. The method for producing a polymer according to claim 4, wherein The component (D) is a compound having a tertiary Group 15 element structure, or a heteroaryl compound containing a Group 15 element in an aromatic ring.

7. The method for producing a polymer according to claim 4, wherein 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.

8. The method for producing a polymer according to claim 1, wherein The component (A) is one or more selected from the group consisting of diepoxy compounds, triepoxy compounds, tetraepoxy compounds, and polymers having an epoxy group.

9. The method for producing a polymer according to claim 1, wherein The functional group of component (B) is a hydroxyl group, a formyl group, a carboxyl group, an amino group, an imino group, an azo group, an azido group, a thiol group, a sulfo group, an amide group, an imide group, a thiocarboxyl group, a dithiocarboxyl group, a phosphoric acid group, a phosphite group, a phosphonic acid group, a phosphite group, a phosphinic acid group, a trivalent phosphonic acid group, a phosphine group, an acid anhydride or an acid chloride.

10. The method for producing a polymer according to claim 1, wherein The equivalent ratio of the epoxy group contained in the component (A) to the functional group contained in the component (B) is (A):(B)=0.1:1.0 to 1.0:0.

1.

11. The method for producing a polymer according to claim 1, wherein The mixing ratio of the components (C) and (D) is 0.1:1.0 to 1.0:0.1 in terms of molar ratio, and the total amount of the components (C) and (D) is 0.0001 to 0.5 mol per 1 mol of the component (A).

12. The method for producing a polymer according to claim 1, wherein Furthermore, as the organic solvent, an organic solvent selected from 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- One or more of ethyl hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

13. The method for producing a polymer according to claim 12, wherein The amount of the organic solvent used is 0.1 to 100 times by mass relative to the mass of the component (A).

14. A method for producing a resist underlayer film-forming composition, comprising: The polymer obtained by the production method according to any one of claims 1 to 13 is mixed with an organic solvent.

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