TW200848449A - Hyperbranched polymer and process for producing the same - Google Patents

Abstract

Disclosed is a hyperbranched polymer having a main chain of polyamide structure and a terminal amino group, which does not require a large amount of an organic solvent during production. This hyperbranched polymer has high transparency and high storage stability, and is mass producible by a simple process. Also disclosed are a method for producing such a hyperbranched polymer, a method for producing a monomer which is used in the method for producing the polymer, a varnish of the polymer, a coating film composed of the polymer, and a solid support coated with the polymer. Specifically disclosed is a hyperbranched polymer having a structurerepresented by the following formula (1). (In the formula, A1 represents a straight, branched or cyclic alkylene group having 1-30 carbon atoms and optionally containing an amide bond or an ether bond in the group, or a phenylene group having 6-10 carbon atoms; A2 and A3 represent a straight, branched or cyclic alkylene group having 1-30 carbon atoms and optionally containing an amide bond or an ether bond in the group; and n represents an integer of 2-100,000.)

Description

200848449 IX. INSTRUCTIONS OF THE INVENTION [Technical Field of the Invention] The present invention relates to a hyperbranched polymer and a method of producing the same. That is, the present invention relates to a hyperbranched polymer having a polyamine structure in a main chain of a repeating unit and having an amine group at a molecular terminal, and a method for producing the same. These are suitable as coatings, inks, adhesives, resin materials, various forming materials, nano-sized porous forming agents, chemical mechanical honing agents, functional materials, holding materials, nanocapsules, photonic crystals (photonic Crystals), photoresist materials, optical materials, electronic materials, data recording materials, printed materials, battery materials, medical materials, magnetic materials, etc. [Prior Art] Hyperbranched polymer systems and dendrimers are classified as Dendritic polymer. The dendrimers are generally in a rope-like (linear) shape with respect to conventional polymer compounds. These dendrimers achieve a specific polymer structure or produce various functions by actively introducing branches. For example, by the above-described multi-branched structure, a molecular size of a nanometer degree or a polymer structure having a surface state capable of retaining many functions is obtained, and the intermolecular complexation exhibiting low viscosity is less than that of the linear polymer. The behavior of the fine particles is amorphous, and various characteristics such as controllability of solvent solubility are generated, and these characteristics are expected to be applied to a wide range of technical fields. In particular, as the most prominent feature of the dendrimer, for example, the terminal number of the terminal -5 - 200848449 is large. In the dendrimer, since the number of branches generally increases as the molecular weight increases, the absolute number of terminal groups is the higher the molecular weight of the dendrimer. The dendrimer having such a large number of terminal groups has characteristics which are not affected by the influence of intermolecular interaction, and which are generally changed by a general linear polymer such as glass transition temperature, solubility, and film formability. Among the two kinds of dendrimers, the hyperbranched polymer is simple in the production method, and particularly in industrial production, it has the advantages of lower cost than the dendrimer and mass production. This is because the repeated densification-deprotection of the general dendrimer is carried out in many steps, and the hyperbranched polymer has a total of three or more substituents in one molecule, that is, an ABX monomer. The one-stage polymerization is synthesized. Various polymers as hyperbranched polymers have been introduced so far, one of which is a polyamine structure, and a hyperbranched polymer having an amine group at the terminal group has high solubility in a water-soluble medium, and the introduction function is based on a terminal amine group. The high efficiency and super-branched polymer surface are excellent in characteristics such as cationicity, and have attracted attention. For example, a fluorene type monomer having a carboxyl group and two or more amine groups in the molecule and a hyperbranched polymer produced from the monomer have been disclosed (for example, Non-Patent Documents 1 and 2). Further, an aliphatic amine-based terminal hyperbranched polymer produced by the reaction of a polyamine compound and an alkyl acrylate is disclosed (Patent Document 1). Non-Patent Document 1 : G. Yang, M. Jieki and M. Kakimoto, 200848449

Macromolecules, 32, 22 1 5-2220 (1 999) Non-Patent Document 2: Y. Ishida, ACF Sun, M. Jieki and M. Kakimoto, Macromolecules, 33, 283 2-28 3 8 (2000) Patent Document 1: The present invention disclosed in the above Non-Patent Documents 1 and 2, since the monomer disclosed in the above Non-Patent Documents 1 and 2 has an aromatic amine group in the molecule, A condensing agent must be used in the organic solvent during the polymerization. That is, after the reaction, the condensing agent component must be removed by a reprecipitation operation or the like. Therefore, a large amount of organic solvent is required, and there is room for improvement in terms of manufacturing environment. Further, oxygen in the aromatic amine gene in the polymer terminal is easily oxidized and easily colored, so that the problem of preservation stability remains. Further, the polymer described in Patent Document 1 is in the production step, and in order to prevent polymerization of the alkyl acrylate alone, it is necessary to add a polymerization inhibitor such as hydroquinone monomethyl ether to the reaction system, and thus the resulting polymer is produced. The coloration from the polymerization inhibitor. Further, in order to remove the polymerization inhibitor, a reprecipitation operation is required, and a large amount of an organic solvent is required. The present invention solves the above problems and provides a hyperbranched polymer which is highly transparent and does not require a large amount of an organic solvent at the time of production, and which can be easily and mass-produced. In detail, it provides a polyamine structure in a main chain and has a polyamine structure at the terminal group. A super-branched polymer having a high storage stability (transparency) of an amine group. Further, the present invention provides a method for producing a hyperbranched polymer which does not require a large amount of an organic solvent, a simple method, and which can be mass-produced in the production of the above-mentioned hyperbranched polymer, and a method for producing a monomer used therein. Further, the present invention provides a varnish of the above-mentioned hyperbranched polymer, a film formed of the polymer, and a solid phase carrier coated with the polymer, and is expected to be used in various applications in the future. Solution to Problem In order to solve the above problems, the present invention has been made in an effort to review the results of the following findings. That is, the first aspect of the present invention relates to having the formula (1)

(1) (wherein Ai represents a linear, branched or cyclic alkyl group having a carbon number of 1 to 30 which may contain a guanamine bond or an ether bond in the group, or a carbon number of 6 to 1 Arylene or alkylarylene, a2 and A3 are linear, branched or cyclical extensions having a carbon number of 1 to 30 which may contain a guanamine bond or an ether bond in the group. The alkyl group, η is an integer of 2 to 1 0 0,0 0 0.) The hyperbranched polymer of the structure shown. As the second viewpoint, there is a formula (2): -8 - (2) 200848449 [Chemical 2]

(wherein, Ai, A2, a3 and ^ are the same as defined in the above formula (1), and represent a hydrogen atom, an alkyl group having a carbon number of 丨 to 5, a trans-group having a carbon number of 1 to 5, and a carbon number of 6 to 10. The arylene group or the arylalkyl group having 7 to 12 carbon atoms.) The super-branched polymer described in the first aspect of the structure shown. As the third viewpoint, there is a formula (3): [Chemical 3] Bu 2 - N Η Α Α 3-Ν Η

(3) -C—C—N II 1 II ^ Ο 0 (wherein VIII, VIII, VIII, and 11 are the same as defined in the above formula (1)' X is represented by at least a part of the amine end The acid compound to be added may be a hyperbranched polymer described in the first aspect of the structure shown by X.). As the fourth viewpoint, there is a formula (4): [Chem. 4] 八2-Ν, Η Η

(4)

RiO-

-C—A^C—N II 1 II , ο Ο -9- 200848449 (wherein, the η system is the same as defined in the above formula (1), and the R! system is the same as defined in the above formula (2). The X system is the same as defined in the above formula (3).) The hyperbranched polymer described in the first to third aspects of the structure shown. The fifth aspect is the hyperbranched polymer described in the second or fourth aspect of the R+ hydrogen atom or the ethyl group in the above formula (2) or (4). The sixth aspect is a hyperbranched polymer according to any one of the first to fifth aspects, wherein the weight average molecular weight measured by a polyethylene glycol conversion is 400 to 20,000,000 by gel permeation chromatography. As the seventh point of view, by making the formula (5): [Chemical 5], a nh2(x) R^-C-ArC-N (5) 0 ° A3—NH2(X) (where Ai, A2 And the A3 system is the same as defined in the above formula (1), and the fourth aspect of the polymerization of the compound represented by the Ri system is the same as defined in the above formula (2), and the X system is the same as defined in the above formula (3). A method for producing a hyperbranched polymer represented by the formula (4). The eighth aspect is a method for producing a hyperbranched polymer described in the seventh aspect of the block polymerization or solution polymerization in the polymerization step of the compound represented by the formula (5) described in the seventh aspect. In the polymerization step of the compound represented by the formula (5) described in the seventh aspect, the generated water and/or alcohol are removed at a temperature of 50 ° C to 25 (at a temperature of TC). The overspending described in the eighth aspect of the polymerization - 200848449 The method for producing a chain polymer. The first viewpoint is based on the formula (6) [Chem. 6]

Ri Ο—C—A—)—C—NI! II \ Ο 〇, A2—Nx Η (6) −Ν—Α4 Η { where A!, Α2, and Α3 are the same as defined in the above formula (1), I represents an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms, and A4 represents a formula (7). Or formula (8): [Chemical 7] One brother and one 0-R2 (7) Ο [Chemical 8] —C—R2 (8) Ο (In equations (7) and (8), R2 represents carbon number 1 A compound represented by an alkyl group having 5 to 5, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms, which is formed by treatment with an acid, a base or a reducing agent. A method for producing a compound represented by the formula (5). The first aspect is a method for producing a compound represented by the formula (5) in the formula 7 in which I is an ethyl group. As the 1st point of view, the formula (9): -11 - 200848449 [Chemical 9]

式) (wherein A] and A; are the same as defined in the above formula (1), a4 is the same as defined in the above formula (6), and X is the same as defined in the above formula (3)) The compound shown, and the formula (10): [Chemical Formula 10] F^On—Y (10) (wherein the A! system is the same as defined in the above formula (丨), and the Ri system and the above formula (6) The definitions are the same, and the γ system represents a leaving group selected from the group consisting of a fluorine group, a chlorine group, a bromine group, an iodine group, and a sulfonium imino group of a hydroxysuccinate.) The first viewpoint formed by the reaction of the compound shown A method for producing a compound represented by the formula (6). The first aspect is a compound represented by the formula (6) in the viewpoint of the first aspect of the R1-ethyl group in the formula. The 14th aspect relates to a structure in which a part or all of the terminal amine group of the hyperbranched polymer represented by the formula (4) described in the fourth aspect is bonded to an organic functional group by a guanamine bond or an imine bond. Hyperbranched polymer. The ninth aspect relates to a varnish of a super--12-200848449 branched polymer in which a hyperbranched polymer described in any one of the first aspect to the sixth aspect or the fourteenth aspect is dissolved or dispersed. The fifteenth aspect is a hyperbranched polymer film formed of the hyperbranched polymer described in any one of the first aspect to the sixth aspect or the fourteenth aspect. The seventh aspect is a solid phase carrier which covers the surface of the support of the hyperbranched polymer described in any one of the first aspect to the sixth aspect or the fourteenth aspect. EFFECTS OF THE INVENTION The hyperbranched polymer of the present invention and the monomer for producing the hyperbranched polymer, since the terminal group is an aliphatic amine group, does not occur in the air during storage or during polymer production. Oxygen and oxidation color. Further, since the above polymer can be produced by bulk polymerization which does not require an organic solvent, it is possible to obtain a polymer simply and efficiently, without reducing the environmental load. Further, the obtained polymer has an aprotic polar solvent which is soluble or dispersible in N-methylpyrrolidone and dimethyl hydrazine, and can be dissolved or dispersed in a protic polar solvent such as water or methanol. Linear polymers having the same average molecular weight are relatively low in viscosity and high in functional group density (terminal amino group), so they can be easily used in various types of materials in the form of polymer varnishes, and can also be used in combination with the purpose. The dispersion characteristics are easily changed. Next, by using the obtained polymer to form a film on a solid phase carrier, a solid phase carrier which changes the hydrophilicity of the surface or the affinity with a chemical substance -13-200848449 can be easily obtained. BEST MODE FOR CARRYING OUT THE INVENTION [Hyperbranched Polymer] The hyperbranched polymer of the present invention is a hyperbranched polymer having a repeating unit structure represented by the following formulas (1) to (4). [化11]

(In the formula, 'Ai' is a linear, branched or cyclic alkyl group having a carbon number of 1 to 30 which may contain a guanamine bond or an ether bond in the group, or a carbon number of 6 to 〇. Arylene or alkylarylene, octa 2 and a3 represent a linear, branched or cyclic alkyl group having 1 to 3 carbon atoms which may contain an amine bond or an ether bond in the group. , η system shows 2 to 1 〇〇, the integer of 〇〇〇.) [Chem. 12]

(wherein 'Ai, A', As, and η are the same as defined in the above formula (1) 'R! means a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having a carbon number of 5 to 5, An aryl group having 6 to 10 carbon atoms or an arylalkyl group having 7 to 12 carbon atoms - (3) 200848449 [Chemical 13]

(wherein A!, A2, A3 and η are the same as defined in the above formula (1), and X is an acidic compound added to at least a part of the amine group terminal, and may have no X.) ]

—C—N II , 〇 -N Η Α3—Ν Η

(4) (wherein, Ai, A2, A3, and η are the same as defined in the above formula (1), R! is the same as defined in the above formula (2), and X is the same as defined in the above formula (3) Further, as a general structural formula (memory diagram) of the above-mentioned hyperbranched polymer, a hyperbranched polymer having a repeating unit represented by the formula (4) is exemplified as follows. -15- 200848449 [Chem. 15]

(In the formula, Ri is the same as defined in the above formula (2).) In the above formulas (1) to (4), as a linear one having a carbon number of 1 to 30 as shown by Αι, Α2, and A3 Specific examples of the alkylene group include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, and n-hexyl group. Specific examples of the above-mentioned branched alkyl group include isoprene. Base, isobutylene, 2-methylpropyl, and the like. In addition, examples of the cyclic alkyl group include a monocyclic, polycyclic, and crosslinked cyclic alicyclic aliphatic group having a carbon number of 1 to 30, and specifically, for example, having a carbon number of 4 The above single ring, double ring, four ring, five ring structure and the like. Further, specific examples of the arylene or alkylarylene group having 6 to 1 carbon atoms represented by Ai include, for example, a phenyl group, a benzyl group, a phenylethyl group, and a naphthyl group. (naphthylene) and so on. When the above-mentioned alkyl or phenyl group contains a guanamine bond or an ether bond in the group, for example, when the linear alkyl group contains a guanamine bond or an ether bond, the A! to A 3 system may have the following The basis of the structure. (1) When an ether bond is contained: -CH2OCH2-, -CH2OCH2CH2-, ?ch2ch2och2., -CH2OCH2CH2CH2-, -CH2CH2OCH2CH2-, -ch2ch2ch2och2--16-200848449 (2) When a guanamine bond is contained: -CH2C(0)NHCH2 -, -ch2c(o)nhch2ch2-, -ch2ch2c(o)nhch2·, -ch2c(o)nhch2ch2ch2-, -ch2ch2c(o)nhch2ch2-, -ch2ch2ch2c(o)nhch2- In addition, the above cyclic alkyl group ( In the alicyclic aliphatic group, specific examples of the alicyclic moiety are shown in the following structural examples (a) to (S). [化16] 〇0〇〇〇> (a) (b) (c) (d) (e)

Further, the linear, branched or cyclic alkyl groups represented by A!, A2 and A3 may be the same or different. In the above formulas (2) and (4), Ri represents a hydrogen atom, an alkyl group having 1 to 17-48,48,449 to 5, a hydroxyalkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, Or an arylalkyl group having 7 to 12 carbon atoms. In the above, a specific example of the alkyl group having 1 to 5 carbon atoms is exemplified by a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a cyclopentyl group, a n-pentyl group or the like, as the above carbon number 1 to 5. Specific examples of the hydroxyalkyl group include a methylol group, a hydroxyethyl group, a hydroxypropyl group and the like. In addition, as a specific example of the aryl group having 6 to 10 carbon atoms, for example, a phenyl group or the like is exemplified, and specific examples of the arylalkyl group having 7 to 12 carbon atoms include a benzyl group, a phenethyl group, and the like. . Among these organic groups, Ri is preferably a hydrogen atom or an ethyl group. In the above formulas (3) and (4), X represents an acidic compound added to at least a part of the amine group terminal, and examples of the specific example include hydrofluoric acid, hydrochloric acid, hydrobromic acid, and sulfuric acid. Nitric acid, acetic acid, p-toluenesulfonic acid, etc. In addition, X may be absent in formula (3) and formula (4). The hyperbranched polymer of the present invention has a weight average molecular weight of from 400 to 20,000,000, preferably from 600 to 10, 〇〇〇, 〇〇〇, to 800 by gel permeation chromatography. Up to 5,000,000 is especially good. Further, the degree of dispersion {Mw (weight average molecular weight) / Μ (number average molecular weight)} of the hyperbranched polymer of the present invention is from 1. 〇 to 1 〇. 〇, preferably from 1.1 to 9.0, from 1.2 to 8.0. Especially good. [Method for Producing Hyperbranched Polymer] The hyperbranched polymer of the present invention can be produced by polymerizing a compound represented by the following formula (5), -18-(5), (5) 200848449. a2—NH2(X)

Ri°~C~ArC—N 0 0 Α3—ΝΗ2(Χ) (wherein Α!, Α2, and A3 are the same as defined in the above formula (i), and the Ri system is the same as defined in the above formula (2) X is the same as defined in the above formula (3).) As a polymerization method using the compound represented by the formula (5), it is preferred to use a bulk polymerization or a solution polymerization, and it is preferred to use a bulk polymerization. When it is produced by bulk polymerization, the reaction temperature for the polymerization is required to be 50 to 250 ° C, preferably 70 to 220 ° C, and particularly preferably 1 to 190 ° C. At this time, the water and/or the alcohol generated as the reaction proceeds may be removed under reduced pressure while the reaction is carried out. When the solution is produced by solution polymerization, the concentration of the compound represented by the above formula (5) in the solution is arbitrary, but when the polymerization reaction is required, the total weight of the compound represented by the formula (5) and the solvent is 1 to 9% by mass is preferred, preferably 2 to 80% by mass, more preferably 5 to 70% by mass. In addition, the reaction temperature is required to be -8 〇 to 20 (TC, preferably 0 to 180 ° C, preferably 25 to 160 ° C, and the reaction time is required to be 〇·1 to 48 In the hour, it is preferably from 2 to 36 hours, preferably from 3 to 24 hours. In the reaction conditions described in i: the hyperbranched polymer of the present invention produced by solution polymerization, for example, can be dropped into the reaction. The solution is isolated in a poor solvent to precipitate the precipitate 19-200848449. The solvent used for the solution polymerization is preferably a solvent capable of dissolving the compound represented by the formula (5), and is, for example, an aprotic polar solvent. Specific examples of the aprotic polar solvent include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, and the like. In order to promote the reaction, a condensing agent can be used. The condensing agent is not particularly limited as long as it is a compound which promotes a condensation reaction with an amine group by activation of a carboxylic acid, and examples thereof include dicyclohexylcarbamate. Imine, N-ethyl-(3-dimethylaminopropyl)carbodiimide, carbonyl II Imidazole, triphenyl phosphite, diphenyl dichlorophosphoric acid, diphenyl (2,3-dihydro-2-thio-3-benzoxandodinyl) phosphate, etc. In addition, solution polymerization When necessary, an acid acceptor (neutralizer) can be used, and specific examples of the acid acceptor include triethylamine, tributylamine, trioctylamine, diisopropylethylamine, and decidyl D. Further, in the case of bulk polymerization and solution polymerization, the molecular weight, molecular weight distribution, and degree of divergence can be adjusted without impairing the range of the structure of the hyperbranched polymer. As a method of adjusting the molecular weight, molecular weight distribution, and degree of divergence, For example, in the polymerization reaction, a compound having two or more primary or secondary amine groups in the molecule is used, by using, for example, ethylidene diamine, propylene diamine, butyl diamine, and propylpropyl The amine, the butyl triamine, etc., can adjust the molecular weight, etc. -20- 200848449 [Production method of the compound represented by the formula (5) and the compound] Further, the compound represented by the above formula (5) can be acid, The test or reducing agent is produced by treating a compound represented by the following formula (6). 18]

R^-C-Ai-CN (6) 〇0 \-N-A4 Η {wherein, Ai, Α2 and Α3 are the same as defined in the above formula (1), and R! represents an alkyl group having 1 to 5 carbon atoms. a hydroxyalkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms, and Α4 represents a formula (7) or a formula (8): f 0 0 1 2 (7) [Chemical 20] ~if_R2 (8) Ο (In the formula (7) and the formula (8), R2 represents an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, Or an arylalkyl group having a carbon number of 7 to I.). In the above formula (7) or (8), specific examples of the hospital base having 1 to 5 carbon atoms represented by I include, for example, a methyl group, an ethyl group, a t-butyl group, a vinyl group, an allyl group, and the like. Chloromethyl, trichloromethyl, trifluoromethyl, and the like. Further, specific examples of the aryl group having a carbon number of ό to 10 include a phenyl group and the like, and specific examples of the arylalkyl group having 7 to 15 carbon atoms include benzyl group and *-21. - 200848449 Nitrobenzyl, 4-methoxybenzyl, 2,4-dimethoxybenzyl, diphenylmethyl and the like. The compound represented by the formula (5) can be produced by treating the compound represented by the following formula (6) with an acid, a base or a reducing agent. In this case, depending on the kind of the functional group represented by A4 in the formula (6), the treatment method is preferably selected from the group consisting of an acid, a base or a reducing agent. In the functional group represented by the above A4, R2 in the formula (7) represents methyl, ethyl, t-butyl, vinyl, allyl, benzyl, 4-nitrobenzyl, diphenyl. When a methyl group or the like is used, when R2 in the formula (8) represents a methyl group, an ethyl group, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group or a phenyl group, it is preferred to use an acid. In this case, the acid to be used is not particularly limited as long as the compound represented by the formula (6) can be changed to the compound represented by the formula (5), and for example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, or the like can be used. A known acid of p-benzenesulfonic acid, trifluoroacetic acid or the like. The acid is used in an amount of from 1 to 100 moles per mole of the functional group represented by A4 in the compound of the formula (6), preferably from 1 to 50 moles, and from 1 to 20 moles. Equivalent is especially good. As the reaction conditions when the acid is used, it can be appropriately selected from the reaction time of from 〇1 to 1 Torr, and the reaction temperature of from -50 to 200 °C. The reaction time is 〇. 1 to 50 hours, and the reaction temperature is preferably from 0 to 13 〇 °C. In the functional group represented by the above A4, when R2 in the formula (7) represents a methyl group, an ethyl group, a 4-nitrobenzyl group or the like, and R2 in the formula (8) represents a methyl group or a When the phenyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, -22-200848449 phenyl group or the like is used, it is preferred to use a base. In this case, as the base system to be used, the formula (6) can be changed. The base of the compound represented by the formula (5) is not particularly limited, and for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium t-butoxide, sodium hydroxide or the like can be used. Known base. The amount of the base used is from 1 to 100 times the molar equivalent of the compound represented by the formula (6) in the range of from 1 to 100 moles, preferably from 1 to 20 moles, and from 1 to 20 moles. Equivalent is especially good. As the reaction conditions in the case of using a base, the reaction time is 〇. 〇 1 to 100 hours, and the reaction temperature is appropriately selected from -5 0 to 200 °C. The reaction time is preferably from 0.1 to 50 hours, and the reaction temperature is from 0 to 130 °C. In the functional group represented by the above A4, R2 in the formula (7) represents a tert-butyl group, an ethylidene group, a fluorenyl group, a benzyl group, a 4-nitrobenzyl group, a diphenylmethyl group, or the like. In the case where R2 in the formula (8) represents a trichloromethyl group, a trifluoromethyl group or the like, it is preferred to use a reducing agent. In this case, the reducing agent to be used is not particularly limited as long as the compound represented by the formula (6) can be changed to form a reducing agent of the compound represented by the formula (5), and for example, palladium carbon or platinum carbon can be used. Hydrogenation of hydrogen, hydrogen sulfide, lithium aluminum hydride, sodium borohydride, tributyltin hydride, tris(trimethylmethyl decyl) decane, hydrazine, hydrogenation of hydrogen, hydrogen, hydrogen, lithium hydride, hydrogen hydride A known reducing agent such as acetic acid or the like. The reducing agent is used in an amount of from 1 to 100 moles per mole of the functional group represented by A4 in the compound of the formula (6), preferably from 1 to 50 moles, and from 1 to 20 moles. Ear equivalents are especially good. -23- 200848449 As a reaction condition when a reducing agent is used, it can be appropriately selected from the reaction time of from 0.01 to 100 hours, and the reaction temperature of from -50 to 200 °C. The reaction time is from 0.1 to 50 hours, and the reaction temperature is from 〇 to 130 °C. Further, the present invention relates to a compound represented by the above formula (5) (a monomer for producing a hyperbranched polymer), and a compound wherein Ri is an ethyl group is preferred. [Production Method of the Compound of the Formula (6) and the Compound] The compound represented by the above formula (6) can be represented by the following formula (9) [Chem. 21]

(X)H

N-A4 Η (9) Ν - Α 4 Η (wherein Α 2 and Α 3 are the same as defined in the above formula (1), Α 4 is the same as defined in the above formula (6), and X is the above formula (3) The definition in ) is the same.) The compound shown, formula (1 0 ): [Chem. 22]

RiO-C-ArC—Υ(10) Ο 0 (wherein Ai is the same as defined in the above formula (1), and Ri is the same as defined in the above formula (6), and Y is selected from fluorine. A leaving group of a group of a chloro group, a bromo group, an iodine group and a quinone iminosuccinate group.) The compound shown is reacted. -24- 200848449 The above formula (ίο), γ represents a leaving group, and specific examples thereof include a fluorine group, a chlorine group, a bromine group, an iodine group, a quinone iodide group, and the like. Specific examples of the compound represented by the above formula (9) include the following compounds. [Chem. 23]

Compound name: 1: [2-(2-Benzyloxycarbonylaminoethylamino)ethyl]aminobenzoic acid benzyl ester hydrochloride 2: [2 - (2-tert-butyloxycarbonylamino group) Ethylamino)ethyl]aminocarboxylic acid tert-butyl ester hydrochloride 3: [3-(3-Benzyloxycarbonylaminopropylamino)propyl] propyl carbamate hydrochloride - 25- 200848449 4: [3 -(3-tert-Butyloxycarbonylaminopropylamino)propyl]aminocarboxylic acid tert-butyl ester hydrochloride 5: [4 - (4-phenylmethyloxycarbonylamino) Butylamino)butyl]aminobenzoic acid benzyl ester hydrochloride 6: [4-(4-tert-butyloxyaminoaminobutylamino)butyl]aminocarboxylic acid tert-butyl ester hydrochloride Further, specific examples of the compound represented by the above formula (10) include the following compounds. [Chem. 24]

Br compound name = 1: ethyl amber oxime chloride 5: ethyl amber 醯 bromo 2 : methyl amber 醯 chloro 6 : methyl amber 醯 bromo-26 - 200848449 3: methyl pentane chloride 7: methyl pentane醯Bromo 4: Ethyl pentane ruthenium chloride 8: Ethyl pentane ruthenium bromide. When a compound of the formula (9) is reacted with a compound of the formula (10), it is required to be in a solvent which can be dissolved. The compound represented by the formula (9), the compound represented by the formula (10) is preferably 1.0 mole equivalent to 5.0 mole equivalent, and is preferably reacted at 1.0 mole equivalent to 2.0 mole equivalent. Further, the total amount of the compound represented by the formula (9) and the compound represented by the formula (1) in the solution is based on the total mass (the compound represented by the formula (9) and the compound represented by the formula (10). The total mass of the solvent is from i% by mass to 80% by mass, preferably from 2% by mass to 70% by mass, particularly preferably from 5% by mass to 60% by mass. When the compound represented by the formula (9) and the compound represented by the formula (10) are reacted, the solvent to be used is not particularly limited as long as it can simultaneously dissolve the two compounds, and examples thereof include N-methylpyrrolidone. N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, tetrahydrofuran, i,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone . The reaction of the compound represented by the formula (9) and the compound represented by the formula (1 〇) is carried out at a temperature of from -80 to 120 ° C, from 0 to 1 Torr. (^ is preferably carried out at 20 to 80 ° C. The reaction time is 0.1 to 48 hours, preferably from 0.2 to 36 hours, preferably from 3 to 24 hours. When a compound represented by the formula (1) and a compound represented by the formula (1) are reacted, an acid acceptor (neutralizing agent) may be used as necessary. Specific examples of the acid acceptor include triethylamine and tributyl. Amine, trioctylamine, di-27-200848449 isopropylethylamine, pyridine, quinoline, etc. Further, the present invention contains a compound represented by the above formula (6), especially wherein Ri is an ethyl group (6) a compound which is not a compound. [Addition of an organofunctional group-based hyperbranched polymer based on a terminal amine group] The present invention also relates to a part or all of the terminal amine group of the hyperbranched polymer of the above formula (4) by a guanamine bond or a hyperbranched polymer in which an imide bond is bonded to an organic functional group. The introduced organic functional group is functionally equivalent to an amine group of a hyperbranched polymer of the above formula (4), for improving the film forming property and the like. It is preferred to use an organic functional group having a bond 〇·5 to 2·0 times the molar equivalent, and a bond of 1·0 to 1. 5 times. The organic functional group is particularly preferred. The polymer having a structure in which the above organic functional group is bonded can form a guanamine by reacting the hyperbranched polymer of the above formula (4) with a terminal amine group of the polymer. A compound obtained by reacting a bond or an imine bond. <A compound which reacts with a terminal amine group to form a guanamine bond or an imine bond> a) A compound which can form a guanamine bond as a compound which can form the above guanamine bond The compound which can form an amine bond can be formed by reacting with a terminal amine group of the hyperbranched polymer which is not represented by the above formula (4), and is not particularly limited, and examples thereof include a carbonyl compound or an acid anhydride compound having a leaving group. . 0-1 carbonyl compound having leaving group -28- 200848449 The above carbonyl compound having a leaving group is represented by the following formula (11): Y1—f — R3 (11) (wherein Yi represents The leaving group, R3 represents an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cationic group having 7 to 12 carbon atoms. In (11), specific examples of the leaving group represented by Yi include a fluorine group, a chlorine group, a bromine group, an iodine group, or a quinone iminosuccinate group. Further, specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a cyclopentyl group, a n-pentyl group, a n-hexyl group, and an n-octyl group. Specific examples of the hydroxyalkyl group having 1 to 20 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, and a hydroxyoctyl group. Specific examples of the aryl group having a carbon number of 6 to 10, for example, phenyl group such as phenyl group, and the arylalkyl group having 7 to 12 carbon atoms may, for example, be a benzyl group or a phenethyl group. Specific examples of the compound represented by the above formula (1 1 ) include ethyl hydrazine chloride, propyl hydrazine chloride, butyl sulfonium chloride, amyl hydrazine chloride, hexamethylene chloride, helium ruthenium chloride, octyl chloride, and hydrazine chloride. Hexachlorobenzene, benzoquinone chloride, etc. -29-200848449 a) -2 acid anhydride compound Specific examples of the acid anhydride compound include acetic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride, and known acid anhydride compounds can be used. b) a compound capable of forming an imine bond as a compound capable of forming the above imine bond, as long as it reacts with a terminal amine group of the hyperbranched polymer represented by the above formula (4) to form an imine bond compound, and There is no particular limitation, and examples thereof include a compound having a leaving group or a (meth) acrylate compound. M-1 has a leaving group compound The above-mentioned compound having a leaving group is represented by the following formula (12). W 匕 26] Y2 - R3 (12) (wherein R 3 is the same as defined in the above formula (1 2 ), and γ 2 is a leaving group.) In the above formula (12), the departure is shown as Υ 2 Specific examples of the group include a fluorine group, a chlorine group, a bromine group, an iodine group, a toluenesulfonyl group, and a methanesulfonyl group. Specific examples of the compound represented by the above formula (1 2 ) include methyl iodide, ethyl iodide, propyl chloride, butyl chloride, pentyl chloride, hexyl chloride, g--30-200848449-based chlorine, and octane. Chlorine and the like. b) -2 (meth) acrylate compound As a specific example of the (meth) acrylate compound, methyl (meth) acrylate, ethyl (meth) acrylate or propyl (meth) acrylate may be used ( A known (meth) acrylate compound such as butyl methacrylate or 2-hydroxyethyl (meth)acrylate. Further, in the present specification, the (meth) acrylate compound means both an acrylate compound and a methacrylate compound. For example, methyl (meth)acrylate means methyl acrylate and methyl methacrylate. In addition, since the reaction of the amine group of the hyperbranched polymer represented by the above formula (4) with the (meth) acrylate compound is Michael addition. (Michael addition), theoretically, the (meth) acrylate compound can be added up to 2 times the molar equivalent relative to the amount of the amine group. <Reaction of a polymer terminal amine group with a compound capable of forming a guanamine bond or an imine bond> An amine group of the hyperbranched polymer represented by the formula (4) and a compound capable of forming a guanamine bond or an imine bond A guanamine bond or an imine bond can be formed between the two compounds by mixing in a solvent which can be dissolved or dispersed together. In this case, examples of the solvent to be used include water, methanol, ethanol, n-propanol, 2-propanol, butanol, ethylene glycol, diethylene glycol, propylene glycol, ethyl alcohol monoformic acid, and ethylene glycol. Ether, diethylene glycol monomethyl ether, diethyl-31 - 200848449 glycol dimethyl ether, propylene glycol monomethyl ether, tetrahydrofuran, 1,4-dioxane, acetone, N-methylpyrrolidone, n, N - two Methylformamide, N,N-dimethylacetamide, acetonitrile, dimethyl hydrazine, and the like. Further, 'the ratio of the amine group of the hyperbranched polymer represented by the above formula (4) to the compound capable of forming a guanamine bond or an imine bond is '〇·〇1 to 100 times the molar equivalent, It is preferably from 0.05 to 50 times the molar equivalent, and more preferably from 1 to 20 times the molar equivalent. Further, as the reaction conditions, the reaction time may be from 0.01 to 200 hours, the reaction temperature is from -50 to 200 °C, and the reaction time is from 0.1 to 1 hour, and the reaction temperature is preferably from 130 to 130 °C. Further, in the above reaction, when the compound capable of forming a guanamine bond or an imine bond is the acid anhydride compound or the compound represented by the above formula (1 1 ), the amine of the hyperbranched polymer represented by the formula (4) For the base reaction, an acid acceptor can be used as needed. Specific examples of the acid acceptor include triethylamine, tributylamine, trioctylamine, diisopropylethylamine, hydrazine, and porphyrin. The hyperbranched polymer obtained by the above reaction having a structure in which an organic functional group is based on a part or all of the terminal amine group of the hyperbranched polymer represented by the formula (4) by a guanamine bond or an imine bond can be used. The solvent is distilled off in the reaction solution, or the solvent is separated by solid-liquid separation. Further, the above-mentioned super-branched polymer having an addition functional organic structure may be subjected to powder recovery by adding a reaction solvent to a poor solvent such as heptane or hexane. -32- 200848449 [A varnish for dissolving or dispersing a hyperbranched polymer]. The hyperbranched polymer of the present invention (hereinafter referred to as a hyperbranched polymer (I)) represented by the above formulas (1) to (4) is dissolved or It can be used as a varnish of a hyperbranched polymer in an organic medium which is not only a single medium of water but also has compatibility with water or such a mixed medium. Further, the hyperbranched chain of the present invention having a structure in which a part or all of the terminal amine group of the hyperbranched polymer of the above formula (3) or (4) is added by a guanamine bond or an imine bond The polymer (hereinafter referred to as a hyperbranched polymer (II)) is dissolved or dispersed in an organic medium and can be used as a varnish of a hyperbranched polymer. The above-mentioned hyperbranched polymers (I) and (II) are both dissolved varnishes. Examples of the medium in which the above-mentioned hyperbranched polymer (I) or (II) can be dissolved or dispersed are as follows: water, methanol, ethanol, n-propanol, 2-propanol, butanol, ethylene glycol, diethylene glycol , propylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, tetrahydrofuran, 1,4-dioxane, acetone, N-methylpyrrolidone, N,N-dimethylformamide, n,N-dimethylacetamide, acetonitrile, dimethylhydrazine, and the like. These media may be used singly or in combination of two or more media. To adjust the pH of these media, a pH buffered aqueous solution can also be used. Further, any inorganic salt or organic salt can be used to adjust the salt strength. Dissolving or dispersing the concentration of the above-mentioned hyperbranched polymer (I) or (π) in the above-mentioned -33-200848449 solvent, relative to the total mass of the hyperbranched polymer (I) or (II) and the medium (total mass) The concentration of the hyperbranched polymer (I) or (Π) is 0.001 to 90% by mass, preferably 0.002 to 80% by mass, particularly preferably 0.005 to 70% by mass. [Coated film of hyperbranched polymer and solid phase carrier coated with the polymer film] The above-mentioned hyperbranched polymer (I) or (II) of the present invention is coated or adsorbed by any solid phase carrier as defined below A film of the hyperbranched polymer (I) or (II) of the present invention or a solid phase carrier coated on the surface of the support with the polymer can be obtained. The solid phase carrier used in the present invention refers to a solid which can be coated by coating or adsorbing the hyperbranched polymer (I) or (II) of the present invention, and particularly has no limitation on the material, shape, size, etc., and any one can be used. Specific examples of the solid phase carrier material as the solid phase carrier material include various resin materials such as polyalkene, polystyrene, polyethylene, polycarbonate, polyamide, polyester, and acrylic resin, and glass. Inorganic materials such as alumina, carbon, and metals. Further, examples of the shape of the solid phase carrier include a flat plate shape, a granular shape, a fibrous shape, a film shape, and a sheet shape. These solid phase carriers may be used alone or in combination of two or more materials depending on the material, shape, size, etc., or may be used at a specific ratio. For example, a glass flat plate shape, a resin flake shape, a resin flake shape, a resin film shape, a laminate of an inorganic material and a resin material, or a particulate form of various materials, a fibrous individual, such a mixture, or the like, or -34- 200848449 A mixture of resin film and inorganic materials. Further, the solid phase carrier may be used as it is, or may be coated with a surface treatment (e.g., surface-coated with a coating material such as a metal or a metal oxide), and then coated with the hyperbranched polymer of the present invention on the surface. Further, in order to bond the solid phase carrier to the hyperbranched polymer (I) or (Π) of the present invention, a functional group may be introduced based on the solid phase carrier. The functional group may be any one, and examples thereof include a carboxyl group, an aldehyde group, a halogen group, a carbonyl group, an epoxy group, a vinyl group, a succinimide group, and the like, and the solid carrier and the hyperbranched polymer of the present invention can be bonded by a chemical bond. (I) or (II) a functional group bonded. In addition, the super-branched polymer of the present invention (the bond mode of the ruthenium or (11) and the solid support may be a chemical bond of a covalent bond, a hydrogen bond, a coordinate bond, an ionic bond, or the like, or may be physically adsorbed, and As a method of coating the super-branched polymer (I) or (II) of the present invention on a solid phase carrier, the above-mentioned overrun is covered by an impregnation method, a brush coating method, a casting method, a spin coating method, or the like. The varnish of the chain polymer (I) or (II) is coated on the solid phase carrier. Alternatively, the solid phase carrier may be coated only by immersing the above solid phase carrier in the varnish liquid of the hyperbranched polymer (I) or (II). [Embodiment] The present invention will be further described by the following examples, but the present invention is not limited thereto. -35 - 200848449 [Physical property measurement conditions] In the following examples, the physical properties of the samples were measured. The apparatus and measurement conditions are as follows: (1) Identification of compound and polymer: iH-NMR spectroscopy apparatus: JNM-LA400 manufactured by JEOL DATUM, solvent: CDC13, DMSO-d6, D20 (2) Determination of molecular weight (polymerization) Ethylene oxide conversion : Gel Permeation Chromatography Apparatus: Showa Denko (shares) manufactured by GPC-101 Column: of TOSOH (shares) manufactured by TSK-GEL a -5000 + TSK-GEL a -2500

Column temperature: 40 °C Solvent: 0.5 M acetic acid / sodium acetate aqueous solution Detector · RI (differential refractometer) (3) Determination of transparency · UV_vis spectrum

Device: (share) UV-2400PC manufactured by Shimadzu Corporation (4) Measuring contact angle device · Concord interface science (share) automatic contact angle meter CA-W type temperature: 2 3 · 0 t: -36- 200848449 Humidity: 50%

Liquid amount: 3 // L Stability time after liquid administration: 5 seconds [Production Example 1: Synthesis of benzyl phenyl carbonate] Add 54 g of benzyl alcohol (manufactured by Kanto Chemical Co., Ltd.), 50 mL of pyridine (pure) IE Chemical Co., Ltd., and 8 7 m L·dichloromethane (manufactured by Kanto Chemical Co., Ltd.) in a reactor of 500 mL, and then, 78 g of phenyl chloroformate was added dropwise (Tokyo Chemical Industry Co., Ltd.) System] 'Manage temperature to 25 ± 5 ° C, stir for 3 hours. After the reaction, the organic phase was sequentially subjected to a liquid separation treatment using a 2N aqueous hydrochloric acid solution followed by distilled water. The organic phase was evaporated under reduced pressure, and the obtained residue was evaporated to dryness, mjjjjjjj The NMR spectrum measurement results of the obtained compound are shown below.

NMR j-NMR (solvent: CDC13) : 5 5.27 ( s, 2H ) ' 7.17 - 7.43 ( m, 1 0H ) [Production Example 2: Synthesis of [2-(2-phenylmethyloxycarbonylaminoethylamino) ) Ethyl] benzyl carbazate hydrochloride] Addition of 15 g of diethyltriamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 mL of dimethylformamide (Kanto Chemicals ( (manufacturing)) in a reactor of 1000 mL, after which, a preparation example of dissolving 72 6 g is added dropwise; [Synthetic benzyl phenyl carbonate in 50 g of dimethylformamide solution, tube -37-200848449 Stir at 15 ° ± 5 ° C for 15 hours. After the reaction, 300 g of 2N aqueous hydrochloric acid solution was added dropwise, and the deposited precipitate was filtered, and solid-liquid washed with ethanol (manufactured by Kanto Chemical Co., Ltd.). The obtained powder was dried under reduced pressure to give 51.6 g (yield: 87%) of white crystals of [2-(2-phenylmethyloxycarbonylaminoethylamino)ethyl] salt. The NMR spectrum measurement results of the obtained compound are shown below.

NMR W-NMR (solvent · DMSO-d6 ) ·· (5 3.00 ( t, 4H ), 3.32 (t, 4H), 5.04 (s, 4H), 7.32 - 7.37 (m, 8H), 7.48 (t, 2H), 8.88 (s, 2H) [Example 1: Synthesis of N,N-bis(2-phenylmethyloxycarbonylaminoethyl) succinic acid] Addition of 7 g of the synthesis example 2 [2 - ( 2-Benzyloxycarbonylaminoethylamino)ethyl]aminobenzoic acid benzyl ester hydrochloride, l〇〇g of dimethylformamide (manufactured by Kanto Chemical Co., Ltd.), and 3 · 7 g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) was placed in a 500 mL reactor, and then 1.7 g of succinic anhydride (manufactured by Kanto Chemical Co., Ltd.) was dissolved in 1 g of dimethylformamide (Kanto). A solution of a chemical (manufactured by a chemical) system. Thereafter, the temperature was adjusted to 25 ± 5 ° C, stirred for 15 hours, and the solvent was evaporated under reduced pressure. chloroform (manufactured by Kanto Chemical Co., Ltd.) was added in that order. The aqueous solution of 0.5 N hydrochloric acid was then subjected to liquid separation treatment, and the organic phase was evaporated under reduced pressure, and the residue was evaporated to dryness to give 7.8 g (yield: 97%) of oily yt. Oxycarbonylaminoethyl ethyl succinic acid The structure of the resulting compound of structural formula of -38-200848449 (formula (13)) and the NMR spectrum shown below based Cloth results

[271

NMR W-NMR (solvent: CDC13): 5 2.53 (br s, 4H), 3.29 (brs, 4H), 3.41 (brs, 4H), 5.05 (d, 4H),

5.55 (brs, lH), 5.07 (brs, lH), 7.32 (brs, 10H) [Example 2: Synthesis of N,N-bis(2-aminoethyl) succinic acid] Example of adding 7.2 g 1 Synthesis of N,N-bis(2-benzyloxycarbonylaminoethyl) succinic acid, 144 g of methanol (manufactured by Kanto Chemical Co., Ltd.), 0.72 g of 5% Pd carbon powder (aqueous product) The PE type (manufactured by NECHEMCAT Co., Ltd.) was placed in a 500 mL reactor, and the reactor was replaced with hydrogen. After that, the temperature was adjusted to 50 ± 5 ° C, and the mixture was stirred for 10 hours. After filtering the Pd carbon powder, the solvent was evaporated under reduced pressure, and the residue was evaporated to dryness to dryness to give the oil (yield: 100%). - bis(2-aminoethyl) succinic acid. -39- 200848449 The structural formula (formula (14)) and NMR spectrum measurement results of the obtained compound are shown below. Structural formula W 匕 28]

NMR iH-NMR (solvent: DMSO-d6): 6 2.32 (t, 2H), 2.38 (t, 2H), 2.65-2.73 (m, 2H), 2.84-2.96 (m, 4H), 3 · 1 8 ( Br s, 2H ) [Example 3: Synthesis of N,N-bis(2-benzyloxycarbonylethyl)ethyl succinate]

27.5 g of [2-(2-benzyloxycarboylaminoethylamino)ethyl]aminocarbamic acid benzyl ester hydrochloride synthesized in Preparation Example 2, 25 g of tetrahydrofuran (Kantong Chemical ( (manufactured by the company), and 8.2 g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) in a reactor of 1,100 m, and then dropped into 13.3 g of ethyl ruthenium chloride (Tokyo Chemical Industry Co., Ltd.) Stock system)). Thereafter, the temperature was adjusted to 2 5 ± 5 ° C, stirred for 3 hours, and 1 〇 g of distilled water was added to stop the reaction, and the solvent was evaporated under reduced pressure. 500 g of toluene (manufactured by Kanto Chemical Co., Ltd.) was added thereto, followed by liquid separation treatment with 0. 1N aqueous hydrochloric acid solution, 1N-40-200848449 sodium hydroxide aqueous solution, and distilled water, followed by distillation under reduced pressure. The residue obtained was dried under reduced pressure to give 25 g (yield: 75%) of N,N-bis(2-phenylmethyloxycarbonylaminoethyl) succinic acid ethyl ester. The structural formula (formula (15)) and the NMR spectrum measurement results of the obtained compound are shown below. Structural formula

(wherein Et is an ethyl group)

NMR iH-NMR (solvent: CDC13): 5 1.23 (t,3H), 2.53 - 2.62 (m, 4H), 3.36 (brs, 4H), 3.46 (brs, 4H), 4.06 (q, 2H), 5.34 ( Brs,lH), 5.37 (brs,lH), 7.27 — 7.34 ( m,1 OH ) [Example 4: Synthesis of N,N-bis(2-aminoethyl) succinic acid ethyl ester] Add 5 g Example 3 Synthesis of N,N-bis(2-benzyloxycarbonyl-41 - 200848449-aminoethyl) succinic acid ethyl ester, 50 g of methanol (manufactured by Kuan), and 〇.5g 5% Pd carbon powder (aqueous product) NECHEMCAT (manufactured by NECHEMCAT) was replaced by hydrogen in a 200 mL reactor. Thereafter, the management temperature was 25 ± 5 ° C, and the Pd carbon powder was filtered by stirring for 1 Torr. The solvent was evaporated under reduced pressure and dried under reduced pressure to give 2.7 g of N,N-bis(2-aminoethyl) Ester crude. The structural formula (formula (16)) and the NMR results of the obtained compound are shown below. Structural formula [Chem. 30] Dongchemistry (PE type (in the reactor, hour, residue, prolybdic acid B spectrometry)

(wherein Et is an ethyl group)

NMR, 2.66 (t, 3.52- 'H-NMR (solvent: D2 〇): 5 1.24 (t,3H), 2H), 2.83 (t, 2H), 2.93-3.0 3 (m, 4H) 3·58 ( m, 4H ) , 4· 14 ( q ' 2H ) [Example 5: Synthesis of hyperbranched polymer A] -42- 200848449 N,N-bis(2-amino-based) synthesized in Example 2 The succinic acid was synthesized in a 50 mL reactor at a temperature of 180 ± 5 ° C under a reduced pressure, and subjected to bulk polymerization for 5 hours to synthesize a hyperbranched polymer A. The obtained polymer was subjected to gel permeation chromatography to have a weight average molecular weight of 2,500 in terms of polyethylene oxide and a degree of dispersion (weight average molecular weight / number average molecular weight) of 1.49. The obtained hyperbranched polymer A can be dissolved in water and methanol to a concentration of 5% by mass, respectively. The structural formula (formula (17)) and the NMR spectrum measurement results of the obtained hyperbranched polymer A are shown below. Structural formula [Chem. 31]

(17) (where A!, A2, and A3 are respectively expressed as an ethyl group)

NMR JH-NMR (solvent: D20): δ 2.73 - 2·82 (m, 4H), 3.51 - 3.63 (m, 4H), 3.82 - 4.04 (m, 4H) [Example 6: Synthesis of Hyperbranched Polymerization Add b. 2g of the n, N-bis(2-aminoethyl-43-200848449) ethyl succinate prepared in Example 4 in a 50 mL reactor, and manage the temperature to 120 ± 5 °C. The bulk polymerization was carried out for 9 hours under reduced pressure to synthesize hyperbranched polymer B. The obtained polymer was subjected to gel permeation chromatography to have a weight average molecular weight of 15,000 in terms of polyethylene oxide and a degree of dispersion (weight average molecular weight / number average molecular weight) of 2.58. The obtained hyperbranched polymer B system can be dissolved in water and methanol to a concentration of 5% by mass, respectively. Further, when the aqueous solution of 0.002% by mass of the polymer B was subjected to UV-vi s spectrum measurement, it was found that no absorption was observed at 35 nm or more, and high transparency was obtained. The structural formula (formula (18)) of the obtained hyperbranched polymer B and the NMR spectrum measurement results are shown below. Structural formula

(In the formula, Et is not ethyl, and Αι, A2 and A3 are respectively expressed as ethyl.)

NMR iH-NMR (solvent: D20): 52.70 - 2.81 (m, 4H), 3.37 - 3.66 (m, 4H), 3.83 - 4.03 (m, 4H) -44 - 200848449 [Example 7: Evaluation of hyperbranched polymerization Hydrophilization of the surface of the glass piece treated with the material B] The methanol solution of 1% by mass of the branched polymer B synthesized in Example 6 was adjusted. Next, the glass piece was immersed in the solution for 1 hour, and then washed with methanol, and dried under reduced pressure at a temperature of 40 ° C to carry out surface treatment of the glass piece. Pure water The contact angle of the surface-treated glass piece was 29.2 ° ° On the other hand, pure water was washed with methanol for 1 hour after being immersed in (pure) methanol at a temperature of 40. (The contact angle of the glass sheet which was dried under reduced pressure was 33.8°. That is, the hydrophilicity of the surface of the glass piece coated with the surface of the hyperbranched polymer B synthesized in Example 6 was obtained. [Example 8] : Synthesis of Hyperbranched Polymer C] The branched polymer B synthesized in Example 6 was added to a 50 mL reactor and dissolved in 2 g of methanol (manufactured by Kanto Chemical Co., Ltd.). Next, 〇.2 g was added. Methyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), the temperature was 25 ± 5 ° C, and the mixture was stirred for 90 hours. Thereafter, the solvent (methanol) was evaporated under reduced pressure, and the residue obtained was dried under reduced pressure to give y. The results of NMR spectroscopy of 2 g of the hyperbranched polymer C obtained from the ultra-branched polymer C ° of the amine group terminal of the branched polymer B by the imine bond-bonding function are shown below.

NMR -45-200848449^-NMR (solvent: D2〇) : 5 2.33 (br s 2.71 (brs, 4H), 3.07 (brs, 2.8H) > 3.3 (cannot be measured with the peak from the water in the solvent) s, 4.2H), 3.73 - 3.92 (m, 4H) From the results of the above iH-NMR measurement, it was confirmed that the ethyl group (in the formula (18), hexa, VIII, or 4H) was bonded to the polymer B. Ethyl group (2·8Η, 2·8Η, 4.2Η) represented by formula (19) having 1.4 times molar equivalent. Further, regarding the over-branch, since the number of amine-terminated ends is theoretically substantially the same as the number of repeating units of ethyl groups, the obtained hyperbranched polymer is shown to be in an amount relative to the amine-based terminal of the above-mentioned hyperbranched polymer. base. /^OMe (19) (wherein Me represents a methyl group) The obtained hyperbranched polymer C is soluble in dimethylpyrrolidone to a concentration of 5% by mass. [Example 9: Formation of film of hyperbranched polymer C] A solution of 5 fluorene of the hyperbranched polymer c obtained in Example 8 was adjusted. After using a solution of PTFE of 〇·2//ιη, on a glass substrate, at 30 rpm, 5, 2.8H), and a 3·5 1 (in, 3 · 5 6 (br The hyperbranched chain A3 is a methoxycarbonyl chain polymer B η, that is, each of the C extensions, which is guided by 4 times Mo 砺 砺 and Ν 质量 质量 二甲 二甲 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤 滤5 0 0 rp m, 20 seconds rotation coating method, heating at a temperature of 200 ° C for 10 minutes to obtain a film-like formation of 126 nm. Industrial Applicability The hyperbranched polymer system of the present invention, resin coating Various molding materials, chemical mechanical honing agents, photonic crystals of functional materials, sub-materials, data recording materials, printing materials, magnetic materials, etc., especially coated on the surface of the carrier, are effectively used as coating materials. After that, on the heating plate, the film thickness on the glass substrate is a coating, an ink, a nano-sized porous forming agent, a carrier material, a nanocapsule, a photoresist material, an optical material, an electric material, a battery material. When the medical material is on the solid phase carrier, change it. Solid -47-

Claims (1)

200848449 X. Patent application scope 1. A hyperbranched polymer characterized by having the formula (1) [Chemical 1] (wherein Ai represents a linear, branched or cyclic alkyl group having a carbon number of 1 to 30 or a carbon number of 6 to 10 in which a guanamine bond or an ether bond is contained in the group; Arylene or alkylarylene, A2 and A3 are linear, branched or cyclic alkyl groups having from 1 to 30 carbon atoms which may contain a guanamine bond or an ether bond in the group. The η system represents a structure represented by an integer of 2 to 100,000. 2) A hyperbranched polymer as claimed in claim 1 which has the formula (2): (wherein, Ai'Az'As and η are the same as defined in formula (1), and Ri is a gas atom, a ash number of 1 to 5, a carbon number of 1 to 5, and a carbon. A structure represented by an aryl group of 6 to 10 or an arylalkyl group having 7 to 12 carbon atoms. 3 · For example, the hyperbranched polymer of claim 1 has the formula (3): -48- 200848449 (wherein A!, A2, A3 and η are the same as defined in the formula (}), and the oxime means an acidic compound added to at least a part of the amine group terminal, and may have no structure represented by X). 4. The hyperbranched polymer according to any one of claims 1 to 3, which has the formula (4): [Chemical 4] (wherein A!, A2, A3, and n are the same as defined in formula (i), and 1 is the same as defined in formula (2), and the lanthanide is the same as defined in formula (3)) structure. 5. The hyperbranched polymer of claim 2 or 4, wherein in the formula (2) or (4), Ri is a hydrogen atom or an ethyl group. 6. The hyperbranched polymer of any one of claims 1 to 5 wherein the weight average molecular weight measured by gel permeation chromatography in terms of polyethylene glycol is from 400 to 20,000,000. 7 - A method for producing a hyperbranched polymer as shown in the formula (4) of claim 4, which is characterized in that -49- (5) 200848449 (5) ΝΗ2(Χ) RfO—C~~A'- C~N α3——ΝΗ2(Χ) ο δ, (wherein Ai, Α2, and Α3 are the same as defined in formula (1)' Rl system and formula ( The definitions in 2) are the same, and the X system is the same as the one defined in the formula (·3). 8. The method of producing a hyperbranched polymer according to claim 7 of the patent application, wherein in the polymerization step of the compound represented by the formula (5) of claim 7 of the patent, by bulk polymerization or solution polymerization. 9. The method for producing a hyperbranched polymer according to item 8 of the patent application, wherein in the polymerization step of the compound represented by the formula (5) in claim 7 of the patent application, the generated water and/or alcohol are removed while Block polymerization was carried out at a temperature of 50 ° C to 250 ° C. 10. A method for producing a compound as shown in the formula (5) of claim 7 which is characterized by the formula (6): [Chemical 6] A2-N~A4 r^^-c-.nh (6) 6 Ο Α3-Ν -~ Η {wherein, Α!, 八二和Α; is the same as defined in formula (1), R1 is an alkyl group having 1 to 5 carbon atoms, and carbon number 1 to 5 a hydroxyalkyl group, an aryl group having 6 to 1 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms, wherein the phantom system represents the formula (7) or the formula (8) = -50- 200848449 [Chem. 7] - C- 〇-R2 (7) Ο [Chemical 8] —C-R2 (8) Ο (In the formulas (7) and (8), R2 represents an alkyl group having 1 to 5 carbon atoms and a carbon number of 6 to 10 A compound represented by a group or an arylalkyl group having 7 to 15 carbon atoms, which is formed by treatment with an acid, a base or a reducing agent. A compound represented by the formula (5) of claim 7 which is characterized in that it is an ethyl group. 1 2 - A method for producing a compound represented by the formula (6) of claim 10, which is characterized by the formula (9): [Chem. 9] A2-N-A4 (X)HN (H) (9) A3——N-A4 H (wherein a2 and A3 are the same as defined in formula (1), A4 is the same as defined in formula (6), and X is defined in formula (3) The compound shown in the same formula, and the formula (1 〇): [Chemical 10] R^-c-ArC-Y (10) 0 0 (wherein the A! system is the same as defined in the formula (1), and The Ri system is the same as defined in the formula (6), and the Y system represents a group selected from the group consisting of a fluorine group, a chlorine group, a bromo group, a -51 - 200848449 iodine group and a quinone group of a hydroxy succinic acid group. The compound is formed by the reaction of the compound. The compound represented by the formula (6) of the first aspect of the patent application is characterized in that it is an ethyl group. 14. A hyperbranched polymer characterized by A part or all of the terminal amine groups of the hyperbranched polymer represented by the formula (4) of claim 4 of the patent application are bonded to an organic functional group by a guanamine bond or an imine bond. Ultra-branched polymer varnish To dissolve or disperse the hyperbranched polymer of any one of claims 1 to 6 or 14 to the medium. 1 6. A hyperbranched polymer film characterized by the scope of the patent application The super-branched polymer of any one of items 1 to 6 or item 14 is formed. 17. A solid phase carrier characterized by covering the scope of claim 1 to item 6 or item 14 Any of the super-branched polymers on the surface of the carrier 0 - 52 - 200848449 VII, the designated representative figure: (a), the representative figure of the case is: no (two), the representative symbol of the representative figure is a simple description: no eight If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention.