TWI391423B - Polyimide having an alcoholic hydroxyl group and a process for producing the same - Google Patents

Description

Polyimine with alcoholic hydroxyl group and preparation method thereof

The present invention relates to a novel polyimine and a method for producing the same, which are suitable for use as a protective insulating film for a semiconductor element, an insulating film for a multilayer printed substrate, and solder protection because of heat resistance, chemical resistance, insulation, and flexibility. A film, a cover lay film or the like is a novel polyimine having a first-order hydroxyl group and a method for producing the same.

Various reviews of the polyhydroxyimine having a hydroxyl group have been proposed.

For example, Japanese Patent Publication No. 2001-335619 (Patent Document 3) discloses a polyimine having a phenolic hydroxyl group in JP-A-H06-200216 (Patent Document 1) and Japanese Patent No. 3329677 (Patent Document 2). A polyimine having an epoxy group or an unsaturated hydrocarbon group and a second-order alcoholic hydroxyl group is proposed. However, a highly reactive polyimine having a primary alcoholic hydroxyl group has not been developed.

[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2001-335619.

[disclosure of the invention]

The present invention has been made in view of the above, and provides a novel polyimine having a first-order alcoholic hydroxyl group and a process for producing the same.

In order to achieve the above object, the present inventors have completed the present invention by repeatedly obtaining the novel polyimine having an alcoholic hydroxyl group represented by the following general formula (1).

A polyimine having a primary alcoholic hydroxyl group represented by the following general formula (1).

Wherein X is a tetravalent organic group, Y is a divalent organic group represented by the general formula (2), Z is a divalent organic group, W is a divalent organic group having an organic decane structure, and 1 is a positive number. m, n are each 0 or a positive number, 0.1≦1/(1+m+n)≦1,0≦m/(1+m+n)≦0.8, 0≦n/(1+m+n)≦0.8.

(wherein A is selected from Any of the divalent organic groups may be the same or different, and each of B and C is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, which may be the same or different from each other, and a and b are 0 or 1, c. It is an integer from 0 to 10.

Further, in the formula, R ¹ is a monovalent group selected from a phenolic hydroxyl group, a carboxyl group or an organic group having an alcoholic hydroxyl group, and at least one of R ¹ is an organic group having an alcoholic hydroxyl group.

The polyimide having a primary alcoholic hydroxyl group of the present invention has excellent adhesion to a substrate, is excellent in heat resistance and electrical insulation, and can be suitably used as a protective film for electric appliances, electronic parts, and semiconductor elements.

[Best form of implementing the invention]

The invention is described in more detail below. The polyimine of the present invention is a repeating unit represented by the following general formula (1).

X in the general formula (1) in the above formula is a tetravalent organic group, and specifically contains at least one group represented by the following formula.

Y in the general formula (1) is a divalent organic group having a primary alcoholic hydroxyl group represented by the general formula (2).

In the formula, A, a, b, and c are in accordance with the foregoing, and each of B and C is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and may be mutually different or the same. Specifically, a methyl group or a The group is preferably a propyl group or a butyl group in which a methyl group or a hydrogen atom is easily obtained from a raw material.

In the above formula, R ¹ is a valent group selected from a phenolic hydroxyl group, a carboxyl group or an organic group having an alcoholic hydroxyl group, and at least one of R ¹ is an organic group containing a primary alcoholic hydroxyl group. Specifically, it represents -OH, -COOH, -OCH ₂ CH(OH)CH ₂ OH, -OCH(CH ₂ OH)CH ₂ OH, a COOCH ₂ CH(OH)CH ₂ OH or a COOCH (CH ₂ OH) ) CH ₂ OH.

In the Y aspect, specifically, the following structure can be exemplified.

Further, Z in the general formula (1) is a divalent organic group represented by the following general formula (3).

In the above formula, D is selected from The divalent organic groups of any one of them may be the same or different from each other, and e, f and g are 0 or 1.

In the Z aspect, specifically, the following structure can be exemplified.

Further, in the general formula (1), W is a divalent organic group represented by the following general formula (4).

In the general formula (4), R ³ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different. Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an aryl group such as a phenyl group; An alkenyl group such as phenethyl group, an alkenyl group such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group or a butenyl group; an acryl group or a methacryl group; and the like. From the viewpoint of easy availability of the raw materials, methyl, ethyl, phenyl, and vinyl are preferred. Further, h is a positive number of 1 to 80, preferably 3 to 70, more preferably 5 to 50.

Further, in the general formula (1), 1, m, n are each a positive number of 2≦1≦2000, 0≦m≦2000, 0≦n≦2000, which satisfies 0.1≦1/(1+m+n)≦1.0,0≦m / (1 + m + n) ≦ 0.8, 0 ≦ n / (1 + m + n) 正 0.8 positive number. When 1/(1+m+n) is less than 0.1, the effect of the primary alcoholic hydroxyl group is not easily exhibited, so it is not preferable.

The molecular weight of the polyimine represented by the general formula (1) of the present invention is usually from 2,000 to 800,000, preferably from 5,000 to 500,000. When the molecular weight is 5,000 or less, the film strength of the obtained polyimide resin is lowered, which is not preferable. When the molecular weight is 5,000,000 or more, the compatibility with the solvent is not preferable.

The polyethylenimine having an alcoholic hydroxyl group represented by the general formula (1) of the present invention, a phenolic hydroxyl group and/or a diamine having a carboxyl group and an acid dianhydride may be used as needed with a diamine having no phenolic hydroxyl group and hydroxyl group. And/or diaminopolyoxyl reaction, obtaining polyamic acid, and obtaining a polyimine having a phenolic hydroxyl group and/or a carboxyl group represented by the general formula (5) by a dehydration ring closure reaction. This is followed by reaction with glycidide.

In the formula, X, Z, W, l, m, n are as described above, and Y' is a divalent organic group represented by the following general formula (6).

Wherein A, B, C, a, b, and c are as disclosed above, and R ² is selected from the group consisting of -OH or -COOH.

The polyimine having a phenolic hydroxyl group and/or a carboxyl group is a diamine having an phenol group and/or a carboxyl group and an acid dianhydride, and may be a diamine and/or a diamino group having no phenol group or carboxyl group as needed. Oxygen reaction, after obtaining polyamic acid, can be obtained by a dehydration ring closure reaction.

The acid dianhydride used for the polymerization of polyamic acid may, for example, be 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetra Carboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3- Cyclohexene-1,2-dicarboxylic acid anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride , 1,2,3,4-butane tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 4,4'-hexafluoropropylene bis-o-benzene Dicarboxylic acid dianhydride, 2,2-bis(p-trimethoxyphenyl)propane, 1,3-tetramethyldioxane diphthalic dianhydride, 4,4'-oxydi-phenylene Formic acid dianhydride.

Further, the phenolic hydroxyl group and the diamine of the carboxyl group may, for example, be 3,3'-diamino-4,4'-dihydroxybiphenyl or 2,2'-diamino-4,4'-dihydroxyl linkage. Phenyl, 2,2-bis(4-amino-3-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 9,9'-bis(3-amino- 4-hydroxyphenyl)indole, 2,2'-methylenebis[6-(4-amino-3,5-dimethylbenzyl)-4-methyl]phenol, 3,3'-diamino -4,4'-dihydroxydiphenyl ether, a diamine having a phenol group such as 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4 , 4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-dicarboxy-4,4'-diaminodiphenyl ether, and the like.

Further, the phenolic hydroxyl group and the diamine of the carboxyl group may, for example, be 4,4'-diaminobenzamide, 4,4'-diaminodiphenyl ether or 3,4'-diaminodiphenyl. Ether, 4,4'-diaminodiphenylanthracene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-(p-phenylene diisopropylidene Diphenylamine, 4,4'-(m-phenylenediisopropylidene)diphenylamine, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy) Benzene, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4- Aminophenoxy)phenyl]hexafluoropropane, bis[4-(4-aminophenoxy)phenyl]]indole, bis[4-(3-aminophenoxy)phenyl]indole, 4,4 '-Bis(4-aminophenoxy)biphenyl, 9,9-bis(4-aminophenyl)anthracene, and the like.

In the synthesis of polyamic acid, the ratio of the diamine component to the tetracarboxylic dianhydride component can be appropriately determined depending on the adjustment of the molecular weight of the polyimine, and the molar ratio is usually 0.95 to 1.05, preferably 0.98. The range of 1.02. Further, in order to adjust the molecular weight of the polyimine, it is also possible to add a monofunctional acid anhydride such as phthalic anhydride or aniline and an amine compound. In this case, the amount of addition is preferably 5 mol% or less based on the tetracarboxylic dianhydride component or the diamine component.

The synthesis of polyimine is carried out by heating the polyamic acid solution obtained above, usually at a temperature of 80 to 200 ° C, preferably 140 to 180 ° C, or by adding acetic anhydride/pyridine mixed in a polyamic acid solution. The solution is then heated to about 50 ° C by the resulting solution to carry out a dehydration ring-closure reaction on the acid amide portion of the polylysine to obtain a polyimine.

The reaction of the diamine with the acid dianhydride is usually carried out in a solvent. In terms of the solvent to be used, it is preferred to dissolve the polyimine. Specific examples of the solvent include ethers such as tetrahydrofuran and anisole; ketones such as cyclohexanone, 2-butanone, methyl isobutyl ketone, 2-heptanone, 2-octanone, and ethyl benzene. Ester of butyl acetate, methyl benzoate, γ-butyrolactone, etc.; cellosolve of butyl cellosolve acetate, propylene glycol monomethyl ether acetate, etc.; N, N-dimethyl Amidoxime, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like, and an aromatic hydrocarbon such as toluene or xylene, preferably a ketone or an ester. And cellosolve, particularly preferably γ-butyrolactone, propylene glycol monomethyl ether acetate, N,N-dimethylacetamide, N-methyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more. Usually, the concentration of each batch, the viscosity, and the like are considered to adjust the concentration of the polyimine to be in the range of 10 to 40% by weight.

In the molecule represented by the above general formula (5) obtained in this manner, the necessary equivalent amount of glycidol is added to the phenolic hydroxyl group or the organic solvent solution of the polyimine having a carboxyl group, and the purpose can be obtained by heating. The polyimine having an alcoholic hydroxyl group represented by the above general formula (1). The amount of glycidol added needs to be appropriately changed depending on the amount of introduction of the alcoholic hydroxyl group. Often, it is preferably from 0.3 to 3 times the molar amount of the phenolic hydroxyl group or the carboxyl group. The reaction temperature is from 40 ° C to 180 ° C, preferably from 60 ° C to 130 ° C. The reaction time is from several minutes to 12 hours. Further, in order to accelerate the reaction, a catalyst such as triethylamine may be added.

The polyimine obtained by this method is mainly a polyimine having a primary alcoholic hydroxyl group and a hydroxyl group because of reactivity and the like. The novel polyimine having a primary alcoholic hydroxyl group can be used for a protective insulating film for a semiconductor element, a multilayer printed substrate by utilizing reactivity of a hydroxyl group thereof, heat resistance, chemical resistance, insulation property, and flexibility. Use an insulating film, a solder protective film, a cover film, and the like.

[Examples]

The following is a description of the synthesis examples, examples and comparative examples of the present invention, and the present invention is not limited to the following examples.

Example 1

In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 41.0 g (0.1 mol) of 4,4'-oxydiphthalic dianhydride and 150 g of N-methyl-2-pyrrolidone were added. Next, while adjusting 2,2-bis(4-amino-3-hydroxyphenyl)propane 25.8 g (0.1 mol) dissolved in 100 g of N-methyl-2-pyrrolidone, the temperature of the reaction system was not After dropping more than 50 ° C, it was dropped into the above flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, after the flask was equipped with a reflux condenser equipped with a moisture receiver, 70 g of xylene was added thereto, and the mixture was heated to 150 ° C. After maintaining the temperature for 6 hours, a brown solution was obtained.

After the brown solution obtained as described above was cooled to room temperature (25 ° C), the IR spectrum analysis of the product was carried out, and the absorption from the poly-proline was not observed, and 醯 based on 780 cm-1 and 1720 cm-1 was observed. Further, in the absorption of the imine group, absorption from the phenol group in the vicinity of 3400 cm-1 was observed, and it was found that the following formula was a polymer of a repeating unit. Further, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight (Mn) in terms of polystyrene was 547,000.

Next, 200 g of the obtained polymer solution (resin solid content of 17%) and glycidol 11.4 g were placed in a flask, and heated at 120 ° C for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction solution was poured into 1 L of methanol, and after drying, the desired polyimine was obtained. As a result of ¹ H-NMR analysis of the polymer, it was found that the peak of 10 ppm from the phenolic hydroxyl group disappeared, and the peaks derived from the primary and secondary alcoholic hydroxyl groups at 4.4 ppm and 4.6 ppm were observed to have The polymer of the unit structure is repeated as shown in the following formula. Further, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight of the polymer was 59,200.

Example 2

4,4'-oxydiphthalic dianhydride 54.3 g (0.175 mol), 4,4'-hexafluoropropylene bis-phthalate in a flask equipped with a stirrer, thermometer and nitrogen substitution unit Formic acid dianhydride 33.3 g (0.075 mol) and N-methyl-2-pyrrolidone 400 g. Then, a solution of 2,2-bis(4-amino-3-hydroxyphenyl)propane 64.5 g (0.25 mol) dissolved in 200 g of N-methyl-2-pyrrolidone was adjusted on one side so that the temperature of the reaction system was not After dropping more than 50 ° C, it was dropped into the above flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, after the flask was equipped with a reflux condenser equipped with a moisture receiver, 150 g of toluene was added, and the mixture was heated to 150 ° C, and the temperature was maintained for 6 hours to obtain a brown solution.

After the brown solution thus obtained was cooled to room temperature (25 ° C), a polyimine solution having a phenolic hydroxyl group (resin solid content of 20.3%) was obtained. Next, 300 g of the polyimine solution and 10.4 g of glycidol were placed in a flask, and heated at 120 ° C for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction solution was poured into methanol, and after drying, the desired polyimine having a primary alcoholic hydroxyl group was obtained. As a result of ¹ H-NMR analysis of the polymer, a polymer having an average structure represented by the following formula was obtained. Further, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight of the polymer was 82,500.

Example 3

4,4'-hexafluoropropylenediphthalic dianhydride 44.4 g (0.1 mol) and γ-butyrolactone 180 g were placed in a flask equipped with a stirrer, a thermometer and a nitrogen substitution device. Next, 25.6-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 25.6 g (0.07 mol) and 2,2-bis[4-(4-aminophenoxy)phenyl] were adjusted on one side. Propane 12.3 g (0.03 mol) was dissolved in a solution of γ-butyrolactone 120 g so that the temperature of the reaction system did not exceed 50 ° C and was dropped into the above flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, after the flask was equipped with a reflux condenser with a moisture receiver, 100 g of toluene was added, and the temperature was raised to 150 ° C. When the temperature was maintained for 6 hours, the brown solution thus obtained was cooled to room temperature ( After 25 ° C), a polyimine solution having a phenolic hydroxyl group (resin solid content of 21%) was obtained. Next, 200 g of this polyimine solution and 6.7 g of glycidol were placed in a flask, and heated at 120 ° C for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction solution was poured into 1 L of methanol, and dried to obtain the desired polyimine. As a result of ¹ H-NMR analysis of the polymer, a polymer having the structure shown by the following formula was obtained. Further, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight of the polymer was 36,500.

Example 4

In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride 89.5 g (0.25 mol) and N,N-dimethyl group were charged. Acetamide 500 g. Next, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane 35.8 g (0.125 mol) and 9,9-bis(4-aminophenyl)indole 43.5 g (0.125 Mo) were adjusted on one side. The ear was dissolved in 200 g of N,N-dimethylacetamide so that the temperature of the reaction system did not exceed 50 ° C and was dropped into the above flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, after the flask was equipped with a reflux condenser equipped with a moisture receiver, 180 g of toluene was added thereto, and the mixture was heated to 150 ° C. When the temperature was maintained for 6 hours, a brownish solution was obtained.

After the brown solution thus obtained was cooled to room temperature (25 ° C), a polyimine solution having a phenolic hydroxyl group (resin solid content of 20%) was obtained. Next, 300 g of the polyimine solution and 6.6 g of glycidol were placed in a flask, and heated at 100 ° C for 5 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction solution was poured into methanol, and after drying, the desired polyimine was obtained. As a result of ¹ H-NMR analysis of the polymer, a polymer having a structure represented by the following formula was obtained. Further, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight of the polymer was 84,000.

Example 5

In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 77.5 g (0.25 mol) of 4,4'-oxydiphthalic dianhydride and 500 g of N,N-dimethylacetamide were charged. Next, 21.6-bis(4-amino-3-hydroxyphenyl)propane 51.6 g (0.2 mol) and diaminoadenine were adjusted on one side (however, the average of f of the general formula (6) was 9 42.0 g (0.05 mol) was dissolved in a solution of 200 g of N,N-dimethylacetamide so that the temperature of the reaction system did not exceed 50 ° C and was dropped into the flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, after the flask was equipped with a reflux condenser equipped with a moisture receiver, 150 g of toluene was added, and the temperature was raised to 150 ° C. When the temperature was maintained for 6 hours, a brown solution was obtained.

After the brown solution thus obtained was cooled to room temperature (25 ° C), a polyimine solution having a phenolic hydroxyl group (resin solid content of 20.5%) was obtained. Next, 300 g of the polyimine solution and 13.3 g of glycidol were placed in a flask, and heated at 120 ° C for 5 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction solution was poured into methanol, and after drying, the desired polyimine was obtained. As a result of ¹ H-NMR analysis of the polymer, a polymer having a structure represented by the following formula was obtained. Further, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight of the polymer was 63,200.

Example 6

In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 4,4'-hexafluoropropylenediphthalic dianhydride 111 g (0.25 mol) and N,N-dimethylacetamide were charged. 600 g. Next, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 64.1 g (0.175 mol), 1,3-bis(3-aminophenoxy)benzene 14.6 g (0.05) Mohr) and diamino oxirane (however, the average of the general formula (6) f is 9) 21.0 g (0.025 mol) dissolved in a solution of N,N-dimethylacetamide 250 g, The temperature of the reaction system was not more than 50 ° C and was dropped into the above flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, after the reflux cooler equipped with the moisture receiver was attached to the flask, 100 g of toluene was added, and the mixture was heated to 150 ° C, and when the temperature was maintained for 6 hours, a yellow-brown solution was obtained.

After the brown solution thus obtained was cooled to room temperature (25 ° C), a polyimine solution having a phenolic hydroxyl group (resin solid content of 20%) was obtained. Next, 300 g of the polyimine solution and 9.1 g of glycidol were placed in a flask, and heated at 120 ° C for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction solution was poured into methanol, and after drying, the desired polyimine was obtained. As a result of ¹ H-NMR analysis of the polymer, a polymer having a structure represented by the following formula was obtained. Further, as a result of gel permeation chromatography (GPC) analysis, the polymer had a number average molecular weight of 42,700.

[Fig. 1] A ¹ H-NMR chart of the polyfluorene polysiloxane synthesized in Example 1.

[Fig. 2] A ¹ H-NMR chart of the polyfluorene iodide synthesized in Example 2.

[Fig. 3] ¹ H-NMR chart of the polyfluorene polysiloxane synthesized in Example 5.

[Fig. 4] A GPC chart of the polyfluorene polysiloxane synthesized in Example 1.

[Fig. 5] GPC chart of polyfluorene polysiloxane synthesized in Example 2.

[Fig. 6] GPC chart of polyfluorene polysiloxane synthesized in Example 3.

[Fig. 7] GPC chart of polyfluorene polysiloxane synthesized in Example 4.

[Fig. 8] GPC chart of polyfluorene polysiloxane synthesized in Example 5.

[Fig. 9] A GPC chart of the polyfluorene polysiloxane synthesized in Example 6.

Claims (6)

a polyimine having a primary alcoholic hydroxyl group represented by the following general formula (1), Wherein X is a tetravalent organic group, Y is a divalent organic group represented by the general formula (2), Z is a divalent organic group, W is a divalent organic group having an organic decane structure, and 1 is a positive number. , m, n are each 0 or a positive number, 0.1≦1/(1+m+n)≦1,0≦m/(1+m+n)≦0.8,0≦n/(1+m+n)≦ 0.8, (where A is selected from Any of the two valent organic groups may be the same or different from each other, and each of B and C is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, which may be the same or different from each other, and a and b are 0 or 1, c is an integer from 0 to 10, and wherein R ¹ is selected from a carboxyl group or -OCH ₂ CH(OH)CH ₂ OH, -OCH(CH ₂ OH)CH ₂ OH, -COOCH ₂ CH(OH)CH ₂ OH Or a monovalent group in -COOCH(CH ₂ OH)CH ₂ OH, at least one of R ¹ being selected from the group consisting of -OCH ₂ CH(OH)CH ₂ OH, -OCH(CH ₂ OH)CH ₂ OH, -COOCH ₂ CH(OH)CH ₂ OH or a monovalent group in -COOCH(CH ₂ OH)CH ₂ OH)]. In the above general formula (1), X is a tetravalent organic group having at least one selected from the group consisting of the following formula: The polyimine having a primary alcoholic hydroxyl group according to claim 1 or 2, wherein in the above general formula (1), Z is a divalent organic group represented by the following general formula (3), (D in the above formula is selected from Any of the divalent organic groups may be the same or different from each other, and e, f and g are 0 or 1). The polyimine having an alcoholic hydroxyl group according to claim 1 or 2, wherein in the above general formula (1), Z is a divalent organic group represented by the following general formula (4), (wherein R ³ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and h is a positive number of 1 to 80). The polyoxyalkylene modified polyimine having an alcoholic hydroxyl group as in the first or second aspect of the patent application, wherein n in the general formula (1) is 3≦n≦400. A method for producing a polyimine having an alcoholic hydroxyl group as shown in the general formula (1) of the first aspect of the patent application, characterized in that a diamine having an phenolic hydroxyl group and/or a carboxyl group and an acid dianhydride are reacted It is required to react with a diamine having no phenolic hydroxyl group and no carboxyl group and/or a diaminopolyphosphoric acid to obtain a polyglycine, and then obtain a phenolic hydroxyl group represented by the general formula (5) by a dehydration ring closure reaction. Or a carboxy quinone imine, which is then obtained by reacting with glycidol, Wherein X is a tetravalent organic group, Y' is a divalent organic group represented by the following general formula (6), Z is a divalent organic group, and W is a divalent organic group having an organic decane structure; 1 is a positive number, m and n are each 0 or a positive number, 0.1≦1/(1+m+n)≦1,0≦m/(1+m+n)≦0.8,0≦n/(1+m+ n) ≦0.8, (where A is selected from Any of the two valent organic groups may be the same or different from each other, and each of B and C is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, which may be the same or different from each other, and a and b are 0 or 1, c is an integer of 0 to 10, and further, wherein R ² is a group selected from -OH or -COOH)].