KR101139091B1 - Polyimide having alcoholic hydroxyl group and process for preparing the same - Google Patents

Abstract

The present invention provides a novel polyimide having an alcoholic hydroxyl group and a method for producing the same.

The polyimide has a primary alcoholic hydroxyl group represented by the following formula (1).

<Formula 1>

In the above formula, X is a tetravalent organic group, Y has a monovalent group selected from a phenolic hydroxyl group, a carboxyl group or an alcoholic hydroxyl group, at least one is a divalent organic group having an alcoholic hydroxyl group, Z is a divalent organic group , W is a divalent organic group having an organosiloxane structure, l is positive, m, n are each 0 or positive, 0.1≤l / (l + m + n) ≤1, 0≤m / (l + m + n) ≦ 0.8, 0 ≦ n / (l + m + n) ≦ 0.8.

Polyimide, alcoholic hydroxyl group, insulating film, protective film, coverlay film

Description

POLYIMIDE HAVING ALCOHOLIC HYDROXYL GROUP AND PROCESS FOR PREPARING THE SAME}

1 is a ¹ H-NMR chart of the polyimide silicon synthesized in Example 1. FIG.

2 is a ¹ H-NMR chart of the polyimide silicon synthesized in Example 2. FIG.

3 is a ¹ H-NMR chart of the polyimide silicone synthesized in Example 5. FIG.

4 is a GPC chart of polyimide silicon synthesized in Example 1. FIG.

5 is a GPC chart of polyimide silicon synthesized in Example 2. FIG.

6 is a GPC chart of polyimide silicon synthesized in Example 3. FIG.

7 is a GPC chart of polyimide silicon synthesized in Example 4. FIG.

8 is a GPC chart of polyimide silicon synthesized in Example 5. FIG.

9 is a GPC chart of polyimide silicone synthesized in Example 6. FIG.

<Patent Document 1> Japanese Unexamined Patent Publication No. 6-200216

<Patent Document 2> Japanese Patent No. 3329677

<Patent Document 3> Japanese Patent Application Laid-Open No. 2001-335619

The present invention relates to a novel polyimide having a primary hydroxyl group suitable for a protective insulating film for semiconductor elements, an insulating film for a multilayer printed circuit board, a solder protective film, a coverlay film, and the like in terms of heat resistance, chemical resistance, insulation and flexibility, and a manufacturing method thereof. will be.

Conventionally, the polyimide which has a hydroxyl group is examined and proposed variously.

For example, Japanese Patent Laid-Open No. Hei 6-200216 (Patent Document 1) and Japanese Patent No. 3329677 (Patent Document 2) include polyimide having a phenolic hydroxyl group. In 335619 (the above Patent Document 3), a polyimide having an epoxy group or an unsaturated hydrocarbon group and a secondary alcoholic hydroxyl group is proposed. However, polyimide having a reactive primary alcoholic hydroxyl group has not been developed yet.

This invention is made | formed in view of the said situation, and provides the novel polyimide which has a primary alcoholic hydroxyl group, and its manufacturing method.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present inventors came to complete this invention by obtaining the novel polyimide which has the alcoholic hydroxyl group represented by following formula (1).

Polyimide which has a primary alcoholic hydroxyl group represented by following formula (1).

In the formula, X is a tetravalent organic group, Y is a divalent organic group represented by the following formula (2), Z is a divalent organic group, W is a divalent organic group having an organosiloxane structure, l is positive , m and n are each 0 or positive, 0.1≤l / (l + m + n) ≤1, 0≤m / (l + m + n) ≤0.8, 0≤n / (l + m + n) ≤ 0.8.

A in the above,

It is a divalent organic group selected from the group which consists of, and may be same or different, B and C are a C1-C4 alkyl group or a hydrogen atom, respectively, and may mutually differ or may be the same, and a and b are 0 or 1, and c is an integer of 0-10.

In addition, in said formula, R <^1> is monovalent group chosen from phenolic hydroxyl group, a carboxyl group, or alcoholic hydroxyl group containing organic group, and at least ¹ of R <^1> is an alcoholic hydroxyl group containing organic group.

Best Mode for Carrying Out the Invention

Hereinafter, the present invention will be described in more detail. The polyimide of this invention has a repeating unit represented by following formula (1).

<Formula 1>

In said formula, X of General formula (1) is a tetravalent organic group, Specifically, It is group containing 1 or more types represented by following formula.

Y in General formula (1) is a divalent organic group which has a primary alcoholic hydroxyl group represented by General formula (2).

<Formula 2>

In said formula, A, a, b, c are the same as above, B and C are a C1-C4 alkyl group or a hydrogen atom, respectively, and may mutually differ or may be the same, specifically, a methyl group, an ethyl group, and a propyl group And a butyl group are mentioned, and a methyl group and a hydrogen atom are especially preferable from a viewpoint of the availability of a raw material.

In said formula, R <^1> is monovalent group chosen from phenolic hydroxyl group, a carboxyl group, or alcoholic hydroxyl group containing organic group, One or more of R <^1> is a primary alcoholic hydroxyl group containing organic group. Specifically, _{-OH, -COOH, -OCH 2 CH (} OH) CH 2 OH, -OCH (CH 2 OH) CH 2 OH, -COOCH 2 CH (OH) CH 2 OH or -COOCH (CH ₂ OH) CH ₂ OH is shown.

Specifically as Y, the following structure is mentioned.

In addition, Z in Formula 1 is a divalent organic group represented by following formula (3).

In the formula, D

It is a divalent organic group chosen from the group which consists of, and may be same or different, and e, f, and g are 0 or 1.

As Z, the following structure is mentioned specifically ,.

In addition, W in General formula (1) is a divalent organic group represented by following General formula (4).

In Formula 4, R ³ includes a monovalent hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, aryl groups such as phenyl group, aralkyl groups such as benzyl group and phenethyl group, Alkenyl groups, such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, butenyl group, an acryl group, methacryl group, etc. are mentioned. A methyl group, an ethyl group, a phenyl group, and a vinyl group are preferable from a viewpoint of the availability of a raw material. In addition, h is a positive number of 1 to 80, preferably 3 to 70, more preferably 5 to 50.

In addition, l, m, and n in the general formula (1) are each a positive number of 2≤l≤2000, 0≤m≤2000, 0≤n≤2000, and 0.1≤l / (l + m + n) ≤1.0, 0≤m It is a positive number satisfying /(l+m+n)≦0.8 and 0 ≦ n / (l + m + n) ≦ 0.8. When l / (l + m + n) is less than 0.1, since the effect of a primary alcoholic hydroxyl group is hard to express, it is not preferable.

The molecular weight of the polyimide represented by the general formula (1) of the present invention may generally be about 2000 to 800000, preferably 5000 to 500000. When molecular weight is 5000 or less, since the film strength of the obtained polyimide resin falls, it is unpreferable, and in 5 million or more, since compatibility with a solvent runs short, it is not preferable.

The polyimide which has an alcoholic hydroxyl group represented by General formula (1) of this invention is the diamine which has phenolic hydroxyl group and / or carboxyl group, and acid dianhydride, diamine and / or diamino which does not have phenolic hydroxyl group and carboxyl group as needed. After making silicon react and obtaining a polyamic acid, it can carry out dehydration ring-closure reaction, and the polyimide which has the phenolic hydroxyl group and / or carboxyl group represented by following formula (5) is obtained, and can be obtained by making glycidol react after that.

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

In said formula, A, B, C, a, b, c are as above, R <^2> is group chosen from -OH or -COOH.

The polyimide which has the said phenolic hydroxyl group and / or carboxyl group reacts the diamine which has a phenol group and / or carboxyl group, an acid dianhydride, the diamine which does not have a phenol group and a carboxyl group as needed, and / or diamino silicone. After obtaining a polyamic acid, it can obtain by a dehydration ring closure reaction.

As an acid dianhydride used for superposition | polymerization of a polyamic acid, 3,3 ', 4,4'- diphenyl sulfone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyl tetracarboxylic 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 acid anhydride, 1,2 , 3,4-butanetetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-hexafluoropropylidene bisphthalic dianhydride, 2,2 -Bis (p- trimellithoxyphenyl) propane, 1,3-tetramethyldisiloxane bisphthalic dianhydride, and 4,4'- oxydiphthalic dianhydride.

Moreover, as a diamine which has a phenolic hydroxyl group and a carboxyl group, 3,3'- diamino-4,4'- dihydroxy biphenyl, 2,2'- diamino-4,4'- dihydroxy biphenyl, 2,2-bis (4-amino-3-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 9,9'-bis (3-amino-4-hydrate Oxyphenyl) fluorene, 2,2'-methylenebis [6- (4-amino-3,5-dimethylbenzyl) -4-methyl] phenol, 3,3'-diamino-4,4'-dihydrate Diamines having phenol groups such as oxydiphenyl ether, 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.

Moreover, as a diamine which does not have a phenolic hydroxyl group and a carboxyl group, 4,4'- diamino benzanilide, 4,4'- diamino diphenyl ether, 3,4'- diamino diphenyl ether, 4,4'- Diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4 '-(p-phenylenediisopropylidene) dianiline, 4,4'-(m-phenylenedi Isopropylidene) dianiline, 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] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-bis (4-aminophenoxy) biphenyl, 9,9-bis (4-aminophenyl) fluorene Etc. can be mentioned.

In the synthesis of the polyamic acid, the ratio of the diamine component to the tetracarboxylic dianhydride component is appropriately determined according to the adjustment of the molecular weight of the polyimide and the like, and is usually in the range of 0.95 to 1.05, preferably 0.98 to 1.02 in a molar ratio. . Moreover, in order to adjust the molecular weight of a polyimide, it is also possible to add monofunctional acid anhydrides and amine compounds, such as phthalic anhydride and aniline. In this case, 5 mol% or less is preferable with respect to the tetracarboxylic dianhydride component or the diamine component.

Synthesis of the polyimide is usually carried out by heating the polyamic acid solution obtained above to a temperature range of 80 to 200 ° C, preferably 140 to 180 ° C, or adding an acetic anhydride / pyridine mixed solution to the polyamic acid solution, and then By heating up the obtained solution about 50 degreeC, a dehydration ring-closure reaction can advance to the acid amide part of polyamic acid, and polyimide can be obtained.

Reaction of diamine and an acid dianhydride is normally performed in a solvent. What is necessary is just to melt | dissolve polyimide as such a solvent. 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 acetophenone; Esters such as butyl acetate, methyl benzoate and γ-butyrolactone; Cellosolves such as butyl cellosolve acetate and propylene glycol monomethyl ether acetate; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and aromatic hydrocarbons such as toluene and xylene, and preferably ketones and esters. And cellosolves, and particularly preferably gamma -butyrolactone, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, and n-methyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more thereof. Usually, in consideration of the quantity per serving, melt viscosity, etc., it adjusts to the range which the density | concentration of a polyimide becomes 10 to 40 weight%.

Thus, the alcoholic hydroxyl group represented by the said General formula (1) is made by adding the required equivalent weight of glycidol to the organic solvent solution of the polyimide which has a phenolic hydroxyl group or a carboxyl group in the molecule | numerator represented by said Formula (5). A polyimide having can be obtained. The amount of glycidol needs to be appropriately changed depending on the amount of alcoholic hydroxyl group, but usually 0.3 to 3 moles is preferred for the phenolic hydroxyl group or carboxyl group. The reaction temperature is 40 ° C to 180 ° C, preferably 60 ° C to 130 ° C. The reaction time is several minutes to 12 hours. In addition, a catalyst such as triethylamine may be added for the purpose of accelerating the reaction.

The polyimide obtained in this way is a novel polyimide which has a primary alcoholic hydroxyl group mainly by the relationship, such as reactivity. The novel polyimide having such a primary alcoholic hydroxyl group is a protective insulating film for semiconductor devices, an insulating film for multilayer printed circuit boards, a solder protective film, a coverlay film, etc., having excellent heat resistance, chemical resistance, insulating property and flexibility by utilizing the reactivity of the hydroxyl group. useful.

<Examples>

Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following example.

Example 1

31.0 g (0.1 mol) of 4,4'- oxydiphthalic dianhydride and 150 g of n-methyl-2-pyrrolidone were charged into a flask equipped with a stirrer, a thermometer, and a nitrogen replacement device. Subsequently, the solution of 25.8 g (0.1 mol) of 2,2-bis (4-amino-3-hydroxyphenyl) propane dissolved in 100 g of n-methyl-2-pyrrolidone was not more than 50 deg. It was dripped in the said flask, adjusting so that it might be. After completion of dropping, the mixture was further stirred at room temperature for 10 hours. Subsequently, after attaching a reflux condenser with a water receiver to the flask, 70 g of xylene was added, and the temperature was raised to 150 ° C. and maintained at that temperature for 6 hours. A brown solution was obtained.

The brown solution thus obtained was cooled to room temperature (25 ° C) and then subjected to IR spectral analysis. When absorption derived from polyamic acid was not observed, the 780 cm ^-1 and 1720 cm ^-1 imide groups were used. Absorption resulting from it was observed, and absorption originating from a phenol group was observed in the vicinity of 3400 cm <^-1> , and it turned out that it is a polymer which makes the following general formula the repeating unit. In addition, the number average molecular weight (Mn) of polystyrene conversion was 54700 as a result of the gel permeation chromatography (GPC) analysis.

Next, 200 g of the obtained polymer solution (17% of resin solid content) and 11.4 g of glycidol were placed in a flask and heated at 120 ° C. for 6 hours. After completion | finish of reaction, it cooled to room temperature, the reaction solution was thrown in 1 L of methanol, and after drying, the target polyimide was obtained. As a result of ¹ H-NMR analysis of this polymer, 10 ppm of peaks derived from phenolic hydroxyl groups were lost, and instead, peaks derived from primary and secondary alcoholic hydroxyl groups were observed at 4.4 ppm and 4.6 ppm. It turned out that it is a polymer which has a structure of the repeating unit represented by the following. Also, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight of this polymer was 59200.

Example 2

54.3 g (0.175 mol) of 4,4'-oxydiphthalic dianhydride, 33.3 g (0.075 mol) of 4,4'-hexafluoropropylidene bisphthalic dianhydride in a flask equipped with a stirrer, a thermometer, and a nitrogen replacement device; and 400 g of n-methyl-2-pyrrolidone was added thereto. Subsequently, a solution obtained by dissolving 64.5 g (0.25 mol) of 2,2-bis (4-amino-3-hydroxyphenyl) propane in 200 g of n-methyl-2-pyrrolidone was not more than 50 ° C in the reaction system. It was dripped in the said flask, adjusting so that it might be. After completion of dropping, the mixture was further stirred at room temperature for 10 hours. Subsequently, after attaching a reflux condenser with a water receiver to the flask, 150 g of toluene was added, and the temperature was maintained at 150 ° C. for 6 hours, whereby a brown solution was obtained.

After cooling the brown solution obtained in this way to room temperature (25 degreeC), the polyimide solution (20.3% of resin solid content) which has a phenolic hydroxyl group was obtained. Subsequently, 30.0 g of this polyimide solution and 10.4 g of glycidol were placed in a flask and heated at 120 ° C. for 3 hours. After completion | finish of reaction, it cooled to room temperature, and after putting the reaction solution in methanol and drying, the polyimide which has a target primary alcoholic hydroxyl group was obtained. As a result of ¹ H-NMR analysis of this polymer, it was found that the polymer had an average structure represented by the following formula. Also, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight of this polymer was 82500.

Example 3

44.4 g (0.1 mol) of 4,4'-hexafluoropropylidene bisphthalic dianhydride and 180 g of gamma -butyrolactone were charged into a flask equipped with a stirrer, a thermometer, and a nitrogen replacement device. Then 25.6 g (0.07 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 12.3 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane ( 0.03 mol) was dissolved in 120 g of γ-butyrolactone dropwise into the flask while adjusting the temperature of the reaction system not to exceed 50 ° C. After completion of dropping, the mixture was further stirred at room temperature for 10 hours. Subsequently, after attaching a reflux condenser with a water receiver to the flask, 100 g of toluene was added, the temperature was raised to 150 ° C, and the temperature was maintained for 6 hours. A brown solution was obtained.

The brown solution obtained in this way was cooled to room temperature (25 degreeC), and the polyimide solution (21% of resin solid content) which has a phenolic hydroxyl group was obtained. Subsequently, 200 g of this polyimide solution and 6.7 g of glycidol were placed in a flask and heated at 120 ° C. for 6 hours. After completion | finish of reaction, it cooled to room temperature, the reaction solution was thrown in 1 L of methanol, and after drying, the target polyimide was obtained. As a result of ¹ H-NMR analysis of this polymer, it was found that it was a polymer having a structure represented by the following formula. Also, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight of this polymer was 36500.

Example 4

89.5 g (0.25 mol) of 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride and 500 g of N, N-dimethylacetamide were charged into a flask equipped with a stirrer, a thermometer, and a nitrogen replacement device. . Subsequently, 35.8 g (0.125 mol) of 3,3'-dicarboxy-4,4'-diaminodiphenylmethane and 43.5 g (0.125 mol) of 9,9-bis (4-aminophenyl) fluorene were added to N, N. The solution dissolved in 200 g of dimethylacetamide was added dropwise into the flask while adjusting the temperature of the reaction system not to exceed 50 ° C. After completion of dropping, the mixture was further stirred at room temperature for 10 hours. Subsequently, after attaching a reflux condenser with a water receiver to the flask, 180 g of toluene was added, the temperature was raised to 150 ° C, and the temperature was maintained for 6 hours. A brown solution was obtained.

The brown solution obtained in this way was cooled to room temperature (25 degreeC), and the polyimide solution (20% of resin solid content) which has a phenolic hydroxyl group was obtained. Subsequently, 300 g of this polyimide solution and 6.6 g of glycidol were placed in a flask and heated at 100 ° C. for 5 hours. After completion | finish of reaction, after cooling to room temperature, the reaction solution was thrown in methanol and dried, and the target polyimide was obtained. As a result of ¹ H-NMR analysis of this polymer, it was found that the polymer had a structure represented by the following chemical formula. Also, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight of this polymer was 84000.

Example 5

77.5 g (0.25 mol) of 4,4'-oxydiphthalic dianhydride and 500 g of N, N-dimethylacetamide were charged into a flask equipped with a stirrer, a thermometer, and a nitrogen replacement device. Subsequently, 51.6 g (0.2 mol) of 2,2-bis (4-amino-3-hydroxyphenyl) propane and 42.0 g (0.05 mol) of diaminosiloxane (where the average of f in formula 6 is 9) The solution dissolved in 200 g of N, N-dimethylacetamide was added dropwise into the flask while adjusting the temperature of the reaction system not to exceed 50 ° C. After completion of dropping, the mixture was further stirred at room temperature for 10 hours. Subsequently, after attaching a reflux condenser with a water receiver to the flask, 150 g of toluene was added, and the temperature was maintained at 150 ° C. for 6 hours, whereby a brown solution was obtained.

After cooling the obtained brown solution to room temperature (25 degreeC), the polyimide solution (20.5% of resin solid content) which has a phenolic hydroxyl group was obtained. Subsequently, 300 g of this polyimide solution and 13.3 g of glycidol were placed in a flask and heated at 120 ° C. for 5 hours. After completion | finish of reaction, after cooling to room temperature, the reaction solution was thrown in methanol and dried, and the target polyimide was obtained. As a result of ¹ H-NMR analysis of this polymer, it was found that it was a polymer having a structure represented by the following formula. Also, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight of this polymer was 63200.

Example 6

111 g (0.25 mol) of 4,4'-hexafluoropropylidene bisphthalic dianhydride and 600 g of N, N-dimethylacetamide were charged into a flask equipped with a stirrer, a thermometer, and a nitrogen replacement device. Then 64.1 g (0.175 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 14.6 g (0.05 mol) of 1,3-bis (3-aminophenoxy) benzene, and dia While the solution of 21.0 g (0.025 mol) of minoxysiloxane (where the average of f in Formula 6 was 9) in 250 g of N, N-dimethylacetamide was adjusted so that the temperature of the reaction system did not exceed 50 ° C. It was dripped in the flask. After completion of dropping, the mixture was further stirred at room temperature for 10 hours. Subsequently, after attaching a reflux condenser with a water receptor to the flask, 100 g of toluene was added, and the temperature was raised to 150 ° C. and maintained at that temperature for 6 hours. A yellowish brown solution was obtained.

The brown solution obtained in this way was cooled to room temperature (25 degreeC), and the polyimide solution (20% of resin solid content) which has a phenolic hydroxyl group was obtained. Subsequently, 300 g of this polyimide solution and 9.1 g of glycidol were placed in a flask and heated at 120 ° C. for 6 hours. After completion | finish of reaction, after cooling to room temperature, the reaction solution was thrown in methanol and dried, and the target polyimide was obtained. As a result of ¹ H-NMR analysis of this polymer, it was found that it was a polymer having a structure represented by the following formula. Also, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight of this polymer was 42700.

The polyimide which has a primary alcoholic hydroxyl group of this invention is excellent in adhesiveness with a base material, heat resistance, and electrical insulation, and is used suitably as a protective film, such as an electric, an electronic component, and a semiconductor element.

Claims (7)

Polyimide which has a primary alcoholic hydroxyl group represented by following formula (1). <Formula 1>

In the formula, X is a tetravalent organic group, Y is a divalent organic group represented by the following formula (2), Z is a divalent organic group, W is a divalent organic group having an organosiloxane structure, l is positive , m and n are each 0 or positive, 0.1≤l / (l + m + n) ≤1, 0≤m / (l + m + n) ≤0.8, 0≤n / (l + m + n) ≤ 0.8. <Formula 2>

(A in the above formula,

It is a divalent organic group selected from the group which consists of, and may be same or different, B and C are a C1-C4 alkyl group or a hydrogen atom, respectively, and may mutually differ or may be the same, and a and b are 0 or 1, , c is an integer from 0 to 10, and R ¹ has a phenolic hydroxyl group, a carboxyl group or a _{-OCH 2 CH (OH) CH 2} OH, -OCH (CH 2 OH) of the formula CH ₂ OH, -COOCH ₂ CH ( OH) CH ₂ OH or -COOCH (CH ₂ OH) CH ₂ OH, a monovalent group selected from at least ^one of R ¹ -OCH ₂ CH (OH) CH ₂ OH, -OCH (CH ₂ OH) CH ₂ OH, -COOCH ₂ CH (OH) CH ₂ OH or -COOCH (CH ₂ OH) CH ₂ OH) The polyimide of Claim 1 which has an alcoholic hydroxyl group which is a tetravalent organic group containing 1 or more types represented by following formula in said Formula (1).

The polyimide of Claim 1 or 2 which has an alcoholic hydroxyl group which is a divalent organic group represented by following formula (3) in the said General formula (1). <Formula 3>

In the formula, D

It is a divalent organic group chosen from the group which consists of and can be same or different, e, f, and g are 0 or 1. The polyimide of Claim 1 or 2 which has an alcoholic hydroxyl group in which W is a divalent organic group represented by following formula (4). <Formula 4>

In said formula, R <^3> is a C1-C8 monovalent hydrocarbon group, respectively, may be same or different, h is a positive number of 1-80. The siloxane-modified polyimide of Claim 1 or 2 which has an alcoholic hydroxyl group whose n in said General formula (1) is 3 <= n <= 400. After reacting a diamine having a phenolic hydroxyl group, a carboxyl group, or both and an acid dianhydride to obtain a polyamic acid, a polyimide having a phenolic hydroxyl group, a carboxyl group, or both represented by the following formula (5) by a dehydration ring closure reaction The polyimide which has an alcoholic hydroxyl group represented by following formula (1) by obtaining and then making glycidol react. <Formula 1>

In the formula, X is a tetravalent organic group, Y is a divalent organic group represented by the following formula (2), Z is a divalent organic group, W is a divalent organic group having an organosiloxane structure, l is positive , m and n are each 0 or positive, 0.1≤l / (l + m + n) ≤1, 0≤m / (l + m + n) ≤0.8, 0≤n / (l + m + n) ≤ 0.8. <Formula 2>

(A in the above formula,

It is a divalent organic group selected from the group which consists of, and may be same or different, B and C are a C1-C4 alkyl group or a hydrogen atom, respectively, and may mutually differ or may be the same, and a and b are 0 or 1, , c is an integer from 0 to 10, and R ¹ has a phenolic hydroxyl group, a carboxyl group or a _{-OCH 2 CH (OH) CH 2} OH, -OCH (CH 2 OH) of the formula CH ₂ OH, -COOCH ₂ CH ( OH) CH ₂ OH or -COOCH (CH ₂ OH) CH ₂ OH, a monovalent group selected from at least ^one of R ¹ -OCH ₂ CH (OH) CH ₂ OH, -OCH (CH ₂ OH) CH ₂ OH, -COOCH ₂ CH (OH) CH ₂ OH or -COOCH (CH ₂ OH) CH ₂ OH) <Formula 5>

In said formula, X, Z, W, l, m, n are as above, Y 'is a divalent organic group represented by following formula (6). <Formula 6>

(Wherein A, B, C, a, b, c are the same as above, and R ² is a group selected from -OH or -COOH) 7. The diamine, diaminosilicone, or phenolic hydroxyl group according to claim 6, wherein the polyamic acid has, in addition to the diamine and acid dianhydride having the phenolic hydroxyl group, carboxyl group, or both, The manufacturing method of the polyimide which is obtained by making diamine which does not have a carboxyl group, and diamino silicone react.

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