Material for insulating film, coating varnish for insulating film, and insulating film and semicondu

专利摘要:
A material for insulating films comprising a polyamide having a specific structure and a copolymer obtained by reacting a reactive oligomer as a film-forming component, a coating varnish for insulating films containing this material and an organic solvent, heat treatment and condensation reaction and crosslinking reaction The present invention relates to a semiconductor device comprising an insulating film having a fine pore and an interlayer insulating film for multilayer wiring and / or a surface protective layer made of the insulating film. Provided are insulating film materials having excellent electrical characteristics, thermal characteristics, mechanical properties, and the like and capable of lowering the dielectric constant, coating varnishes for insulating films containing the same, insulating films and semiconductor devices using the same.
公开号:KR20040030416A
申请号:KR10-2003-7004154
申请日:2001-09-20
公开日:2004-04-09
发明作者:에노키다카시；사이토히데노리；히가시다노부히로；이시다유이치
申请人:스미토모 베이클리트 컴퍼니 리미티드；
IPC主号:

专利说明:

MATERIAL FOR INSULATING FILM, COATING VARNISH FOR INSULATING FILM, AND INSULATING FILM AND SEMICONDUCTOR DEVICE USING THE SAME}
[2] Inorganic materials and organic materials are used in various parts depending on the characteristics required for semiconductor materials. For example, inorganic oxide films such as silicon dioxide produced by chemical vapor deposition are used as interlayer insulating films for semiconductors. In recent years, with high speed and high performance of semiconductors, the inorganic oxide film as described above has a problem of high relative dielectric constant. Application of organic materials has been considered as one of these improvement means.
[3] Examples of the organic material for semiconductor use include polyimide resins excellent in heat resistance, electrical properties, and mechanical properties, and are used in solder resists, coverlays, liquid crystal alignment films, and the like. However, polyimide resins generally have a carbonyl group in the imide ring. It has two, and there exists a problem in absorbency and an electrical characteristic. In order to solve such a problem, the improvement of an absorbency and an electrical characteristic by introducing a fluorine or a fluorine-containing group into an organic polymer has been tried and put into practical use.
[4] In addition, polybenzoxazole resins, which exhibit superior performance in terms of heat resistance, water absorption, and electrical properties, have been applied to various fields in comparison with polyimide resins. For example, 4,4'-diamino 3,3 And a polybenzoxazole resin having a structure consisting of '-dihydroxy biphenyl and terephthalic acid, and a structure consisting of 2,2-bis (3-amino 4-hydroxy phenyl) hexafluoropropane and terephthalic acid.
[5] However, in the high-tech field, where the improvement of heat resistance, electrical properties, and absorbency is required, materials that satisfy all of these requirements have not been obtained until now. The characteristics are not sufficient or the electrical properties are improved due to the introduction of fluorine, but abnormalities occur that cause a decrease in heat resistance. In particular, when an organic material is applied as an interlayer insulating film for semiconductors, the heat resistance corresponding to the inorganic material Its characteristics and absorbency are required, and newer low dielectric constants are required.
[6] In response to such a demand for high performance, a method of reducing the density and reducing the dielectric constant by opening a minute hole in the membrane of the inorganic oxide film which is an inorganic material has been studied. The relative dielectric constant of air is 1, and introduction of air into the membrane to reduce the relative dielectric constant is inferred from the process for producing a foamed polymer having an average pore diameter of about 20 μm described in US Pat. No. 3,883,452. In order to introduce air into the film and make it an effective insulator, the film thickness needs to have a relative dielectric constant averaged in sub-micrometer units, and the mechanical properties of the film itself must also be able to withstand the respective processes. Overcoming these problems, the mineral material is still not obtained.
[7] On the other hand, in the technical aspect of obtaining micropores in submicrometer units in organic materials, a technique is disclosed in which a block copolymer is heated to generate a resin having micropores in submicrometer units (US Pat. No. 5,776,990). The technique of phase separation of block copolymers in sub-micrometer units is also known as T.Hashimoto, M.ShibayaJna, M.Fujimura and H.Kawai, "Microphase Separation and the Polymer-polymer Interphase in Block Polymers". in "Block Copolymers-Science and Technology", p.63, Ed. By D. J. Meier (Academic Pub., 1983)], It is generally known in the field of polymer chemistry that polymers with low ceiling temperature are easily decomposed. However, in order to obtain a resin composition having fine pores while satisfying not only the relative dielectric constant but also mechanical properties, electrical properties, water absorption, heat resistance, etc., the combination selection of the resin, blocking technology, and thermally decomposable components is very limited. It is a fact that what has been satisfied is not yet obtained.
[8] SUMMARY OF THE INVENTION In view of the above, the present invention provides an insulating film material having excellent electrical characteristics, thermal characteristics, mechanical properties, and the like, and capable of lowering the dielectric constant, an insulating coating coating including the same, an insulating film using the same, and a semiconductor device having the insulating film. It is made for the purpose of providing.
[1] The present invention relates to an insulating film material, an insulating film coating varnish, and an insulating film and semiconductor device using the same. Further, the present invention is excellent in electrical characteristics, thermal characteristics, mechanical characteristics, and the like, and has a low dielectric constant. Insulator material for surface insulation film, surface protection film, interlayer insulation film of multilayer circuit, cover coat of flexible copper plate, solder resist film, liquid crystal alignment film, etc. It relates to a semiconductor device having.
[9] The inventors of the present invention, as a result of earnestly overlapping research to achieve the above object, by using a copolymer of a specific structure of polyamide and a reactive oligomer, by using as a film forming component of the insulating film material, the object is achieved Discovering what can be done, and came to complete this invention based on this knowledge.
[10] That is, the present invention,
[11] (1) general formula 1
[12]
[13] [Wherein, R ¹ to R ⁴ independently represent a hydrogen atom or a monovalent organic group, X represents a tetravalent group selected from the group represented by the following formula (A), and two X's may be the same or different, and Y represents the following formula: At least one divalent group selected from the group represented by (B), formula (C), formula (D) and formula (E), Z represents a divalent group selected from the group represented by formula (F), m and n is an integer that satisfies the relationship of m> 0, n≥0, 2≤m + n≤1000 and 0.05≤m / (m + n) ≤1, respectively, and the array of repetition units is either block or random type And a copolymer obtained by reacting a polyamide represented by the above formula and a reactive oligomer having a substituent obtained by reacting with a carboxyl group, an amino group or a hydroxyl group in the polyamide structure as a film-forming component. material,
[14] Formula (A):
[15]
[16] Formula (B) -1:
[17]
[18] Formula (B) -2:
[19]
[20] Formula (C) -1:
[21]
[22] Equation (C) -2:
[23]
[24] Formula (D):
[25]
[26] Formula (E):
[27]
[28] Formula (F):
[29]
[30] [X ¹ in Formula (A) and Formula (F) is, the following Formula (G).
[31] Formula (G):
[32]
[33] A divalent group selected from the groups represented by is represented, and R in the formula (C) represents a monovalent group selected from an alkyl group or a group represented by the following formula (H).
[34] Formula (H):
[35]
[36] In the group represented by formula (A), formula (B), formula (C), formula (D), formula (E), formula (F) and formula (G), the hydrogen atom on the benzene ring has 1 to 4 carbon atoms. May be substituted with at least one group selected from alkyl, fluorine and trifluoromethyl groups.
[37] (2) The material for insulating films according to (1), wherein the polyamide has Y as a general formula [1] and has a divalent group selected from the group represented by formula (B).
[38] (3) The material for insulating films according to (1), wherein the polyamide has Y as a general formula [1] and has a divalent group selected from the group represented by the formula (C).
[39] (4) The material for insulating films according to (1), wherein the polyamide has Y as a general formula [1] and has a divalent group selected from the group represented by the formula (D).
[40] (5) The material for insulating films according to (1), wherein the polyamide has Y as a general formula [1] and has a divalent group selected from the group represented by formula (E).
[41] (6) Agents (1) to (5), wherein the reactive oligomer is at least one selected from polyoxy alkylene, polymethyl methacrylate, poly α-methylstyrene, polystyrene, polyester, polyether ester, polycaprolactone, and polyurethane Material for insulating film according to any one of items)
[42] (7) The material for insulating films according to any one of (1) to (6), wherein the reactive oligomer has a number average molecular weight of 100 to 40,000.
[43] (8) The insulating film material according to (7), wherein the reactive oligomer has a number average molecular weight of 100 to 20,000.
[44] (9) The insulating film material according to (8), wherein the reactive oligomer has a number average molecular weight of 100 to 10,000;
[45] (10) The material for insulating films according to any one of (1) to (9), wherein the copolymer introduces 5 to 70 wt% of a reactive oligomer unit.
[46] (11) The material for insulating films according to item (10), wherein the copolymer is introduced by 5 to 50% by weight of a reactive oligomer unit.
[47] (12) The insulating film material according to the item (11), wherein the copolymer introduces 5 to 40 wt% of a reactive oligomer unit.
[48] (13) A coating varnish for insulating films comprising the insulating film material according to any one of (1) to (12) and an organic solvent capable of dissolving or dispersing the insulating film material,
[49] (14) The main structure is a polybenzoxazole obtained by heat treatment of the insulating film material according to any one of (1) to (12) or the coating varnish for insulating film according to (13), condensation reaction and crosslinking reaction. An insulating film comprising a resin layer and having fine pores;
[50] (15) The insulating film according to the item (14), wherein the size of the fine pores of the insulating film is 1 µm or less;
[51] (16) the insulating film according to the item (15), wherein the size of the fine pores of the insulating film is 500 nm or less;
[52] (17) the insulating film according to the item (16), wherein the size of the fine pores of the insulating film is 100 nm or less;
[53] (18) The insulating film according to item (17), wherein the size of the fine pores of the insulating film is 20 nm or less;
[54] (19) The insulating film according to any one of (14) to (18), wherein the insulating film has a porosity of 5 to 70%.
[55] (20) The insulating film according to item (19), wherein the insulating film has a porosity of 5 to 50%.
[56] (21) The insulating film according to item (20), wherein the insulating film has a porosity of 5 to 40%.
[57] (22) The insulating film according to any one of (14) to (21) used as an interlayer insulating film for multilayer wiring of a semiconductor,
[58] (23) The insulating film according to any one of (14) to (21) used as a surface protective film of a semiconductor, and
[59] (24) A semiconductor device comprising an interlayer insulating film for multilayer wiring made of the insulating film according to (22) and / or a surface protective layer made of the insulating film according to (23).
[60] The insulating film material of the present invention comprises a copolymer obtained by reacting a polyamide with a reactive oligomer as a film forming component, and ethynyl, phenyl ethynyl, alkyl crosslinked by heating to the main chain of the polyamide unit in the copolymer. At least one skeleton of ethynyl, biphenylene and internal acetylene is introduced, and with the conversion of amide groups to polybenzoxazoles by ring closure reaction, ethynyl, phenyl ethynyl, alkyl ethynyl, The crosslinking reaction of phenylene and the internal acetylene skeleton can make the resin structure three-dimensional, thereby providing a resin having high heat resistance. The oligomer unit in the copolymer is pyrolyzed and volatilized in the resin heating step to form polybenzoxa. Porous in which fine pores are formed in the resin film mainly containing sol resin, the dielectric constant is reduced, and both heat resistance and electrical characteristics are compatible. It is a main object of the present invention to obtain an insulating film.
[61] In the insulating film material of the present invention, the polyamide constituting the polyamide unit in the copolymer has a structure represented by the general formula [1]. The polyamide is any one of the tetravalent groups represented by the formula (A). At least one kind of dicarboxylic acid having at least one kind of bisaminophenol compound having and any one of divalent groups represented by formula (B), formula (C), formula (D), and formula (E) Or dicarboxylic acid having any one of the above-mentioned dicarboxylic acid and a divalent group represented by formula (F) as a dicarboxylic acid, and using conventional acid chloride method, activated ester method, polyphosphoric acid or It can carry out by methods, such as a condensation reaction, in presence of dehydrating condensing agents, such as chlorhexyl carbodiimide.
[62] In addition, another kind of polyamide having at least one skeleton of such ethynyl, phenyl ethynyl, alkyl ethynyl, biphenyl and internal acetylene, having no crosslinking reactor used conventionally (not crosslinking) A high heat resistant resin can be similarly obtained by combining polyamide and making the network structure which penetrates each other.
[63] In this case, the polyamide having no ethynyl, phenyl ethynyl, alkyl ethynyl, biphenylene or internal acetylene skeleton is at least one of the bisamino phenolic compounds having any one of the tetravalent groups represented by the above formula (A). It can obtain according to the same method using at least 1 sort (s) of dicarboxylic acid which has either a species and the bivalent group shown by Formula (F).
[64] As a bisaminophenol compound which has a tetravalent group represented by Formula (A) used by this invention, 2.4- diamino resorcinol, 4, 6- diamino resorcinol, 2, 2-bis (3-amino 4- Hydroxyphenyl) hexafluoro propane, 2,2-bis (4-amino 3-hydroxyphenyl) hexafluoro propane, 2,2-bis (3-amino 4-hydroxyphenyl) propane, 2,2-bis ( 4-amino 3-hydroxy phenyl) propane, 3,3'-diamino-4,4'-dihydroxy diphenyl sulfone, 4,4'-diamino 3,3'-dihydroxy diphenyl sulfone, 3,3'-diamino-4,4'-dihydroxy biphenyl, 4,4'-diamino-3,3'-dihydroxy biphenyl, 9,9-bis (4-((4- Amino 3-hydroxy) phenoxy) phenyl) fluorene, 9,9-bis (4-((3-amino 4-hydroxy) phenoxy) phenyl) fluorene, 9,9-bis ((4-amino -3-hydroxy) phenyl)) fluorene, 9,9-bis ((3-amino-4-hydroxy) phenyl)) fluorene, 9,9-bis (4-((4 amino 3-hydroxy ) Oxy) -3-phenyl-phenyl) fluorene, 9,9-bis (4-((3 amino-4-hydroxy) phenoxy) -3-phenyl-phenyl) -fluorene, 9,9-bis ( (2-amino 3-hydroxy 4 phenyl) -phenyl) fluorene, 9,9-bis ((2-hydroxy-3-amino-4-phenyl) -phenyl) fluorene, 3,3'-diamino -4,4'-dihydroxy diphenyl ether, 4,4'-diamino-3,3'-dihydroxy diphenyl ether, 2,2-bis (3-amino-4-hydroxy-2- Trifluoro methylphenyl) propane, 2,2-bis (4-amino-3-hydroxy-2-trifluoro methylphenyl) propane, 2,2-bis (3-amino-4-hydroxy-5-trifluoro methylphenyl) Propane, 2,2-bis- (4-amino-3-hydroxy-5-trifluoromethylphenyl) propane, 2,2-bis (3-amino-4-hydroxy-6-trifluoro methylphenyl) propane, 2 , 2-bis (4-amino-3-hydroxy-6-trifluoro methylphenyl) propane, 2,2-bis (3-amino-4-hydroxy-2-trifluoro methylphenyl) hexafluoro propane, 2,2-bis (4-amino-3-hydroxy-2-trifluoromethylphenyl) hexafluoro propane, 2,2 bis (3-amino-4-hydroxy-5-trifluoro methylphenyl) hexafluoro propane ， 2 , 2-bis (4-amino-3-hydroxy-5-trifluoro methylphenyl) hexafluoro propane ， 2,2-bis (3-amino-4-hydroxy-6-trifluoro methylphenyl) hexafluoro propane ， 2 , 2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) hexafluoro propane, 3,3'-diamino-4,4'-dihydroxy-2,2'-bis (trifluor Methyl) biphenyl, 4,4'-diamino-3,3'-dihydroxy-2,2'-bis (trifluoromethyl) biphenyl, 3,3'-diamino-4,4'-di Hydroxy-5,5'-bis (trifluoromethyl) biphenyl, 4,4'-diamino 3,3'-dihydroxy-5,5'-bis (trifluoromethyl) biphenyl, 3,3 '-Diamino-4,4'-dihydroxy-6,6'-bis (trifluoromethyl) biphenyl, 4,4'-diamino-3,3'-dihydrate When the like -6,6'- bis (trifluoromethyl) biphenyl. They may be used in may be used alone or in combination of two or more.
[65] Examples of the dicarboxylic acid having an ethynyl skeleton having a divalent group represented by formula (B) used in the present invention include 3-ethynyl phthalic acid, 4-ethynyl phthalic acid, 2-ethynyl isophthalic acid and 4-ethynyl iso Phthalic acid, 5-ethynyl isophthalic acid, 2-ethynyl terephthalic acid, 3-ethynyl terephthalic acid, 5-ethynyl terephthalic acid, 2-ethynyl-1,5-naphthalene dicarboxylic acid, 3-ethynyl-1,5 -Naphthalene dicarboxylic acid, 4-ethynyl-1,5-naphthalene dicarboxylic acid, 1-ethynyl-2,6- naphthalene dicarboxylic acid, 3-ethynyl- 2,6- naphthalene dicarboxylic acid Acid, 4-ethynyl-2,6-naphthalene dicarboxylic acid, 2-ethynyl-1,6-naphthalene dicarboxylic acid, 3-ethynyl-1,6-naphthalenedicarboxylic acid, 4-e Tinyl-1,6-naphthalene dicarboxylic acid, 5-ethynyl-1,6-naphthalene dicarboxylic acid, 7-ethynyl-1,6-naphthalene dicarboxylic acid, 8-ethynyl-1,6 -Naphthalene dicarboxylic acid, 3,3'- dietinyl-2,2'-bipe Dicarboxylic acid, 4,4'- dietinyl-2,2'-biphenyl dicarboxylic acid, 5,5'- dietinyl-2,2'-biphenyl dicarboxylic acid, 6,6'- Dietinyl-2,2'-biphenyl dicarboxylic acid, 2,2'-dietinyl-3,3'-biphenyl dicarboxylic acid, 4,4'-dietinyl-3,3'-biphenyl Dicarboxylic acid, 5,5'- dietinyl-3,3'-biphenyl dicarboxylic acid, 6,6'- dietinyl-3,3'-biphenyl dicarboxylic acid, 2,2'- Diethanyl 4,4'-biphenyl dicarboxylic acid, 3,3'- dietinyl-4,4'-biphenyl dicarboxylic acid, 2,2-bis (2-carboxy-3-ethynyl phenyl) Propane, 2,2-bis (2-carboxy 4-ethynyl phenyl) propane, 2,2-bis (2 carboxy-5-ethynyl phenyl) propane, 2,2-bis (2-carboxy 6-ethynyl phenyl ) Propane, 2,2-bis (3-carboxy-2-ethynyl phenyl) propane, 2,2-bis (3-carboxy-4-ethynyl phenyl) propane, 2,2-bis (3-carboxy-5- Ethynyl phenyl) propane, 2,2-bis (3-carboxy-6-ethynyl phenyl) propane, 2,2-bis (4-carboxy-2- Thynyl phenyl) propane, 2,2-bis (4- carboxy-3-ethynyl phenyl) propane, 2,2-bis (2-carboxy-4-ethynyl phenyl) hexafluoro propane, 2,2-bis ( 3-carboxy-5-ethynyl phenyl) hexafluoro propane, 2,2-bis (4-carboxy-2-ethynyl phenyl) hexafluoro propane, 2,2-bis (4-carboxy-3-ethynyl phenyl) Hexafluoro propane, 4-ethynyl-1,3-dicarboxyl cyclopropane, 5-ethynyl-2,2-dicarboxyl cyclopropane, 1,3-bis (4-carboxy-phenoxy) -5-ethynyl Structural Isomers of Benzene, 1,3-bis (4-carboxyphenyl) -5 ethynyl Structural Isomers of Benzene, 5- (3-ethynylphenoxy) isophthalic acid, 5- (1-ethynylphenoxy) -iso Phthalic acid, 5- (2-ethynyl-phenoxy) isophthalic acid, 2- (1-ethynyl-phenoxy) terephthalic acid, 2- (2-ethynyl-phenoxy) terephthalic acid, 2- (3-ethynyl- Phenoxy) terephthalic acid, 5- (1-ethynyl-phenyl) -isophthalic acid, 5- (2-ethynyl-phenyl) isopropyl Deoxidation, 5- (3-ethynyl-phenyl) -isophthalic acid, 2- (1-ethynyl-phenyl) -terephthalic acid, 2- (2 ethynyl-phenyl) terephthalic acid, 2- (3-ethynyl-phenyl) -Terephthalic acid and the like, but are not limited thereto. These may be used alone or in combination of two or more kinds. In addition, two or more kinds of bisaminophenol compounds may be used in combination.
[66] Examples of dicarboxylic acid having a divalent group represented by formula (C) used in the present invention
[67] As examples, 3-phenylethynyl phthalic acid, 4-phenylethynyl phthalic acid, 2-phenylethynyl isophthalic acid, 4-phenylethynyl isophthalic acid, 5-phenylethynyl isophthalic acid, 2-phenylethynyl terephthalic acid, 3-phenyl Ethynyl terephthalic acid, 2-phenylethynyl-1,5-naphthalene dicarboxylic acid, 3-phenylethynyl-1,5-naphthalene dicarboxylic acid, 4-phenylethynyl-1,5-naphthalene dicarboxylic acid Acid, 1-phenylethynyl-2,6-naphthalene dicarboxylic acid, 3-phenylethynyl-2,6-naphthalene carboxylic acid, 4-phenylethynyl-2,6-naphthalene dicarboxylic acid, 2 -Phenylethynyl-1,6-naphthalene dicarboxylic acid, 3-phenylethynyl-1,6-naphthalene dicarboxylic acid, 4-phenylethynyl-1,6-naphthalene dicarboxylic acid, 5-phenyl Ethynyl-1,6-naphthalene dicarboxylic acid, 7-phenylethynyl-1,6-naphthalene dicarboxylic acid, 8-phenylethynyl-1,6-naphthalene dicarboxylic acid, 3,3'- Diphenylethynyl-2,2'-biphenyldicarboxylic acid, 4,4'- Diphenylethynyl-2,2'-biphenyl dicarboxylic acid, 5,5'-diphenylethynyl-2,2'-biphenyl dicarboxylic acid, 6,6'-diphenylethynyl-2 , 2'-biphenyl dicarboxylic acid, 2,2'-diphenylethynyl-3,3'-biphenyl dicarboxylic acid, 4,4'-diphenylethynyl-3,3'-biphenyl Dicarboxylic acid, 5,5'-diphenylethynyl-3,3'-biphenyl dicarboxylic acid, 6,6'-diphenylethynyl-3,3'-biphenyl dicarboxylic acid, 2 , 2'-diphenylethynyl 4,4'-biphenyl dicarboxylic acid, 3,3'-diphenylethynyl-4,4'-biphenyl dicarboxylic acid, 2,2-bis (2- Carboxy-3-phenylethynyl phenyl) propane, 2,2-bis (2-carboxy-4-phenylethynyl phenyl) propane, 2,2-bis (2-carboxy-5-phenylethynyl phenyl) propane, 2 , 2-bis (2-carboxy 6-phenylethynyl phenyl) propane, 2,2-bis (3-carboxy-2-phenylethynyl phenyl) propane, 2,2-bis (3-carboxy-4-phenyl Tinyl phenyl) propane, 2,2-bis (3-carboxy-5-phenylethynyl phenyl) propane, 2,2-bis (3 -Carboxy-6-phenylethynyl phenyl) propane, 2,2-bis (4-carboxy-2-phenylethynyl phenyl) propane, 2,2 bis (4-carboxy-3-phenylethynyl phenyl) propane, 2 , 2-bis (2-carboxy-4-phenylethynyl phenyl) hexafluoro propane, 2,2-bis (3-carboxy-5-phenylethynyl phenyl) hexafluoro propane, 2,2-bis (4-carboxy 2-phenylethynyl phenyl) hexafluoro propane ， 2,2-bis (4-carboxy-2-phenylethynyl phenyl) hexafluoro propane ， 4-phenylethynyl-1, 3-dicarboxy cyclopropane ， 5- Phenylethynyl-2,2-dicarboxyl cyclopropane, structural isomer of 1,3-bis (4-carboxy-phenoxy) -5-phenylethynyl benzene, 1,3-bis (4-carboxy-phenyl)- Structural isomers of 5-phenylethynyl benzene, 5- (1-phenylethynyl-phenoxy) isophthalic acid, 5- (2-phenylethynyl-phenoxy) isophthalic acid, 5- (3-phenylethynyl-phenoxy Isophthalic acid, 2- (1-phenylethynyl-phenoxy) terephthalic acid, 2- ( 2-phenylethynyl-phenoxy) terephthalic acid, 2- (3-phenylethynyl-phenoxy) terephthalic acid, 5- (1-phenylethynyl-phenyl) -isophthalic acid, 5- (2-phenylethynyl-phenyl ) -Isophthalic acid, 5- (3-phenylethynyl-phenyl) -isophthalic acid, 2- (1-phenylethynyl-phenyl) terephthalic acid, 2- (2-phenylethynyl-phenyl) terephthalic acid, 2- (3 And -phenylethynyl-phenyl) terephthalic acid.
[68] Moreover, in the structure represented by Formula (C) used by this invention, as an example of the dicarboxylic acid which has a biphenyl ethynyl group which is a biphenyl group in the monovalent group represented by Formula (H), 3-biphenyl ethynyl phthalic acid is mentioned. ， 4-biphenyl ethynyl phthalic acid, 2-biphenyl ethynyl isophthalic acid, 4-biphenyl ethynyl isophthalic acid, 5-biphenyl ethynyl isophthalic acid, 2-biphenyl ethynyl terephthalic acid, 3-biphenyl ethynyl Terephthalic acid, 5-biphenyl ethynyl terephthalic acid, 2-biphenyl ethynyl-1,5-naphthalene dicarboxylic acid, 3-biphenyl ethynyl-1,5-naphthalene dicarboxylic acid, 4-biphenyl ethynyl 1,5-naphthalene dicarboxylic acid, 1-biphenyl ethynyl-2,6-naphthalene dicarboxylic acid, 3-biphenyl ethynyl 2,6-naphthalene dicarboxylic acid, 4-biphenyl ethynyl- 2,6-naphthalene dicarboxylic acid, 2-biphenylethynyl-1,6-naphthalene dicarboxylic acid, 3-biphenyl ethynyl-1,6-naphthalene dicarboxylic acid Acid, 4-biphenyl ethynyl 1,6-naphthalene dicarboxylic acid, 5-biphenyl ethynyl-1,6-naphthalene dicarboxylic acid, 7-biphenyl ethynyl-1,6-naphthalene dicarboxyl Acid, 8-biphenyl ethynyl-1,6-naphthalene dicarboxylic acid, 3,3'-dibiphenyl ethynyl-2,2'-biphenyl dicarboxylic acid, 4,4'-dibiphenyl ethynyl -2,2'-biphenyl dicarboxylic acid, 5,5'-dibiphenyl ethynyl-2,2'-biphenyl dicarboxylic acid, 6,6'-dibiphenyl ethynyl-2,2'- Biphenyl dicarboxylic acid, 2,2'-dibiphenyl ethynyl-3,3'-biphenyl dicarboxylic acid, 4,4'-dibiphenyl ethynyl-3,3'-biphenyl dicarboxylic acid ， 5,5'-dibiphenyl ethynyl-3,3'-biphenyl dicarboxylic acid ， 6,6'-dibiphenyl ethynyl-3,3'-biphenyl dicarboxylic acid ， 2,2'- Dibiphenyl ethynyl-4,4'-biphenyl dicarboxylic acid, 3,3'-dibiphenyl ethynyl-4,4'-biphenyl dicarboxylic acid, 2,2-bis (2-carboxy-3 -Biphenyl ethynyl phenyl) propane, 2,2'-bis (2-carboxy-4-biphenyl) Tinyl phenyl) propane, 2,2'-bis (2-carboxy-5-biphenyl ethynyl phenyl) propane, 2,2'-bis (2-carboxy-6-biphenyl ethynyl phenyl) propane, 2,2 '-Bis (3-carboxy-2-biphenyl ethynyl phenyl) propane, 2,2'-bis (3-carboxy-4-biphenyl ethynyl phenyl) propane, 2,2'-bis (3-carboxy- 5-biphenyl ethynyl phenyl) propane, 2,2'-bis (3-carboxy-6-biphenyl ethynyl phenyl) propane, 2,2'-bis (4-carboxy 2-biphenyl ethynyl phenyl) propane ， 2,2'-bis (4-carboxy-3-biphenyl ethynyl phenyl) propane, 2,2'-bis (2-carboxy-4-biphenyl ethynyl phenyl) hexafluoro propane ， 2,2'- Bis (3-carboxy-5-biphenyl ethynyl phenyl) hexafluoro propane, 2,2'-bis (4-carboxy-2-biphenyl ethynyl phenyl) hexafluoro propane, 4-biphenyl ethynyl-1, 3-dicarboxycyclopropane, 5-biphenyl ethynyl-2,2-dicarboxycyclopropane, 1,3-bis (4-carboxy phenoxy Structural isomers of) -5-biphenyl ethynyl benzene, Structural isomers of 1,3-bis (4-carboxyphenyl) -5-biphenyl ethynyl benzene, 5- (3-biphenyl ethynyl phenoxy) -iso Phthalic acid, 5- (1-biphenyl ethynyl phenoxy) -isophthalic acid, 5- (2-biphenyl ethynyl phenoxy) -isophthalic acid, 2- (1-biphenyl ethynyl phenoxy) -terephthalic acid, 2 -(2-biphenyl ethynyl phenoxy) -terephthalic acid, 2- (3-biphenyl ethynyl phenoxy) -terephthalic acid, 5- (1-biphenyl ethynyl phenyl) -isophthalic acid, 5- (2-bi Phenyl ethynyl phenyl) isophthalic acid, 5- (3 biphenyl ethynyl phenyl) isophthalic acid, 2 (1-pipe)
[69] Nitrile ethynyl phenyl) -terephthalic acid, 2- (2-biphenyl ethynyl phenyl) terephthalic acid, 2- (3-biphenyl ethynyl phenyl) terephthalic acid, and the like, but are not limited to these. It is also good to use two or more types in combination. Moreover, it can use in combination of 2 or more types of bisaminophenol compounds.
[70] Examples of R being an alkyl group include 3-hexynyl phthalic acid, 4-hexynyl phthalic acid, 2-hexynyl isophthalic acid, 4-hexynyl isophthalic acid, 5-hexynyl isophthalic acid, 2-hexynyl terephthalic acid, 3-hexynyl terephthalic acid , 2-hexynyl-1,5-naphthalene dicarboxylic acid, 3-hexynyl-1,5-naphthalene dicarboxylic acid, 4-hexynyl-1,5-naphthalene dicarboxylic acid, 1-hexynyl -2,6-naphthalene dicarboxylic acid, 3-hexynyl-2,6-naphthalene dicarboxylic acid, 4-hexynyl-2,6-naphthalene dicarboxylic acid, 2-hexynyl-1,6- Naphthalene dicarboxylic acid, 3-hexynyl-1,6-naphthalene dicarboxylic acid, 4-hexynyl-1,6-naphthalene dicarboxylic acid, 5-hexynyl-1,6 naphthalene dicarboxylic acid, 7-hexynyl-1,6-naphthalene dicarboxylic acid, 8-hexynyl-1,6-naphthalene dicarboxylic acid, 3,3'-dihexynyl-2,2'-biphenyl dicarboxylic acid , 4,4'-dihexynyl-2,2'-biphenyl dicarboxylic acid, 5,5'-dihexynyl-2,2'-biphenyl dicarboxylic acid, 6, 6'-dihexynyl-2,2'-biphenyl dicarboxylic acid, 2,2'-dihexynyl-3,3'-biphenyl dicarboxylic acid, 4,4'-dihexynyl-3 , 3'-biphenyl dicarboxylic acid, 5,5'-dihexynyl-3,3'-biphenyl dicarboxylic acid, 6,6'-dihexynyl-3,3'-biphenyl dicarboxylic acid Acids, 2,2'-dihexynyl-4,4'-biphenyl dicarboxylic acid, 3,3'-dihexynyl-4,4'-biphenyl dicarboxylic acid, 2,2-bis (2-carboxy-3-hexynylphenyl) propane, 2,2-bis (2-carboxy-4-hexynylphenyl) propane, 2,2-bis (2-carboxy-5-hexynylphenyl) propane ， 2 , 2-bis (2-carboxy-6-hexynylphenyl) propane, 2,2-bis (3-carboxy-2-hexynylphenyl) propane, 2,2-bis (3-carboxy-4-hexynylphenyl ) Propane, 2,2-bis (3-carboxy-5-hexynylphenyl) propane, 2,2-bis (3-carboxy-6-hexynylphenyl) propane, 2,2-bis (4-carboxy-2 Hexynylphenyl) propane ， 2,2-bis (4-carboxy-3-hexynylphenyl) propane ， 2,2-bis (2-carboxy-4-hexynylphenyl) hexafluoro Le propane, 2,2-bis (3-carboxy-5-hexynylphenyl) hexafluoro propane, 2,2-bis (4-carboxy-2-hexynylphenyl) hexafluoro propane, 4-hexynyl-1, 3-dicarboxycyclo propane, 5-hexynyl-2,2-dicarboxy cyclopropane, structural isomers of 1,3-bis (4-carboxy-phenoxy) -5-hexynyl benzene, 1,3-bis ( Structural isomer of 4-carboxy-phenyl) -5-hexynyl benzene, 5- (3-hexynyl-phenoxy) isophthalic acid, 5- (1-hexynyl-phenoxy) -isophthalic acid, 5- (2- Hexynyl-phenoxy) -isophthalic acid, 2- (1-hexynyl-phenoxy) -terephthalic acid, 2- (2-hexynyl-phenoxy) -terephthalic acid, 2- (3-hexynyl-phenoxy)- Terephthalic acid, 5- (1-hexynyl-phenyl) -isophthalic acid, 5- (2-hexynyl-phenyl) -isophthalic acid, 5- (3-hexynyl-phenyl) -isophthalic acid, 2- (1-hexyl) Nyl-phenyl) -terephthalic acid, 2- (2-hexynyl-phenyl) -terephthalic acid, 2- (3-hexynyl-phenyl) -terephthalic acid, etc. are mentioned, It is limited to these. S. These may be used in may be used alone or in combination of two or more. It is also possible to use a combination of the bisaminophenol compound of two or more thereof.
[71] As an example of the dicarboxylic acid which has a biphenylene skeleton which has a bivalent group represented by Formula (D) used by this invention, a 1, 2- biphenylene dicarboxylic acid, a 1, 3- biphenylene dicarboxylic acid ， 1,4-biphenylene dicarboxylic acid ， 1,5-biphenylene dicarboxylic acid ， 1,6-biphenylene dicarboxylic acid ， 1,7-biphenylene dicarboxylic acid ， 1 , 8-biphenylene dicarboxylic acid, 2,3-biphenylene dicarboxylic acid, 2,6-biphenylene dicarboxylic acid, 2,7-biphenylene dicarboxylic acid, etc. are mentioned. 2,6-biphenylene dicarboxylic acid and 2,7-biphenylene dicarboxylic acid are particularly preferable in terms of performance of the obtained coating film. These may be used alone or in combination of two or more kinds thereof. It is also good.
[72] As an example of the dicarboxylic acid which has a bivalent group represented by Formula (E) used by this invention, 4,4'-tran dicarboxylic acid, 3,4'-tran dicarboxylic acid, 3,3'-tran Dicarboxylic acid, 2,4'-tran dicarboxylic acid, 2,3'-tran dicarboxylic acid, 2,2'-tran dicarboxylic acid, etc. can be used 1 type or in mixture of 2 or more types. have.
[73] As an example of the dicarboxylic acid which has a bivalent group represented by Formula (F) used by this invention, isophthalic acid, terephthalic acid, 4,4'-biphenyl dicarboxylic acid, 3,4'-biphenyl dicarboxylic acid ， 3,3'-biphenyl dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-sulfonyl Bis benzoic acid, 3,4'-sulfonyl bis benzoic acid, 3,3'-sulfonyl bis benzoic acid, 4,4'-oxy bis benzoic acid, 3,4'-oxy bis benzoic acid, 3,3'-oxy bis benzoic acid, 2,2 bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxy phenyl) propane, 2,2-bis (4-carboxy phenyl) hexafluoro propane, 2,2-bis (3-carboxy phenyl Hexafluoro propane, 2,2'-dimethyl-4,4'-biphenyl dicarboxylic acid, 3,3'-dimethyl-4,4'-biphenyl dicarboxylic acid, 2,2'-dimethyl- 3,3'-biphenyldicarboxylic acid, 2,2'-bis (trifluorometh) ) -4,4'-biphenyl dicarboxylic acid, 3,3'-bis (trifluoromethyl) -4,4'-biphenyl dicarboxylic acid, 2,2'-bis (trifluoromethyl)- 3,3'-biphenyl dicarboxylic acid, 9,9-bis (4- (4-carboxyphenoxy) phenyl) fluorene, 9,9-bis (4- (3-carboxyphenoxy) phenyl) flu Orene, 4,4'-bis (4-carboxy phenoxy) biphenyl, 4,4'-bis (3-carboxy phenoxy) biphenyl, 3,4'-bis (4-carboxy phenoxy) biphenyl, 3,4'-bis (3-carboxy phenoxy) biphenyl, 3,3'-bis (4-carboxy phenoxy) biphenyl, 3,3'-bis (3-carboxy phenoxy) biphenyl, 4, 4'bis (4-carboxy phenoxy) -p-ter-phenyl, 4,4'-bis (4-carboxy phenoxy) -m-ter-phenyl, 3,4'-bis (4-carboxy phenoxy) -p-ter-phenyl, 3,3'-bis (4-carboxy phenoxy) -p-ter-phenyl, 3,4'-bis (4-carboxy phenoxy) -m-ter-phenyl, 3,3 '-Bis (4-carboxyphenoxy) -m-ter-phenyl, 4,4'-bis (3-carboxyphenoxy) -p-ter-phenyl 4,4'-bis (3-carboxy phenoxy) -m-ter-phenyl, 3,4'-bis (3-carboxy phenoxy) -p-ter-phenyl, 3,3'-bis (3-carboxy Phenoxy) p-ter-phenyl, 3,4'-bis (3-carboxy phenoxy) -m-ter-phenyl, 3,3'-bis (3-carboxy phenoxy) -m-ter-phenyl, 3 -Fluoro isophthalic acid, 2-fluoro isophthalic acid, 2-fluoro terephthalic acid, 2,4,5,6-tetra fluoro isophthalic acid, 2,3,5,6-tetra fluoro terephthalic acid, 5-trifluoromethyl isophthalic acid, 9 , 9-bis- (2-carboxyphenyl) fluorene, 9,9-bis- (3-carboxyphenyl) fluorene, 9,9 bis- (4carboxyphenyl) fluorene, bis-((2-carboxy- 3-phenyl) -phenyl) -fluorene, bis ((4-carboxy-3-phenyl) phenyl) -fluorene, bis ((5-carboxy-3-phenyl) -phenyl) fluorene, bis-((6 -Carboxy-3-phenyl) -phenyl) fluorene, 9,9-bis (4- (2-carboxyphenoxy) -phenyl) -fluorene, 9,9-bis (4- (3-carboxype -Phenyl) fluorene, 9,9-bis (4- (4-carboxy phenoxy) -phenyl) fluorene, 9,9-bis ((4- (2 carboxy phenoxy) -3-phenyl)- Phenyl) fluorene, 9,9-bis ((4- (3-carboxyphenoxy) -3-phenyl) phenyl) fluorene, 9,9-bis ((4- (4-carboxyphenoxy) -3- Phenyl) phenyl) fluorene, etc., These may be used independently, or may be used in combination of 2 or more type.
[74] In the group represented by the formulas (A), (B), (C), (D), (E), (F) and (G), the hydrogen atom of the benzene ring has 1 to 4 carbon atoms. May be substituted with at least one group selected from an alkyl group, a fluorine atom, and a trifluoromethyl group. The alkyl group having 1 to 4 carbon atoms may be a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group or t-butyl group. Etc. can be mentioned.
[75] The polyamide in the present invention is a number of repeating units having a crosslinking skeleton and a repeating unit having no crosslinking skeleton, and m and n are m> 0 in relation to m and n in the general formula [1]. Is an integer that satisfies the relationship of n≥0, 2≤m + n≤1000 and 0.05≤m / (m + n) ≤1. The sum of m and n is preferably 5 or more and 100 or less. In the case of less than 2, the film formability is lowered and the mechanical strength of the resin film is insufficient. Moreover, when it exceeds 1000, molecular weight will become large and it will become difficult to melt | dissolve in a solvent, and even if melt | dissolved, it will become viscous varnish and it is not practical. It is essential that m and n are integers satisfying 0.05 ≦ m / (m + n) ≦ 1, and furthermore, it is desirable to satisfy 0.5 ≦ m / (m + n) ≦ 1. 0.05> m / (m + n), it means that the number of repeating units having a crosslinked skeleton is small, and therefore, the crosslinking reaction site is small, so that the heat resistance does not improve, and micropores cannot be maintained or uneven micropores are not preferable.
[76] The array of repeating units in the general formula [1] may be a block type or a random type. For example, as a manufacturing method of a block type repeating unit, the chloride of the dicarboxylic acid which has the bivalent group selected from the bivalent aminophenol compound which has a tetravalent group selected from Formula (A), and the formula (F), by the acid chloride method. After reacting in advance to increase the molecular weight, the bisaminophenol compound having a tetravalent group selected from the formula (A), and is represented by the formula (B), formula (C), formula (D) and formula (E) It can obtain by making the chloride of the dicarboxylic acid which has a bridge | crosslinking contribution structure selected from bivalent groups react.
[77] Also on the contrary, a bisaminophenol compound having a tetravalent group selected from formula (A) and a crosslinking contribution structure selected from divalent groups represented by formulas (B), (C), (D) and (E) The chloride of dicarboxylic acid is reacted in advance to increase the molecular weight, and then the bisaminophenol compound having a tetravalent group selected from formula (A) and the dicarboxylic acid having divalent group selected from formula (F) are subsequently reacted. You may let it.
[78] In the case of a random repeating unit, a chloride of a bicarboxylic acid group having a tetravalent group selected from formula (A), a dicarboxylic acid having a divalent group selected from formula (F), a formula (B), a formula (C), It can obtain by making the chloride of the dicarboxylic acid which has a bridge | crosslinking contribution structure selected from the bivalent group represented by Formula (D) and Formula (E) react simultaneously.
[79] In this invention, the reactive oligomer used for reaction with a polyamide has a reactive substituent which can react with the carboxyl group, amino group, or hydroxyl group in a polyamide structure in the structure, As a reactive substituent, a carboxyl group, an amino group, or a hydroxyl group is mentioned. It is necessary to have the actual group and to pyrolyze to a temperature lower than the thermal decomposition temperature of the polyamide and the decomposition product must be a vaporizable oligomer.
[80] Specifically, polyoxy methylene, polyoxy ethylene, polyoxy methylene oxy ethylene copolymer, polyoxy methylene oxy propylene copolymer, polyoxy ethylene oxy propylene copolymer, polyoxy alkylene such as polytetra hydrofuran, poly Methyl methacrylate, polyurethane, poly α-methylstyrene, polystyrene, polyester, polyether ester, polycaprolactone and the like are very suitable. These may be used alone or in combination of two or more thereof. It is also good.
[81] As the reactive oligomer, a reactive substituent may be used at the one end or the sock end of the side chain or the main chain. The commercially available one is a reactive oligomer obtained by cutting the end of the main chain. More specifically, 4-amino benzoic acid Esterified styrene oligomers, 4-amino benzoic acid esterified poly (propylene glycol) oligomers, hydroxy-terminated poly (ethylene glycol) -block-poly (propylene glycol) -block-polyethylene glycol), poly (propylene glycol) Bis (2-amino propyl ether) etc. are mentioned.
[82] The reactive oligomer is preferably in the range of number average molecular weight of 100 to 40,000. More preferably, the number average molecular weight is 100 to 20,000, and even more preferably in the range of number average molecular weight of 100 to 10,00. Since the pores after decomposition vaporization are small and brittle, it is impossible to obtain a reduction in the dielectric constant. If the molecular weight exceeds 40,000, the voids become too large and the mechanical properties of the insulating film are extremely degraded, resulting in a problem that cannot provide practicality. There is concern.
[83] In the present invention, the amount of the reactive oligomer unit introduced into the copolymer is preferably 5 to 70% by weight. More preferably, 5 to 50% by weight and still more preferably 5 to 40% by weight. If it is less than, the porosity in the insulating film is small, the decrease in dielectric constant is insufficient, and if it exceeds 70% by weight, the porosity in the film is increased, the mechanical strength of the film is extremely lowered, the voids are continuously uneven, and the dielectric constant varies from place to place. Is not desirable because it occurs.
[84] Therefore, when the polyamide is reacted with the reactive oligomer, it is important to adjust the amount of each used so that the amount of the reactive oligomer unit introduced into the copolymer is in the above range.
[85] In the present invention, as an example of the method for producing a copolymer, a conventional acid chloride method, an activated ester method, a condensation reaction in the presence of a dehydrating condensate such as polyphosphoric acid or dicyclohexyl carbodiimide can be used. For example, in the acid chloride method, the used dicarboxylic acid chloride is first reacted with a dicarboxylic acid and an excessive amount of thionyl chloride in a solvent such as N, N-dimethyl formamide at a temperature of about room temperature to about 130 ° C. to give an excess. After the amount of thionyl chloride is removed by heating and depressurization, the residue can be obtained by recrystallization with a solvent such as hexane.
[86] When using the dicarboxylic acid chloride produced in this way and the said other dicarboxylic acid together, the acid chloride obtained similarly together with a bisamino phenol compound is usually N-methyl- 2-pyrrolidone, N, N- dimethyl acetate. Dissolved in a polar solvent such as amide, and reacted at a temperature of about room temperature to about -30 ° C. in the presence of an acid acceptor such as pyridine or triethyl amine to synthesize polyamide, followed by dissolving the reactive oligomer in butyrolactone or the like. The reaction solution may then be added to a mixed solution of ice and isopropyl alcohol, and the precipitate is collected and dried to obtain a copolymer in which the polyamide and the reactive oligomer are reacted. It is also possible to simultaneously react phenolic compounds and reactive oligomers and to synthesize copolymers at random.
[87] The molar ratio of dicarboxylic acid chloride and bisaminophenol compound has a great influence on the molecular weight of the polyamide obtained and is also important for controlling the end group structure of the polyamide. That is, in the copolymerization reaction with the reactive oligomer, the terminal of the polyamide should be allowed to react with the reactive group of the oligomer. That is, when the molar ratio of dicarboxylic acid chloride / bisaminophenol compound is less than 1, The terminal has an amino group and a hydroxyl group, and copolymerization with an oligomer having a carboxyl group becomes possible. Further, when the acid chloride / bisaminophenol molar ratio is greater than 1, the terminal of the resulting polyamide has a carboxyl group and has an amino group or a hydroxyl group. Copolymerization with a reactive oligomer or the like becomes possible. In this case, as for the terminal reactor of an oligomer, the amino group with strong nucleophilicity is more preferable.
[88] At this time, as an example of converting the terminal hydroxyl group of the oligomer into an amino group, the hydroxyl group terminal reactive oligomer and 4-nitro benzoic acid chloride are usually in a solvent such as tetrahydrofuran at a temperature of about room temperature to about -30 ° C in the presence of an acid aqueous solution such as pyridine. It is possible to obtain 4-nitro benzoic acid ester terminal oligomer by reacting. The terminal oligomer is then dissolved in a solvent such as tetrahydrofuran and reacted in the presence of a reducing catalyst such as palladium carbon or in a hydrogen gas atmosphere. After the catalyst is removed, the solvent is concentrated to remove the 4-amino benzoic acid ester terminal oligomer, which can be used as an amino group terminal reactive oligomer. The hydroxyl group in the main chain structure of the polyamide unit has a carboxyl group or an isocyanate group. Reactive up Although it is also possible to synthesize | combine a graft copolymer and to react with a oligomer, if it is a reactive oligomer which reacts with a hydroxyl group, it is not specifically limited to these.
[89] Examples of the additive for the insulating film of the present invention include catalysts such as surfactants, coupling agents represented by silanes, radical initiators generated by heating oxygen radicals and sulfur radicals, and disulfides.
[90] In the present invention, polyamide is used in combination with a naphthoquinone diazide compound as a photosensitive agent when at least one of R ¹ and R ² and R ³ and R ⁴ in the general formula [1] is a hydrogen atom. As a photosensitive resin composition, when at least one of R <^1> and R <^2> or R <^3> and R <^4> is group which has photocrosslinkable groups, such as a methacryloyl group, it uses a photoinitiator and can use it as a negative photosensitive resin composition.
[91] The method of using the insulating film material of the present invention can be dissolved in a suitable organic solvent or uniformly dispersed and used as a coating varnish. Specifically, the insulating film material is dissolved or uniformly dissolved in an organic solvent. It is dispersed and applied to a suitable support, for example, glass, fiber, metal, silicon wafer, ceramic substrate, etc. This coating method is immersion, screen printing, spray, rotational coating, roll coating, etc. Then, the solvent may be volatilized to form a wrinkle-free coating film. It is then preferable to heat-treat and convert the polybenzoxazole resin crosslinked body into use. Further, the dicarboxylic acid component, the bisaminophenol compound component and the reactivity may be used. The oligomer component can be selected and used as a soluble polybenzoxazole resin for a solvent.
[92] As the organic solvent for dissolving or dispersing the insulating film material of the present invention, a solvent which completely dissolves the solid content is preferable. For example, N-methyl 2-pyrrolidone, γ-butyrolactone, N, N-dimethyl acetase Amides, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol di Acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3- monomethyl ether, Methyl pyruvate, ethyl pyruvate, methyl 3-methoxy propionate, cyclohexanone, cyclopentanone Anisole, 4-ethylcyclohexanone, phenyl cyclohexanone, dipropylene glycol propyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether, tripropyllan glycol propyl ether, tripropylene glycol butyl ether, and the like. have. These can mix and use 1 type (s) or 2 or more types.
[93] The amount of the solvent used when preparing the coating varnish may be any amount that can completely dissolve the insulating film material, and is not particularly limited and can be appropriately adjusted depending on the application. 95 weight% is preferable.
[94] In the insulating film material of the present invention, the polyamide unit in the insulating film material undergoes a cyclocondensation reaction by evaporating the solvent at a temperature in the range of 80 to 200 ° C. and heating the temperature to a temperature of about 200 to 500 ° C. And a polybenzoxazole resin to cause a crosslinking reaction, and an oligomer unit in the insulating film material thermally decomposes at this time to vaporize and volatilize the decomposed product, and to form micropores in a layer of a resin mainly composed of polybenzoxazole. In this way, the insulating film of the present invention, which is a porous insulating film, can be obtained. The thermal history at this time is also important for forming micropores.
[95] In the insulating film having a micropore and a layer of resin mainly composed of the polybenzoxazole of the present invention, the size of the fine pores varies depending on the use of the insulating film and the thickness of the film, but is generally 1 탆 or less. 500 nm or less, More preferably, it is 100 nm or less, and it is preferable that it is 20 nm or less, More preferably, it is 5 nm or less from a viewpoint of the use of an interlayer insulation film for semiconductors.
[96] In the interlayer insulating film for semiconductors, when the pore diameter is larger than 20 nm, the gap of the insulating film used between wirings becomes uneven and the electrical characteristics are not constant. Moreover, the problem that the mechanical strength of the film decreases and adversely affects the adhesiveness. However, depending on the use of the film, the optimum film thickness and the optimum micropore size need not necessarily be 5 nm.
[97] In addition, the porosity of the insulating film is preferably 5 to 70%, more preferably 5 to 50%, and even more preferably 5 to 40%. If the porosity is less than 5%, sufficient dielectric constant reduction is difficult to be exhibited and is greater than 70%. There is a fear that a problem occurs that the mechanical strength of the membrane is lowered and adversely affects the adhesion.
[98] Although the thickness of the insulating film of this invention depends on the purpose of use, it is 0.1-100 micrometers normally, Preferably it is 0.1-50 micrometers, More preferably, it is the range of 0.1-20 micrometers.
[99] The insulating film material and the insulating film of the present invention can be used for forming an interlayer insulating film or protective film for semiconductors, an interlayer insulating film for multilayer circuits, a cover coat of a flexible copper plate, a solder resist film, a liquid crystal alignment film, and the like.
[100] As an example of the case where the insulating film of the present invention is used for an interlayer insulating film for multilayer wiring of a semiconductor device, first, when the adhesiveness is improved, an adhesive coating agent is applied onto the semiconductor substrate to form a coating film. Coating, spray coating by spray coater, dipping, printing, roll coating, etc. Thereafter, preliminary pressure reduction is carried out to the temperature above the boiling point of an organic solvent, and the organic solvent is evaporated to dry and an adhesive coating film is formed.
[101] Next, a solution of the insulating film material of the present invention is applied on the adhesive coating film to be laminated by the same method to form a coating film. Subsequently, the coating film is preliminarily decompressed under the above conditions to evaporate and dry the organic solvent. By heat-processing, an interlayer insulation film can be formed as a resin film which has a micropore.
[102] Similarly, it is also possible to form a resin film and use it as a surface protective film.
[103] Example
[104] Hereinafter, the present invention will be described in detail by way of examples.
[105] It is not limited by.
[106] In addition, in the film produced by the Example and the comparative example, the cross section of the film was observed with measuring relative dielectric constant, heat resistance, glass transition temperature, and water absorption according to the following method.
[107] (1) relative dielectric constant
[108] JIS-K6911 was observed, and it measured using the HP-4284A Precision LCR meter by the Hewlett-Packard company at the frequency of 100 kHz.
[109] (2) heat resistance
[110] Using TG / DTA6200 manufactured by Seiko Instruments Co., Ltd., the temperature at the time of weight loss of 5% was measured under the conditions of 200 mL / min of nitrogen gas flow, and the temperature increase rate of 10 degreeC / min.
[111] (3) glass transition temperature (Tg)
[112] Using DMS6100 manufactured by Seiko Instruments Co., Ltd., the tensile mode was measured under a flow of 300 mL / min nitrogen gas at a frequency of 1 Hz and a heating rate of 3 ° C./min, and the peak temperature of the loss tangent value (tanδ) was referred to as the glass transition temperature. It was.
[113] (4) water absorption
[114] The weight change rate after immersing the test film of 5 cm of each part and 10 micrometers in thickness for 24 hours in 23 degreeC pure water was computed.
[115] (5) film cross section observation
[116] Regarding the cross section of the film, the presence of micropores and the diameter of the holes were observed using a transmission electron microscope (TEM).
[117] Preparation Example 1
[118] 10 g (96 mmol) of styrene was dissolved in 100 g of dry tetrahydrofuran under anhydrous nitrogen atmosphere, cooled to -78 ° C, and 0.77 mL of sec-butyllithium solution (solvent: cyclohexane) at a concentration of 1.3 mo1 / L was added thereto as a reaction reagent. Then, the mixture was stirred for 3 hours. Subsequently, 0.044 g (1.0 mmol) of ethylene oxide was added thereto, followed by stirring for 3 hours. Then, 3 g of methyl alcohol was added thereto, the solution was concentrated and the solvent was removed, dissolved in 100 g of tetrahydrofuran, and filtered. . The obtained filtrate was concentrated under reduced pressure and dried to obtain a styrene oligomer having a number average molecular weight of 9,600 as a hydroxyl group.
[119] The obtained oligomer 93g (9.68mmo1) was dissolved in 80g of dried tetrahydrofuran under anhydrous nitrogen atmosphere, 1.15g (14.52mmo1) of pyridine was added dropwise, and then 2.63g (14.52) of 4-nitro benzoic acid chloride was added to 20g of tetrahydrofuran at 5 ° C. After dissolving mmo1) was added dropwise for 30 minutes. After completion of the dropping, the mixture was returned to room temperature and stirred at room temperature for 24 hours. Thereafter, the reaction solution was filtered, pyridine hydrochloride was removed, and the solvent was concentrated to remove 4-nitrobenzoate ester of styrene oligomer. After dissolving 4-nitro benzoic acid ester of this styrene oligomer in 100 g of tetrahydrofuran, 0.5 g of 5 wt% palladium carbon was mixed in a hydrogen gas atmosphere and stirred at room temperature for 24 hours. Thereafter, the reaction solution was filtered through celite and the solvent was concentrated, whereby a 4-amino benzoic acid esterified styrene oligomer was obtained.
[120] Preparation Example 2
[121] Production Example Except for using the number average molecular weight 9,600 styrene oligomer 93g (9.68mmo1) used instead of the number average molecular weight of 4,000 poly (propylene glycol) monobutyl ether 38.72g (9.68mmo1) [manufactured by Aldrich Co., Ltd.] In the same manner as in 1, 4-amino benzoic acid ester-terminated poly (propylene glycol) oligomer having a number average molecular weight of 2,500 with 4-amino benzoic acid esterified at the terminal was obtained.
[122] Preparation Example 3
[123] In the same manner as in Production Example 1, except that 10 g (96 mmol) of styrene was replaced with 49.9 g (480 mmol) of styrene, polystyrene having a number average molecular weight of 50,000 having a terminal hydroxyl group was obtained.
[124] 100 g (2 mmol) of the obtained polystyrene was dissolved in 100 g of dried tetrahydrofuran under anhydrous nitrogen atmosphere, 1.15 g (14.52 mmol) of pyridine was added dropwise, and 2.63 g (14.52 mmol) of 4-nitrobenzoate was added to 20 g of tetrahydrofuran at 5 ° C. ) Was added dropwise for 30 minutes. After completion of the dropwise addition, the reaction mixture was returned to room temperature and stirred at room temperature for 24 hours. Then, the reaction solution was filtered, pyridine hydrochloride was removed, and the solvent was concentrated to remove 4- of the polystyrene. Nitro benzoic acid ester was obtained. After dissolving 4-nitrobenzoic acid ester of this polystyrene in 100 g of tetrahydrofuran, 0.5 g of 5 wt% palladium carbon was mixed in a hydrogen gas atmosphere and stirred at room temperature for 24 hours. Thereafter, the reaction solution was filtered through celite and a solvent Was concentrated to obtain 4-amino benzoic acid ester-terminated polystyrene terminally 4-amino benzoic acid esterified.
[125] Preparation Example 4
[126] Preparation of 5-ethynyl isophthalic acid dichloride
[127] (1) Synthesis of 5-trifluoromethane sulfonyloxy isophthalic acid dimethyl
[128] 190.0 g (0.904 mo1) of 5-hydroxy isophthalate, 3 L of anhydrous toluene, 214.7 g (2.718 mol) of pyridine anhydride in a 5 L flask with 4 inlets equipped with thermometer, dimloth cooling tube, calcium chloride tube and stirrer The mixture was cooled to -30 DEG C while stirring. Here, 510.2 g (1.808 mo1) of trifluoromethane anhydrous anhydrous acid was slowly added dropwise, taking care not to raise the temperature above -25 DEG C. In this case, until the dropping was completed, 1 After the completion of the dropping, the reaction temperature was raised to 0 ° C. for 1 hour, and the reaction temperature was again raised to room temperature for 5 hours. The obtained reaction mixture was poured into 4 L of ice water and separated into an aqueous layer and an organic layer. Was extracted twice with 500 mL toluene and combined with the preceding organic layer. The organic layer was washed twice with 3 L of water, dried over 100 g of anhydrous magnesium sulfate, filtered and dried over anhydrous sulfuric acid. Magnesium was removed, toluene was removed with a rotary evaporator, and dried under reduced pressure to obtain 294.0 g of dimethyl pale yellow solid 5-trifluoromethane sulfonyloxy isophthalate. (Yield 95%). The crude product was recrystallized from hexane to give white needle crystals, which were used in the next reaction.
[129] (2) Synthesis of 4- [3,5-bis (methoxy carbonyl) phenyl] -2-methyl-3-butyn-1-ol
[130] 125 g (0.365mo1) of dimethyl 5-trifluoromethane sulfonyloxy isophthalate obtained in (1) above in a 1 L flask equipped with a thermometer, a dimlot cooling tube, a nitrogen inlet tube, and a stirrer. 1.1 g (0.00419 mo1), copper iodide 0.275 g (0.00144 mo1), and 33.73 g (0.401 mo1) of 3-methyl-1-butyn-3-ol were added thereto, and nitrogen was flowed. 375 mL of anhydrous triethylamine and 200 mL of anhydrous pyridine were added thereto. The solution was added and dissolved with stirring. After continuously flowing nitrogen for 1 hour, 0.3 g (0.000427 mo1) of dichloro bis (triphenyl phosphine) palladium was added quickly, and the mixture was heated to reflux for 1 hour in an oil bath. Ethylamine and pyridine were removed under reduced pressure to give a viscous brown solution. The precipitated solid was taken out in 500 mL of water, and then washed twice with 500 mL of water, 500 mL of hydrochloric acid at a concentration of 5 mol / liter, and 500 mL of water. The solid was dried under reduced pressure at 50 ° C. to obtain 98.8 g of 4- [3. , 5-bis (methoxy carbonyl) phenyl] -2-methyl-3-butyn-1-ol (yield 98%).
[131] (3) Synthesis of 5-ethynyl isophthalic acid dipotassium salt
[132] 3 L of n-butanol and 182 g of potassium hydroxide (85%) were added to a 4-liter 1 L flask equipped with a thermometer, a dimlot cooling tube, a nitrogen inlet tube, and a stirrer to heat and reflux. To this was added 95 g (0.344 mol) of 4- [3,5-bis (methoxy carbonyl) phenyl] -2-methyl-3-butyn-1-ol synthesized in the above (2), followed by heating to reflux for 30 minutes. This crystal was cooled in a water bath to precipitate precipitated crystals. The crystals were washed twice with 1 L of ethyl alcohol and dried under reduced pressure at 60 DEG C to obtain 88.87 g of 5-ethynyl isophthalic acid dipotassium salt. (Yield 97%).
[133] (4) Synthesis of 5-ethynyl isophthalic acid dichloride
[134] Into a 4-liter 1 L flask equipped with a thermometer, a dimlot cooling tube, a nitrogen introduction tube, and a stirrer, 80 g (0.3mo1) of 5-potynyl isophthalic acid dipotassium salt obtained in the above (3) was added 400 mL of chloroform, It cooled to 0 degreeC. To this, 391 g (4.5 mol) of thionyl chlorides were dripped at 5 degrees C or less for 1 hour. Then, 4 mL of dimethyl formamide and 4 g of hydroquinone were added, and it stirred at 45-50 degreeC for 3 hours. After cooling, the crystals were separated by filtration, and the crystals were washed with 150 mL of chloroform. The filtrate and washings were combined and concentrated under reduced pressure at 40 ° C. or lower. The residue obtained was extracted and filtered twice with 200 mL of diethyl ether. The ether was distilled under reduced pressure to give a semi-solid crude product. It was washed with anhydrous n-hexane and subsequently recrystallized with diethyl ether to obtain 13 g of 5-ethynyl isophthalic acid dichloride. (Yield 19%).
[135] In addition, 5-ethynyl terephthalic acid dichloride was prepared according to the above method.
[136] Preparation Example 5
[137] Preparation of 5-phenylethynyl isophthalic acid dichloride
[138] (1) Synthesis of 5-bromo isophthalic acid
[139] Into a four-liter 1 L flask equipped with a thermometer, agitator, and a dropping lot, 99.18 g (0.55 mol) of 5-amino isophthalic acid, 165 mL of 48 wt% hydrobromic acid, and 150 mL of distilled water were added and stirred. The flask was cooled to 5 ° C. or lower, and 39.4 g (0.57 mol) of sodium nitrite was added dropwise to 525 mL of distilled water for 1 hour to obtain a diazonium salt solution. A 4-liter 3L flask bromide (1) 94.25g (0.66mo1) of four inlets equipped with a thermometer, a dimlot cooling tube, a dropping lot and a stirrer was added and stirred with 48 mL of 48 wt% hydrobromic acid. The flask was cooled to 0 ° C. or lower, and the above diazonium salt solution was added dropwise for 2 hours. After completion of the dropwise addition, the flask was stirred at room temperature for 30 minutes and then refluxed for 30 minutes. After cooling, the precipitate was separated and distilled water was poured into 2 L. The white solid obtained by washing twice was dried under reduced pressure at 50 degreeC for 2 days, and 117 g of raw material products were obtained. It was used for the next reaction without purification.
[140] (2) Synthesis of 5-bromo isophthalate dimethyl
[141] Into a 50 mL flask equipped with a stirrer and a dimlot cooling tube, 110 g of 5-bromo isophthalic acid obtained in the above (1), 500 mL of methyl alcohol and 10 g of concentrated sulfuric acid were added and refluxed for 6 hours. After cooling to room temperature, the mixture was added to 1 L of distilled water and neutralized with 5% by weight aqueous sodium hydrogen carbonate solution. The precipitate was separated, washed twice with 2 L of distilled water, and the white solid obtained was dried under reduced pressure at 50 ° C. for 2 days to obtain 5-bromoiso. 109 g (0.4 mo1) of dimethyl phthalate were obtained. (Yield 89%).
[142] (3) Synthesis of 5-phenylethynyl isophthalic acid dichloride
[143] In Production Example 4 (2), 125 g (0.365 mo1) of dimethyl 5-trifluoromethane sulfonyloxy isophthalate was used as 99.7 g (0.365 mo1) of 5-bromo isophthalate obtained in (2). 80.8 g of 1- [3,5-bis (methoxy carbonyl) phenyl] -2-phenylethine was obtained in the same manner except for the above. (Yield 75%).
[144] In the same manner as in Production Example 4 (3) and (4), 5- (2-phenylethynyl) isophthalate dipotassium salt was obtained, and 5- (2-phenylethynyl) isophthalic acid dichloride was obtained. .
[145] Preparation Example 6
[146] Preparation of 4,4'-Tran Dicarboxylic Acid Dichloride
[147] (1) Synthesis of 4-ethynyl methyl benzoate
[148] First, J. Org. 4-ethynyl benzoic acid chloride was synthesized according to the method described in Chem. Vol. 57, pp. 6998-6999 (1992).
[149] Next, 24.7 g (0.15 mo1) of 4-ethynyl benzoic acid chloride dissolved in 30 mL of tetrahydrofuran was added dropwise to 300 mL of ethanol in a water bath. After 20 minutes of completion of the dropwise addition, the solution began to become cloudy and stirred for 2 hours. Thereafter, the mixture was further stirred at room temperature for 2 hours, separated, filtered and dried to obtain 21 g of 4-ethynyl benzoate. (Yield 87%).
[150] (2) Synthesis of 4,4'-Trandicarboxylic Acid Dimethyl
[151] 16.0 g (0.1 mol) of methyl 4-ethynyl benzoate obtained in the above (1), 21.5 g (0.1 mo1) of methyl-4-bromo benzoate, 0.288 g (0.0011 mo1) of triphenyl phosphine, and cuprous iodide 0.07 A mixture of g (0.00037 mo1), 250 mL of triethylamine and 37.5 mL of pyridine was stirred, and the temperature was raised to 87 ° C (reflux). After that, the mixture was cooled to a temperature that does not reflux, and dichlorobis (triphenyl phosphine) palladium 0.098 g (0.00014 mo1) was added to reflux for 3 hours. The reaction solution was cooled, concentrated by an evaporator, the resulting precipitate was filtered and dried and washed twice with 50OmL of ethyl acetate.
[152] Thereafter, the mixture was heated and stirred in tetrahydrofuran, and after thermal filtration, 14.7 g of dimethyl 4,4'-dicarboxylic acid was obtained through recrystallization from the filtrate. (50% yield).
[153] (3) Synthesis of 4,4'-Tran Dicarboxylic Acid Dichloride
[154] 16.83 g (0.3 mo1) of potassium hydroxide was dissolved in 450 mL of methyl alcohol, and 8.22 g (0.033 mo1) of 4,4'-dicarboxylic acid dimethyl obtained in (2) was added thereto, and then the temperature was raised to reflux for 18 hours. It was then cooled, and the precipitate was recovered by filtration and dissolved in 1 L of water. The residue was filtered off from this solution, and the filtrate was gradually adjusted to pH 3 using hydrochloric acid at a concentration of 0.1 mol / liter to precipitate 4,4'-tran dicarboxylic acid, followed by filtration and drying. Obtained 4,4'-tran dicarboxylic acid. (Yield 76%).
[155] Next, 6.5 g (0.024 mo1) of this 4,4'-trans dicarboxylic acid, 60 mL of 1,2-dichloroethane, 10.013 g of benzyl triethyl ammonium chloride, and 3.9 mL of thionyl chloride were mixed and warmed up for 10 hours. It was refluxed. 40 mL of n-hexane was added to the reaction solution, and the filtrate obtained by filtration under heating was recrystallized. The obtained crystals were recrystallized again with a mixed solvent of 1,2-dichloroethane and hexane to give 3 g of 4,4'-transdica. Leric acid dichloride was obtained. (Yield 41%).
[156] Preparation Example 7
[157] Preparation of 2,2'-bis (phenylethynyl) -4,4'-biphenyl dicarboxylic acid dichloride
[158] (1) Synthesis of 2,2'-bis (phenylethynyl) -4,4'-biphenyl dicarboxylic acid dimethyl
[159] 25 g (0.092 mo1) of 4,4′-biphenyl dicarboxylic acid dimethyl was added together with 55 g (0.22 mo1) of iodine in 300 mL of concentrated sulfuric acid, and the sulfuric acid was stirred at room temperature for 1 hour using 85 g as a catalyst. Thereafter, the reaction temperature was raised to 80 ° C. and stirred for 18 hours. The reaction solution was added dropwise to ice water to obtain a yellow precipitate. The precipitate was washed once more with water, filtered and dried for 24 hours at 80 ° C. and reduced pressure. The resulting dried product was purified with Soxhlet extraction for 24 hours using methyl alcohol as a solvent, and yellow crystalline 2,2'-diiodine-4,4'-biphenyl dicarboxyl according to methyl alcohol recrystallization. 41 g of acid dimethyl was obtained. (Yield 85%).
[160] 26 g (0.05 mo1) of this 2,2'-diiodine-4,4'-biphenyl dicarboxylic acid dimethyl, 0.08 g of copper iodide, and 0.11 g of bis (triphenyl phosphine) palladium dichloride were added to 120 mL of pyridine. It was added and stirred at room temperature for 1 hour. Subsequently, a solution in which 12.5 g (0.122 mo1) of phenyl acetylene was added to 60 mL of pyridine was slowly added to the reaction system, and the temperature was raised to 80 ° C. and stirring was continued at this temperature for 5 hours. Thereafter, the resulting salt was allowed to cool at room temperature, and the precipitated salt was filtered off, and pyridine was evaporated to remove the crude product. This crude product was dissolved in 200 mL of diethyl ether, washed with 5% by weight of hydrochloric acid and water, and then recrystallized with hexane / toluene (90 / 10v / v) to give 2,2'-bis (phenylethynyl) -4, 16 g of 4'-pipeenyl dicarboxylic acid dimethyl were obtained. (Yield 68%).
[161] (2) Synthesis of 2,2'-bis (phenylethynyl) -4,4'-biphenyl dicarboxylic acid dichloride
[162] 14 g (0.03 mo1) of 1,2 mol / liter of potassium hydroxide / ethyl alcohol solution of 2,2'-bis (phenyl ethynyl) -4,4'-biphenyl dicarboxylic acid dimethyl obtained in the above (1) The mixture was refluxed with 120 mL for 2 hours, and then deprotected with dilute hydrochloric acid to obtain a yellow precipitate. After filtration drying, 12 g of 2,2'-bis (phenylethynyl) -4,4'-biphenyl dicarboxylic acid was obtained by recrystallization using toluene / methyl alcohol (90 / 10v / v). (Yield 90%).
[163] Next, 6 hours with 2,2'-bis (phenylethynyl) -4,4'-biphenyl dicarboxylic acid 4.5g (0.01mo1), 1 mL of N, N-dimethyl formamide, 100 mL of thionyl chloride After refluxing, the excess thionyl chloride was removed under reduced pressure, and then the crude product was treated by recrystallization with hexane / chloroform (90 / 10v / v) to give 2,2'-bis (phenyl ethynyl) 4,4. 4.0 g (yield 82%) of '-biphenyl dicarboxylic acid dichloride were obtained.
[164] Also, 2,2'-bis (naphthyl ethynyl) 4,4'-biphenyl dicarboxylic acid dichloride was prepared according to the above method.
[165] Preparation Example 8
[166] Preparation of 2,7-biphenylene dicarboxylic acid dichloride
[167] `` J. Poly. 2,7-biphenylene dicarboxylic acid dichloride was prepared according to the method described in Sci.:Polymer Letters Edition, Vol. 16, pages 653-656 (1978).
[168] Example 1
[169] 35.9 g (0.098 mol) of 2,2-bis (3 amino 4-hydroxy phenyl) hexafluoro propane were dissolved in 330 mL of anhydrous N-methyl 2-pyrrolidone and added to this solution with 4-ethynyl-2,6-naphthalene. 27.7 g (0.1 mo1) of dicarboxylic acid dichloride were added at 10 ° C. under anhydrous nitrogen. After addition, the mixture was stirred at 10 ° C. for 1 hour and then at 20 ° C. for 1 hour. After stirring at 10 DEG C, 22.3 g (0.22 mo1) of triethylamine was added, followed by 38.4 g (0.004 mo1, number average) of 4-amino benzoic acid ester terminated styrene oligomer synthesized in Preparation Example 1 in 100 mL of γ-butyrolactone. A solution in which molecular weight 9,600) was dissolved was added at 10 DEG C under anhydrous nitrogen. After addition, the solution was stirred at 10 DEG C for 1 hour and then at 20 DEG C for 20 hours. After completion of the reaction, the reaction solution was filtrated and triethylamine hydrochloride was removed. The filtered liquid was dripped at the mixed solution of 6.6 L of ion-exchange water and 6.6 L of isopropanol, and 80.9 g of copolymers were obtained by collecting and drying a precipitate. When the molecular weight of the obtained copolymer was calculated | required in conversion of polyethylene using GPC by Toso Corporation, the weight average molecular weight was 30,000 and molecular weight distribution was 2.23. ^As measured by ¹ H-NMR, the introduction rate of the reactive oligomer component was 36% by weight.
[170] 5.00 g of the obtained copolymer was dissolved in 20.00 g of N-methyl-2-pyrrolidone and filtered through a 0.2 µm Teflon filter to obtain a varnish. The varnish was applied onto an aluminum-deposited silicon wafer using a spin coater. At this time, the rotation speed and time of the spin coater were set so that the film thickness after the heat treatment was about 5 μm. For 240 seconds on a hot plate at 120 ° C. after application. After drying, the film of polybenzoxazole resin which made terminal react with an oligomer was obtained by heating at 300 degreeC for 60 minutes using the oven which introduced nitrogen and controlled oxygen concentration to 100 ppm or less. Furthermore, the oligomer unit was decomposed | disassembled by heating at 400 degreeC for 60 minutes, and the coating film of the polybenzoxazole resin which has a pore was obtained. Aluminum was deposited on the film and patterned to form an electrode of a predetermined size. The aluminum wafer on the silicon wafer side and the capacitance by the electrode were measured, and the electrode adjacent parts of the film were etched by oxygen plasma after the measurement. After that, the film thickness was measured with a surface roughness meter and the dielectric constant at a frequency of 1 MHz was calculated to be 2.54. The cross section of the film was observed by TEM, and the voids were discontinuous as pores of 15 nm or less. , Tg, water absorption are also shown together in Table 1.
[171] Example 2
[172] 33.0 g (0.09 mo1) of 2,2-bis (3-amino-4-hydroxy phenyl) hexafluoro propane are dissolved in 330 mL of anhydrous N-methyl 2-pyrrolidone and in this solution 5-ethynyl terephthalic acid dichloride 22.7 g (0.1 mo1) was added at 10 ° C. under anhydrous nitrogen. After addition, the mixture was stirred at 10 ° C. for 1 hour and then at 20 ° C. for 1 hour. After stirring at 10 ° C., 22.3 g (0.22 mo1) of triethylamine Then, to 100 mL of γ-butyrolactone, 56.0 g (0.02 mol, number average molecular weight 2,800) of both hydroxy-terminated poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) manufactured by Aldrich Corporation The solution was dissolved at 10 DEG C under anhydrous nitrogen. After addition, the solution was stirred at 10 DEG C for 1 hour and then at 20 DEG C for 20 hours. After the reaction was completed, the reaction solution was filtered, triethylamine hydrochloride was removed, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain 89.1 g of a copolymer. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Isoso Co., Ltd., and the weight average molecular weight was 20,000 and the molecular weight distribution was 2.2. ^As measured by ¹ H-NMR, the introduction ratio of the reactive oligomer component was 48% by weight.
[173] Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results thereof are summarized in Table 1.
[174] Example 3
[175] 53.6 g (0.095 mo1) of 9,9-bis (4-((4-amino-3-hydroxy) phenoxy) phenyl) fluorene was dissolved in 330 mL of anhydrous N-methyl 2-pyrrolidone and 22.7 g (0.1 mo1) of ethynyl isophthalic acid dichloride were added at 10 ° C. under anhydrous nitrogen. After addition, the mixture was stirred at 10 ° C. for 1 hour and then at 20 ° C. for 1 hour. After stirring at 10 ° C., 22.3 g (0.22 mo1) of ethylamine was added, followed by dissolving a solution of 40.0 g (0.02 mol, number average molecular weight 4,000) of poly (ethylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich in 100 mL of γ-butyrolactone. It was added at 10 ° C. under anhydrous nitrogen. After addition, the mixture was stirred at 10 ° C. for 1 hour, and then at 20 ° C. for 20 hours. After the reaction was completed, the reaction solution was filtered, triethylamine hydrochloride was removed, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain 96.7 g of a copolymer. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Dongso Corporation, and found to be a weight average molecular weight of 25,200 and a molecular weight distribution of 2.20. ^When measured by ¹ H-NMR, the introduction ratio of the reactive oligomer component was 34% by weight.
[176] Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results thereof are summarized in Table 1.
[177] Example 4
[178] 69.6 g (0.19 mo1) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 330 mL of anhydrous N-methyl 2-pyrrolidone and in this solution 5-ethynyl-terephthalic acid dichloride 22.7 g (0.1 mo1) and 25.3 g (0.1 mol) of 2,6-naphthalene dicarboxylic acid dichloride were added at 10 ° C. under anhydrous nitrogen. After addition, 1 hour at 10 ° C. and then 1 hour at 20 ° C., respectively. After stirring at 10 ° C., 44.5 g (0.44 mo1) of triethylamine was added, followed by 50 g of 4-amino benzoic acid ester-terminated poly (propylene glycol) oligomer obtained in Preparation Example 2 in 100 mL of γ-butyrolactone. A solution of (0.02 mol, number average molecular weight 2,500) was added at 10 ° C. under anhydrous nitrogen. After addition, the solution was stirred at 10 ° C. for 1 hour and then at 20 ° C. for 20 hours. After the reaction was completed, the reaction solution was filtered, triethylamine hydrochloride was removed, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain 138.6 g of a copolymer. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Dongso Corporation, and was found to have a weight average molecular weight of 25,000 and a molecular weight distribution of 2.25. ^When measured by ¹ H-NMR, the introduction ratio of the reactive oligomer component was 27% by weight.
[179] Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results thereof are summarized in Table 1.
[180] Example 5
[181] 34.8 g (0.095 mo1) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 330 mL of anhydrous N-methyl 2-pyrrolidone and dissolved in 5-phenylethynyl isophthalic acid di 30.3 g (0.1 mo1) of chloride were added at 10 DEG C under anhydrous nitrogen. After addition, the mixture was stirred at 10 DEG C for 1 hour, followed by 20 DEG C for 1 hour. After stirring at 10 DEG C, 22.3 g (0.22 triethylamine) was added. mo1) was added, followed by adding a solution of 40 g (0.01 mol, number average molecular weight 4,000) of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich in 100 mL of γ-butyrolactone at 10 ° C under anhydrous nitrogen. After addition, the mixture was stirred at 10 ° C. for 1 hour and then at 20 ° C. for 20 hours. After the reaction was completed, the reaction solution was filtered, triethylamine hydrochloride was removed, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain 87.9 g of a copolymer. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Toso Corporation, and was a weight average molecular weight of 25,000 and a molecular weight distribution of 2.20. ^When measured by ¹ H-NMR, the introduction ratio of the reactive oligomer component was 36% by weight.
[182] Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results thereof are summarized in Table 1.
[183] Example 6
[184] 34.8 g (0.095 mo1) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 330 mL of anhydrous N-methyl 2-pyrrolidone and dissolved in 2,7-biphenylene dica 27.6 g (0.1mo1) of carboxylic acid dichloride was added at 10 DEG C under anhydrous nitrogen. After addition, the mixture was stirred at 10 DEG C for 1 hour, followed by 20 DEG C for 1 hour. After stirring at 10 DEG C, triethylamine was added. 22.3 g (0.22 mo1) was added, followed by dissolving a solution of 40 g (0.01 mol, number average molecular weight 4,000) of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich in 100 mL of γ-butyrolactone under anhydrous nitrogen. It was added at 10 DEG C. After addition, the mixture was stirred at 10 DEG C for 1 hour and then at 20 DEG C for 20 hours. After the reaction was completed, the reaction solution was filtered, triethylamine hydrochloride was removed, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain 87.7 g of a copolymer. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Toso Corporation, and was found to have a weight average molecular weight of 25,300 and a molecular weight distribution of 2.21. ^When measured by ¹ H-NMR, the introduction ratio of the reactive oligomer component was 38% by weight.
[185] Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results thereof are summarized in Table 1.
[186] Example 7
[187] 34.8 g (0.095 mo1) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane are dissolved in 330 mL of anhydrous N-methyl 2-pyrrolidone and added to 4,4'-trans dicar 30.3 g (0.1 mo1) of acid dichloride were added at 10 ° C. under anhydrous nitrogen. After addition, the mixture was stirred at 10 ° C. for 1 hour, and then at 20 ° C. for 1 hour. After stirring at 10 ° C., triethylamine 22.3 g (0.22 mo1) was added, followed by dissolving 40 g (0.01 mol, number average molecular weight 4,000) of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich in 100 mL of γ-butyrolactone. After the addition, the mixture was stirred at 10 ° C. for 1 hour and then at 20 ° C. for 20 hours. After the reaction was completed, the reaction solution was filtered, triethylamine hydrochloride was removed, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain 90.8 g of a copolymer. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Dongso Corporation, and was found to have a weight average molecular weight of 25,100 and a molecular weight distribution of 2.21. The introduction rate of the reactive oligomer component was 37% by weight when measured by ¹ H-NMR.
[188] Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results thereof are summarized in Table 1.
[189] Example 8
[190] 119.2 g (0.21 mo1) of 9,9-bis (4-((4-amino-3-hydroxy) phenoxy) phenyl) fluorene was dissolved in 900 mL of anhydrous N-methyl 2-pyrrolidone and 22.7 g (0.1 mol) of ethynyl isophthalic acid dichloride, 30.3 g (0.1 mol) of 5-phenylethynyl isophthalic acid dichloride and 4.5 g (0.022 mol) of isophthalic acid dichloride were added at 10 ° C. under anhydrous nitrogen. After the addition, the mixture was stirred at 10 ° C. for 1 hour and then at 20 ° C. for 1 hour. After stirring at 10 ° C., 49.5 g (0.49 mo 1) of triethylamine was added, followed by poly (Aldrich's poly) in 250 mL of γ-butyrolactone. A solution of 88.9 g (0.022 mol, number average molecular weight 4,000) of (propylene glycol) bis (2-aminopropyl ether) was added at 10 DEG C under anhydrous nitrogen. After addition, at 10 DEG C for 1 hour, and then at 20 DEG C. Stir for 20 hours. After the reaction was completed, the reaction solution was filtered, triethylamine hydrochloride was removed, and the filtered solution was added dropwise to a mixed solution of 15 L of ion-exchanged water and 15 L of isopropanol, and the precipitate was collected and dried to obtain 211.8 g of a copolymer. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Toso Corporation, and was a weight average molecular weight of 25,000 and a molecular weight distribution of 2.20. ^When measured by ¹ H-NMR, the introduction ratio of the reactive oligomer component was 33% by weight.
[191] Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results thereof are summarized in Table 1.
[192] Example 9
[193] 71.5 g (0.13 mo1) of 9,9-bis (4-((4-amino-3-hydroxy) phenoxy) phenyl) fluorene was dissolved in 550 mL of anhydrous N-methyl 2-pyrrolidone and 7.6 g (0.033 mo1) of ethynyl isophthalic acid dichloride and 30.3 g (0.1 mol) of 5-phenylethynyl isophthalic acid dichloride were added at 10 ° C. under anhydrous nitrogen. After addition, 1 hour at 10 ° C., followed by 20 After stirring at 10 ° C. for 1 hour, respectively, after stirring at 10 ° C., 29.7 g (0.29 mo 1) of triethylamine was added, followed by poly (propylene glycol) bis (2-aminopropyl) manufactured by Aldrich in 150 mL of γ-butyrolactone. Ether) 53.3 g (0.013 mol, number average molecular weight 4,000) was added at 10 DEG C under anhydrous nitrogen. After addition, the solution was stirred at 10 DEG C for 1 hour and then at 20 DEG C for 20 hours. After the reaction was completed, the reaction solution was filtered, triethylamine hydrochloride was removed, and the filtered solution was added dropwise to a mixed solution of 11 L of ion-exchanged water and 11 L of isopropanol, and the precipitate was collected and dried to obtain 137.7 g of a copolymer. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Toso Corporation, and was found to have a weight average molecular weight of 24,000 and a molecular weight distribution of 2.10. ^When measured by ¹ H-NMR, the introduction ratio of the reactive oligomer component was 32% by weight.
[194] Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results thereof are summarized in Table 1.
[195] Example 10
[196] 34.8 g (0.095 mo1) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 330 mL of anhydrous N-methyl 2-pyrrolidone and dissolved in 2,2'-bis (phenyl) 47.9 g (0.1 mo1) of ethynyl) -4,4'-biphenyl dicarboxylic acid dichloride were added at 10 ° C. under anhydrous nitrogen. After addition, the mixture was stirred at 10 ° C. for 1 hour and then at 20 ° C. for 1 hour. After stirring at 10 ° C., 22.3 g (0.22 mo1) of triethylamine was added, followed by 100 mL of γ-butyrolactone, both of the hydroxy-terminated poly (ethylene glycol) -block-poly (propylene glycol) -made by Aldrich. A solution of 28.0 g (0.01 mol, number average molecular weight 2,800) of block-poly (ethylene glycol) was added at 10 DEG C under anhydrous nitrogen. After addition, the solution was stirred at 10 DEG C for 1 hour and then at 20 DEG C for 20 hours. . After the reaction was completed, the reaction solution was filtered, triethylamine hydrochloride was removed, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain 88.1 g of a copolymer. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Toso Corporation, and was found to have a weight average molecular weight of 25,000 and a molecular weight distribution of 2.2. ^When measured by ¹ H-NMR, the introduction rate of the reactive oligomer component was 25.8 wt%.
[197] Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results thereof are summarized in Table 1.
[198] Example 11
[199] 34.8 g (0.095 mo1) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 330 mL of anhydrous N-methyl 2-pyrrolidone and dissolved in 2,2'-bis (naph) in this solution. 57.9 g (0.1mo1) of thyltynyl) -4,4'-biphenyl dicarboxylic acid dichloride were added at 10 DEG C. under anhydrous nitrogen. After addition, 1 hour at 10 DEG C, followed by 20 DEG C for 1 hour, respectively. After stirring at 10 ° C., 22.3 g (0.22 mo1) of triethylamine was added, followed by 100 ml of γ-butyrolactone, both hydroxy-terminated poly (ethylene glycol) -block-poly (propylene glycol) manufactured by Aldrich. A solution of 28.0 g (0.01 mol, number average molecular weight 2,800) of -block-poly (ethylene glycol) was added at 10 DEG C under anhydrous nitrogen. After addition, 1 hour at 10 DEG C, followed by stirring at 20 DEG C for 20 hours. It was. After the reaction was completed, the reaction solution was filtered, triethylamine hydrochloride was removed, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain 98.5 g of a copolymer. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Toso Corporation, and was found to have a weight average molecular weight of 24,000 and a molecular weight distribution of 2.1. ^When measured by ¹ H-NMR, the introduction rate of the reactive oligomer component was 23.5 wt%.
[200] Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results thereof are summarized in Table 1.
[201] Example 12
[202] 34.8 g (0.095 mo1) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 330 mL of anhydrous N-methyl 2-pyrrolidone and dissolved in 2,2'-bis (phenyl) 33.5 g (0.07 mo1) of ethynyl) -4,4′-biphenyl dicarboxylic acid dichloride and 6.1 g (0.03 mol) of isophthalic acid dichloride were added at 10 ° C. under anhydrous nitrogen. Then, the mixture was stirred at 20 ° C. for 1 hour. After stirring at 10 ° C., 22.3 g (0.22 mo 1) of triethylamine was added, followed by poly (propylene glycol) bis (by Aldrich Co., Ltd.) in 100 mL of γ-butyrolactone. A solution of 40.0 g (0.01 mol, number average molecular weight 4,000) of 2-aminopropylethynyl) was added at 10 DEG C under anhydrous nitrogen. After addition, the solution was stirred at 10 DEG C for 1 hour and then at 20 DEG C for 20 hours. . After the reaction was completed, the reaction solution was filtered, triethylamine hydrochloride was removed, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain 91.3 g of a copolymer. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Toso Corporation, and was found to have a weight average molecular weight of 26,000 and a molecular weight distribution of 2.2. ^When measured by ¹ H-NMR, the introduction ratio of the reactive oligomer component was 35.05% by weight.
[203] Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results thereof are summarized in Table 1.
[204] Comparative Example 1
[205] 34.8 g (0.095 mo1) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 330 mL of anhydrous N-methyl 2-pyrrolidone and dissolved in this solution with 5-ethynyl-2,6 7.7 g (0.1 mo1) of naphthalene dicarboxylic acid dichloride were added at 10 ° C. under anhydrous nitrogen. After addition, the mixture was stirred at 10 ° C. for 1 hour and then at 20 ° C. for 1 hour. After stirring at 10 ° C., After adding 22.3 g (0.22 mo1) of triethylamine, the mixture was stirred at 10 DEG C for 1 hour, and then at 20 DEG C for 20 hours. After the reaction was completed, the reaction solution was filtered, triethylamine hydrochloride was removed, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain 53.5 g of a polymer. The molecular weight of the obtained polymer was determined in terms of polystyrene using GPC manufactured by Toso Corporation.
[206] Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results thereof are summarized in Table 1.
[207] Comparative Example 2
[208] 34.8 g (0.095 mo1) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane are dissolved in 330 mL of anhydrous N-methyl 2-pyrrolidone and 20.3 g (0.1 mo1) of terephthalic acid dichloride in this solution. ) Was added at 10 ° C. under anhydrous nitrogen. After addition, the mixture was stirred at 10 ° C. for 1 hour and then at 20 ° C. for 1 hour. After stirring at 10 ° C., 22.3 g (0.22 mo 1) of triethylamine was added. Then, a solution obtained by dissolving 28 g (0.01 mol, number average molecular weight 2,800) of poly (propylene glycol) -block-poly (ethylene glycol) hemdan copolymer in 100 mL of γ-butyrolactone was added at 10 ° C. under anhydrous nitrogen. . After addition, the mixture was stirred at 10 ° C. for 1 hour, and then at 20 ° C. for 20 hours. After the reaction was completed, the reaction solution was filtered, triethylamine hydrochloride was removed, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain 50.3 g of a copolymer. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Toso Corporation, and was found to have a weight average molecular weight of 20,100 and a molecular weight distribution of 2.22. ^When measured by ¹ H-NMR, the introduction ratio of the reactive oligomer component was 33% by weight.
[209] Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results thereof are summarized in Table 1.
[210] Comparative Example 3
[211] 36.4 g (0.0995 mo1) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 330 mL of anhydrous N-methyl 2-pyrrolidone and in this solution 5-ethynyl-terephthalic acid dichloride 22.7 g (0.1 mo1) were added at 10 DEG C under anhydrous nitrogen. After addition, the mixture was stirred at 10 DEG C for 1 hour, followed by 20 DEG C for 1 hour. After stirring at 10 DEG C, 22.3 g (0.22 mo1 of triethylamine) were added. ), And then a solution of 50.0 g (0.001 mol, number average molecular weight 50,000) of 4-amino benzoic acid terminated polystyrene obtained in Preparation Example 3 in 100 mL of γ-butyrolactone was added at 10 ° C. under anhydrous nitrogen. After addition, the mixture was stirred at 10 ° C. for 1 hour, and then at 20 ° C. for 20 hours. After the reaction was completed, the reaction solution was filtered, triethylamine hydrochloride was removed, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain 81.4 g of a copolymer. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Toso Corporation, and was found to have a weight average molecular weight of 80,000 and a molecular weight distribution of 2.12. ^When measured by ¹ H-NMR, the introduction ratio of the reactive oligomer component was 42% by weight.
[212] Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results thereof are summarized in Table 1.
[213] Comparative Example 4
[214] 126.2 g (0.13 mo1) of 9,9-bis (4-((4-amino-3-hydroxy) phenoxy) phenyl) fluorene was dissolved in 600 mL of anhydrous N-methyl 2-pyrrolidone and 7.8 g (0.033 mol) of 4'-biphenyl dicarboxylic acid dichloride, 20.3 g (0.1 mol) of terephthalic acid dichloride and 4.8 g (0.024 mol) of isophthalic acid dichloride were added at 10 DEG C under anhydrous nitrogen. Then, the mixture was stirred at 10 ° C. for 1 hour, and then at 20 ° C. for 1 hour. After stirring at 10 ° C., 49.8 g (0.49 mo 1) of triethylamine was added, followed by poly (Aldrich Co., Ltd.) in 250 mL of γ-butyrolactone. A solution of 94.1 g (0.024 mol, number average molecular weight 4,000) of propylene glycol) bis (2-aminopropyl ether) was added at 10 DEG C under anhydrous nitrogen. After addition, 1 hour at 10 DEG C, and then continued at 20 DEG C. Stir for hours. After the reaction was completed, the reaction solution was filtered, triethylamine hydrochloride was removed, and the filtered solution was added dropwise to a mixed solution of 18 L of ion-exchanged water and 18 L of isopropanol, and the precipitate was collected and dried to obtain 210.4 g of a copolymer. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Toso Corporation, and was found to have a weight average molecular weight of 24,000 and a molecular weight distribution of 2.10. ^When measured by ¹ H-NMR, the introduction ratio of the reactive oligomer component was 34% by weight.
[215] Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results thereof are summarized in Table 1.
[216] Table 1
[217] ItemRelative dielectric constantHeat resistanceTgWater absorptionMicropore observation unit-(℃)(℃)(weight%)Example 12.1543> 4500.215 nm or less Example 21.7545> 4500.3Pores of 10 nm or less Example 32.2539> 4500.3Pores of 10 nm or less Example 42.1542> 4500.3Pores less than 8nm Example 52.0560> 4500.2Pores of 10 nm or less Example 61.9562> 4500.29 nm or less pores Example 71.9555> 4500.2Pores of 10 nm or less Example 82.1544> 4500.2Pores of 10 nm or less Example 92.2548> 4500.2Pores of 10 nm or less Example 102.15474560.2Pores of 10 nm or less Example 111.95684470.2Pores of 10 nm or less Example 121.95234150.2Pores of 10 nm or less Comparative Example 12.8545> 4500.2Pore not observed Comparative Example 22.85393760.2Pore not observed Comparative Example 3*One546> 4500.31㎛ or more void Comparative Example 4*One5333800.3No void observed
[218] * 1 The measurement was shorted and could not be measured.
[219] [week]
[220] The copolymer was prepared and evaluated in the same manner as in Example 2 except that the introduction rate of the reactive oligomer was increased to 72% by weight. There was no.
[221] From the evaluation results of Examples and Comparative Examples as summarized in Table 1, it is confirmed that the insulating film (film) obtained from the insulating film material of the present invention enables low dielectric constant while maintaining excellent heat resistance and low water absorption. In addition, the porosity calculated from the logarithmic mixing equation using the measured dielectric constant was almost identical to the introduction rate of the reactive oligomer.
[222] The insulating film obtainable by the insulating film material and varnish for coating of the present invention can achieve excellent thermal characteristics, electrical characteristics and absorbency, and in particular, has a very low dielectric constant, an interlayer insulating film or protective film for semiconductors, and an interlayer of a multilayer circuit. It can be suitably used for applications such as an insulating film, a flexible copper plate cover coat, a solder resist film, and a liquid crystal alignment film.

权利要求:
Claims (24)
[1" claim-type="Currently amended] General formula [1]
[Wherein, R ¹ to R ⁴ independently represent a hydrogen atom or a monovalent organic group, X represents a tetravalent group selected from the group represented by the following formula (A), and two X's may be the same or different, and Y represents the following formula: At least one divalent group selected from the group represented by (B), formula (C), formula (D) and formula (E), Z represents a divalent group selected from the group represented by formula (F), m and n is an integer that satisfies the relationship of m> 0, n≥0, 2≤m + n≤1000 and 0.05≤m / (m + n) ≤1, respectively, and the array of repetition units is either block or random type And a copolymer obtained by reacting a polyamide represented by the above formula and a reactive oligomer having a substituent obtained by reacting with a carboxyl group, an amino group or a hydroxyl group in the polyamide structure as a film-forming component. material.
Formula (A):

Formula (B) -1:

Formula (B) -2:

Formula (C) -1:

Equation (C) -2:

Formula (D):

Formula (E):

Formula (F):

[X ¹ in Formula (A) and Formula (F) is, the following Formula (G).
Formula (G):

A divalent group selected from the groups represented by is represented, and R in the formula (C) represents a monovalent group selected from an alkyl group or a group represented by the following formula (H).
Formula (H):

In the group represented by formula (A), formula (B), formula (C), formula (D), formula (E), formula (F) and formula (G), the hydrogen atom on the benzene ring has 1 to 4 carbon atoms. May be substituted with at least one group selected from alkyl, fluorine and trifluoromethyl groups.
[2" claim-type="Currently amended] The method of claim 1,
A polyamide has a divalent group selected from the group represented by formula (B) as Y in General formula [1], The insulating film material characterized by the above-mentioned.
[3" claim-type="Currently amended] The method of claim 1,
The polyamide has Y as the general formula [1], and has a divalent group selected from the group represented by the formula (C).
[4" claim-type="Currently amended] The method of claim 1,
A polyamide has a divalent group selected from the group represented by formula (D) as Y in General formula [1], The insulating film material characterized by the above-mentioned.
[5" claim-type="Currently amended] The method of claim 1,
The polyamide has Y as the general formula [1], and has a divalent group selected from the group represented by the formula (E).
[6" claim-type="Currently amended] The method according to any one of claims 1 to 5,
The reactive oligomer is at least one member selected from polyoxy alkylene, polymethyl methacrylate, poly α-methylstyrene, polystyrene, polyester, polyether ester, polycaprolactone and polyurethane.
[7" claim-type="Currently amended] The method according to any one of claims 1 to 6,
The reactive oligomer has a number average molecular weight of 100 to 40,000.
[8" claim-type="Currently amended] The method of claim 7, wherein
A material for insulating films, wherein the reactive oligomer has a number average molecular weight of 100 to 20,000.
[9" claim-type="Currently amended] The method of claim 8,
A material for insulating films, wherein the reactive oligomer has a number average molecular weight of 100 to 10,000.
[10" claim-type="Currently amended] The method according to any one of claims 1 to 9,
A material for insulating films, characterized in that the copolymer has introduced 5 to 70% by weight of a reactive oligomer unit.
[11" claim-type="Currently amended] The method of claim 10,
A material for insulating films, characterized in that the copolymer has introduced 5 to 50% by weight of a reactive oligomer unit.
[12" claim-type="Currently amended] The method of claim 11,
A material for insulating films, characterized in that the copolymer has introduced 5 to 40% by weight of a reactive oligomer unit.
[13" claim-type="Currently amended] A coating varnish for insulating films comprising the insulating film material according to any one of claims 1 to 12 and an organic solvent capable of dissolving or dispersing the insulating film material.
[14" claim-type="Currently amended] A layer of a resin mainly containing polybenzoxazole obtained by heat treatment of the insulating film material according to any one of claims 1 to 12 or the coating varnish for an insulating film according to claim 13, followed by a condensation reaction and a crosslinking reaction. And an insulating film characterized by having fine pores.
[15" claim-type="Currently amended] The method of claim 14,
An insulating film, wherein the size of the micropores of the insulating film is 1 µm or less.
[16" claim-type="Currently amended] The method of claim 15,
An insulating film, wherein the size of the micropores of the insulating film is 500 nm or less.
[17" claim-type="Currently amended] The method of claim 16,
An insulating film, characterized in that the size of the fine pores of the insulating film is 100nm or less.
[18" claim-type="Currently amended] The method of claim 17,
An insulating film characterized in that the size of the micropores of the insulating film is 20 nm or less.
[19" claim-type="Currently amended] The method according to any one of claims 14 to 18,
An insulating film, wherein the porosity of the insulating film is 5 to 70%.
[20" claim-type="Currently amended] The method of claim 19,
An insulating film, wherein the porosity of the insulating film is 5 to 50%.
[21" claim-type="Currently amended] The method of claim 20,
An insulating film, wherein the porosity of the insulating film is 5 to 40%.
[22" claim-type="Currently amended] The method according to any one of claims 14 to 21,
An insulating film used as an interlayer insulating film for multilayer wiring of a semiconductor.
[23" claim-type="Currently amended] The method according to any one of claims 14 to 21,
An insulating film used as a surface protective film of a semiconductor.
[24" claim-type="Currently amended] A semiconductor device comprising an interlayer insulating film for multilayer wiring made of the insulating film according to claim 22 and / or a surface protective layer made from the insulating film according to claim 23.

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JP4868183B2|2012-02-01|Novel fluorinated tetracarboxylic dianhydride, polyimide precursor obtained therefrom, polyimide and its use

---

JP2002530505A|2002-09-17|Composition containing crosslinkable matrix precursor and porogen, and porous matrix produced therefrom

---

JP4041019B2|2008-01-30|Dielectric with barrier effect against copper diffusion

---

JP3653499B2|2005-05-25|Poly | copolymer

---

WO2008072915A1|2008-06-19|Polyimide resin and liquid crystal alignment layer and polyimide film using the same

---

JP2007091701A|2007-04-12|Tetracarboxylic acid containing fluorenyl group and ester group, polyester imide precursor containing fluorenyl group, polyester imide containing fluorenyl group and method for producing the same

---

US8512596B2|2013-08-20|Composition for producing a board and printed circuit board using the same

---

WO1987002620A1|1987-05-07|Flexible printed circuit board and process for its production

---

US4720539A|1988-01-19|Polyimide precursor compositions, their manufacture, the resultant polyimides and their use, particularly for manufacturing enamelling varnishes for electric wires

---

US7521167B2|2009-04-21|Ester group-containing poly | copolymer, ester group-containing poly | copolymer, and positive photosensitive resin composition

---

EP1810963A1|2007-07-25|Fluorine-containing polymerizable monomer and polymer compound using same

---

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CN101423609A|2009-05-06|Method for preparing polyimide powder containing active ethylene group

同族专利:

---

公开号 | 公开日

---

EP1333050B1|2006-12-27|

---

AT349481T|2007-01-15|

---

EP1333050A4|2005-03-02|

---

DE60125575T2|2007-04-19|

---

TWI277629B|2007-04-01|

---

KR100787265B1|2007-12-21|

---

US7049371B2|2006-05-23|

---

CN1231525C|2005-12-14|

---

EP1333050A1|2003-08-06|

---

CN1461323A|2003-12-10|

---

JP2002167442A|2002-06-11|

---

WO2002024788A1|2002-03-28|

---

US20040002572A1|2004-01-01|

---

DE60125575D1|2007-02-08|

---

JP3492316B2|2004-02-03|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2000-09-22|Priority to JPJP-P-2000-00288271

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2000-09-22|Priority to JP2000288271

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2000-12-28|Priority to JPJP-P-2000-00401237

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2000-12-28|Priority to JP2000401237A

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2001-09-20|Application filed by 스미토모 베이클리트 컴퍼니 리미티드

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2001-09-20|Priority to PCT/JP2001/008210

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2004-04-09|Publication of KR20040030416A

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2007-12-21|Application granted

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2007-12-21|Publication of KR100787265B1

优先权:

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申请号 | 申请日 | 专利标题

---

JPJP-P-2000-00288271|2000-09-22|

---

JP2000288271|2000-09-22|

---

JPJP-P-2000-00401237|2000-12-28|

---

JP2000401237A|JP3492316B2|2000-09-22|2000-12-28|Material for insulating film, coating varnish for insulating film, insulating film using the same, and semiconductor device|

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PCT/JP2001/008210|WO2002024788A1|2000-09-22|2001-09-20|Material for insulating film, coating varnish for insulating film, and insulating film and semiconductor device using the same|