JP2003160665A - Method of manufacturing polyimide precursor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain in a simple way a copolymer which is a polyimide precursor and has an amide-ester structure and an imide structure. <P>SOLUTION: In a method of manufacturing a polyimide precursor, (a) a compound represented by formula (1): (R<SP>3</SP>OC)<SB>2</SB>R<SP>1</SP>(COOR<SP>2</SP>)<SB>2</SB>(wherein, R<SP>1</SP>is a tetravalent organic group; R<SP>2</SP>is a monovalent organic group having one or more carbons; and R<SP>3</SP>is OH or Cl), (b) an acid dianhydride and (c) a diamine or a dicyanate are polymerized and an amide acid portion thus obtained is imidated with an addition of a dehydration and ring closing agent and/or a catalyst. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an optical material, an optical component, a protective film for a semiconductor element, a multilayer wiring, which has a high solvent solubility, is excellent in storage stability, and can form a pattern by printing or photolithography. The present invention relates to a method for producing a polyimide precursor suitable for forming an insulating film for a substrate and the like.

[0002]

2. Description of the Related Art JP-B-55-30207 proposes a polyamic acid molecule in which a photosensitive group is ester-bonded to a carboxyl group. This photosensitive polyimide precursor is reacted with an alcohol containing a carbon-carbon unsaturated bond having photoreactivity to tetracarboxylic dianhydride to produce a tetracarboxylic acid diester, and a free carboxyl group in the diester is converted into a dicarboxylic acid. Converted to the acid chloride group,
It is produced by subjecting the obtained diester-bis-acid chloride to a polycondensation reaction with a diamine. However, all parts of the polyimide precursor have an amic acid ester structure, and there is a large problem in volume change during polyimidization,
In addition, it lacks general versatility in that it requires a photosensitive ester bond, or cannot improve solvent solubility.

In JP-A-6-102667, ring-opening addition of alcohol to tetracarboxylic acid dianhydride to form tetracarboxylic acid ester anhydride, and then the tetracarboxylic acid ester anhydride or the tetracarboxylic acid anhydride is carried out. A terminally esterified polyamic acid is formed by ring-opening addition of a diamine to a mixed solution of an ester anhydride and a tetracarboxylic dianhydride, and then a photopolymerization initiator is mixed to prepare a photosensitive polyimide precursor. A method has been proposed.

However, even in this method, all parts of the polyimide precursor have an amic acid ester structure, and there is a problem that the volume change during polyimidization is large.

Japanese Unexamined Patent Publication No. 9-59379 discloses a method of obtaining a polyamic acid in which at least one of the molecular terminals is an acid ester of alcohol by ring-opening addition of alcohol to a polyamic acid oligomer. However, in this method, since the polyamic acid structure is mostly occupied, storage stability is poor and solvent solubility is a problem.

In polyimide synthesis using an aliphatic diamine, a method has been proposed in which a specific aliphatic carboxylic acid dianhydride is converted to a dimethyl ester, which is then introduced into an acid chloride for polymerization (high performance polymer, 10
Vol. 11, 11 (1998)).

However, even in this method, all parts of the polyimide precursor have an amic acid ester structure, and there is a problem in that the volume change during polyimidization is large. Moreover, since it is limited to a specific aliphatic carboxylic acid dianhydride, it is not versatile.

Similarly, Japanese Unexamined Patent Publication No. 2001-72768 discloses an example of studying polymerization of an alicyclic carboxylic acid dianhydride and a bissilylated diamine. However, all parts of a polyimide precursor have an amic acid ester structure. However, there is a problem in that the volume change during polyimidization is large. Moreover, since it is limited to a specific aliphatic carboxylic acid dianhydride, it is not versatile.

As described above, there has been no method for easily producing a polyimide precursor having a structure in which a polyamide ester structure and a polyimide structure are copolymerized, which are excellent in solvent solubility and storage stability.

[0010]

In order to solve the above-mentioned problems of the prior art, a simple processing method such as printing is possible and is useful as a material for optical waveguides and the like in solvent solubility, heat resistance, It is to provide a method for producing a polyimide precursor having excellent storage stability.

[0011]

Means for Solving the Problems (a) The following general formula (1):

[0012]

[Chemical 4] (Wherein R ¹ is a tetravalent organic group, R ² is a monovalent organic group having 1 or more carbon atoms, R ³ is OH or Cl), and (b) an acid dianhydride. c) A method for producing a polyimide precursor, which comprises polymerizing a diamine or dicyanate and adding a dehydration ring-closing agent and / or a catalyst to imidize an amic acid moiety. (Claim 1) The method for producing a polyimide precursor according to claim 1, wherein at least one of (a), (b) and (c) contains fluorine.
(Claim 2) The diamine has the following general formula (2):

[0013]

[Chemical 5] (Wherein R ⁴ may be the same or different and is at least one selected from hydrogen, deuterium, fluorine and perfluoroalkyl groups). Production method. (Claim 3) The acid dianhydride has the following general formula (3):

[0014]

[Chemical 6] (Where R in the formula^FourMay be the same or different, water
Selected from elemental, deuterium, fluorine and perfluoroalkyl groups
Is at least one of the following).
A method for producing the above-mentioned polyimide precursor. (Claim 4) R in the general formula (1)²Is a hydrocarbon group having 1 to 6 carbon atoms
The method for producing the polyimide precursor according to claim 1.
Law. (Claim 5) [R²OC (= O)]₂-R¹-(COCl)₂And diamine
Reacting and then adding acid dianhydride to polymerize
Item 1. A method for producing a polyimide precursor according to items 1 to 5 (R ¹Is
Tetravalent organic group, R²Represents a monovalent organic group having 1 or more carbon atoms
You ). (Claim 6) [R²OC (= O)]₂-R¹-(COCl)₂And amine powder
The imide oligomer at the end is polymerized.
Method for producing polyimide precursor (R¹Is a tetravalent organic group,
R²Represents a monovalent organic group having 1 or more carbon atoms. ). (Claim
(Item 7) [R²OC (= O)]₂-R¹-(COOH)₂And amine powder
Contract to polymerize in the presence of a condensation agent with the imide oligomer at the edge
The method for producing a polyimide precursor according to claim 1 to 6 (R
¹Is a tetravalent organic group, R²Is a monovalent organic group having 1 or more carbon atoms
Indicates. ). (Claim 8) [R²OC (= O)]₂-R¹-(COOH)₂And diamine
Is reacted in the presence of a condensing agent, and then acid dianhydride is added.
Of the polyimide precursor according to claim 1, wherein the polyimide precursor is polymerized.
Build method (R¹Is a tetravalent organic group, R²Is 1 with 1 or more carbons
Indicates a valent organic group. ). (Claim 9) [R²OC (= O)]₂-R¹-(COOH)₂And dianhydride
6. Reacting a dicyanate with an object
Method for producing polyimide precursor of (R¹Is a tetravalent organic
Group, R²Represents a monovalent organic group having 1 or more carbon atoms. ).
(Claim 10) Dehydration ring-closing agent and / or catalyst is acetic anhydride and tertiary amine
The method for producing the polyimide precursor according to claim 1, wherein
Law. (Claim 11)

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The polyimide precursor component in the present invention has the following general formula (4):

[0016]

[Chemical 7] (Wherein R ⁵ and R ⁸ are tetravalent organic groups, R ⁶ is a monovalent organic group having 1 or more carbon atoms, R ⁷ and R ⁹ are divalent organic groups,
n and m are positive numbers of 1 or more, and k is a positive number of 1 or more. ) A method for producing a polyimide precursor having a repeating unit. The polyimide precursor having the structure of the general formula has high solvent solubility and storage stability and is excellent in processing such as printing.

The presence of fluorine is preferable in that it lowers the moisture absorption rate, enhances solvent solubility and has excellent optical properties. Especially, when hydrogen in the alkyl group is replaced with fluorine, etc., in the near infrared region. The vibration absorption based on the C—H bond of an alkyl group or the like, which causes the light loss, is small, which is preferable. However, since absorption due to the C—H bond of the hydrogen atom directly bonded to the benzene ring is considered to have little absorption and does not affect the effect of the present invention, it does not contain hydrogen directly bonded to the benzene ring. Although it does not matter, it is preferable that all hydrogens are substituted with at least one selected from deuterium, fluorine and perfluoroalkyl groups.

(A) used as a raw material of the precursor in the present invention
The following general formula (1):

[0019]

[Chemical 8] A compound represented by the formula (wherein R ¹ is a tetravalent organic group, R ²
Is a monovalent organic group having 1 or more carbon atoms, R ³ is OH or Cl
Indicates. ) May be produced by any route.

The diester compound in which R ³ is OH can be produced, for example, by the following method. That is, the acid dianhydride is dissolved in a solvent, then mixed with an alcohol having 1 to 6 carbon atoms, heated and placed under reflux. After reacting under reflux for 0.2 to 24 hours, the solvent is removed to obtain a reaction product. If necessary, this is purified by a general purification method such as recrystallization or column chromatography resolution.

The dichloride compound in which R ³ is Cl can be produced, for example, by the following method. That is, the above ester compound is suspended in a solvent such as ethyl acetate, oxalyl chloride in an amount equal to or more than twice the ester compound is added (if necessary, divided into several times), and a small amount of dimethylformamide is added. This solution is heated, for example, at 40 ° C. to reflux for 0.5 hour to 48 hours, and if necessary, further 0.5 hour to 4 hours.
The reaction is completed under reflux for 8 hours. After this, the solvent is removed under reduced pressure and, if necessary, further dried under reduced pressure. If necessary, it is purified by a general purification method such as recrystallization.

In the general formula (Formula 20), R8 has 7 carbon atoms.
In the above cases, there are problems that the versatility of the raw material is lost and that the film loss after printing the precursor is large.

The acid dianhydride as the raw material of (a) and the acid dianhydride of (b) may be the same or different. This example is described below.

Examples of the acid dianhydride component containing fluorine include (trifluoromethyl) pyromellitic dianhydride, di (trifluoromethyl) pyromellitic dianhydride and di (heptafluoropropyl) pyromellitic. Acid dianhydride, pentafluoroethylpyromellitic dianhydride, bis {3,5-di (trifluoromethyl) phenoxy} pyromellitic dianhydride, 2,2-bis (3,4-
Dicarboxyphenyl) hexafluoropropane dianhydride, 5,5′-bis (trifluoromethyl) -3,
3 ', 4,4'-tetracarboxybiphenyl dianhydride, 2,2', 5,5'-tetrakis (trifluoromethyl) -3,3 ', 4,4'-tetracarboxybiphenyl dianhydride, 5 , 5'-bis (trifluoromethyl)
-3,3 ', 4,4'-tetracarboxydiphenyl ether dianhydride, 5,5'-bis (trifluoromethyl) -3,3', 4,4'-tetracarboxybenzophenone dianhydride, bis {( Trifluoromethyl) dicarboxyphenoxy} benzene dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} trifluoromethylbenzene dianhydride, bis (dicarboxyphenoxy) trifluoromethylbenzene dianhydride, bis (dicarboxy Phenoxy) bis (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) tetrakis (trifluoromethyl) benzene dianhydride, 2,2
-Bis {(4- (3,4-dicarboxyphenoxy) phenyl} hexafluoropropane dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} biphenyl dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy } Bis (trifluoromethyl) biphenyl dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} diphenyl ether dianhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) biphenyl dianhydride, and the like.

If not only the alkyl group in the molecule but all monovalent elements bonded to carbon such as phenyl ring are fluorine or perfluoroalkyl group, absorption in the near-infrared region will be improved. Small and preferable. In order to obtain such an acid dianhydride, tetracarboxylic acid or a derivative thereof is converted into an anhydride by a usual method and heated to, for example, 100 ° C. or higher to obtain a desired perfluorinated dihydrate. Such acid anhydrides, acid chlorides, etc. are: 2,5-difluoropyromellitic acid, 2-trifluoromethyl-5-fluoropyromellitic acid, 2,5-di (trifluoromethyl)
Pyromellitic acid, 2,5-di (pentafluoroethyl)
Pyromellitic acid, hexafluoro-3,3 ', 4,4'
-Biphenyltetracarboxylic acid, hexafluoro-3,
3 ', 4,4'-benzophenone tetracarboxylic acid,
2,2-bis (3,4-dicarboxytrifluorophenyl) hexafluoropropane, 1,3-bis (3,4
-Dicarboxytrifluorophenyl) hexafluoropropane, 1,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene, hexafluoro-3,3 '(or 4,4')-oxybisphthalic acid And so on.

An acid dianhydride component containing no fluorine may be used, for example, tan tetracarboxylic dianhydride, 1,
2,3,4-cyclobutanetetracarboxylic dianhydride,
1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbonane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 5- (2,2
5-dioxotetrahydrofural) -3-methyl-3-
Cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5
Aliphatic or alicyclic tetracarboxylic dianhydride such as 6-tetracarboxylic dianhydride; pyromellitic dianhydride,
3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride Anhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3'
3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic acid Dianhydride, 4,4'-bis (3,3
4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane Dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3', 4,4'-
Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-
Phenylene-bis (triphenylphthalic acid) dianhydride,
Bis (triphenylphthalic acid) -4,4'-diphenylether dianhydride, bis (triphenylphthalic acid)-
Aromatic tetracarboxylic dianhydrides such as 4,4'-diphenylmethane dianhydride; para-terphenyl-3,4
3 ", 4" -tetracarboxylic dianhydride, 3,3 ',
4,4'-benzophenone tetracarboxylic acid dianhydride,
1,4-hydroquinone dibenzoate-3.3 ′, 4
4'-tetracarboxylic dianhydride, 3,3 ', 4,4'
-Biphenyltetracarboxylic dianhydride, 3,3 ',
4,4'-biphenyl ether tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 2,3,3 5,6-Pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4'-sulfonyl Diphthalic dianhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, meta-terphenyl-3,3 ",
4,4 "-tetracarboxylic dianhydride, 3,3 ', 4,
4'-diphenyl ether tetracarboxylic dianhydride,
1,3-bis (3,4-dicarboxyphenyl) -1,
1,3,3-tetramethyldisiloxane dianhydride, 1-
(2,3-Dicarboxyphenyl) -3- (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 1,3,3a, 4,5,9b-
Hexahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3
3a, 4,5,9b-hexahydro-5-methyl-5-
(Tetrahydro-2,5-dioxo-3-furanyl)-
Naphtho [1,2-c] furan-1,3-dione, 1,
3,3a, 4,5,9b-hexahydro-8-methyl-
5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione and the like can be mentioned.

As the diamine used for producing the polyimide precursor in the present invention, a diamine containing fluorine is suitable in the sense that solvent solubility and moisture absorption are lowered. Further, it is preferable that the compound does not contain a hydrogen atom such as an alkyl group, an allyl group, a propargyl group, or a hydroxyl group, because the light loss of near infrared light is low. As the diamine component containing fluorine, 4- (1H, 1
H, 11H-eicosafluoroundecaneoxy) -1,
3-diaminobenzene, 4- (1H, 1H-perfluoro-1-butanoxy) -1,3-diaminobenzene, 4
-(1H, 1H-perfluoro-1-heptanoxy)-
1,3-diaminobenzene, 4- (1H, 1H-perfluoro-1-octanoxy) -1,3-diaminobenzene, 4-pentafluorophenoxy-1,3-diaminobenzene, 4- (2,3,5 , 6-Tetrafluorophenoxy) -1,3-diaminobenzene, 4- (4-fluorophenoxy) -1,3-diaminobenzene, 4-
(1H, 1H, 2H, 2H-perfluoro-1-hexanoxy) -1,3-diaminobenzene, 4- (1H, 1
H, 2H, 2H-perfluoro-1-dodecanoxy)-
1,3-diaminobenzene, (2,5) -diaminobenzotrifluoride, bis (trifluoromethyl) phenylenediamine, diaminotetra (trifluoromethyl) benzene, diamino (pentafluoroethyl) benzene, 2,5-diamino ( Perfluorohexyl) benzene, 2,5-diamino (perfluorobutyl) benzene, 2,2′-bis (trifluoromethyl) -4,4 ′
-Diaminobiphenyl, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, octafluorobenzidine, 4,4'-diaminodiphenyl ether, 2,2-bis (4-aminophenyl) hexafluoropropane , 1,3-bis (anilino) hexafluoropropane, 1,4-bis (anilino) octafluorobutane, 1,5-bis (anilino) decafluoropentane, 1,7-bis (anilino) tetradecafluoroheptane, 2,2'-bis (trifluoromethyl) -4,
4'-diaminodiphenyl ether, 3,3'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetrakis (trifluoromethyl) -4,4'-diaminodiphenyl ether , 3,3'-bis (trifluoromethyl) -4,4 '
-Diaminobenzophenone, 4,4'-diamino-p-
Terphenyl, 1,4-bis (p-aminophenyl) benzene, p- (4-amino-2-trifluoromethylphenoxy) benzene, bis (aminophenoxy) bis (trifluoromethyl) benzene, bis (aminophenoxy) Tetrakis (trifluoromethyl) benzene,
2,2-bis {4- (4-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis {4- (3
-Aminophenoxy) phenyl} hexafluoropropane, 2,2-bis {4- (2-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis {4-
(4-Aminophenoxy) -3,5-dimethylphenyl} hexafluoropropane, 2,2-bis {4- (4
-Aminophenoxy) -3,5-ditrifluoromethylphenyl} hexafluoropropane, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3) -Trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfone, 4,4'-bis (3-amino-5-
Trifluoromethylphenoxy) diphenyl sulfone,
2,2-bis {4- (4-amino-3-trifluoromethylphenoxy) phenyl} hexafluoropropane,
Bis {(trifluoromethyl) aminophenoxy} biphenyl, bis [{(trifluoromethyl) aminophenoxy} phenyl] hexafluoropropane, bis {2-
Examples include [(aminophenoxy) phenyl] hexafluoroisopropyl} benzene and 4,4′-bis (4-aminophenoxy) octafluorobiphenyl.

All monovalent elements bonded to carbon such as alkyl groups other than amino groups in the molecule and phenyl rings are fluorine,
Alternatively, a perfluoroalkyl group is preferable because it has a smaller near infrared absorption. For example 3,4,5,6-
Tetrafluoro-1,2-phenylenediamine, 2,
4,5,6-Tetrafluoro-1,3-phenylenediamine, 2,3,5,6-tetrafluoro-1,4-phenylenediamine, 4,4'-diaminooctafluorobiphenyl, bis (2,3,3 5,6-tetrafluoro-4
-Aminophenyl) ether, bis (2,3,5,6-)
Tetrafluoro-4-aminophenyl) sulfone, hexafluoro-2,2'-bis (trifluoromethyl)-
4,4'-diaminobiphenyl and the like can be mentioned.

As a synthetic component, a diamine component containing no fluorine may be contained, for example, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, Benzidine, metaphenylenediamine, paraphenylenediamine, 1,5-naphthalenediamine, 2,6
-Naphthalenediamine, bis- (4-aminophenoxyphenyl) sulfone, bis- (4-aminophenoxyphenyl) sulfide, bis- (4-aminophenoxyphenyl) biphenyl, 1,4-bis- (4-aminophenoxy) benzene , 1,3-bis- (4-aminophenoxy) benzene, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether-3-sulfonamide, 3,4'-diaminodiphenyl ether-
4-sulfonamide, 3,4'-diaminodiphenyl ether-3'-sulfonamide, 3,3'-diaminodiphenyl ether-4-sulfonamide, 4,4'-diaminodiphenyl sulfone-3-sulfonamide, 3,
4'-diaminodiphenylsulfone-4-sulfonamide, 3,4'-diaminodiphenylsulfone-3'-sulfonamide, 3,3'-diaminodiphenylsulfone-4-sulfonamide, 4,4'-diaminodiphenylsulfide- 3-sulfonamide, 3,4'-diaminodiphenyl sulfide-4-sulfonamide, 3,
3'-diaminodiphenyl sulfide-4-sulfonamide, 3,4'-diaminodiphenyl sulfide-
3'-sulfonamide, 1,4-diaminobenzene-2
-Sulfonamide, 4,4'-diaminodiphenyl ether-3-carbonamide, 3,4'-diaminodiphenyl ether-4-carbonamide, 3,4'-diaminodiphenyl ether-3'-carbonamide, 3,
3'-diaminodiphenyl ether-4-carbonamide, 4,4'-diaminodiphenylmethane-3-carbonamide, 3,4'-diaminodiphenylmethane-4-
Carbonamide, 3,4'-diaminodiphenylmethane-3'-carbonamide, 3,3'-diaminodiphenylmethane-4-carbonamide, 4,4'-diaminodiphenylsulfone-3-carbonamide, 3,4'-diamino Diphenylsulfone-4-carbonamide, 3,
4'-diaminodiphenylsulfone-3'-carbonamide, 3,3'-diaminodiphenylsulfone-4-carbonamide, 4,4'-diaminodiphenylsulfide-3-carbonamide, 3,4'-diaminodiphenylsulfide- 4-carbonamide, 3,3'-diaminodiphenyl sulfide-4-carbonamide,
3,4'-diaminodiphenyl sulfide-3'-sulfonamide, 1,4-diaminobenzene-2-carbonamide, 4,4'-bis (4-aminophenoxy) biphenyl, bis {4- (3-aminophenoxy) ) Phenyl} sulfone and the like. The above-mentioned acid anhydride component and diamine component may be used in combination of two or more kinds.

In the present invention, the above-mentioned compound (a) or (b)
It is preferable to include a fluorine-containing compound in any or all of the acid dianhydride or the (c) diamine.

Particularly preferable combinations are (a) compound as dichloride compound, diester compound as 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, pyromellitic dianhydride, 2,2. 2'-bis (trifluoromethyl)-
Diester compounds synthesized from 4,4′-diaminobiphenyl, dichloride compounds and mixtures thereof,
(B) 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, pyromellitic dianhydride, 2,2'-bis (trifluoromethyl) -4, as an acid dianhydride 4'-Diaminobiphenyl or a mixture thereof, and as the diamine, 4,4'-diaminodiphenyl ether is preferable. Particularly, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and pyromellitic dianhydride or 2,2-bis (3,4-
Dicarboxyphenyl) difluoro compound synthesized from hexafluoropropane dianhydride, by mixing with a diester compound and copolymerized, it is possible to bring the refractive index, linear expansion coefficient, etc. to desired values. It is preferable in terms of solvent solubility and ease of synthesis of dichloride compound and diester compound.

The solution containing the polymer for obtaining the polyimide precursor is such that the total number of moles of the compound (a) and the acid anhydride (b) and the number of moles of the diamine or dicyanate (c) are substantially equimolar. It can be obtained by polymerizing by using

When the compound (a) is a dichloride compound, it is preferably obtained by dissolving or diffusing a diamine, a dichloride compound and a carboxylic acid dianhydride in an organic polar solvent in an inert atmosphere such as argon or nitrogen.
Further, it is general to mix a small amount of triethylamine, pyridine, or the like. The addition order of each monomer is not particularly limited, and the dichloride compound and the acid dianhydride may be previously added to the organic polar solvent, and the diamine component may be added to prepare a polymer solution. An appropriate amount may be added to the solvent first, and then the dichloride compound and the acid dianhydride may be added. As a preferred method, a method in which a diamine component and a dichloride compound are first reacted and then an acid dianhydride is added to form a polymer is easy to control the reaction, and the degree of polymerization is increased, and a good polyimide precursor is easily obtained.

When the compound (a) is a diester compound, it is preferably obtained by dissolving or diffusing a diamine and a diester compound and a carboxylic acid dianhydride in an organic polar solvent in an inert atmosphere such as argon or nitrogen. . In addition, it is common to mix the diester compound and a condensing agent in an amount of 2 times or more. The order of addition of each monomer is not particularly limited, the diester compound and the acid dianhydride are first added to the organic polar solvent, and the diamine component is added.
A solution of the polyamide ester may be used, or an appropriate amount of the diamine component may be first added to the organic polar solvent, and then the ester compound and the acid dianhydride may be added. In addition, the above diamine was used as a diisocyanate without using a condensing agent at high temperature (4
You may mix and polymerize at 0 degreeC-200 degreeC).

As the condensing agent used above, those used in the condensation synthesis of polyamide can be generally used. Examples thereof include phosphite ester, phosphorus chloride, phosphoric acid amide, phosphoric acid ester, phosphoric acid anhydride and the like. Triphenyl phosphite and its derivatives as phosphite, phosphorus trichloride and phosphorus oxychloride as phosphorus chloride, and 2,3-dihydro-2-thioxo-3-benzoxazolylphosphone as phosphorus amide. Examples include acids. The condensing agent is 2 to 3 times the equivalent of the ester compound, preferably 2.1 to 2.
Add 3 equivalents. If necessary, pyridine, triethylamine and the like are added to enhance the activity of the condensation reaction.
The addition amount is usually about the same amount as the condensing agent.

It is necessary to add a dehydration ring-closing agent and / or a catalyst to the solution of the polymer obtained by the above reaction to imidize the amic acid moiety. Examples of the dehydration ring-closing agent include aliphatic acid anhydride, aromatic acid anhydride, N, N'-dialkylcarbodiimide, lower aliphatic halide, halogenated lower aliphatic halide, halogenated lower fatty acid anhydride, arylphosphonic acid. Examples thereof include dihalides, thionyl halides, and mixtures of two or more thereof.
Among them, aliphatic anhydrides such as acetic anhydride, propionic anhydride, and lactic acid anhydride, or a mixture of two or more thereof can be preferably used. It is preferable to add 1 to 10 times, preferably 1 to 7 times, and more preferably 2 to 5 times the amount of these dehydrating and cyclizing agents with respect to the number of moles of amic acid sites in the polymer solution. Further, in order to effectively carry out imidization, it is preferable to simultaneously use a catalyst for the dehydration ring-closing agent. Aliphatic tertiary amines, aromatic tertiary amines, heterocyclic tertiary amines and the like are used as the catalyst. Among them, those selected from heterocyclic tertiary amines can be particularly preferably used. Specifically, quinoline, isoquinoline,
β-picoline, pyridine and the like are preferably used. These catalysts are 1/20 to 10 relative to the number of moles of the dehydration ring-closing agent.
Double amount, preferably 1/15 to 5 times amount, more preferably 1
/ 10 to 2 times the number of moles is added. Of these, the dehydration ring-closing agent and the catalyst, if the amount is small, imidization does not proceed effectively, and conversely, if it is too large, it tends to remain in the polyimide precursor, and optical loss of the optical waveguide may increase. .

The temperature of imidization using a dehydration ring-closing agent and / or a catalyst is preferably 150 ° C to -10 ° C. If the temperature exceeds 150 ° C, the ester portion may be imidized and a desired polyimide precursor may not be obtained.
If the temperature is lower than 10 ° C, imidization may take a long time.

The organic polar solvent used in the reaction for producing the polyimide precursor is, for example, a sulfoxide-based solvent such as dimethyl sulfoxide or diethyl sulfoxide,
Formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, and pyrrolidone solvents such as N-methyl-2-pyrrolidone. , Phenol, o-, p-, m- or p-
Phenol solvents such as cresol, xynol, halogenated phenol and catechol, hexamethylphosphoramide, γ-butyrolactone and the like can be mentioned. Furthermore, if necessary, these organic polar solvents may be used in combination with an aromatic hydrocarbon such as xylene or toluene. The concentration of the solution is 5 to 40% by weight (preferably 10 to 25% by weight), and the rotational viscosity (25 ° C.) of the polymer solution is 50 to 50%.
It is preferably 00 poise. When the compound (a) is a dichloride compound, acetamide-based solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, and pyrrolidone-based solvents such as N-methyl-2-pyrrolidone are preferable because side reactions do not easily occur.

The polyimide precursor is synthesized as described above, but the polyimide precursor can form a pattern by printing because of its high solvent solubility and good storage stability. Further, by adding a photoinitiator or the like, it is possible to impart photosensitivity and form a pattern by photolithography.

When it is used for printing, it is dissolved in a suitable solvent to obtain a polyimide precursor composition.

For example, the above reaction solution is poured into deionized water, alcohol or the like to cause precipitation, and if necessary, further washed with deionized water or alcohol and dried under reduced pressure. A solvent is added to this polyimide precursor to obtain a polyimide precursor composition. In addition, the solvent synthesized without performing precipitation or the like may be partially removed as needed to form a polyimide precursor composition.

At this time, as the solvent, various kinds of solvents can be used within a range in which the polyimide precursor is dissolved. For example, methanol, ethanol, propanol, isopropanol, butanol, alcohol solvents such as pentanol, acetone, dimethyl ether, methyl ethyl ketone, ethyl acetate, tetrahydrofuran, dioxane, acetonitrile and the like, toluene, aromatic hydrocarbon solvents such as xylene, hexane, heptane, Aliphatic hydrocarbon solvents such as octane and cyclohexane, halogenated hydrocarbon solvents such as methylene chloride, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamides such as N, N-dimethylformamide and N, N-diethylformamide. System solvent, N, N-dimethylacetamide,
Acetamide-based solvents such as N, N-diethylacetamide, pyrrolidone-based solvents such as N-methyl-2-pyrrolidone, phenol, phenols such as o-, p-, m- or p-cresol, xynol, halogenated phenol, and catechol. Examples include system solvents, hexamethylphosphoramide, γ-butyrolactone, and the like. Further, two or more kinds of these solvents may be combined, and deionized water may be optionally mixed.

The solid content concentration of the polyimide precursor composition is preferably 30 parts by weight or more and 95 parts by weight or less, more preferably 30 parts by weight or more and 80 parts by weight or less. If the solid content concentration is higher than 95 parts by weight, the viscosity of the composition may be too high to be suitable for printing. If it is less than 30 parts by weight, the viscosity may be too low to be suitable for printing, or the film may be greatly reduced and the surface There are cases where it will happen.

When used for printing, the printing method is not particularly limited, but there are screen printing, ink jet printing, convex plate printing, flat plate printing, concave plate printing and the like.

By imidizing all parts of the polyimide precursor to form a polyimide, high heat resistance (260 ° C. or higher) can be provided.

Heating is preferably carried out between 200 ° C and 500 ° C. When the temperature is 200 ° C. or lower, imidization may not occur, and when the temperature is 500 ° C. or higher, deterioration may occur.
In addition, it is preferable that the temperature is raised stepwise for heating in many cases because the pattern is less likely to sag and the mechanical strength is improved.
The heating time at this time is preferably 0.1 to 10 hours. The heating atmosphere is preferably under an inert gas such as nitrogen, helium, or argon, or under vacuum.

The precursor polyimide precursor can be used in various applications. Above all, in the structure containing fluorine, an optical material,
Optical parts are preferable because of their low light loss and low hygroscopicity. For example, optical fiber, optical waveguide, optical semiconductor, sealing material, adhesive, lens, optical material for liquid crystal, optical film,
Optical wiring board, optical integrated circuit, 1 / 4λ plate, 1 / 2λ plate, grating, optical filter, optical isolator, optical switch, optical coupler, optical splitter, optical amplifier, optical multiplexer / demultiplexer,
It can be used for optical waveguides, parts and devices using the optical waveguides.

Further, it can also be used for coating semiconductor chips, as a high density mounting substrate material, and the like.

[0049]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

The raw materials used were commercial products. The source of each raw material is shown. 2,2'-bis (trifluoromethyl)-
4,4'-diaminobiphenyl (Central Glass Co., Ltd.), dimethylacetamide (Wako Pure Chemical Industries, Ltd.), pyromellitic dianhydride (Wako Pure Chemical Industries, Ltd.), 2,2-bis (3,4-dicarboxy) Phenyl) hexafluoropropanoic acid dianhydride (Clariant Japan), 4,
4'-diaminodiphenyl ether (manufactured by Wako Pure Chemical Industries, Ltd.),
Methanol (Wako Pure Chemical Industries, Ltd.), Ethanol (Wako Pure Chemical Industries, Ltd.) Isopropanol (Wako Pure Chemical Industries, Ltd.) Ethyl acetate (Wako Pure Chemical Industries, Ltd.), Thionyl chloride (Wako Pure Chemical Industries, Ltd.), Hexane (Wako Pure Chemical Industries, Ltd.) In the examples, light loss, heating 5% by weight weight loss temperature, and refractive index were measured by the following methods. Light loss: A film sample was measured with a spectrophotometer (UV-3100 manufactured by Shimadzu Corporation). Heating 5 wt% weight loss temperature: The film sample was measured by a thermogravimetric measuring device (TG / DTA200 manufactured by Seiko Denshi KK). Refractive index: Film sample is a precision Abbe refractometer 3T
(NAR-3T manufactured by Atago Co., Ltd.) (Synthesis of Acid Chloride Compound I) In a three-necked flask equipped with a reflux tube, 10.0 g of pyromellitic dianhydride (46
Ethanol (50 ml) was added to (mmol) and heated under a nitrogen atmosphere while continuing stirring, and the mixture was refluxed and stirred for 3 hours.
After cooling to room temperature, the solvent was removed by an evaporator and vacuum drying was performed to obtain a powder. This powder was dissolved in 60 ml of ethyl acetate, 0.2 g of dimethylformamide was added, and 13.1 g (110.4 m) of thionyl chloride was added.
mol) and heated at 60 ° C. for 2 hours, and further refluxed for 2 hours.
Heated for hours. After cooling to room temperature, the solvent was removed by an evaporator and vacuum drying was performed to obtain a powder. This powder was recrystallized from hexane to obtain 12.5 g of an acid chloride compound. (Synthesis of Acid Chloride Compound II) In a three-necked flask equipped with a reflux tube, 10.0 g of pyromellitic dianhydride (4
(6 mmol) was added with 50 ml of isopropanol, and the mixture was heated in a nitrogen atmosphere with continuous stirring and refluxed for 3 hours. After cooling to room temperature, the solvent was removed by an evaporator and vacuum drying was performed to obtain a powder. This powder was dissolved in 60 ml of ethyl acetate, 0.2 g of dimethylformamide was added, and 13.1 g of thionyl chloride (11
0.4 mmol) was added and the mixture was heated at 60 ° C. for 2 hours and further heated under reflux for 2 hours. After cooling to room temperature, the solvent was removed by an evaporator and further vacuum drying was performed to obtain a powder containing a viscous liquid. This powder was recrystallized from hexane to obtain 3.5 g of acid chloride compound II. (Synthesis of Acid Chloride Compound III) In a three-necked flask equipped with a reflux tube, 1,4-hydroquinone dibenzoate-
20 g of 3.3 ', 4,4'-tetracarboxylic dianhydride
50 ml of methanol and N-methylmyrrolidone were added to and heated under reflux with stirring under a nitrogen atmosphere for 3 hours. After cooling to room temperature, the solvent was removed by an evaporator, recrystallization was carried out with 70% by weight of water and 30% by weight of methanol, and then vacuum drying was performed 1
8.7 g of powder was obtained. 10.4g of this powder (20mm
is dissolved in 60 ml of ethyl acetate, 0.2 g of dimethylformamide is added, and 5.7 g of thionyl chloride (48 m) is added.
mol) and heated at 60 ° C. for 2 hours, and further refluxed for 2 hours.
Heated for hours. After cooling to room temperature, the solvent was removed by an evaporator, and vacuum drying was performed to give 10.6 g.
The acid chloride compound III was obtained.

(Example 1) (Synthesis of Polyimide Precursor I) 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (3.2) in a container under a nitrogen atmosphere.
0 g, 10 mmol) was added to dimethylacetamide (35
g), followed by triethylamine (1.06 g, 1
0.5 mmol) was added and the compound I (1.74 g,
5 mmol) was added, the container was ice-cooled, stirred for 2 hours, and further stirred at room temperature (about 20 ° C.) for 24 hours. 2, in this solution
2.22 g (5 mmol) of 2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl dianhydride was added, and the mixture was ice-cooled, stirred for 2 hours, and further stirred at room temperature (about 20 ° C) for 24 hours. 0.93 g (10 mmol) of β-picoline as a chemical curing agent and 6.12 of acetic anhydride were added to this solution.
Add 5 g (60 mmol) and stir at room temperature for 1 hour.
After stirring at ℃ for 3 hours, it was cooled to room temperature. Next, the above solution was mixed with methanol, the precipitate was filtered, subjected to Soxhlet treatment with methanol for 8 hours, and then vacuum dried to obtain a polyimide precursor I.

Example 2 (Synthesis of Polyimide Precursor II) 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (3.2) in a container under a nitrogen atmosphere.
0 g, 10 mmol) was added to dimethylacetamide (35
g), followed by triethylamine (1.06 g, 1
0.5 mmol) was added and compound II (1.86 g,
5 mmol) was added, the container was ice-cooled, stirred for 2 hours, and further stirred at room temperature (about 20 ° C.) for 24 hours. 2, in this solution
2.22 g (5 mmol) of 2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl dianhydride was added, and the mixture was ice-cooled, stirred for 2 hours, and further stirred at room temperature (about 20 ° C) for 24 hours. 0.93 g (10 mmol) of β-picoline as a chemical curing agent and 6.12 of acetic anhydride were added to this solution.
Add 5 g (60 mmol) and stir at room temperature for 1 hour.
After stirring at ℃ for 3 hours, it was cooled to room temperature. Next, the above solution was mixed with methanol, the precipitate was filtered, subjected to Soxhlet treatment with methanol for 8 hours and then vacuum dried to obtain a polyimide precursor II.

(Example 3) (Synthesis of Polyimide Precursor III) 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (3.2) in a container under a nitrogen atmosphere.
0 g, 10 mmol) was added to dimethylacetamide (35
g), followed by triethylamine (1.06 g, 1
0.5 mmol) was added and compound III (2.78) was added.
g, 5 mmol) was added, the container was ice-cooled, stirred for 2 hours, and further stirred at room temperature (about 20 ° C.) for 24 hours. 2.22 g (5 mmol) of 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl dianhydride was added to this solution.
Add ice and stir for 2 hours at room temperature (about 20 ° C).
Stir for 4 hours. Β as a chemical curing agent in this solution
-Picoline 0.93 g (10 mmol), acetic anhydride 6.
125 g (60 mmol) was added and stirred at room temperature for 1 hour,
After stirring at 70 ° C. for 3 hours, the mixture was cooled to room temperature. Next, the above solution was mixed with methanol, the precipitate was filtered, subjected to Soxhlet treatment with methanol for 8 hours, and then vacuum dried to obtain a polyimide precursor III. (Evaluation for Example 1) Polyimide precursor was used as dimethylformamide (DMF), tetrahydrofuran (TH
The solvent solubility of F) was confirmed.

When 1 g of dimethylformamide was added to 1 g of the polyimide precursor I, it was dissolved without any problem to obtain a composition I. This composition was screen-printed on an aluminum plate with a screen having a pattern with a width of 50 μm. This is evacuated at 80 ° C for 10 minutes at 100 ° C and 1 hour at 150 ° C.
0 minutes, 200 ° C for 10 minutes, 250 ° C for 10 minutes, 300 ° C
After heating for 10 minutes at 350 ° C. for 10 minutes and at 400 ° C. for 10 minutes, a good relief structure was obtained. Further, the composition I was uniformly applied onto an aluminum plate without screen printing, and it was vacuumized at 80 ° C. for 100 minutes at 100 ° C. for 1 minute at 150 ° C.
0 minutes, 200 ° C for 10 minutes, 250 ° C for 10 minutes, 300 ° C
10 minutes, 350 ° C. for 10 minutes, and 400 ° C. for 10 minutes to produce a 50 μm polyimide film. The heating 5 wt% weight loss temperature was measured. The results are shown in Table 1. After leaving the composition I for 2 months at room temperature (15 ° C. to 30 ° C.), a polyimide film was prepared in the same manner. The evaluation results are shown in Table 1.

(Evaluation for Example 2) Evaluation was performed in the same manner as in Example 1 except that the polyimide precursor II was used. The evaluation results are shown in Table 1.

(Evaluation for Example 3) Evaluation was performed in the same manner as in Example 1 except that the polyimide precursor II was used. The evaluation results are shown in Table 1. Comparative Example 1 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (3.20 g, 10 mmol) was dissolved in dimethylacetamide (36.9 g) in a container under a nitrogen atmosphere. , Pyromellitic dianhydride (1.09 g, 5 mmol) and 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl dianhydride 2.22 g (5 mmol) were added, and the container was ice-cooled. While stirring, the mixture was stirred for 5 hours. Next, the temperature was raised to 20 ° C. and the mixture was further stirred for 5 hours to obtain a polyamic acid composition I (solid content: 15% by weight). This composition is allowed to stand at room temperature (15-30
When left to stand at (° C.), the viscosity was lowered and a good polyimide could not be obtained.

[0057]

[Table 1] As can be seen from the results in the table, Examples 1 to 3 have high solvent solubility, and polyimide films can be produced without problems even when stored at room temperature for a long period of 2 months. Comparative Example 1 is not practical for long-term storage. Further, as shown in Examples 1 and 2, good physical properties can be obtained even if polymerization is performed by changing the kind of ester moiety. It is possible to change the structure of the dichloride compound as in Example 3.

[0058]

EFFECT OF THE INVENTION By using the method for producing a polyimide precursor of the present invention, it is possible to obtain a polyimide precursor suitable for printing and the like.

Continued front page    F-term (reference) 4J043 PA01 PA19 PC075 QB21                       QB23 QB24 QB26 QB33 RA08                       RA31 RA34 RA35 SA06 TA11                       TA12 TA21 TA22 TA25 TA26                       TA31 TA32 TA47 UA11 UA13                       UB01 UB03 UB05 UB06 UB12                       UB22 UB29 UB30 XA01 XA11                       XA13 XA16 XA17 XA19 XB11                       XB12 XB13 XB16 XB19 YA05                       YA07 ZA12 ZA21 ZA51 ZA52                       ZB02 ZB21 ZB23 ZB25 ZB50

Claims (11)

[Claims] (A) The following general formula (1): (Wherein R ¹ is a tetravalent organic group, R ² is a monovalent organic group having 1 or more carbon atoms, R ³ is OH or Cl), and (b) an acid dianhydride. c) A method for producing a polyimide precursor, which comprises polymerizing a diamine or dicyanate and adding a dehydration ring-closing agent and / or a catalyst to imidize an amic acid moiety. 2. The method for producing a polyimide precursor according to claim 1, wherein at least one of (a), (b) and (c) contains fluorine. 3. A diamine has the following general formula (2): (Wherein R ⁴ may be the same or different and is at least one selected from hydrogen, deuterium, fluorine and perfluoroalkyl groups). Production method. 4. An acid dianhydride is represented by the following general formula (3): (Wherein R ⁴ may be the same or different and is at least one selected from hydrogen, deuterium, fluorine and perfluoroalkyl groups). Production method. 5. R ² in the general formula (1) has 1 to 6 carbon atoms.
5. The method for producing a polyimide precursor according to claim 1, wherein the polyimide precursor is a hydrocarbon group. 6. [R ² OC (═O)] ₂ —R ¹ — (COC
l) ₂ and a diamine are reacted, and then an acid dianhydride is added thereto for polymerization, wherein the method for producing a polyimide precursor (R ¹ is a tetravalent organic group, R ² is a carbon number 1). Above 1
Indicates a valent organic group. ). 7. [R ² OC (═O)] ₂ —R ¹ — (COC
l) ₂ and an amine-terminated imide oligomer are polymerized.
¹ represents a tetravalent organic group, and R ² represents a monovalent organic group having 1 or more carbon atoms. ). 8. [R ² OC (═O)] ₂ —R ¹ — (COO
H) ₂ is polymerized in the presence of an amine-terminated imide oligomer and a condensing agent (R ¹ is a tetravalent organic group, R ² is a C 1 or more carbon atom). Indicates a monovalent organic group.). 9. [R ² OC (═O)] ₂ —R ¹ — (COO
H) ₂ and diamine are reacted in the presence of a condensing agent, and then an acid dianhydride is added to carry out polymerization, wherein R ¹ is a tetravalent organic group, R ² represents a monovalent organic group having 1 or more carbon atoms.). 10. [R ² OC (═O)] ₂ —R ¹ — (COO
H) ₂ is reacted with acid dianhydride and dicyanate. The method for producing a polyimide precursor according to claims 1 to 5 (R ¹
Represents a tetravalent organic group, and R ² represents a monovalent organic group having 1 or more carbon atoms. ). 11. The method for producing a polyimide precursor according to claim 1, wherein the dehydration ring-closing agent and / or the catalyst are acetic anhydride and a tertiary amine.