JP2000281783A - Novel diamine and novel polyimide composition prepared by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound which is useful as a material of a polymer having both photoreactivity and thermal reactivity by selecting a phenylenediamine compound having a photosensitive group. SOLUTION: This diamine compound is represented by formula I (wherein, X and Y are each a divalent organic group, preferably X is a single bond, CH2, COO, NH or O and Y is a single bond, COO, OOC, (CH2)mO, (CH2)mCOO, (CH2)mOOC or (CH2)m; (m) is 1-15; Z is a photosensitive group represented by one of formulas II to XI; and A is H, CH3, F, Cl Br or CH3O). The compound is reacted with an acid dianhydride in an organic polar solvent to give a polyamic acid, which is thermally or chemically imidized to give a polyimide composition containing a polyimide represented by formula XII having photosensitive groups. In the formulas, B and D are each a tetravalent organic group; E is a divalent organic group; (p) is 1-100; and (q) is 0-99. Preferably, the polyamic acid has an average mol.wt. of 5,000-1,000,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel diamine and a method for producing the same, a novel polyimide composition using the novel diamine as a raw material, and a method for producing the same. More specifically, the present invention relates to a novel diamine serving as a raw material of a polymer having a photosensitive group in the structure of the diamine and having both photoreactivity and heat reactivity specific to the photosensitive group, and a polyimide composition using the same.

[0002]

2. Description of the Related Art A well-known polymer having a cinnamic acid skeleton is polyvinyl cinnamate (polyvinyl having a cinnamic acid skeleton) (Jpn. J. App.
l. Phys. , 31 (1992), 2155;
Photopolymer Sci. and Tec
h. 8 (1995), 257). Polyvinyl cinnamate is a useful photosensitive resin that utilizes a reaction in which a cinnamic acid skeleton is dimerized by light (J. Appl Polym).
er Sci. , 2, 302 (1995)). This polyvinyl cinnamate is used as a negative photosensitive resin. It is presumed that a useful photosensitive resin can be obtained by introducing a photosensitive group into a polymer. However, at present, a raw material for a polymer, that is, a reactive monomer is not provided.

[0003] In particular, polyimide or polyamide is excellent in heat resistance among various organic polymers. Therefore, although it is an excellent resin widely used from the fields of space and aviation to the field of electronic communication, it is not limited to these resins. Almost no known monomer having a photosensitive group such as a cinnamic acid skeleton can be used.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel diamine having a photosensitive group, a method for producing the same, a polyimide composition using the diamine as a raw material, and a method for producing the same.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have developed a novel diamine having a specific structure,
The present inventors have found that the predetermined object can be achieved, and have completed the present invention. The first aspect of the present invention is to provide the following general formula (1):

[0006]

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(Where X and Y are divalent organic groups, and Z is

[0008]

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A represents one or more photosensitive groups selected from
H, CH_Three, F, Cl, Br, CH_ThreeO- is shown. )so
The novel diamine represented by the general formula (1)
Where X is-, -CH_Two-, -COO-, -NH-,-
A divalent organic group selected from O-, Y is-, -COO
-, -OOC-,-(CH_Two)_mO-,-(CH_Two)_m
COO-,-(CH_Two)_mOOC-,-(CH _Two)_m−
A divalent organic group selected from (m represents an integer of 1 to 15)
You. )), The second of the present invention is that the structure is
The following general formula (2)

[0010]

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(Where X is-, -CH_Two-, -COO
A divalent organic group selected from-, -NH-, -O-, Y
Is -COO-, -OOC-,-(CH_Two)_mO-,-
(CH _Two)_mCOO-,-(CH_Two)_mOOC-,-
(CH_Two)_mA divalent organic group selected from-, m is 1 to
15 is an integer, and Z is

[0012]

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One or more photosensitive groups selected from the group consisting of A, H, CH ₃ , F, Cl, Br, CH ₃ O—, B and D a tetravalent organic group, and E a divalent organic group. A group, p is 1-10
0 and q represent 0 to 99. ) Is 1% by weight or more.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of a novel diamine and a novel polyimide composition according to the present invention will be described. The novel diamine according to the present invention,
It is a novel diamine which is a raw material of a polymer having a photosensitive group and having both photoreactivity and thermal reactivity peculiar to the photosensitive group. Specifically, the diamine according to the present invention has the general formula (1)

[0015]

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(Where X is-, -CH _2- , -COO
A divalent organic group selected from-, -NH-, -O-, Y
Is, -, - COO -, - OOC -, - (CH 2) m O
_{-, - (CH 2) m} COO -, - (CH 2) m OOC
A divalent organic group selected from —, — (CH ₂ ) _m —, m
Is an integer of 1 to 15, and Z is

[0017]

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A represents one or more photosensitive groups selected from the group consisting of A, H, CH ₃ , F, Cl, Br and CH ₃ O—. ).

Further, the polyimide composition according to the present invention is a novel polyimide composition using the above-mentioned novel diamine having a photosensitive group as a diamine component.

Hereinafter, a method for producing a novel diamine and a method for producing a polyimide composition according to the present invention will be described in detail. The new diamine is obtained by synthesizing the corresponding dinitrate and reducing the nitrate.

For example, in the presence of an esterification catalyst such as dinitrobenzoic acid chloride or toluenesulfonic acid chloride, dinitrobenzoic acid and Z-OH (Z is
1

[0022]

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Represents a photosensitive group selected from ) To obtain a dinitrate corresponding to X = COO and Y =-in the general formula (1).

Dinitrobenzyl alcohol and Z-COC
By reacting with Z-COOH in the presence of an esterification catalyst such as 1 or toluenesulfonic acid chloride, X = —CH ₂ — and Y = —OOC— in the general formula (1).
Can be obtained.

By reacting dinitroaniline with Z-COCl, X = -NH- and Y =-in the general formula (1).
A dinitrate corresponding to OC- can be obtained.

By reacting dinitrophenol with Z-COOH in the presence of an esterification catalyst such as Z-COCl or toluenesulfonic acid chloride, X = -OOC- and Y =-in the general formula (1) are obtained. To obtain a dinitrate.

Dinitrobenzoic acid chloride and HO- (C
_{H 2) m OH (m =} 1~15) or toluenesulphonic in the presence of an esterification catalyst such as acid chloride and dinitrobenzoic acid _{HO- (CH 2) m OH (} m = 1~1
By reacting (5), (NO ₂ ) ₂ -C ₆ H ₃ C
OO (CH ₂₎ After synthesizing the _m OH _(m = _1~15),
By reacting with Z-COOH in the presence of an esterification catalyst such as Z-COCl or toluene sulfonic acid chloride, X = -OOC- and Y =
- (CH _{2) m} corresponding dinitro compound to OOC- can be obtained.

Further, dinitrobenzoic acid chloride and HO
-(CH ₂ ) _m -Br and the like are reacted with a halogenated alkyl alcohol (m = 1 to 15) to give (NO ₂ ) ₂ -C ₆
H ₃ —COO— (CH ₂ ) _m —Br, and N-methyl-2
-By reacting Z-COOK or Z-COOCs with a polar aprotic solvent such as pyrrolidone or dimethylformamide, X = COO, Y = (CH ₂ ) _m
A dinitrated product corresponding to -OOC can also be obtained.

By reacting dinitrophenol with Z-COCl, a dinitrate corresponding to X = O, Y =-can be obtained.

Dinitrophenol and Br- (CH ₂ ) _m
Bis alkyl halides such as -Br the (m = 1 to 15) are reacted in the presence of an _{alkali, (NO 2) 2 -C 6} H
₃ -O- (CH ₂₎ and _m -Br, by reacting Z-COOK or Z-COOCs in a polar aprotic solvent such as N- methyl-2-pyrrolidone or dimethylformamide, X = O, Y = (CH ₂₎ dinitro compound corresponding to _m -OOC can be obtained.

Br— (CH ₂ ) _m —COCl (m = 1 to
15) and by the reaction of _{Z-OH, Br- (CH 2} ) m -
COO-Z, and alkali metal salts such as cesium dinitrobenzoate and potassium dinitrobenzoate are N-methyl-2
-By reacting in a polar aprotic solvent such as pyrrolidone or dimethylformamide, X = COO, Y =
A dinitrate corresponding to (CH ₂ ) _m —COO— can be obtained.

The diamine of the present invention can be obtained by Bechamp reduction of these dinitrates or hydrogenation using a special catalyst.

The term “special catalyst” used in the present invention refers to a catalyst in which platinum is supported on carbon black (Pt-carbon black) or a catalyst in which platinum containing sodium or iron is supported on activated carbon ( Pt-activated carbon). As these catalysts, those obtained by supporting a noble metal on activated carbon are usually used. However, when supported on activated carbon, the ratio of reducing the double bond of the photosensitive group is lower than that of the catalyst supported on carbon black. More. Therefore, it is desirable to use a catalyst supported on carbon black. However, when using a catalyst supported on activated carbon, if iron or sodium is mixed into platinum, it is possible to suppress the reduction of photosensitive groups to double bonds and selectively reduce nitro groups. Becomes

When a palladium-based catalyst is used, the activity of the catalyst is reduced by mixing a poisoning substance such as sulfur, so that the reduction of the photosensitive group to a double bond is suppressed and the nitro group is selected. It becomes possible to reduce it.

The conditions for reducing this dinitrate will be described. Since the dinitro compound has a double bond of a photosensitive group, the double bond may be reduced if severe reduction conditions are selected, and decomposition may occur if the reaction is performed under strong acidity. Furthermore, under alkaline conditions, Michael
Since there is a possibility of addition, it is necessary to optimize reduction conditions.

The catalyst suitable for reduction of the dinitro compound is a catalyst in which platinum is supported on carbon black (Pt-
This is hydrogenation performed in an organic solvent using a catalyst (Fe-Pt-activated carbon or Na-Pt-activated carbon) in which activated carbon is loaded with platinum mixed with carbon or sodium or iron. Normally, a catalyst in which palladium is supported on activated carbon used for hydrogenation (Pd-activated carbon) has a strong reaction activity and reduces the double bond of the photosensitive group, so the activity is reduced by containing sulfur or the like. It is necessary to use a Pd-activated carbon catalyst. Further, Pt-carbon black or a catalyst in which platinum mixed with sodium or iron is supported on activated carbon (Fe-Pt-activated carbon or Na-P
In the present reduction system, (t-activated carbon) suppresses reduction to a double bond and selectively reduces a nitro group, so that a desired diamine can be obtained in a high yield, which is desirable.

Pt-carbon black or Fe-Pt-
In the activated carbon system or the Na-Pt-activated carbon system, the platinum concentration in the catalyst is about 0.1 to 40% by weight,
If the content is 0.1% or more, the effect of the catalyst is exhibited. The higher the platinum concentration, the higher the reaction rate tends to be. However, since it is a noble metal, it is preferable to use a catalyst having a platinum concentration of about 1 to 20%.

Similarly, in the case of Pd-activated carbon,
The concentration of palladium in the catalyst is about 0.1 to 40% by weight, and the effect of the catalyst is exhibited if it is contained in an amount of 0.1% or more. The reaction rate tends to increase as the palladium concentration increases, but since it is a noble metal, it is preferable to use a catalyst having a palladium concentration of about 1 to 30%. Fe-P
In t-activated carbon system or Na-Pt-activated carbon system,
The content of iron or sodium is 0.1 to 4% by weight.
It is about 0%, preferably about 0.1 to 20%, particularly preferably about 0.1 to 10%. The effects of these catalysts are the same whether they are used in a dry state or in a state containing water. It is industrially desirable to use the powder in a water-containing state, since the dust does not fly up and the handleability is good.

Examples of the solvent used for the reduction include alcohols, dioxane, aromatic solvents such as toluene and xylene, sulfoxide solvents such as dimethylsulfoxide and diethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide and the like. Formamide solvents, acetamido solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, phenol, o-, m- or p-cresol, xylenol, halogenated phenol, phenolic solvent such as catechol, or hexamethylphosphoramide, γ-butyrolactone, etc., which do not inhibit the reaction and dissolve diamine or dinitrate Not limited.

As a condition of Bechamp reduction, a dinitrate is reduced by adding Fe powder in a solvent and heating at a temperature of 130 ° C. or less. As the solvent, the solvents described above can be used, and acetic acid, alcohols, dioxane and the like are particularly preferable.

Next, a method for synthesizing the polyimide of the present invention represented by the general formula (2) using the diamine according to the present invention produced as described above will be described.

By reacting the above diamine and acid dianhydride in an organic polar solvent to obtain a polyamic acid and thermally or chemically imidizing it, a polyimide composition having a photosensitive group can be obtained. Here, the thermal imidization method is a method in which a tertiary amine and an azeotropic solvent are added to the above-described polyamic acid copolymer to carry out dehydration imidization. Generally, in the method of thermally imidizing, 150
If heated above ℃, imidization reaction occurs, but 180 ℃
Under the above temperature conditions, the double bond contained in the photosensitive group is undesirably reacted. Therefore, it is desirable to thermally imidize the above-mentioned tertiary amine at a temperature of 180 ° C. or lower, or to chemically imidize at a temperature of 180 ° C. or lower.

The method of chemically imidizing is a method of adding a dehydrating agent having a stoichiometric amount or more and a catalytic amount of a tertiary amine to a polyamic acid polymer or a solution thereof, followed by heating to effect imidization.

Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride, aromatic acid anhydrides and the like. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline and isoquinoline.

The average molecular weight of the obtained polyamic acid is desirably 5,000 to 1,000,000. If the average molecular weight is less than 5000, the molecular weight of the produced polyimide composition becomes small, and if the polyimide composition is used as it is as a photoreactive resin, the resin becomes brittle, which is not preferable. On the other hand, if it exceeds 1,000,000, the viscosity of the polyamic acid varnish becomes too high and handling becomes difficult, which is not preferable.

Further, various organic additives, inorganic fillers, or various reinforcing agents can be compounded with the polyimide composition.

Examples of the organic polar solvent used in the polyamic acid formation reaction include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamides such as N, N-dimethylformamide and N, N-diethylformamide. Acetamide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone,
A pyrrolidone solvent such as N-vinyl-2-pyrrolidone,
Examples include phenolic solvents such as phenol, o-, m-, or p-cresol, xylenol, halogenated phenol, and catechol, and hexamethylphosphoramide, γ-butyrolactone, and the like. These can be used alone or as a mixture, but it is also possible to use a part of aromatic hydrocarbons such as xylene and toluene.

The acid dianhydride used in the polyimide composition, that is, the acid dianhydride corresponding to B or D in the general formula (2) is not particularly limited as long as it is an acid dianhydride. , Chemical 12

[0049]

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Butanetetracarboxylic 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-tetrahydrofurantetracarboxylic dianhydride, 5- (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; 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic Acid dianhydride, 3,3 ', 4,4'-
Dimethyldiphenylsilanetetracarboxylic dianhydride,
3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (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 dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene- Aromatics such as bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride Tetracarboxylic 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 represented by the following general formula (3)

[0051]

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(In the formula, R ₁ represents a divalent organic group having an aromatic ring, and R ₂ and R ₃ each represent a hydrogen atom or an alkyl group.)

[0053]

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(Wherein R ₄ represents a divalent organic group having an aromatic ring, and R ₅ and R ₆ each represent a hydrogen atom or an alkyl group), such as a compound represented by the following formula: Carboxylic dianhydrides and the like can be mentioned. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

Various diamines can be used as the diamine used in the polyimide composition, that is, the diamine corresponding to E in the general formula (2). Although it is not particularly limited as long as it is a diamine, for example, H ₂ NG-NH ₂ (where G is

[0056]

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(T is H, CH ₃ , F, Cl, Br, CH
Represents ₃ O-. ), 4, and 4,
4'-diaminophenylethane, 4,4'-didiaminophenyl sulfide, 1,5-diaminonaphthalene,
3,3-dimethyl-4,4'-diaminobiphenyl, 5
-Amino-1- (4'-aminophenyl) -1,3,3
-Trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,
5-diamino-3′-trifluoromethylbenzanilide, 3,5-diamino-4′-trifluoromethylbenzanilide, 3,4′-diaminodiphenylether,
2,7-diaminofluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-
Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) Biphenyl, 9,9-bis (4
-Aminophenyl) fluorene, 4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-
(M-phenyleneisopropylidene) bisaniline,
2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [4- (4-amino-2-trifluoromethyl) phenoxy]- Aromatic diamines such as octafluorobiphenyl; aromatic diamines having two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene and a hetero atom other than a nitrogen atom of the amino group; 1,1-metaxylylenediene Amine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,
4-diaminocyclohexane, isophoronediamine,
Tetrahydrodicyclopentadiene cyclopentadienylide diamine, hexahydro-4,7-meth Noin mite range diamine, tricyclo [6,2,1,0 ^2.7] - undecylenate range methyl diamine, 4,4'-methylenebis such (cyclohexylamine) Aliphatic diamine and alicyclic diamine; the following general formula (6):

[0058]

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(Wherein R ₇ represents —O—, —COO—, —O
CO -, - CONH- and -CO- represents a divalent organic group selected from, R ₈ is a monovalent organic group having a steroid skeleton. A) monosubstituted phenylenediamine represented by the following formula:

[0060]

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(R ₉ represents a hydrocarbon group having 1 to 12 carbon atoms, y is an integer of 1 to 3, and z is an integer of 1 to 20). .

Next, the polymerization method will be specifically described.

First, in an inert atmosphere such as argon or nitrogen, the compound represented by the general formula (1)

[0064]

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(Where X is-, -CH _2- , -COO
A divalent organic group selected from-, -NH-, -O-, Y
Is, -, - CO -, - OOC -, - (CH 2) m O-,
_{- (CH 2) m COO -} , - (CH 2) m OOC -, -
(CH ₂ ) _m-a divalent organic group selected from m-
15 is an integer, and Z is

[0066]

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A represents one or more photosensitive groups, and A represents H, CH ₃ , F, Cl, Br, CH ₃ O—. And a diamine represented by the general formula (7):

[0068]

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(Where B is one or two or more tetravalent organic groups) is reacted by dissolving or diffusing the acid dianhydride in the organic solvent.

In this case, when the diamine and the acid dianhydride are substantially equimolar, a polyamic acid solution represented by the general formula (2) and having p = 100 is obtained. If the molar ratio of diamine and dianhydride are different, further the polyamic acid solution in the general formula _{(8) H 2 N-E} -NH 2 ( wherein E is one or more divalent organic group Is dissolved in an organic solvent and added in a state of being dispersed in a slurry or in a solid state. The solution has the general formula (9)

[0071]

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(Wherein D is one or more kinds of tetravalent organic groups), and one or more acid dianhydrides are added to an organic solvent to obtain a polyamic acid copolymer. Obtain a solution. By adjusting the molar ratio of these acid dianhydride component and diamine component, the relationship between p and q in the general formula (2) is m = 1 to 100, n
= 0-99 and m + n = 100 can be arbitrarily obtained.

The order of addition of each monomer is as follows. The diamine components represented by the above general formulas (1) and (8) are added to an organic polar solvent first, and then the acid dianhydride component is added. An acid dianhydride component represented by the formula (7) is added,
Thereafter, an acid dianhydride component represented by the general formula (9) may be added to form a polyamic acid copolymer solution. Further, the diamine component represented by the general formula (8) is first added to the organic polar solvent, the general formula (7) which is an acid dianhydride component is added, and then the general formula (1) is represented. A diamine component may be added, and then an acid dianhydride component represented by the general formula (9) may be added to form a polyamic acid copolymer solution. Further, the above-mentioned general formulas (1) and (8), which are diamine components, are added to an organic polar solvent first, and then the general formulas (7) and (9), which are acid dianhydride components, are added. At the same time, the solution may be a polyamic acid copolymer solution, and is not particularly limited.

The same is true even if the above addition method is reversed, and the acid dianhydride is added first and the diamine component is added later.

It is also possible to synthesize a polyamide using the novel diamine according to the present invention. Specifically, the diamine of the present invention and any dicarboxylic acid are heated in a homogeneous solution using an amide-based solvent such as N, N-dimethylacetamide or N-methyl-2-pyrrolidone in the presence of a condensing agent. Done. (PhO) as a condensing agent
₃ P, (PhO) PCl ₂ , PhPOCl ₂ , Me ₂ S
iCl _{2 and the} like, which can be used in combination with pyridine in an amide solvent.

Further, a polyamide can be synthesized by reacting the diamine of the present invention with dicarboxylic acid chloride. The reaction between the dicarboxylic acid chloride and the diamine may be carried out at a low temperature in an amide-based solvent, or in a two-phase system of an organic solvent not mixed with water and water. And sodium hydroxide or sodium carbonate as an acid acceptor may be dissolved and polymerized at the interface between the organic phase and the aqueous phase. A general method of synthesizing a polyamide by heating and melting a diamine and a dicarboxylic acid at a high temperature is not desirable because the double bond of the photosensitive group is decomposed.

The novel diamine and novel polyimide composition according to the present invention obtained as described above have good reactivity to light and heat, and can be used for various applications such as printing and semiconductor production.

Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

[0079]

EXAMPLES In the examples, ESDA was 2,2-bis (4-
(Hydroxyphenyl) propanedibenzoate-3,
3 ', 4,4'-tetracarboxylic dianhydride, 6FDA
Represents 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, DMAc represents N, N-dimethylacetamide, and DMF represents N, N-dimethylformamide.

The weight average molecular weight was measured by GPC manufactured by Waters.
Was measured under the following conditions. (Column: Shodex
KD-806M two, temperature 60 ° C, detector: R
I, flow rate: 1 ml / min, developing solution: DMF (lithium bromide 0.03 M, phosphoric acid 0.03 M), material concentration: 0.2 w
t%, injection volume: 20 μl, reference substance: polyethylene oxide)

Example 1 Synthesis of 3,5-dinitrobenzoic acid chloride 3,5-dinitrobenzoic acid and ethyl acetate were placed in a reaction vessel, and a few drops of DMF were added to thionyl chloride (2 to 3 parts by weight of dinitrobenzoic acid). And the mixture is stirred under reflux until hydrogen chloride gas is no longer generated. The reaction solution is concentrated until a solid precipitates out, poured into hexane, the precipitate is separated by filtration and dried, and 3,5-dinitrobenzoic acid chloride is obtained in a yield of 97%.
I got it.

2 '-(3,5-dinitrobenzoate)
Synthesis of chalcone 3,5-dinitrobenzoic acid chloride 115.3 g
(0.5 mol), 700 ml of methyl ethyl ketone was placed in a reaction vessel, and heated and stirred at 60 ° C. under a stream of nitrogen.
112.1 g (0.5 mol) of hydroxychalcone, 800 ml of methyl ethyl ketone and 80 g of pyridine were added dropwise. After completion of the dropwise addition, the mixture was stirred under reflux for about 2 hours. After completion of the reaction, the reaction mixture is filtered off, the solution is concentrated, washed with water and dried to give 2 ′-(3,
193 g of 5-dinitrobenzoate) -chalcone were obtained.

2 '-(3,5-diaminobenzoate)
-Synthesis of chalcone synthesis 2 '-(3,5-dinitrobenzoate) -chalcone 4
1.8 g (100 mmol), 10 g of 5% Pt-2% iron-containing activated carbon powder and 500 ml of 1,4-dioxane were placed in a reaction vessel (hydrogenation apparatus), and heated and stirred at 60 ° C. in a hydrogen atmosphere. Absorbs 14.4 liters of hydrogen,
Since the absorption of hydrogen ceased, the reaction was stopped, the reaction solution was filtered off, the catalyst was removed, and the mixture was concentrated to give 2 ′-(3,5).
-Diaminobenzoate) -chalcone was obtained in an amount of 35.8 g.

Synthesis of Polyimide 2 ′-(3,5-diaminobenzoate) -chalcone 3 was placed in a 2000 ml separable flask equipped with a stirrer.
Take 5.8 g (0.1 mol) and 250 g of DMAc,
57.65 g (0.1 mol) of SDA was added at once with vigorous stirring, and stirring was continued for 30 minutes.

18.61 g (0.2 mol) of β-picoline,
50 g of acetic anhydride and 100 g of DMAc were added to the above reaction solution, and heated to about 120 ° C. to imidize. These reactions were performed under a nitrogen stream.

After the completion of the reaction, the mixture was poured into methanol, vigorously stirred with a mixer, and then separated by filtration and dried to obtain 88 g of a yellow polyimide powder. The weight average molecular weight of this polyimide powder was 100,000.

Example 2 Synthesis of 7 ′-(3,5-dinitrobenzoate) -coumarin 115.3 g of 3,5-dinitrobenzoic acid chloride
(0.5 mol) and 700 ml of methyl ethyl ketone were placed in a reaction vessel and heated and stirred at 60 ° C. under a nitrogen stream, and 81.1 g (0.5 mol) of 7-hydroxycoumarin, 800 ml of methyl ethyl ketone and 50 g of pyridine were added dropwise. After completion of the dropwise addition, the mixture was stirred under reflux for about 2 hours. After completion of the reaction, the mixture is filtered off.
After concentration, the solution was washed with water and dried to obtain 177 g of 7 '-(3,5-dinitrobenzoate) -coumarin.

7 '-(3,5-diaminobenzoate)
-Synthesis of coumarin synthesis 7 '-(3,5-dinitrobenzoate) -coumarin 3
5.6 (100 mmol), 10 g of activated carbon powder containing 5% Pt-2% iron and 500 ml of 1,4-dioxane were placed in a reaction vessel (hydrogenation apparatus), and heated and stirred at 60 ° C. under a hydrogen atmosphere. After absorbing 14.4 liters of hydrogen, the absorption of hydrogen ceased. The reaction was stopped, the reaction solution was separated by filtration, the catalyst was removed, and the mixture was concentrated to obtain 2 '-(3,5-
29.6 g of diaminobenzoate) -coumarin were obtained.

Synthesis of Polyimide 2 ′-(3,5-diaminobenzoate) -coumarin 2 was placed in a 2000 ml separable flask equipped with a stirrer.
Take 9.6 g (0.1 mol) and 250 g of DMAc,
28.8 g (0.05 mol) of SDAg were added at once with vigorous stirring, and stirring was continued for 30 minutes. Next, 22.2 g (0.05 mol) of 6FDA was added at once with vigorous stirring, and stirring was continued for 30 minutes. 18.61 g (0.2 mol) of β-picoline, 50 g of acetic anhydride,
100 g of DMAc was added to the above reaction solution, heated to about 120 ° C., and imidized. These reactions were performed under a nitrogen stream.

After the completion of the reaction, the mixture was poured into methanol, vigorously stirred with a mixer, and then separated by filtration and dried to obtain 75 g of a pale yellow polyimide powder. The weight average molecular weight of this polyimide powder was 120,000.

Example 3 Synthesis of Coumarin-3-Carboxylic Chloride Take coumarin-3-carboxylic acid and ethyl acetate in a reaction vessel and add a few drops of DMF to thionyl chloride (twice the amount of dinitrobenzoic acid). And the mixture is stirred under reflux until hydrogen chloride gas is no longer generated. The reaction solution was concentrated until a solid was deposited, poured into hexane, and the precipitate was separated by filtration and dried to obtain coumarin-3-carboxylic chloride in a yield of 87%.

Coumarin-3-carboxylate- (3,
Synthesis of 5-dinitrobenzyl) Coumarin-3-carboxylic chloride 104.3
g (0.5 mol) and 700 ml of methyl ethyl ketone were placed in a reaction vessel, and heated and stirred at 60 ° C. under a nitrogen stream.
99.1 g (0.5 mol) of 5-dinitrobenzyl alcohol, 800 ml of methyl ethyl ketone, 80 g of pyridine
Was added dropwise. After completion of the dropwise addition, the mixture was stirred under reflux for about 2 hours. After completion of the reaction, the reaction mixture was filtered off, the solution was concentrated, washed with water and dried to obtain 183.3 g of coumarin-3-carboxylate- (3,5-dinitrobenzyl).

Coumarin-3-carboxylate- (3,
Synthesis of 5-diaminobenzyl) Coumarin-3-carboxylate- (3,5-dinitrobenzyl) 37.03 g (100 mmol), 5% Pt
10 g of the contained carbon graphite and 500 ml of 1,4-dioxane were placed in a reaction vessel (hydrogenation apparatus), and heated and stirred at 60 ° C. in a hydrogen atmosphere. Since 14.4 liters of hydrogen were absorbed and the absorption of hydrogen ceased, the reaction was stopped, the reaction solution was separated by filtration, the catalyst was removed, and the mixture was concentrated and concentrated to give coumarin-3-carboxylate- (3,5- 31 g of diaminobenzyl) were obtained.

Synthesis of Polyimide In a 2000 ml separable flask equipped with a stirrer, 31 g (0.1 mol) of coumarin-3-carboxylate- (3,5-diaminobenzyl) and 250 g of DMAc were taken, and 28.8 g (0.05%) of ESDA was added. Mol) was rapidly added with vigorous stirring, and stirring was continued for 30 minutes. Next, 22.2 g (0.05 mol) of 6FDA was added at once with vigorous stirring, and stirring was continued for 30 minutes.

18.61 g (0.2 mol) of β-picoline,
50 g of acetic anhydride and 100 g of DMAc were added to the above reaction solution, and heated to about 120 ° C. to imidize. These reactions were performed under a nitrogen stream.

After completion of the reaction, the mixture was poured into methanol, vigorously stirred with a mixer, and separated by filtration and dried to obtain 78 g of a yellow polyimide powder. The weight average molecular weight of this polyimide powder was 120,000.

Example 4 Synthesis of Coumarin-3-carboxylate-1- (3,5-dinitrophenyl ester) Coumarin-3-carboxylic chloride 104.3
g (0.5 mol) and 700 ml of methyl ethyl ketone were placed in a reaction vessel, and heated and stirred at 60 ° C. under a nitrogen stream.
78.05 g (0.5 mol) of 5-dinitrophenol,
800 ml of methyl ethyl ketone and 80 g of pyridine were added dropwise. After completion of the dropwise addition, the mixture was stirred under reflux for about 2 hours. After completion of the reaction, the reaction solution was filtered off, and the solution was concentrated.
155.9 g of 3-carboxylate-1- (3,5-dinitrophenyl ester) was obtained.

Coumarin-3-carboxylate-1-
Synthesis of (3,5-diaminophenyl ester) 32.8 g (100 mmol) of coumarin-3-carboxylate-1- (3,5-dinitrophenyl ester) 10 g of 5% Pt-containing carbon graphite,
500 ml of 4-dioxane in a reaction vessel (hydrogenator)
And heated and stirred at 60 ° C. in a hydrogen atmosphere. 1
After absorbing 4.4 liters of hydrogen and the absorption of hydrogen ceased, the reaction was stopped, the reaction solution was filtered off, the catalyst was removed, and then concentrated to give coumarin-3-carboxylate-1.
26.8 g of-(3,5-diaminophenyl ester) were obtained.

Synthesis of Polyimide 26.8 g (0.1 mol) of coumarin-3-carboxylate-1- (3,5-diaminophenyl ester) was placed in a 2000 ml separable flask equipped with a stirrer.
Take 250 g of MAc and 28.8 g of ESDA (0.05
Mol) at once with vigorous stirring.
Stirring was continued for minutes. Next, 22.2 g of 6FDA (0.05
Mol) at once with vigorous stirring.
Stirring was continued for minutes.

18.61 g (0.2 mol) of β-picoline,
50 g of acetic anhydride and 100 g of DMAc were added to the above reaction solution, and heated to about 120 ° C. to imidize. These reactions were performed under a nitrogen stream.

After the completion of the reaction, the mixture was poured into methanol, vigorously stirred with a mixer, filtered and dried to obtain 80 g of a pale yellow polyimide powder. The weight average molecular weight of this polyimide powder was 130,000.

Example 5 Synthesis of 1- (3,5-dinitrophenoxy) -2-bromoethane 187.9 g (1 mol) of 1,2-dibromoethane
18.4 g (0.1 mol) of 5-dinitrophenol, 138.2 (1 mol) of potassium carbonate, and 400 ml of dimethylformamide were placed in a reaction vessel, and placed in a nitrogen gas stream for 24 hours.
Reflux stirring was performed for hours. The reaction solution is poured into water, and the precipitate is purified by a column, and 1- (3,5-dinitrophenoxy)
20 g of -2-bromoethane was obtained.

Synthesis of Cesium Coumarin-3-carboxylate 95 g (0.5 mol) of coumarin-3-carboxylic acid and 81.5 g (0.25 mol) of cesium carbonate were placed in a reaction vessel, and acetone: water = 1: 1. (Volume ratio) 600ml of mixed solution
Was added and stirred. When the solution became homogeneous, it was concentrated and dried to give cesium coumarin-3-carboxylate 16.
1.5 g (0.5 mol) were obtained.

1- (3,5-dinitrophenoxy) -2
Synthesis of-(coumarin-3-carboxylate) ethane 1- (3,5-dinitrophenoxy) -2-bromoethane 19.44 g (0.08 mol), coumarin-3-carboxylate 32.3 g (0.1 Mol) and 200 ml of dimethylformamide were added to the reaction solution, and 100 ⁰¹ ,
The reaction was carried out for 8 hours under a nitrogen stream. After completion of the reaction, the reaction solution was poured into water. The precipitate was purified by column and 1- (3,
26.5 g of 5-dinitrophenoxy) -2- (coumarin-3-carboxylate) ethane were obtained.

1- (3,5-diaminophenoxy) -2
Synthesis of-(coumarin-3-carboxylate) ethane Synthesis was performed in the same manner as in Example 4.

Synthesis of Polyimide In a 2000 ml separable flask equipped with a stirrer, 20.5 g (0.07 g of 1- (3,5-diaminophenoxy) -2- (coumarin-3-carboxylate) ethane was added.
Mol), 250 g of DMAc, and 15.5 g of 6FDA
(0.035 mol) at once with vigorous stirring.
Stirring was continued for 30 minutes. Next, 6FDA 15.5
g (0.035 mol) was added at once with vigorous stirring, and stirring was continued for 30 minutes.

18.61 g (0.2 mol) of β-picoline,
50 g of acetic anhydride and 100 g of DMAc were added to the above reaction solution, and heated to about 120 ° C. to imidize. These reactions were performed under a nitrogen stream. After the completion of the reaction, the reaction mixture was poured into methanol, stirred vigorously with a mixer, and then filtered and dried to obtain 50 g.
A white solid was obtained.

Example 6 Synthesis of Cesium α-Pyrone-5-carboxylate 70 g (0.5 mol) of α-pyrone-5-carboxylic acid and 81.5 g (0.25 mol) of cesium carbonate were placed in a reaction vessel. Take acetone: water = 1: 1 (volume ratio) mixture 600ml
Was added and stirred. When the solution became homogeneous, the solution was concentrated and dried to obtain 151.5 g of α-pyrone-5-carboxylic acid.
(0.5 mol).

1- (3,5-dinitrophenoxy) -2
Synthesis of-(α-pyrone-5-carboxylate) ethane 1- (3,5-dinitrophenoxy) -2-bromoethane 19.44 g (0.08 mol), α-pyrone-5-carboxylate 30.5 g (0.1 mol), 200 ml of dimethylformamide was added to the reaction solution,
0 ⁰¹ , and reacted for 8 hours under a flow of nitrogen gas.

After completion of the reaction, the reaction solution was poured into water. The precipitate was purified by column to give 26.0 g of 1- (3,5-ditrophenoxy) -2- (α-pyrone-5-carboxylate) ethane.

1- (3,5-diaminophenoxy) -2
Synthesis of-(α-pyrone-5-carboxylate) ethane Synthesis was performed in the same manner as in Example 4.

Synthesis of polyimide 1- (3,5-diaminophenoxy) -2- (coumarin-3-carboxylate) ethane was converted to 1- (3,5-diaminophenoxy) -2- (α-pyrone-5-carboxy). (Rate) It was synthesized in the same manner as in Example 5 except that ethane was used. The obtained polyimide was 45 g of a white solid and had a molecular weight of 150,000.

Example 7 Synthesis of 3-bromopropionate- (2-chalcone) 67.3 g (mol) of 2-hydroxychalcone, 32 g of pyridine and 500 ml of methyl ethyl ketone were placed in a reaction vessel, and 3-bromopropionic acid chloride was added. 51.4g
(0.3 mol) was dissolved in 300 ml of methyl ethyl ketone and slowly added dropwise. After completion of the dropwise addition, reflux stirring was performed for 2 hours under a nitrogen gas stream. The reaction solution was concentrated, washed with water, dried and purified by column to obtain 100 g of 3-bromopropionate- (2-chalcone).

3- (3,5-dinitrobenzoate)-
Synthesis of propionate- (2-chalcone) 3-bromopropionate- (2-chalcone) 71.8
g (0.2 mol), 68.8 g (0.2 mol) of cesium 3,5-dinitrobenzoate, dimethylformamide 6
00 ml was placed in a reaction vessel and reacted at 100 ° C. in a nitrogen stream for 8 hours. After completion of the reaction, the reaction solution was poured into water. The precipitate was purified by column to obtain 73.6 g (0.15 mol) of 3- (3,5-dinitrobenzoate) -propionate- (2-chalcone).

3- (3,5-diaminobenzoate)-
Synthesis of propionate- (2-chalcone) Synthesis was performed in the same manner as in Example 1.

Synthesis of polyimide Diamine component 3- (3,5-diaminobenzoate)-
Synthesis was carried out in the same manner as in Example 1 except that propionate- (2-chalcone) was used, to obtain 95 g of a yellow solid. The molecular weight was 120,000.

Example 8 Synthesis of 3,5-dinitrobenzoate-2-bromoethane 134.8 g of 3,5-dinitrobenzoic acid chloride
(0.5 mol) and 700 ml of acetone were placed in a reaction vessel and heated and stirred at 60 ° C. under a nitrogen stream, and 75 g (0.6 mol) of 2-bromoethanol, 200 ml of acetone and 80 g of pyridine were added dropwise. After completion of the dropwise addition, the mixture was stirred under reflux for about 2 hours. After completion of the reaction, the reaction mixture was filtered off, the solution was concentrated, washed with water and dried to obtain 144 g of 3,5-dinitrobenzoate-2-bromoethane.

1- (3,5-dinitrobenzoate)-
Synthesis of 2- (coumarin-3-carboxylate) -ethane 96.6 g (mol) of cesium coumarin-3-carboxylate, 95.7 g (0.3 mol) of 3,5-dinitrobenzoate-2-bromoethane, dimethylform 1000 ml of amide is placed in a reaction vessel, and is heated at 100 ° C.
For 8 hours. After completion of the reaction, the reaction solution was poured into water, and the precipitate was purified by column to obtain 107 g of 1- (3,5-dinitrobenzoate) -2- (coumarin-3-carboxylate) -ethane.

1- (3,5-diaminobenzoate)-
Synthesis of 2- (coumarin-3-carboxylate) -ethane Synthesis was performed in the same manner as in Example 1.

Synthesis of Polyimide The diamine component was converted to 1- (3,5-diaminobenzoate)
Synthesis was carried out in the same manner as in Example 1 except that -2- (coumarin-3-carboxylate) -ethane was obtained, to obtain 90 g of a yellow solid. The molecular weight was 140,000.

Example 9 Synthesis of 1- (3,5-dinitrophenyl) -coumarin-3-carboxamide 91.6 g (0.5 mol) of 3,5-dinitroaniline
Pyridine 600 ml, 1,8-diazabicyclo- [5,
76 g (0.5 mol) of [4,0] -7-undecene was placed in a reaction vessel, 104.3 g (0.5 mol) of coumarin-3-carboxylic chloride was added, and the mixture was refluxed and stirred for 3 hours under a nitrogen gas stream. Was. After completion of the reaction, the mixture was concentrated, washed with water, dried, purified by recrystallization, and purified by 1- (3,5-dinitrophenyl) -coumarin-3-carboxamide 1
42 g were obtained.

Synthesis of 1- (3,5-diaminophenyl) -coumarin-3-carboxamide Synthesis was performed in the same manner as in Example 1.

Synthesis of polyimide Synthesis was carried out in the same manner as in Example 1 except that the diamine component was changed to 1- (3,5-diaminophenyl) -coumarin-3-carboxamide to obtain 80 g of a yellow solid. . The molecular weight was 160,000.

[0124]

As described above, the novel diamine according to the present invention becomes a raw material of a polymer having both photoreactivity and thermal reactivity peculiar to a photosensitive group, and the novel polyimide composition according to the present invention is useful. It can be a photosensitive resin.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 219/32 C07C 219/32 C07D 309/32 C07D 309/32 311/12 311/12 311/16 101 311 / 16 101 G03F 7/027 514 G03F 7/027 514 7/038 504 7/038 504 F term (reference) 2H025 AA10 AB17 AC01 AD01 BC03 BC04 BC05 BC06 BC08 BC10 BC69 BC81 4C062 CC76 EE12 EE30 4H006 AA01 AB46 BJ BM BM73 BP10 BP30 BR30 BT12 BT32.

Claims (4)

[Claims] [Claim 1] The following general formula (1) (Where X and Y are divalent organic groups, and Z is chemical formula 2) Wherein A is H, CH ₃ ,
F, Cl, Br, CH ₃ O— are shown. ). 2. X in the general formula (1) is-, -CH
₂ selected from _2- , -COO-, -NH-, -O-
The novel diamine according to claim 1, which is a valent organic group. 3. Y of the general formula (1) is-, -COO
-, -OOC-,-(CH_Two)_mO-,-(CH_Two)_m
COO-,-(CH_Two)_mOOC-,-(CH _Two)_m−
2. The novel compound according to claim 1, which is a divalent organic group selected from the group consisting of:
Diamine. (However, m represents an integer of 1 to 15.) 4. The compound represented by the following general formula (2): ## STR3 ## (However, X _{is, -, - CH 2 -,} - COO -, - NH
A divalent organic group Y selected from —, —O— is —, —CO
O -, - OOC -, - (CH 2) m O -, - (CH 2)
_{m COO -, - (CH 2} ) m OOC -, - (CH 2) m
-, (Where m is 1 to 15) a divalent organic group selected from the group consisting of Wherein one or more photosensitive groups selected from
H ₃ , F, Cl, Br, CH ₃ O—) B and D are 4
A divalent organic group, E is a divalent organic group, p is 1 to 100,
q shows the integer of 0-99. A) a novel polyimide composition comprising 1% by weight or more.