JPS6021167B2 - Polyamideimide prepolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel polyamideimide prepolymers.

The polyamide-imide prepolymer of the present invention has the general formula (in the formula, R is a divalent organic group having 2 or more carbon atoms; R2 is a trivalent organic group having 3 or more carbon atoms, and 3 carbonyls bonded to R2). Two of the groups are bonded to adjacent carbon atoms.

R3 is a trivalent organic group having 3 or more carbon atoms; R4 is an aromatic ring residue; R5 is a hydrogen atom, a halogen atom, an alkyl group or a cyano group. 1 represents an integer of 1 to 10, m represents an integer of 1 to 5, and n represents an integer of 1 to 20.

) It consists of a unit prepolymer represented by:

Usually it is a composition of these unit prepolymers. Polyamideimide of the present invention.

The brepolymer is characterized by having a Q-arylmaleimide group (here, the aryl group refers to the R4 group and is used to refer to an aromatic ring residue) in its side chain,
It has the property of crosslinking and polymerizing when exposed to light to produce a heat-resistant polyamide-imide polymer. Conventionally, polyamideimide' is generally obtained by reacting tricarboxylic acid anhydride (or its functional derivative) with diamine or diisocyanate in a polar organic solvent such as dimethylformamide, dimethylacetamide, or N-methyl-2-pyrrolidone. It is being These polymers have excellent properties that compensate for the disadvantages of polyimide, such as processability and bending resistance, but they have the drawback of being considerably inferior in heat resistance compared to polyimide. Furthermore, since an imide environment cannot be completely formed before baking, the viscosity stability of the polymer solution is poor, and when stored at room temperature, it also has drawbacks such as gelation and viscosity reduction. On the other hand, the polyamideimide prepolymer of the present invention has the property of further photo-crosslinking the conventional polyamideimide, and therefore has the characteristic of providing a polymer with significantly increased heat resistance.

Furthermore, since it has a photosensitive Q-arylmaleimide group, there is no need to add a sensitizer, and there is no fear of deterioration of resin properties caused by additives. Next, a method for producing the polyamideimide prepolymer of the present invention will be described. Although the manufacturing method is not particularly limited, the following method is preferably used. That is, a tricarboxylic acid anhydride represented by the general formula (wherein R2 is as defined above) and a tricarboxylic acid anhydride represented by the general formula (wherein R3, R4, and R5 are as defined above).

) with Q-arylmaleimide diol,
General formula OCN-R, -NC○ (W) (wherein, R is as defined above.

) The polyamideimide prepolymer of the present invention can be obtained by reacting with the diisocyanate represented by (). In the tricarboxylic anhydride (0) described above, the group R2 is an organic group having 3 or more carbon atoms, and two of the three carbonyl groups bonded to it are bonded to adjacent carbon atoms in R2. be.

It may be aliphatic, aromatic or alicyclic, but aromatic is preferred because it provides a particularly excellent heat-resistant polymer.
The preferred number of carbon atoms is 6 to 18. Examples of such tricarboxylic anhydrides include trimellitic acid, 2,3,
6-naphthalenetricarboxylic acid, 2,3,5-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-naphthalenetricarboxylic acid 2-(3
,4-dicarboxyphenyl)-2-(3-carboxyphenyl)propane, 2,3,5-pyrazinetricarboxylic acid, 2-(2,3-dicarboxyphenyl)-2-(
3-carboxyphenyl)propane, 1-(2,3-dicarboxyphenyl)-11-(3-carboxyphenyl)ethaso, 1-(3,4-dicarboxyphenyl)-1
-(4-carboxyphenyl)ethane, (2,3-dicarboxyphenyl)(2-carboxyphenyl)methane, 1,2,3-benzenetricarboxylic acid, 3,3',4
and the respective anhydrides of tricarboxylic acids such as penzophenone tricarboxylate. These may be used alone or in combination. The group R8 in Q-arylmaleimidodiol (Machi) is a trivalent organic group having 3 or more carbon atoms,
The carbon atom bonded to the Q-arylmaleimide group is preferably a carbon atom via at least one carbon atom from the hydroxyl group.

The preferred number of carbon atoms in R3 is 4 to 7. Further, R4 is an aromatic ring residue, and refers to one in which the core carbon atom of an aromatic compound in a broad sense is bonded to the Q-1 position of maleimide. Not only an aryl group having a benzene nucleus, but also one of the nuclear carbon atoms is S,
A heterocyclic ring substituted with 0 or N may also be used. The preferred number of carbon atoms in R4 is 4-20. R5 is a hydrogen atom,
It is a halogen atom, an alkyl group, or a cyano group, and the alkyl group preferably has 1 to 10 carbon atoms. Examples of such Q-arylmaleimide diols include 2-methyl-2-(Q phenylmaleimido)-1,3-propanediol, 2-methyl-2-(Q tolylmaleimide)-1,3-propanediol, 2-methyl-2(Q-phenyl-8-methylmaleimide)-1,3-propanediol, 2-methyl-2-(Q-phenyl-8-chloromaleimide)-1,3-propanediol, 2-methyl-2-(Q- phenyl-8-cyanomaleimide)-13
-Propanediol, 2-methyl-21 (Q-naphthylmaleimide)-1,3-butanediol, 2-methyl-21 (Q-thienylmaleimide) 1,3-propanediol, 2-methyl-21 (〇- frill maleimide) 1
, 3-propanediol, 2-methyl-2-(Q-pyridylmaleimide)-1,3-propanediol, and the like. These may be used alone or in combination.
The group R in the diisocyanate (N) to be reacted with the above tricarboxylic anhydride (0) and Q-arylmaleimide diol (m) is a divalent organic group having 2 or more carbon atoms, i.e., an aliphatic group, an alicyclic group. Or each aromatic group,
In particular, aromatic groups are preferred. The number of carbon atoms in R is preferably 6 to 14. Examples of such diisocyanates include tetramethylene (1,4)-diisocyanate, hexamethylene (1,6)-diisocyanate, cyclohexane (1,4)-diisocyanate, dicyclohexylmethane (4,4')-diisocyanate,
Phenylene (1,3) diisocyanate, phenylene (1,4) diisocyanate, tolylene (2,6) diisocyanate, tolylene (2,4) diisocyanate, diphenylmethane (4,4') diisocyanate, diphenyl ether (4) ,4') diisocyanate,
Naphthylene (1,5) diisocyanate, hexahydrodiphenyl (4,4') diisocyanate, 1-methoxybenzene (2,4)-diisocyanate, azobenzene (4,4') diisocyanate, diphenylsulfone (4,4') -diisocyanate, '-dipropyl ether diisocyanate, diphenyl sulfide (
2,4)-diisocyanate, anthraquinone (2,6)
)-diisocyanate, etc. These may be used alone or in combination. The above-mentioned reaction materials are used in an amount ratio that allows a substantially quantitative reaction to proceed.

That is, approximately the same number of moles of diisocyanate as the total number of moles of tricarboxylic anhydride and Q-arylmaleimide diol is used.

The usage ratio m/1 of tricarboxylic anhydride and Q-arylmaleimide diol can be varied over a wide range, but in the present invention, the latter is 0.2 to 1.0 mol per 1 mol of the former,
It is preferably used in a range of 0.5 to 2.0 mol. If this ratio is at the lower limit, curing during light irradiation will be insufficient,
This is because sufficient resin strength and heat resistance cannot be obtained, and when the upper limit is exceeded, the imide bond amount ratio decreases and sufficient heat resistance cannot be obtained. The reaction takes place in an organic solvent.

Examples of reaction solvents include N,N-dialkylamides such as dimethylacetamide, diethylacetamide, N-methyl-2-pyrrolidone, N-methylcalactam, dimethylformamide, and diethylformamide; tetramethylurea, pyridine, dimethylsulfo, Examples include hexamethylphosphorylamide, tetramethylene sulfone, formamide, N-methylformamide, butyrolactone, N-acetyl-2-pyrrolidone, trimethyl phosphate, triethyl phosphite, and the like. The organic solvents exemplified above are particularly preferred as reaction solvents, but
In addition, hydroxy organic compounds, hydroxy aromatic compounds, etc. can also be used as reaction solvents. The hydroxy aromatic compound herein means a compound having at least one -OH group directly connected to an aromatic nucleus, and examples thereof include cresol, phenol, xylenol, naphthol, nitrophenol, cresylic acid, and the like. These reaction solvents can be used alone or in combination, and benzene, toluene, nitrobenzene, trichlene, etc. may be added as a diluent. The amount of these organic solvents to be used can be changed as appropriate depending on the purpose of use of the polyamideimide prepolymer of the present invention or the reaction conditions, especially the viscosity, but the amount is sufficient to dissolve the produced polymer, and is generally based on the total amount of the reaction raw materials. 2% or more by weight is used. At the same time, a tertiary amine is added which acts as a catalyst or promoter during the reaction.

Examples of such tertiary amines include pyridine, y-
Examples include picoline, quinoline, triethylamine, triethylenediamine, N,N-dimethylamine, N-methylmorpholine, and N-ethylmorpholine. However, when using a tertiary amine as a reaction solvent, it is natural that it does not need to be used again. The amount of these tertiary amines to be used is 0.05 to 2.0 molar equivalents, preferably 0.5 to 1 molar equivalent per 1 molar equivalent of isocyanate groups in the reaction raw materials.
．． 5 molar equivalents. The general reaction mode for producing the prepolymer as described above is as follows.

First, a diisocyanate and a tertiary amine are dissolved in a reaction solvent.

Tricarboxylic acid anhydride dissolved in the same reaction solvent was added dropwise to this, the temperature was raised to 140-160 oo, and 2-6 oz.
The viscosity increases slightly during reaction time. next,
A resin solution containing the brepolymer of the present invention is obtained by adding Q-arylmaleimide diol to this reaction solution, raising the temperature to 140 to 17,000, and reacting for 3 to 8 hours. The prepolymer of the present invention can be isolated by adding a non-solvent such as acetone to the photosensitive resin solution obtained in this way, but usually this resin solution is used as it is or the reaction solvent or diluting solvent is used. It can be diluted and applied with a brush, or it can be used at a concentration suitable for spraying, etc.

The thus obtained polyamide-imide prepolymer of the present invention is cured to give a cured molded product with excellent heat resistance, abrasion resistance, and solvent resistance, and can therefore be used as a solution, or as a cured molded product, as an electrically insulating material. , laminating adhesives, paints,
It is used for useful purposes such as films. From the above, the effects of the present invention are clear, but the characteristics of the polyamide imide prepolymer of the present invention and its solution are summarized as follows.

■ The imide groups in the prepolymer and the imide groups of the crosslinking agent are all present in an almost completely closed state, so when dissolving this and using it as a prepolymer solution, it is different from that seen in conventional polyamidimide solutions. The problem of foaming during heating has been solved. Furthermore, the stability of the solution during rising was also greatly improved. (2) Curing molding has the property of further photo-crosslinking the polyamideimide state, so the heat resistance of the molded product is significantly increased.

Furthermore, the cyclobutane ring formed by photo-crosslinking of the Q-arylmaleimide group is quite stable against heat, and from this point of view as well, the molded product has excellent heat resistance. ■ There is no need to use a sensitizer during photocrosslinking, so there is no need to worry about deterioration of resin properties due to the use of a sensitizer.

■ Because it uses photocuring, there is no need for the conventional high-temperature treatment, and heating only needs to be used for solvent drying.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 4,4'-diphenylmethane diisocyanate was added to a 300 mm three-necked flask equipped with a condenser, a frame apparatus, and a thermometer.
After 0 minutes, add 100 hours of N-methyl-2-pyrrolidone to prepare a simulated solution.

When it becomes homogeneous, add 4 portions of triethylene diamine and 1
Raise the temperature to 00o0. N-methyl-2-pyrrolidone 5
19 g of trimetic anhydride dissolved in 0.0 ml was added dropwise over 3 minutes. After finishing the bottle, the temperature was raised to 140q0, and the reaction was continued for 2 hours. Next, 2. 26 parts of methyl-2-(Q-phenylmaleimide) 1,3-propanediol was dissolved in 50 parts of N-methyl-2-pyrrolidone and added dropwise over 40 minutes. Reaction inho at 140qo for 3 and a half hours.
A viscous dark brown photosensitive solution of 84 was obtained. Mechrola of the product separated by pouring acetone into this solution
The number average molecular weight was 12,800 based on measurement using a b-membrane osmometer (manufactured by Hewlett Packard, Inc.). In the infrared absorption spectrum of this product using the KBr method, absorption peaks of the imidocarbonyl group were observed at -1 of 1775c and -1 of the 172 ratio, and a peak based on the amide bond was observed at the 1665 arc-1. It was confirmed. The above-mentioned solution was applied to an aluminum slope to a dry coating thickness of 50 mm, and after drying, it was exposed to light using a high-pressure mercury lamp, and the irradiated areas were insolubilized into N-methyl-2-pyrrolidone.

As a result of thermogravimetric analysis of this product, almost no weight loss was observed up to 32,000.

Example 2 Into a 300' three-necked flask equipped with a condenser, rope clothing, and a thermometer, 50 g of 4,4'-diphenyl ether diisocyanate and 100 g of N.methyl-12-pyrrolidone were charged and entrained.

When it becomes homogeneous, add triethylenediamine for 10 minutes.
Raise the temperature to 0qo. N-methyl-2-pyrrolidone 50
19 g of dissolved trimethic anhydride was added dropwise over 3 minutes. After the dropwise addition was completed, the temperature was raised to 14,000 ℃, and the reaction was continued for 2 hours. Next, 2-methyl-1,3-propanediol-2-Q phenylmaleimide was dissolved in N-methyl-2-pyrrolidone and reacted in the same manner as in Example 1.
．． A viscous black-brown photosensitive solution of No. 79 was obtained. The number average molecular weight of the product determined in the same manner as in Example 1 was 1120.
It was 0. The resulting photosensitive solution was applied onto an aluminum plate in the same manner as in Example 1 and exposed, resulting in N-methyl-2.
It was changed to pyrrolidone. As a result of calorimetric analysis of this product, almost no weight loss was observed up to 320°C.

Example 3 4,4'-diphenylmethane diisocyanate 5 was added to a 300-sized three-necked flask equipped with a condenser, a fly clothing layer, and a thermometer.
0 nights, 100 nights of N-methyl-2-pyrrolidone, 4 nights of triethylenediamine, and 19 nights of trimetic anhydride were reacted in the same manner as in Example 1.

Next, 27.5 g of 2-methyl-1,3-propanediol-2-Q-phenyl-8 methylmaleimide was dissolved in 50 g of N-methyl-2-pyrrolidone and added dropwise over 40 minutes.
React as it is for 3.5 hours at 140 oo, then inho.
A viscous black-brown photosensitive solution of No. 93 was obtained. Example 1
The number average molecular weight of the product determined in the same manner as 15,500
Met. When it was coated and exposed on an aluminum plate in the same manner as in Example 1, it became insoluble in N-methyl-2-pyrrolidone.
As a result of gravimetric analysis of this product, almost no weight loss was observed up to 320°C.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is a divalent organic group having 2 or more carbon atoms; R_
2 is a trivalent organic group having 3 or more carbon atoms, and two of the three carbonyl groups bonded to R_2 are bonded to adjacent carbon atoms. R_3 is a trivalent organic group having 3 or more carbon atoms; R_4 is an aromatic ring residue; R_5 is a hydrogen atom, a halogen atom, an alkyl group, or a cyano group. 1 is an integer from 1 to 10, m is 1
An integer of ~10, n represents an integer of 1-20. ) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A polyamide prepolymer consisting of a unit prepolymer represented by