JPS60260625A - Production of polyimide resin - Google Patents

Abstract

PURPOSE:To obtain a polyimide resin excellent in long-term heat resistance and moldability, by heat-curing a specified oligoimide in the presence of a polyallyl compound and/or its oligomer. CONSTITUTION:An oligoamic acid as a precursor is obtained by reacting an aromatic tetracarboxylic acid (anhydride) with an aromatic amine and a compound which can give an addition-polymerizable group in the presence of a polar solvent (e.g., dimethylformamide). The obtained precursor is cyclized to obtain an oligoimide having aromatic imido bonds in the main chain and at least two addition-polymerizable groups of formulas I and II (wherein R1-2 are each H or a lower alkyl) in the terminals and/or the side chains. 20-1pt.wt. this oligoimide is heat-cured in the presence of 1pt.wt. polyallyl compound (MW<=800) of formula III or IV (wherein R10-12 are each R1), having an (iso)cyanuric ring in the molecule and being mutually soluble with said oligoimide and/or its oligomer to obtain a polyimide of a glass transition point >=280 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel method for producing a polyimide resin, and particularly to a method for producing a polyimide resin with excellent heat resistance.

The polyimide resin 1q according to the present invention is a heat-resistant thermosetting resin with a glass transition temperature of 280°C or higher, preferably 320°C or higher, particularly preferably 340°C or higher, and even more preferably 360°C or higher, and 220°C or lower with excellent heat resistance. It has excellent flowability and particularly good moldability.

Therefore, the polyimide resin of the present invention has the following advantages, for example, a high elastic modulus mmt < carbon m 81
, aramid fiber, etc.) as a reinforcing material, it can be used as a highly heat-resistant composite material.

Prior Art Conventional J: A method of curing an oligoimide resin having an aromatic imide bond in the main chain and an addition-polymerizable group at the end of the chain is well known in order to obtain a heat-resistant polyimide resin. There is.

For example, specifically, 1) using benzophenonetetracarboxylic acid as the aromatic tetracarboxylic acid component, using 4,4'-diaminodiphenylmethane as the aromatic diamine component, and using nadic acid as the component providing the addition polymerizable group; , obtained following formula (a) No. 3-, Japanese Patent Publication No. 47-51825, Japanese Patent Publication No. 48-2878
6, etc.), and 2) using benzophenonetetracarboxylic acid as the aromatic tetracarboxylic acid component, using 4,4'-diaminodiphenyl ether as the aromatic diamine line segment, and using allylamine as the component providing the addition polymerizable group. An oligoimide resin represented by the following formula obtained using JP-A-50-2209
(see Publication No. 1).

It is said that when these oligoimides are heated and cured, they produce polyimide resins with high heat resistance; There were drawbacks.

Therefore, N-phenylnadic acid is not suitable for oligoimides.

゛Object 1 of the invention゛Object 1 of the present invention is to provide a polyimide resin with excellent heat resistance and moldability. It is an object of the present invention to provide a composite material with excellent heat resistance when it is incorporated into fibers and hardened by heating to form a composite material, and to provide a method for manufacturing a vine.

Structure of the Invention The present invention provides the following features: 1. An oligoimide having an aromatic imide bond in the main chain and an addition-polymerizable group at the terminal and/or side chain is mutually soluble with the oligoimide and under molecular 11800JX. A method for producing a polyimide resin, which is characterized by heating and curing in the presence of a polyfunctional allyl compound and/or oligomer thereof, and further comprising: , the method for producing a polyimide resin according to item 1 above, wherein the oligoimide is a group represented by 1.

The oligoimide used in the present invention has an aromatic imide bond in its main chain. Such an oligoimide consists of an aromatic tetracarboxylic acid component and an aromatic amine component,
It can be synthesized by a conventionally known method.

Here, the aromatic tetracarboxylic acid component is a derivative of the following formula (I) 7-, for example, one in which a carboxyl group is modified into an acid anhydride group or a lower alkyl ester group.

The aromatic amine component has the following formula (If) (1).

and (IV) 5 8- , and may further include the following formula (V).

The oligoimide used in the present invention has an addition polymerizable group. Here, as (=J polymerization t'1gW, conventionally known ones can be used, such as those represented by the following formula % formula % (). Among these, the formula (V
Those represented by (1) and (■) are preferred.

In this case, the number of addition polymerizable groups is two or more. Incidentally, these addition polymerizable groups can be introduced into the oligoimide according to a known production method described below.
Chi111, The polyfunctional allyl compound used in the present invention has a molecular weight of 80
0 or less, and has mutual solubility with the oligoimide. Such polyfunctional allyl compounds particularly have a cyanuric ring or isocyanuric ring in the molecule, and the ring has the following formula (X).

(XI) 23 "-CH2-C= CI-12...(X)z4 ■ -0-CH2-C= CH2...(XI")
It is a compound having two or more, especially three or more, groups represented by.

Typical examples of such compounds include the following formula % formula % (
).

Therefore, the oligomer of the polyfunctional allyl compound used in the present invention is one in which two or more of the polyfunctional allyl compounds are bonded together, and the molecular weight is not limited to 800 or less. Such oligomers are polyfunctional allyl compounds that are heated, organic peroxides, or specific examples include pyromellitic acid, benzophenone-3,3', 4,4'-tetracarboxylic acid, 3,3', 4. 4'-monodiphenyldetracarboxylic acid, his(3,4-dicarboxyphenyl)
Ether, bis(3,4-dicarboxyphenyl)sulfone, 1,3-bis(3,4-dicarboxyphenoxy)benzene, 2,2-bis(3,4-dicarboxyphenoxyphenyloxyphenoxy) phenyl) sulfone, bis(3,4-
dicarboxyphenoxyphenyl)ketone, bis(2
．． Tetracarboxylic acids such as 3-diolboxyphenoxypheny(15-l) ether, their acid anhydrides, bilomeriz 1-acid dimethyl ester, benzophenone-3.3', 4.4'-te 1-lacarboxylic acid These are esters with lower aliphatic alcohols such as dimethyl ester, 3.3',4.4'-diphenyltetracarboxylic acid diethyl ester, bis(3,4-dicarboxyphenyl)needle dipropyl ester, and dibutyl ester.

Among these, particularly preferred are pyromellitic acid, benzophenonetetracarboxylic acid or derivatives thereof, and even more preferred is benzophenonetetracarboxylic acid or derivatives thereof.

Specific examples of the aromatic amine components represented by the formulas ([) to (V) include p-phenylenediamine, m-phenylenediamine, monomethyl-11-phenylenediamine, monochloro-p-7 to 1,y' ,y′7″−′・4
-'11/l,=-"-7"::L,t>'7 et ketone 2,4-diaminotoluene, 2,6-diamizether, 3,4'-diaminodiphenyl ether, 4,
4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
2.2-bis(4-aminophenyl)propane, 3.3
'-dimethyl-4,4' diaminodiphenylmethane, 3.3'-diethyl-4,4' -diaminodiphenylmethane, 2,4-bis(4-aminobenzyl)aniline as well as 1,4-phenylene diisocyanate, 1
．． 3-phenylene diisocyanate, toluene-2,4
- diisocyanate, and 4,4'-diphenylmethane diisocyanate.

Preferred aromatic amine components, particularly preferred aromatic amine components of the present invention are as described above, and in the aromatic amine component of the present invention, in the formulas (II) and (nu), R5 is a lower alkyl group, and Ra .

R7 is a lower alkyl group when the amino group is in the para position relative to x2, and a hydrogen atom or a lower alkyl group when the amino group is in the meta position, preferably those in which x2 is CH2, -802- .

Which phase is oligoimide and polyfunctional allyl compound? 7 The solubility is the aromatic tetrahelacan that constitutes the oligoimide, 4.4
Once the oligoimide obtained using '-diaminodiphenyl ether is crystallized in the presence or absence of a polyfunctional allyl compound, it does not have mutual solubility with the polyfunctional allyl compound, and as a result, the fluidity of the oligoimide is improved. This is not desirable as it has little effect.

In the present invention, the compound providing an addition polymerizable group has the above formula (
J evident from Vr), (■), (■), and ([X): Sea urchin, for example, allylamine, metaallylamine (β-medylallylamine), β-ethylallylamine, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-hydrate, 5-norbornene-2,3-dicarboxylic acid monomethyl ester, 5-norbornene-2,3-dicarboxylic acid monoethyl ester, 5-norbornene-2,3-dicarboxylic acid monopropyl ester, methyl- 5-norbornene-anhydride, ethyl-5-norbornene-2,3-dicarboxylic acid monobutyl ester, 3-ethynylaniline, 4-
Allyl amines such as ethynylaniline, 4-■ dinylphthalic acid, 3-■ thynylphthalic anhydride, 4-■ thynylphthalic acid monoethyl ester, lower alkyl-substituted allylamine, 5-norbornene-2.3-dicarboxylic acid, lower alkyl-substituted 5- Norbornene-2,3-dicarboxylic acid, acid anhydrides thereof, and lower aliphatic alcohols thereof in the present invention have an aromatic imide bond in the main chain and an addition polymerizable group in the terminal and/or side chain. The oligoimide contains one or more of the above (=l polymerized bamboo groups).

In the present invention, an aromatic imide bond is present in the main chain, and an i-polymerizable group is present in the terminal and/or side chain, for example (A) aromatic tetraboxylic acid or its acid anhydride; An aromatic amine and a compound providing an addition polymerizable group are mixed in the presence of a polar solvent, reacted to form a precursor oligoamic acid, which is further subjected to a ring-closing reaction to form an oligoimide. (B) Aromatic tetracarboxylic acid Acid lower alkyl■ ster,
Aromatic amine and a compound that provides an addition polymerizable group (here, the compound that provides an addition polymerizable group is 5-norbornene-2,
In the case of dicarboxylic acids such as 3-dicarboxylic acid, 5-ethynyl, 11θ'' luphthalic acid, it is preferable to use them in the form of lower alkyl esters) in a polar solvent and/or a lower aliphatic alcohol. A mixed reaction is carried out in the presence of , to form a precursor oligoamic acid, which is further subjected to a ring-closing reaction to form an oligoimide.

(C) A compound that gives an addition-polymerizable group to the isocyanate obtained by mixing an aromatic tetracarboxylic anhydride and an isocyanate obtained from an aromatic amine in the presence of a polar solvent (herein, the compound that gives an addition-polymerizable group 5-norbornene-2
．． In the case of dicarboxylic acids such as 3-dicarboxylic acid and 5-tinylphthalic acid, they are used in the form of acid anhydrides) and reacted.

The following methods are used.

Among these, methods (A> and (B)) are more preferred.

Polar solvents used in the synthesis of oligoimides in the present invention include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, diethyl 20-dioxane, cyclic ethers such as tetrahydrofuran, and dimethylsulfoxide.

In the present invention, the oligoimide is cured in the presence of a polyfunctional allyl compound and/or its oligomer. The polyfunctional allyl compound and the like may be added to the oligoimide at the time of blending the raw materials for the oligoimide, during the synthesis of the oligoimide, or to the obtained oligoimide.

In the present invention, the average molecular weight of the aromatic oligoimide is determined by considering the fluidity of the oligoimide during molding, the heat resistance of the molded product, mechanical performance, etc. However, if the molecular weight of the oligoimide is too small, the fluidity of the oligoimide during molding is determined. This not only improves the heat resistance of the molded product, but also lowers the glass transition temperature of the polyimide resin, improving the mechanical performance of the molded product at high temperatures (
(for example, bending strength) decreases, which is undesirable.

Therefore, the average molecular weight of the oligoimide in the present invention is determined from the loss of raw materials during oligoimide production, and is usually in the range of 600 to 3000, preferably 7.
00-2000, particularly preferably 700-1600, and still more preferably 800-1500.

In the oligoimide of the present invention, the addition polymerizable group is mainly bonded to the terminal end of the oligoimide molecule, and the terminal group of the oligoimide molecule in the oligoimide of the present invention mainly consists of the addition polymerizable group.

The oligoimide constituting the oligoimide composition used in the present invention has, for example, the following formula % formula % () () where the formulas R+, R2 and Q are the same as defined above,
r represents an aromatic diamine residue and can be easily calculated from the equation. In the oligoimide of the present invention, if the proportion is small, the heat resistance of the polyimide resin obtained will be good if the amount of polymerizable IK, J, and IK is small.

231 In the present invention, the oligoimide contains at least one addition polymerizable group.

Among these, those containing an addition polymerizable group represented by the above formula (Vl) or the I1 polymerizable group represented by the above formula (■) are particularly preferable. More preferably, it contains both addition-polymerizable groups represented by formulas (Vl) and (■).

Even if it is a mixture of the oligoimide having an addition polymerizable group represented by the formula (Vl) or (Vl) and the oligoimide represented by the formula (X■), or the oligoimide represented by the formula (X Vl )
Even if the oligoimide is represented by the formula (XVI
), (X■), and (X■) may be a mixture of oligoimides. Such an oligoimide has the advantage that it can be cured at a relatively low temperature and that the temperature and time required for post-curing after molding is low and short.

24- In the present invention, the polyfunctional allyl compound has an intermolecular distance of 800
The following compounds and those having good mutual solubility with oligoimide are used. Such compounds include the above formula (XII)
, (XI[I), (XIV), and (XV) are used.

Allyl cyanurate, trimethallyl cyanurate-I-, ethyl diallyl isocyanurate, propyl diallyl cyanurate, N-allyl-5-norbornene-2,3-dicarboximide, N-methallyl-methyl-imide, N,N' -Diallylbenzophenone-3,3
', 4,4'-tetracarboxydiimide, N.

N'-Diallyldiphenyl ether-3.3'.

In addition to 4,4'-tetracarboxydiimide, among the compounds represented by the above formulas (XI [ The ratio is 1/20 to 1/1, preferably 1/1 by weight.
It is 10 to 1/2, particularly preferably 1/10 to 1/3.

If the amount of the polyfunctional allyl compound is too small, the effect of improving the fluidity of the oligoimide will be small.

On the other hand, if the amount of the polyfunctional allyl compound is too large, the fluidity of the oligoimide is improved, but the heat-resistant mechanical properties of the polyimide resin obtained by heating and curing the oligoimide tend to deteriorate, which is not preferable.

The oligoimide containing the polyfunctional allyl compound of the present invention is
Compared to conventional oligoimides, it has good fluidity during molding, can be molded at relatively low temperatures, and has excellent heat resistance.

The curing of the oligoimide is carried out in two stages: a step of molding under pressure in a molding machine (molding), and a Bostokoring step after molding to further increase heat resistance and dimensional stability.

According to the method of the present invention, the oligoimide can be easily formed at a relatively low temperature, for example, below 280 DEG C., especially in the molding step, and is usually carried out at a temperature of 260 DEG to 280 DEG C. for a period of 1 to 5 hours. Of course, it goes without saying that molding can be performed at temperatures of 280°C to 300°C.

In this case, the time required for molding can be further reduced.

The oligoimide of the present invention can be molded at a relatively low temperature such as 280°C or lower, and the polyimide resin molded here can be post-cured at a higher temperature, for example around 300'C, for 3 to 12 hours to form a polyimide resin with even higher heat resistance. can do.

According to the method of the present invention, the oligoimide itself is cured during molding to provide a polyimide resin having poor heat resistance, and furthermore, by curing in the presence of fibers as a reinforcing material, a polyimide resin is obtained.・(Can be manufactured by the method.

A solution containing an oligoimide or an oligoimide precursor (here, the above-mentioned polar solvent and/or lower aliphatic alcohol is used as the solvent) is brought into contact with the reinforcing material, and the solvent is removed and the oligoimide precursor is ring-closed if necessary. This is a method of reacting and then heating and curing in a molding machine.

Function: According to the method of the present invention, the oligoimide has excellent fluidity during molding, and preferably has a lath transition temperature of 320°C or higher, preferably 340°C or higher, and is particularly preferably 340°C or higher.
It also has excellent heat resistance at temperatures above 50°C. Furthermore, the polyimide resin obtained by the present invention has long-term heat resistance such that it can be used for a long time even at high temperatures of 250° C. or higher.

Furthermore, the polyimide resin of the present invention can be used as a composite material with excellent heat resistance and mechanical properties when, for example, highly elastic heavy woven fabric (carbon fiber, aramid fiber, etc.) is used as a reinforcing material. .

Next, the present invention will be described with reference to Examples.

In the examples, "part F" indicates "part by weight."

Examples 1 to 3 and Comparative Example 1 (1) Synthesis of oligoimide 125.4 parts of benzophenone-3,3,4,4'-tetracarboxylic dianhydride and 5-norbornene-2,3-
25 parts of methyl alcohol to 32.8 parts of dicarboxylic anhydride
Add 88.0 parts of 3.3'-dimethyl-4,4'-diaminodiphenylmethane to the methyl alcohol solution obtained by adding 8 parts and heating under reflux for 3 hours to dissolve, and then cool to room temperature. Then, 11.4 parts of allylamine was added to obtain a methyl alcohol solution of an oligoimide precursor. Here, a predetermined amount of 1-lylyl isocyanurate was added and dissolved. Next, in order to check the fluidity of the oligoimide, a portion of this solution was placed in an oven and heated to 80 to 150 ℃.
℃ for 3 hours, then heated and dried at 220℃ for 1 hour, packed into a cylinder of the desired oligoimine, heated at a rate of 10℃ per minute under a pressure of 50 to 9/ctd, and placed in a cap with a diameter of 1 mm and a land length of 5#. We investigated the temperature at which oligoimide begins to flow out. The results are shown in Table 1.

Here, Comparative Example 1 is the result of an experiment conducted in the same manner as Examples 1 to 3, except that ].reallylisocyanure-1. was not used.

(Left below) Table 1 31 Next, add a methanol solution containing triallyl isocyanurate and an oligoimide precursor to Carbon! MiN (East T-40
0,3600 denier, 6000 filament), and dried in an oven at 80 to 150°C for 3 hours, then heated and dried at 220°C for 1 hour, and then arranged the prepreg in one direction in the mold, and the mold temperature was 275°C. Pressure molded at ℃ for 1 hour and cooled to 200℃ to a thickness of 2 lll1.
A molded piece with a width of 12M and a length of 120m was taken out, and the obtained molded piece was heated in the stomach for 4 hours at 230°C to 300°C.
Curing was performed at 00°C for 4 hours.

Regarding the molded piece thus obtained, DuPont DM
A (Model 1090) was used to evaluate the glass transition temperature and the heat resistance of the resin.

The results are shown in Table 2.

32-Examples 4-6. Comparative Example 2 470 parts of methyl alcohol was added to 283.2 parts of benzophenonetetracarboxylic dianhydride and 59.0 parts of 5-norbornene acid anhydride, heated under reflux for 3 hours, and the resulting methyl alcohol solution was heated to room temperature. Cool, 2,4-diaminotoluene 107,3
20.5 parts of allylamine was added and mixed uniformly with stirring. Here, a predetermined amount of triallyl isocyanurate was added.

Next, in order to examine the fluidity of the oligoimide, a portion of this solution was placed in an oven and heated at 80 to 150°C for 3 hours.
The mixture was then heated and dried at 220° C. for 1 hour to obtain the desired oligoimide.

The flow rate 1/I of this oligoimide was examined using a flow tester as in Examples 1 to 3, and the results are shown in Table 3+.

Comparative Example 2 is an example in which triallylisocyanurate-1 was not used.

Table 3 (blank below) On the other hand, using the methanol solution obtained here, Example 1~
A unidirectional carbon fiber navy blue reinforced polyimide resin molded piece was made in the same manner as in 3, and the glass transition temperature of the polyimide resin therein was measured to evaluate the heat resistance of the resin (1).

The results are shown in Table 4.

Examples 7 to 8 To check the long-term heat resistance of the polyimide resin of the present invention, 250
The molded piece was held at ℃ for 1000 hours to determine the bending strength retention rate. The 0° bending strength was measured at 250° C. using a 3-point bending test method using a sample with a thickness of 2 mm, width of 12 mm, and length of 120 m, with a span of 64 mm. Result is··,
Engineering, shown in Shishi 5. .

35- Table 5 (blank below) 36- Example 12. Comparative Example 3 107.2 parts of benzophenone-3,3',4,4'-te]-racarboxylic dianhydride and 5-norbornene-2
, 321 parts of methyl alcohol was added to 82.0 parts of 3-dicarboxylic anhydride, and the mixture was heated under reflux for 3 hours to form a solution.

In the methyl alcohol solution thus obtained, 3.3'-
Dimethyl-4,4'-diaminodiphenylmethane 13
1.8 parts were added and dissolved to obtain a methyl alcohol solution of the oligoimide precursor. Here, a predetermined amount of triallylisocyanurate was added and dissolved.

Then, for the purpose of evaluating the fluidity of the oligoimide, a portion of this solution was placed in an oven, heated and dried in the same manner as in Example 1, and the temperature at which the oligoimide began to flow was determined using a flow tester. The results are shown in Table 6.

(The following is a blank space) Table 6 (The following is a blank space) Next, the carbon region Ifl is impregnated with the methanonyl solution containing the oligoimide precursor as in Example 1.
The glass transition temperature was measured by forming at 75° C. and by 4:2 ringing at 300″C.

The oligoimide of Example 12 had a glass transition temperature of 400
It was found that a molded piece with good heat resistance at ℃ could be obtained.

On the other hand, the molded piece of oligoimide of Comparative Example 3 blistered during curing, resulting in a molded piece with voids (7%), and as a result, it was found that the oligoimide of Comparative Example 3 had poor moldability. For reference, Table 7 shows the measurement results of the glass transition point of the molded piece immediately after molding.

Table 7 From Table 7, the curing reactivity of oligoimide is Comparative Example 3...i
[Later, you can see that he is dancing.

Furthermore, it is shown that the molded piece of oligoimide of Example 1 may be cured suddenly at 300°C.

Comparative Example 4 134.4 parts of benzophenone-3,3',4,4'-tetracarboxylic dianhydride and 5-norbornene-2,
A methyl alcohol solution of the 3-goimide precursor was obtained.

Here, a predetermined amount of triallylisocyanurate was added, and the fluidity of the oligoimide was examined in the same manner as in Example 1. The oligoimide crystallizes in the oven, with a flow onset temperature of 350
It was above ℃. Note that when triallylisocyanurate is not added, the outflow temperature is 250°C, but when triallylisocyanurate-1 is added, the fluidity becomes worse.

Example 13. Comparative Example 5 32 parts of ethyl alcohol was added to 238.4 parts of benzophenone-3,3',4,4'-tetracarboxylic dianhydride.
After adding 6 parts and heating under reflux for 3 hours, 59.8 parts of 2,4-diaminotoluene and 28.9 parts of allylamine were added and dissolved. Add and dissolve a predetermined amount of 1 to lylyl isocyanurate to the ethyl alcohol solution of the oligoimide precursor obtained here to prepare an oligoimide in the same manner as in Example 1. A piece was made and its glass transition temperature was measured to evaluate the heat resistance 1z1 of the resin.The results are shown in Table 8.

(below margin) Table 8 No molded pieces were given that could be evaluated.

Examples 14 to 18 Oligoimides were prepared in the same manner as Examples 1 to 3, except that various allyl compounds shown in Table 6 were used in predetermined amounts with respect to the oligoimide in place of triallylisodoanule-1. At the same time, a molded piece of unidirectional carbon fiber-reinforced polyimide resin was made, and its glass transition temperature was measured to evaluate the heat resistance of the resin. The results are shown in Table 91 and Table 10.

(Leaving space below) 43- Table 9 44- Table 10 Table 11 46-Example 19 (A> 107.2 parts of benzophenone-3,3', 4.II'-tetracarboxylic dianhydride and 5-norbornene-2 , 321 parts of medylal=1-l was added to 82.0 parts of 3-dicarboxylic anhydride and heated for 3 hours)! Then, 131.8 parts of 3,3'-dimethyl-4,4'-diaminodiphenylmethane were added and dissolved (the methanol solution obtained here is referred to as Solution A).

(B) 323 parts of methyl alcohol was added to 206.3 parts of benzophenone-3,3',4,4'-tetracarboxylic dianhydride, heated under reflux for 3 hours, and then 3.3'
-dimethyl-4,4' -diaminogenylmethane 88
．． 3 parts of allylamine were added and dissolved, and after cold IJ injection, 28.5 parts of allylamine was added and mixed (this solution is referred to as Solution B).

The mixing ratio of liquid A and liquid B is 2:1.1=2, respectively.
12.5 parts of triallyl isocyanurate was added to each 100 parts of this mixed solution, and the flow initiation temperature of the oligoimide was measured in the same manner as in Example 1. Also, carbon fiber reinforced resin was molded, and immediately after molding, curing was performed. The glass transition temperature of the resulting resin was evaluated.

The results are shown in Table 11.

(The following is the margin) ・,j [-47= Table 12 (The following is the margin) 48- In addition to the oligoimide having poor fluidity, this resin has
The curing speed during molding is fast, the glass transition temperature of the resin is high immediately after molding, and the resin is thin during molding.

Patent Applicant 2 [Director of the Board of Industrial Science and Technology Director-General Procedural Amendment Written Patent Application No. 59-116618 No. 2, Title of Invention Method for producing polyimide resin 3, Incident made by the person making the amendment, etc. Relationship between patent applicant's specification and patent claim "Scope of the invention" and "Detailed description of the invention"
Column (1) Ming! The scope of claims for +11 is amended as shown in the attached sheet 1J.

(2) Add the following to the third line of page 50 of the specification.

[Example 20 The procedure was carried out in the same manner as in Example 12, except that instead of triallylisocyanure-1, 1helylylisocyanurate-1~ was subjected to a heat reaction treatment at 230°C and 111% lsi to form an oligomer. Ta.

In this case, the humidity at which the oligomer starts flowing is 180°C. The glass transition point of the molded piece immediately after molding is 275°C, and the humidity is 30°C.
The polyimide cured at 0°C contained no voids and had a glass transition temperature of 400°C, which was one step higher. ” Above 17. i Q"' 1-2, Claim 1, an oligoimide having an aromatic imide bond in the main chain and an addition polymerizable group at the terminal and/or side chain is mutually dissolved with the oligoimide. 1. A method for producing a polyimide resin, which comprises heating and curing the polyimide resin in the presence of a polyfunctional allyl compound having a molecular weight of 800 or less and/or an oligomer thereof.

2. The amount of the polyfunctional allyl compound and/or its oligomer is 1/20 to 1/2 of the oligoimide.
1 (KBffi ratio), the method for producing a polyimide resin according to claim 1.

3. The addition polymerizable group has the following formula (VT) or (W)
2- Method for producing resin.

4. The polyfunctional allyl compound having a molecular m of 800 or less is selected from the group of compounds represented by the following formulas (XII) and (XIV)IG 0 0H2-C=Cf-1z IG 0082C=CI-12 The method for producing a polyimide resin according to claim 1, wherein both are one type of compound.

3- 209-

Claims (1)

[Claims] 1. It has an aromatic imide bond in the main chain, and the terminal and 2. The amount of the polyfunctional alkali compound and/or its ribomer is 1/20 that of the oligoimide. ~1/1
(Specific gravity ratio) The method for producing a polyimide resin according to claim 1. 3. The addition polymerizable group has the following formula (Vl) or (■)2
0. Method for producing polyimide resin. 4. The polyfunctional allyl compound with a molecular weight of 800 or less,
The following formulas (XT[) and (XIV)IO OCH2-C=CH2Rh. The method for producing a polyimide resin according to claim 1, wherein the polyimide resin is at least one compound selected from the group of compounds represented by OCtlz -C-Ctlz.