JPH0485329A - Polyimide resin - Google Patents

Abstract

PURPOSE:To obtain a polyimide resin which is added to a thermosetting resin to give a composition improved in mechanical strengths, heat resistance and toughness by forming a polyimide resin having specified repeating CONSTITUTION:This polyimide resin comprises repeating units of formula I (wherein A is an aromatic residue; and B is a residue of a compound of formula II or III) and has a number-average molecular weight in the range of 3000-30000. Examples of A include one or more residues of aromatic diamines. This resin is used in an amount of about 10-100 pts.wt. per 100 pts.wt. thermosetting resin.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to polyimide resins.

[Conventional technology]

Conventionally, polyimide resins with relatively small molecular weights have been known (Japanese Patent Application Laid-Open No. 62-264631), and they have been used to improve the adhesion of epoxy resins at high temperatures.

In recent years, the uses of thermosetting resins such as epoxy resins have expanded, and more and more applications are requiring high toughness as structural materials.

[Problem to be solved by the invention]

However, in conventionally known polyimide resins,
In terms of increasing the toughness of the thermosetting resin (1), it was not necessarily satisfactory.

An object of the present invention is to provide a new polyimide resin suitable for improving the toughness of thermosetting resins such as epoxy resins.

[Means to solve the problem]

That is, the present invention has a repeating structural unit represented by the following formula (I), and has a number average molecular weight of 3.000 to 30.000.
provides polyimide resins.

Ichinen A-B+-(1) (In the above formula, A is an aromatic residue, B is the following formula (II) and /
Or a compound represented by formula (II[). )/ Hereinafter, the present invention will be explained in detail.

In the polyimide resin of the present invention, A in the above formula (I)
is a mononuclear or polynuclear divalent aromatic residue, and the aromatic ring includes those substituted with a lower alkyl group, halogen, lower alkoxy group, etc., and those unsubstituted. Specifically, A is one or two residues of aromatic diamine.
More than one species can be mentioned.

Examples of the aromatic amines include 4,4°-diaminodiphenylmethane, 3,
3°-diaminodiphenylmethane, 4.4'-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4°-diaminodiphenylpropane, 4.4
'-diaminodiphenylsulfone, 3.3°-diaminodiphenylsulfone, 2,4-toluenediamine,
2.6-Toluenediamine, m-phenylenediamine p
-phenylenecyamine, benzidine, 4,4'-diaminodiphenylsulfide, 3,3'-dichloro-4,
4°-diaminodiphenyl sulfone, 3,3'-dichloro-4,4°-diaminodiphenylpropane, 3,3
°-dimethyl-4,4゛-diaminodiphenylmethane,
4,4°-methylene-bis(2,6-dimethylaniline), 4,4'-methylene-bis-(2-methyl-6-
nitylaniline), 4,4'methylene-bis-(2,
6-dinitylaniline), 3°3°-dimethoxy-44
'-diaminobiphenyl, 3゜3''-dimethyl-4,4
°-diaminobiphenyl, ■, 3-bis(4-aminophenoxy)benzene, L, 3-bis(3-aminophenoxy)hensen, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis( 4-aminophenoxyphenyl)propane, 4,4'-bis(4-aminophenoxy)diphenylsulfone, 4,4'-bis(3-aminophenoxy)diphenylsulfone, α, α゛ -
Bis(4-aminophenyl)-m-diisopropylbenzene, α,α-bis(4-aminophenyl)-p-diisopropylbenzene, α,α゛-bis(4-amino-
3-methyl)-m-diisopropylbenzene, α, α-
Bis(4-amino-3-methyl)-p-diisopropylbenzene, α, α° -bis(4-amino-3°5-dimethylphenyl)-m-diisopropylbenzene, α,
α° -bis(4-amino-3,5-dimethylphenyl)-T)-diisopropylbenzene, 9.9′-bis(
4-aminophenyl)fluorene, 3゜3゛-dicarboxy-4,4゜-diaminodiphenylmethane, 2,4゛-diaminoanisole, bis(3-aminophenyl)methylphosphine oxide, 3,3 diaminobenzophenone, oh-luidine sulfone, 4,4°-methylene-bis-chloroaniline, tetrachlorodiaminodiphenylmethane, m-xylylenediamine, p-xylylenediamine, 4,4°-diaminostilbene, 5-amino-1 -(4'aminophenyl-1,3,3-)limethylindane, 6-amino-1-(4°-aminophenyl)-1,3,3-trimethylindane, 5-amino-6-methyl-I -(3'-amino-4'-methylphenyl)-1,3,3-trimethylindane, 7-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3, 3-trimethylindane, 6-
Amino-5-methyl-1-(4'-amino-3'~
methylphenyl)-1,3,3-)limethylindane,
6-Amino-2-methyl-1-(4°-amino-3′-methylphenyl)-1,3,3-trimethylindan, ~10), in the range of ~20,000.

The polyimide resin (I) of the present invention can be synthesized by performing a conventional imidization reaction with the above-mentioned aromatic cyamine and a compound represented by the following formula (IV) and/or (V).

Examples include one or more of polydimethylsiloxane containing amino groups at both ends, polymethylphenylsiloxane oligomer containing amino groups at both ends, and the like.

The number average molecular weight of the polyimide resin of the present invention is 3.000 to 30.000, preferably 5.000 in order to improve handling properties and toughness of thermosetting resins, such as epoxy resins.The molecular weight is adjusted by the charging molar ratio. Therefore, the charging molar ratio may be appropriately determined so as to obtain a polyimide resin having a desired molecular weight.

Hereinafter, the compounds represented by the above formulas (IV) and (V) are
1, and its isomers are designated as the X component and Y component, respectively.

B1 can be synthesized by known methods such as those disclosed in JP-A-63-93784 and JP-A-63-277667. For example, it is obtained by reacting α-methylstyrene and maleic anhydride at a molar ratio of 1:2 in the absence of a radical polymerization catalyst and in the presence or absence of a radical polymerization inhibitor.

In the synthesis of the polyimide, formulas (rV) and (V)
You may use together the acid anhydride shown by and some aromatic tetracarphonic acid anhydrides. There are no particular limitations on the tetracarboxylic anhydride that is preferably used in combination, and tetracarboxylic anhydrides, which are common raw materials for polyimide, are used.

For example, pyromellitic acid, 3,3°, 4,4'-
Benzophenonetetracarboxylic acid, 2.3.6.7 naphthalenetetracarboxylic acid, 3.3', 4.4°-biphenyltetracarboxylic acid, 1.2.5.6-naphthalenetetracarboxylic acid, 2,2°, 3.3'-biphenyltetracarboxylic acid, 3.4.9.10-pyrenetetracarboxylic acid, 2゜2-bis(3,4-dicarboxyphenyl)propane, 2.2-bis[4-(2, 3-dicarboxyphenoxy)phenyl]propane, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]
Examples include propane, bis(3,4-dicarboxyphenoxy)diphenylsulfone, and tetracarphonic acid anhydrides such as 1,4-his(2,3-dicarboxyphenoxy)benzene, and one or two of these The above can be used.

The polyimide resin of the present invention is generally used by being added to a thermosetting resin to improve physical properties such as toughness, and the quantitative ratio is that the polyimide resin of the present invention is added to 100 parts by weight of the thermosetting resin. 10 to 100 parts by weight of resin, preferably 20 parts by weight
~80 parts by weight. If it is less than 10 parts by weight, the effect of improving toughness will not be significant, and if it exceeds 100 parts by weight, operability, processability, etc. tend to deteriorate.

Examples of thermosetting resins include epoxy resins, bismaleimide resins, cyanate resins, unsaturated polyester resins, melamine resins, phenol resins, urethane resins, etc., and they can be used alone or in combination of two or more. .

To give an example of an epoxy resin, it is a compound that has two or more epoxy groups in its molecule, and it has two or more epoxy groups to improve flexibility.
The functional type is superior, and the polyfunctional type having three or more epoxy groups is superior in terms of heat resistance, and in the present invention, one or more of these are used.

Examples of epoxy resins having two epoxy groups in the molecule include dihydric phenols such as bisphenol A, bisphenol F, bisphenol AD, hydroquinone, and resorcinol, or dihydric phenols derived from halogenated bisphenols such as tetrabromobisphenol A. Glycidyl ether compounds, glycidyl ester compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, and isophthalic acid; 5.
Hydantoin-based epoxy resin derived from 5-dimethylhydantoin etc., 2,2-bis(3,4-epoxycyclobexyl)propane, 2,2-bis(4-(2,3
-Epoxypropyl)cyclohexyl]propane, vinylcyclohexene dioxide, cyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and other N, N
- diglycidylaniline and the like, but are not limited to these.

In addition, examples of epoxy resins having three or more epoxy groups per molecule include p-aminephenol, m-aminophenol, 4-amino-m-cresol, 6-amino-m-cresol, and 4,4-diaminodiphenylmethane. , 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)
Benzene, 1,4-bis(3-aminophenoxybenzene, l,3-bis(4-aminophenoxybenzene, 1
．． 3-bis(3-aminophenoxybenzene, 2,2-
Bis(4-aminophenoxyphenyl)propane, p-
phenylenediamine, m-phenylenediamine, 2,4
-Toluenediamine, 2.6-Toluenediamine, p-
Xylylene diamine, m-xylylene diamine, 1゜4
-Amine-based epoxy resin derived from cyclohexane-bis(methylamine), 1゜3-cyclohexane-bis(methylamine), etc., phenol, 0-cresol,
Novolak epoxy resin derived from novolak resin, which is a reaction product of phenols such as m-cresol and p-cresol and formaldehyde, phloroglycine, tris-(4-hydroxyphenyl)methane, 1.1
．． 2. Glycidyl ether compounds derived from trivalent or higher phenols such as 2-tetrakis(4-hydroxyphenyl)ethane, bis[α-(dihydroxyphenyl)-α-methylethyl]benzene, and other triglycidyl isocyanurates , 2,4.6-triglycidyl-
Examples include, but are not limited to, S-triazine, rubber thereof, and urethane-modified compounds.

Furthermore, examples of the epoxy curing agent include amine curing agents such as the above-mentioned aromatic amines and aliphatic amines, polyphenol compounds such as phenol novolac and talesol novolac, and further acid anhydrides, dicyandiamide, hydrazide compounds, and the like. The ratio of epoxy resin and curing agent is usually that the active hydrogen of the curing agent is 0 per mole of epoxy group.
．． It is blended so that the amount is 5 to 1.5 moles.

Furthermore, a curing accelerator can be added if necessary. For example, curing accelerators include amines such as hensyldimethylamine, 2,4.6-tris(dimethylaminomethyl)phenol, 1,8-diazabicycloundecene, and 2-ethyl-4-methylimidazole. imidazole compounds, boron trifluoride amine complexes, etc.

Examples of the cyanate resin include polyfunctional cyanate esters having two or more cyanato groups, and suitable cyanate esters have the general formula % (1) [where m is 2 or more, usually 5 or less]. R is an integer, and R is an aromatic organic group, and the cyanate ester group is bonded to the aromatic ring of the organic group R. ] It is a compound represented by A specific example is 1.3
- or 1.4-dicyanatobenzene, 1.3.5-tricyanatobenzene, 1.3-1.4-1■, 6, l,
8-12,6- or 2,7-dicyanatonaphthalene,
1,3.6-tricyanatonaphthalene, 4,4°-diaminobiphenyl, bis(4-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane,
2,2-bis(3,5-dichloro-4-cyanatophenylpropane, 2,2-bis(3,5-dibromo-4-cyanatophenyl)propane, bis(cyanatophenyl)
Ether, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, tris(4
-cyanatophenyl) phosphite, tris(4-cyanatophenyl) phosphate, and cyanic acid esters obtained by the reaction of novolacs with cyanogen halides. In addition to these, Tokuko Sho 41-1928, Tokko Sho 44-4791, Tokko Sho 45-11712, Tokko Sho 4
Cyanic acid esters described in JP-A No. 6-41112 and JP-A-51-63149 can also be used.

In addition, as a polymaleimide resin, [wherein R is an aromatic or alicyclic organic group having a valence of 2 or more and usually a valence of 5 or less, Xl and X2 are elemental, halogen, or an alkyl group, and n2 to It is an integer of 5. A bismaleimide resin of the following formula, where R is preferably a divalent group, is preferred.

The bismaleimide resin has the following general formula (X'
, R are the same as above. ).

In the formula, R is cyclohexylene, phenylene, 4-
Methyl-1,3-phenylene, 2-methyl-1,3-phenylene, 5-methyl-1,3-phenylene, 2,5
-diethyl-3-methyl-1,4-phenylene, or the following formula (a) (wherein, T represents a mere valence bond or the following group, Y may be the same or different, each Represents a hydrogen atom, methyl, ethyl or isopropyl group.)
etc., and examples of XX2 include hydrogen, methyl, ethyl, propyl and the like.

The maleimide resin represented by the above formula can be prepared by a known method such as preparing maleamic acid by reacting an acid anhydride corresponding to the above formula such as maleic anhydride with diamines corresponding to the above formula, and then dehydrating and cyclizing the maleamic acid. It can be manufactured by the method. The diamines used are preferably aromatic diamines in terms of heat resistance of the final resin, but if flexibility and flexibility of the resin are desired, ring group amines may be used alone or in combination. Furthermore, it is particularly desirable that the diamines be primary amines in terms of reactivity, but secondary amines can also be used. Suitable amines include meta or paraphenylenediamine, meta or paraxylylenediamine, 1,4- or 1,3-cyclohexanediamine, hexahydroxylylenediamine, 4,4°-diaminobiphenyl, bis(4-amino phenyl)methane, bis(4-aminophenyl)ether, bis(4-aminophenyl)sulfone, bis(4-amino-3methylphenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane, bis( 4-aminophenyl)cyclohexane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-amino-3-methylphenyl)propane, 2,2-bis(3,5-dibromo-4 -aminophenyl)propane, bis(4-aminophenyl)
Phenylmethane, 3,4-diaminophenyl-4'-aminophenylmethane, 1,1-bis(4-aminophenyl)-1-phenylethane, hexamethylene diamine,
Dodecamethylenecyamine, ethylenediaminehexicine, 3,3'-dimethyl-4,4°-diaminobifeninope 3,3'-dichlorobenzidine, 3,3°-dimethoxybenzidine, 1,1-bis(4- aminophenyl)ethane, 2,2-bis(4-aminophenyl)propane,
2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)-1,3
-dichloro-1,1,3,3-tetrafluoropropane, 4,4'-diaminodiphenyl ether, 4,4°-
Diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzofunone, 4,4'-
Diaminobenzophenone, 3,4'-diaminobenzophenone, N, N'-bis(4-aminophenyl)aniline, N.

N-bis(4-aminophenyl)methylamine, N,
N'-bis(4-aminophenyl)-n-butylamine, N,N'-bis(4-aminophenyl)amine,
m-Aminohensyl-p-aminoanilide 4-aminophenyl-3-aminohenzoate, 4,4'-diaminoazobenzene, 3,3"-diaminoazobenzene, bis(3-aminophenyl)cynitranan, bis(4 −
aminophenyl) phenylphosphine oxide, bis(4-aminophenyl)ethylphosphine oxide,
1.5-diaminonaphthalene, 2,6-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, m-xylylenediamine, p-xylylenediamine,
24 (p-β-amino-tertiary butylphenyl)ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)hensen , hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenecyamine, 2,11-diaminododecane, 1,12-diaminooctadecane, 2
, 2-dimethylpropylenediamine, 2,5-dimethylhexamethylenediamine, 3-methylhexamethylenecyamine, 2,5-dimethylhexamethylenecyamine, 4
゜4-dimethylhebutamethylenediamine, 5-methynonamethylenediamine, 1,4-diaminocyclohexane,
Bis(p-aminocyclohexyl)methane, 3-methoxyhexamethylenecyamine, 1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl)sulfide, N, N'-bis(3-aminopropyl) ) Methylamine etc. are exemplified.

Specific examples of typical bismaleimide resins include: N, N'-m-phenylene hismaleimide, N, N'-p-phenylene hismaleimide, N, N
'-4,4°-diphenylmethane bismaleimide, N
, N'-4,4'-diphenylmethane bismaleimide, N, N'-4,4°-diphenylsulfone bismaleimide, N, N'-1,4'-cyclohexylene bismaleimide, N, N'-4, 4°-diphenyl-1,1-cyclohexane bismaleimide, N, N
'-4,4'-diphenyl-2゜2-propane bismaleimide, N, N'-4,4'-triphenylmethane bismaleimide, N, N'-2-methyl-1,3-phenylene hismaleimide, N, N'-4 methyl-1,3
- Phenylene bismaleimide,\.

N"-5-methyl-1,3-phenylene hismaleimide, N, N'-ethylene bismaleimide, \, N°-hexamethylene bismaleimide, N, N'-h decamethylene bismaleimide, and the like.

In particular, N, N' = 4.4'-diphenylmethanehismaleimide alone or together with N, N' 2-methyl-1
, 3-phenylenebismaleimide, N,N'-4-methyl-1,3-phenylenebismaleimide and/or mixtures with N,N'-5-methyl-1,3-phenylenebismaleimide are preferred.

Moreover, these maleimide resins can also be used in the form of prepolymers instead of in the form of monomers.

In addition, bismaleimide resin is N-allyl-maleimide,
It may be substituted with a monomaleimide compound such as N-propyl-maleimide, N-hexyl-maleimide, N-phenyl-maleimide, etc. up to about 40 wt%.

Further, these maleimide resins may be modified with diamines, bis-orthoallyl phenols, bis-orthoallyl alkenyl phenyl ethers, or epoxy resins.

Examples of diamines used in the production of amine-modified maleimide resins include the diamines described above. Examples of modified bismaleimide resins include Japanese Patent Publication No. 63-39614
An example is the one described in the above publication.

In addition, as an etherimide resin, JP-A-63-291
An example is an addition type etherimide resin described in Japanese Patent No. 919.

For example, as an etherimide resin, the following general formula [wherein R, -R, are hydrogen, lower alkyl, lower alkoxy,
Halogen, R5 and R6 are hydrogen, methyl, ethyl, trifluoromethyl, trichloromethyl, D 1. Dr represents an organic group having 2 to 24 carbon atoms. ].

Further, addition reaction products of the above-mentioned etherimide resin with amine compounds, phenol compounds and/or thiocol compounds, and copolymers with compounds having polymerizable functional groups can also be used.

Further, an ether compound having one addition type imide group and - amino groups at the terminal may be used in combination with the above-mentioned etherimide resin.

Alternatively, etherimide resins modified with cyamines, bis-orthoallylphenols, bis-orthoallyl alkenyl phenyl ethers, or epoxy resins may be used.

Further, an addition reaction product of the above addition type etherimide resin and an amine compound can also be used.

Such amine compounds include the diamines mentioned above, 2,4-diaminodiphenylamine, 2゜4-diamino-5-methyl-diphenylamine, 2,4-diamino-4'-methyl-diphenylamine, 1-anilino-
2,4-diaminonaphthalene, 3,3°-diamino-4
-N-aryl substituted aromatic triamines such as -anilinobenzophenone are exemplified.

Note that these amine compounds may be used in combination.

In addition, conventionally known carboxylic dianhydrides can also be used in combination.

In addition, the resin of the present invention and the known formula below, CH3 [In the formula, X is a direct bond, -CH2--N=N-.

] Bis-orthoallylphenols represented by these may be combined. Specifically, the following are exemplified.

In addition, depending on the purpose of use, the resin composition containing the polyimide resin of the present invention may be mixed with particulate materials such as talc, mica, calcium carbonate, alumina hydrate, silicon carbide, carbon black, and silica. It is effective for improving handling properties and handling.

A resin composition whose toughness has been improved by the polyimide resin of the present invention is suitable as a matrix resin for fiber-reinforced composite materials.

In the prepreg made of a thermosetting tree containing the polyimide resin of the present invention, fibers used as reinforcing materials include carbon fiber, graphite fiber, glass fiber, silicon carbide fiber, alumina fiber, titania fiber, and aromatic polyamide fiber. Examples include organic fibers and inorganic fibers such as aromatic polyester fibers, polybenzimidazole fibers, etc., but are not limited to these. In particular, in order to provide a composite material with excellent toughness, the prepreg must have a tensile strength of 50k.
Fibers with a g/mm 2 or more and an elastic modulus of 5 t/mm 2 or more are preferable. In addition, depending on the purpose of use, it is also possible to use two or more types of fibers or fibers with different shapes.

Furthermore, in addition to reinforcing fibers, mixing granular materials such as talc, mica, calcium carbonate, alumina hydrate, silicon carbide, carbon black, and silica improves the viscosity of the resin composition and makes it easier to mold the composite material. It is also effective for improving the physical properties of the resulting composite material, such as compressive strength.

As a method for manufacturing the prepreg, for example, a conventionally known manufacturing method using an epoxy resin as a matrix can be adopted.

The resin content of the prepreg is generally 20 to 90% by volume.
, particularly preferably 25 to 70% by volume. A fiber-reinforced composite material can be obtained by forming these prepregs into a desired shape by stacking or winding them, and then heating and pressurizing them.

〔Effect of the invention〕

The polyimide resin according to the present invention is suitable for adding to a thermosetting resin to obtain a cured thermosetting resin having excellent mechanical strength, heat resistance, and toughness.

〔Example〕

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

In addition, as raw materials for the synthesis of the imide-based polymer, the following were synthesized and used using the exemplified production method.

In addition, the quantity ratio of the X component and the Y component is l in this example.
: o, 6 was used. Hereinafter, this mixture of component X and component Y will be referred to as ASM.

Further, the number average molecular weight of the obtained product was determined by gel permeation chromatography (hereinafter abbreviated as GPC). The columns are Showa Denko AD-805/S and A.
D-803/S was connected and used, a DMF solution of LiBr with 0 and 1 mol/1 of O was used as a solvent, and a standard substance was used as Example I. It was equipped with a stirrer, a thermometer, a cooling condenser, and a Dean Stark water plate device. 41.05 g (0.1 mol) of 2,2-bis(4-aminephenoxyphenyl)propane, 28 mixed cresol in a 5001rtl four-way flask
0g was charged, heated to 70°C under nitrogen atmosphere, and dissolved.
31.42 g (0.1 mol) of ASM was added over several minutes, and the mixture was kept at the same temperature for 4 hours after the addition. After keeping warm, 110g of xylene was charged, the temperature was raised to 160-170℃, and 1
It was azeotropically dehydrated for 4 hours. The amount of distilled water was 3.3 g.

After distilling off the xylene at 180°C, it was cooled to room temperature, and the resin liquid was mixed with methyl alcohol 14001r! When added dropwise to the solution under high speed stirring, a precipitate was obtained. This precipitate was filtered, washed three times with 500 ml of methyl alcohol, and further stirred and washed with 500 ml of methyl alcohol under reflux for 1 hour. The precipitate was filtered, washed with 1001 d of methyl alcohol, filtered, and dried under reduced pressure at 80°C to obtain a powder product 64.2
I got g. As measured by GPC, the number average molecular weight of the obtained product was 9.200. ) The reaction was carried out in exactly the same manner as in Example 1 except for changing to white powder 5.
3.0 g was obtained. The number average molecular weight of the product determined by GPC was 6.400.

Example 3 In Example 1, 41.05 g (0.1 mol) of 2,2-bis(4-aminophenoxyphenyl)propane was replaced with 19.83 4,4°-diaminodiphenylmethane.
The reaction was carried out in exactly the same manner as in Example 1, except that 70.5 g of powdered product was used, except that 70.5 g of powder was used. From the measurement by GPC, the number average molecular weight of the polymer was 7.700.
Met.

Example 4 In Example 1, 41.05 g (0.1 mol) of 2,2-bis(4-aminophenoxyphenyl)propane
The reaction was carried out in exactly the same manner as in Example 1, except that 30.92 g (0,106 mol) of 1,4-bis(4-aminophenoxy)benzene was used instead of 1,4-bis(4-aminophenoxy)benzene, and a powder product of 55.
6g was obtained. As measured by GPC, the number average molecular weight of the polymer was 7.000.

Example 5 In a 500-four-loaf flask equipped with a stirrer, a thermometer, a cooling condenser, and a Dean-Stark water plate apparatus, α,
α゛-bis(4-amino-3,5-dimethylphenyl)
-p-diisopropylbenzene, 100.2g (0,
250 mol) and 119 g of N-methylpyrrolidone were charged, the temperature was raised to 70°C under a nitrogen atmosphere, and dissolved, and 78.55 g (0,250 mol) of ASM was added over -hours.
After the addition, the mixture was kept at the same temperature for 2 hours. 48g xylene after keeping warm
was charged, heated to 160°C to 170°C, and azeotropically dehydrated for 60 hours. The amount of distilled water was 19.4 g. 18
After xylene distillation at 0°C, 596 g of N-methylpyrrolidone
was charged, cooled to room temperature, and this resin liquid was added dropwise to methyl alcohol 1.8j7 under high speed stirring to obtain a precipitate. After washing twice with 4.51 ml of methyl alcohol, stirring washing was further performed with 2.51 ml of methyl alcohol under reflux for 1 hour. After washing and filtering with 1.01 ml of methyl alcohol, the product was dried under reduced pressure at 90°C to obtain 159.1 g of a powder product. The number average molecular weight of the obtained product was 7.500.

Example 6 In Example 5, α,α°-bis(4-amino-3,
120 g of α,α°-bis(4-aminophenyl)-m-diisopropylbenzene instead of 100.2 g of 5'-dimethylphenyl)-m-diisopropylbenzene,
6 g (0.35 mol), N-methylpyrrolidone 122
g to 154g, A S M 78.55g (0,2
50 mol) was changed to 109°97 g (0,350 mol) to obtain a powder product of 204.7 g.
I got g. As measured by GPC, the number average molecular weight of the polymer was 9,600.

Comparative Example 1 In Example 1, the amount of 2,2-bis(4-aminophenoxyphenyl)propane charged was 41.05 g (0,
1 mole) to 59. The reaction was carried out in exactly the same manner as in Example 1, except that the amount was changed to 11 g (0,144 mol), and 66.1 g of white powder was obtained. The number average molecular weight of the product determined by GPC was 2.000.

Reference Examples 1 to 7 and Comparative Reference Examples 1 to 4 Among the components of the resin composition shown in Table 4, components other than the curing agent were kneaded at 120 to 150°C for 30 minutes to 1 hour while degassing under reduced pressure to obtain a uniformly transparent product. A resin composition was obtained.

Next, the temperature is lowered to 60-80℃, a hardening agent is added, and the temperature is lowered to 60-80℃.
A resin composition was obtained by kneading at 80°C. 1 of the resin composition
It was cured at 80° C. for 2 hours and its performance was evaluated. The evaluation results are shown in Table 2.

The physical properties were measured as follows.

(1) The boiling water absorption rate of the obtained cured epoxy resin plate was determined after immersion in boiling water for 48 hours.

(2) The glass transition temperature (T g ) was defined as the peak temperature of loss modulus measured by dynamic viscoelasticity measurement.

(3) Bending strength, bending modulus and bending strain at break are JIS
Compliant with K-6911.

(4) Strain energy release rate was based on ASTM E-399.

The contents of each component shown in Table 1 are shown below.

・ELM434---Tetraglycidyldiaminodiphenylmethane [Sumitomo Chemical (ready-made Sumiepoxy E)
LM434E ・ELMloo... Triglycidyl-4-amino-m-resol [Sumitomo Chemical (ready made Sumiepoxy ■ELM100) ・εPICLON830°-diglycidyl bisphenol F [EPICLON 830 manufactured by Inu Nippon Ink ■]・
3,3°DDS-”-3,3°-diaminodiphenylsulfone [Mitsui Toatsu Chemical Industries (immediately manufactured)] ・4,4°DDS-・-4,4'diaminodiphenylsulfone [Sumitomo Chemical Co., Ltd. ■Made by Sumicure ■S]・Polymer A・・Imide-based polymer of Example 1・Polymer B・
・Imide polymer of Example 2 Polymer C° ・Imide polymer of Example 3 Polymer D° ・Example 4
Imide polymer/Polymer E-...Imide polymer/Polymer F of Example 5/Imide polymer/Polymer G of Example 6...Polymer/Polymer H of Comparative Example 1/Manufactured by ICI Polyether sulfone 50
03P

Claims (1)

[Scope of Claims] A polyimide resin having repeating structural units represented by the following formula (I) and having a number average molecular weight in the range of 3,000 to 30,000. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the above formula, A is an aromatic residue, and B is a compound represented by the following formula (II) and/or formula (III).)▲Mathematical formula , chemical formulas, tables, etc. ▼ (II) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (III)