JPH04110324A - Polyimidephenoxy resin - Google Patents

Abstract

PURPOSE:To prepare the title resin which, when added to a thermoset resin, gives a cured article excellent in mechanical strengths. heat resistance, and toughness by selecting the title resin having two or more kinds of specific structural units and a specified number average mol.wt. CONSTITUTION:The title resin having repeating structural units of formula I (wherein A and R are each an arom. residue; B is a divalent group of formula II and/or III; and n is 4-75), repeating structural units of formula IV (wherein R1 is R), and a number average mol.wt. of 3000-30000 is selected.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to polyimide phenoxy resins.

[Prior Art] ``Conventionally, polyimide resins with relatively small molecular weights have been known (Japanese Patent Application Laid-Open No. 62-264631). It is used.

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,
The results were not necessarily satisfactory in terms of increasing the toughness of thermosetting resins.

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

[Means to solve the problem]

That is, the present invention has repeating structural units represented by the following formulas (I) and (IV), and has a number average molecular weight of 3.0.
It is an object of the present invention to provide a polyimide phenoxy resin having a molecular weight ranging from 0.00 to 30.000.

云0−R6B −A +′TB−R−〇升 (I)(
In the above formula, A and R are aromatic residues, B is a divalent group represented by the following formula (II) and/or formula (1), and n is 4
It is an integer between ~75. ) (R1 represents an aromatic residue) The present invention will be described in detail below.

A and R in the above formula (I) of the polyimide phenoxy resin of the present invention are mononuclear or polynuclear divalent aromatic residues,
The aromatic ring includes those substituted with an alkyl group having 1 to 5 carbon atoms, halogen, an alkoxy group having 1 to 5 carbon atoms, and unsubstituted ones. Specifically, A can include one or more aromatic diamine residues, and R can include aromatic amine phenol residues.

To illustrate the aromatic diamine A, 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-phenylenediamine, benzidine, 4,4'-diaminodiphenylsulfite, 3,3°-dichloro-4,4'-diaminodiphenylsulfone, 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-4°4'-diaminobiphenyl, 3 , 3"-dimethyl-4,4"-diaminobiphenyl, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, ■, 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゛-bis4-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)-p-diisopropylbenzene, 9.9'-bis(4-aminophenyl)fluorene, 3.3'-dicarboxy-4°4°-diaminodiphenylmethane, 2,4- Diaminoanisole, bis(3-aminophenyl)methylphosphine oxide, 3,3'-diaminobenzophenone, 0-toluidine sulfone, 4,4'-methylene-bis-chloroaniline, tetrachlorodiaminodiphenylmethane, m-xylylene di amine, p-xylylenediamine,
4.4'-diaminostilbene, 5-amino-1-(4
°-aminophenyl-1,3,3-1-limethylindane, 6-amino-1-(4′-aminophenyl)-1,
3,3-trimethylindane, 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl) -L
3.3-) Limethylindane, 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-trimethylindane, 6-amino-2-methyl-1-(4°-amino-3'-methylphenyl)-1,3°3-trimethylindane, ~10), polyamide containing amino groups at both ends Examples include one or more of dimethylsiloxane, polymethylphenylsiloxane oligomer containing amino groups at both ends.

To illustrate the aromatic aminophenol R, p
Examples include mononuclear aminophenols such as -aminophenol and m-aminophenol, and polynuclear aminophenols such as 2-(4-aminophenyl)-2-(4°-hydroxyphenyl)-propane.

The terminal phenolimide oligomer having the formula (I) as the main chain of the polyimide phenoxy resin of the present invention can be produced by combining the above-mentioned aromatic diamine and aromatic aminophenol with the following formula (V).
And/or it can be synthesized from a compound represented by formula (VI) by imidization reaction. The molecular weight of the terminal phenolimide oligomer can be easily adjusted by adjusting the molar ratio of the feed.

The compounds of the above formulas (V) and (VI) are prepared by combining α-methylstyrene and maleic anhydride in 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. Obtained by reacting below. In the synthesis of the imide oligomer, the acid anhydrides represented by formulas (V) and (VI) and some aromatic tetracarboxylic acid anhydrides may be used in combination.

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.

Examples include 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 dianhydrides of tetracarboxylic acids such as propane, bis(3,4-dicarboxyphenoxy)diphenylsulfone, and 1,4-bis(2,3-dicarboxyphenoxy)benzene. More than one species can be used.

Further, the above formula (IV) is a repeating unit having a structure in which the epoxy ring of the terminal epoxy compound is opened, and the number average molecular weight of the trifunctional epoxy resin used therein is 190 to 4.
．． 000 is preferred, and 600 to 2.000 is particularly preferred.

R2 (R2 here is an alkyl group having 1 to 3 carbon atoms.) Specifically, it is an epoxy resin having two epoxy groups in the molecule, such as bisphenol A1 bisphenol F1 bisphenol AD.

Diglycidyl ether compounds derived from dihydric phenols such as hydroquinone and resorcinol, or halogenated bisphenols such as tetrabromobisphenol A, and the above-mentioned epoxy resins are combined with bisphenol A1, bisphenol F1, bisphenol AD, hydroquinone, resorcinol, etc. Examples include terminal epoxy resins modified with functional phenols or halogenated bisphenols such as tetrabromobisphenol A.

The polyimidophenoxy resin of the present invention can be synthesized by subjecting the above terminal epoxy compound and a terminal phenolimide oligomer having the main chain of formula (I) to a conventional phenoxy resin reaction.

Although the viscosity of the copolymer composition can be lowered as the content of the component represented by formula (IV) increases, the glass transition temperature is lowered, so it is preferably 30 to 80% by weight of the entire copolymer composition.

The number average molecular weight of the polyimide phenoxy resin of the present invention needs to be in the range of 3.000 to 30.000 in order to simultaneously satisfy the handleability and toughness of the resin composition. Furthermore, 5.000 to 20.00
A polymer having a number average molecular weight of 0 is preferable because it satisfies handleability and toughness of the cured product.

The polyimide phenoxy resin of the present invention is generally used by being added to a thermosetting resin in order to improve physical properties such as toughness, and the quantitative ratio is as follows: The amount of the polyimide resin is 10 to 100 parts by weight, preferably 20 to 80 parts by weight.

If the amount is less than 10 parts by weight, sufficient toughness will not be achieved.

Moreover, if it exceeds 100 parts by weight, the viscosity of the thermosetting resin composition becomes too high, resulting in poor handling and processability. In particular, when processing prepreg for fiber-reinforced composite materials, there is a problem that it is difficult to impregnate the fibers, and the prepreg produced by impregnating the fibers with an epoxy composition has poor drapability.
Problems arise such as loss of tackiness and difficulty in forming into a predetermined shape.

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 A1 bisphenol-M'l-nol F, bisphenol AD, and hydroquinone resorcinol, or halogenated bisphenols such as tetrabromobisphenol A. derived diglycidyl ether compound, p-oxybenzoic acid,
Glycidyl ester compounds derived from aromatic carboxylic acids such as m-oxybenzoic acid, terephthalic acid, and isophthalic acid, hydantoin epoxy resins derived from 5,5-dimethylhydantoin, etc., 2,2-bis(3, 4
-epoxycyclohexyl)propane, 2,2-bisC
4-(2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexene dioxide, 3.4-
Alicyclic epoxy resins such as epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate,
Other examples include N,N-diglycidylaniline, but are not limited thereto.

In addition, examples of epoxy resins having three or more epoxy groups per molecule include p-aminophenol, m-aminophenol, 4-amino-m-cresol, 6-amino-m-cresol, and 4,4'-diaminophenol. diphenylmethane, 3,3′-diaminodiphenylmethane, 4,4”-
Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene,
2,2-bis(4-aminophenoxyphenyl)propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-)luenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-Cyclohexane-bis(methylamine')
, amine-based epoxy resin derived from 1,3-cyclohexane-bis(methylamine), etc., phenol, 0-
Novolac epoxy resin derived from novolak resin, which is a reaction product of formaldehyde and phenols such as cresol, m-cresol, and p-cresol, 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-(dihydroxydiphenyl)-α-memethiethyl]benzene, and other triglycidyl isocyanurates. -), 2,4°6-triglycidyl-s-1 riazine, or rubbers thereof,
Examples include, but are not limited to, urethane-modified compounds.

Examples of the cyanate resin include polyfunctional cyanate esters having two or more cyanate groups, and suitable cyanate esters include -killing % formula (%) [wherein m is an integer of 2 or more and usually 5 or less] 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, 1,3-11,4-11,6-1
1,8-12,6- or 2,7-dicyanatonaphthalene, 1,3,6-) dicyanatonaphthalene, 4,4'-
Dicyanatobiphenyl, 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,
Cyanic acid esters described in Japanese Patent Publications No. 44-4791, No. 45-11712, No. 46-41112, and No. 51-63149 may also be used.

Further, as a polymaleimide resin,
Or it is an alkyl group and is an integer of n2 to 5. ] A bismaleimide resin of the following formula is preferred, where R is preferably a divalent group.

Examples of bismaleimide resins include the following:
R is 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 is a mere valence bond or the following group CH30 CHr-1-C-1-〇-1-S -, CH ]
○, and Y may be the same or different and each represents a hydrogen atom, methyl, ethyl or isopropyl group. ) etc., and Xl and X2 are hydrogen, methyl,
Examples include ethyl and propyl.

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 the heat resistance of the final resin, but if flexibility and flexibility of the resin are desired, alicyclic diamines may be used alone or in combination. . In addition, it is particularly desirable that the diamines be primary amines in terms of reactivity, but secondary amines are particularly desirable.
grade 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-aminophenyl)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, hexamethylenediamine, dodecamethylenediamine, ethylenediaminebenzidine, 3,3'-dimethyl-4,4''-diaminobiphenyl, 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'
-Diamino diphenyl sulfide, 3,3゛-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfoxide, 4,4''-diaminodiphenylsulfone, 3゜3'-diaminobenzophenone, 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-
Aminobenzoyl-p-aminoanilide, 4-aminophenyl-3-aminobenzoate, 4゜4゛-diaminoazobenzene, 3,3'-diaminoazobenzene, bis(3-aminophenyl)diethylsilane, bis(4-amino phenyl) phenylphosphine oxide, bis(
4-aminophenyl)ethylphosphine oxide, 1
, 5-diaminonaphthalene, 2,6-diamitupyridine, 2,5-diamino-1,3,4-oxadiazole,
m-xylylene diamine, p-xylylene diamine, 2
, 4 (p-β-amino-tertiary butylphenyl) ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, p-nibis(1,1-dimethyl-5-aminopentyl)benzene , hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 2.11-diaminododecane, 1゜12-diaminooctadecane, 2,
2-dimethylpropylenediamine, 2,5-dimethylhexamethylenediamine, 3-methylhexamethylenediamine, 2゜5-dimethylhexamethylenediamine, 4,
4-dimethylhebutamethylenediamine, 5-methylnonamethylenediamine, 1,4-diaminocyclohexane,
Bis(p-aminocyclohexyl)methane, 3-methoxyhexamethylenediamine, 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 bismaleimide, N, N'-p-phenylene bismaleimide, N,
N'-4,4'-diphenylmethane bismaleimide,
N, N'-4,4'-diphenyl ether 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, No-4,4°-triphenylmethane bismaleimide, N, N'-2-methyl-1,3-phenylene bismaleimide, N , N'-4-methyl-1,
3-Pheny,...Nbismaleimide, N.

Examples include No-5-methyl-1,3-phenylene bismaleimide, N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-dodecamethylene bismaleimide, and the like.

In particular, N, N'-4,4°-diphenylmethane bismaleimide alone or together with N, N'-2-methyl-1,
3-phenylene bismaleimide, N, N'-4-methyl-1,3-phenylene bismaleimide and/or N
, N'-5-methyl-1,3-phenylene bismaleimide is 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 - sterilization [wherein R1-R4 are hydrogen, lower alkyl, lower alkoxy,
Halogen, R5 and R6 are hydrogen, methyl, ethyl, trifluoromethyl, trichloromethyl, DI and D2 are organic groups 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 diamines, 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.

Examples of such amine compounds include the diamines mentioned above, 2,4-diaminodiphenylamine, 2°4-diamino-5-methyl-diphenylamine, 2,4-diamino-4°-methyl-diphenylamine, and 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 well-known following formula, [wherein, X is a direct bond, -C old-1-N = N-1C
, H, CF, CH.

It is. ] Bis-orthoallylphenols represented by these may be combined. Specifically, CH3 CF3 etc. are illustrated.

The thermosetting resin containing the polyimide phenoxy resin of the present invention further uses a curing agent as necessary. In the case of epoxy resin systems, epoxy hardeners include amine hardeners such as the aromatic amines and aliphatic amines mentioned above;
Examples include polyphenol compounds such as phenol novolak and cresol novolak, as well as acid anhydrides, dicyandiamide, hydrazide compounds, and the like.

The ratio of the epoxy resin to the curing agent is such that the amount of active hydrogen in the curing agent is 0.5 to 1.5 moles per mole of epoxy group.

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

Furthermore, in other thermosetting resins, known curing agents and curing accelerators can be used as necessary.

Furthermore, depending on the purpose of use, the resin composition containing the polyimide phenoxy 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 processability and handleability.

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 an elastic modulus of 5 t/mm 2 or more are preferred. 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, 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 phenoxy 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〕

EXAMPLES Hereinafter, the present invention will be specifically explained 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 1 in this example.
0.6 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 chromatogram (hereinafter abbreviated as GPC). The columns are Showa Denko AD-805/S and AD-
803/S is connected and used as a solvent, and 0.01 mol/
A DMF solution of LiBr in No. 1 and polyethylene glycol were used as a standard substance.

Synthesis Example 1 (Synthesis of terminal phenolimide oligomer) Stirring device,
2,2-bis (4
-aminophenoxyphenyl)propane 368.8 g
(0,898 mol) N-methylpyrrolidone 1500
g, melted at 70°C under nitrogen atmosphere, and ASM
564.6 g (1,797 mol) was added in 4 portions over 1 hour, and stirring was continued for 2 hours. Add 196.1 g (1,797 mol) of meta-aminophenol, then add 5
Stirring was continued at the same temperature for a period of time. Charge 600g of xylene, raise the temperature to 180°C, and heat for 30 minutes at 160-170°C.
Azeotropically dehydrated for hours. The amount of distilled water was 97.2 g.

After xylene was distilled off at 180°C, the mixture was cooled to room temperature to obtain this terminal phenolimide oligomer resin liquid.

100 g of this resin liquid was added to 400 g of methanol to perform precipitation, and the resulting precipitate was filtered.
Washed twice at 0d.

The precipitate was filtered off and dried under reduced pressure at 80°C to obtain 37.8 g of powdered product. As measured by GPC, the number average molecular weight of the obtained product was 1200, and the phenolic hydroxyl equivalent by titration was 645 g/eq.

Example 1 500- with stirrer, thermometer and cooling condenser
In a Yotsuro flask, add bisphenol A epoxy resin (
Sumitomo Chemical Co., Ltd. Sumiepoxy ELA-128
) 74.8g, bisphenol A, 34.2g.

Charge 46.7g of methyl isobutyl ketone, 100°C
0.42 g of tributylamine was added, and stirring was continued for 2 hours under reflux.

As a result of measuring a portion of the epoxy equivalent by sampling, the epoxy equivalent was 1050 g/eq.

After cooling to room temperature, 118g of the terminal phenolimide oligomer resin liquid prepared in Synthesis Example 1 was added, the temperature was raised to 150°C and held for 3 hours, and then N-methylpyrrolidone 7
The resin liquid was diluted with 4.5 g and reacted at the same temperature for 8 hours to thicken the resin liquid to 418.7 g. The mixture was diluted with 1 g of N-methylpyrrolidone.

This resin liquid was added dropwise to 3000 d of methanol under high speed stirring to perform precipitation. Separate the precipitate by filtration and add methanol 150
Washed twice at 0J. Dry under reduced pressure at 80°C, 138,2
g of a white powder product was obtained. From GPC measurements,
The number average molecular weight of the obtained product was 22,000.

Synthesis Example 3 (Synthesis of terminal phenolimide oligomer) The amount of 2,2-bis(4-aminophenoxyphenyl)propane in Synthesis Example 1 was changed to 287.4 g (0,700 mol), and the amount of N-methylpyrrolidone was changed to 287.4 g (0,700 mol). 240.3g, ASM
The amount of charged meta-aminophenol was 21.8 g (0,200 mol),
A terminal phenolimide oligomer resin liquid was obtained by carrying out the same operation as in Example 1, except that the amount of xylene charged was changed to 75.6 g and the amount of diluted N-methylpyrrolidone was changed to 383.2 g.

100 g of this resin liquid was added to 400 d of methanol to perform precipitation, the resulting precipitate was filtered, and 40 g of methanol was added.
Washed twice with 0 gloss. The precipitate was filtered off and dried under reduced pressure at 800C to obtain 38.5 g of powdered product. As measured by GPC, the number average molecular weight of the obtained product was 5350, and the phenolic hydroxyl equivalent by titration was 2980.
g/eq.

Example 2 5007 with stirrer, thermometer and cooling condenser
Bisphenol A epoxy resin (Sumi Epoxy ELA-12 manufactured by Sumitomo Chemical Co., Ltd.) in a NL Yotsuro flask.
8) 29.9 g, bisphenol A 13.7 g.

Pour 1.8.7g of methyl isobutyl ketone, 100°
0.16 g of tributylamine was added, and stirring was continued for 2 hours under reflux.

As a result of sampling a portion and measuring the epoxy equivalent,
The epoxy equivalent was 1050 g/eq.

After cooling to room temperature, 205.4 g of the terminal phenolimide oligomer resin liquid prepared in Synthesis Example 2 was added, the temperature was raised to 150° C., maintained for 11 hours, and then diluted with 424.5 g of N-methylpyrrolidone. This resin liquid was added dropwise to 300 tW of methanol under high speed stirring to effect precipitation. The precipitate was filtered off and washed twice with 1500 i methanol.

It was dried under reduced pressure at 80°C to obtain 123.2 g of a white powder product. As measured by GPC, the number average molecular weight of the obtained product was 15.000.

Synthesis Example 3 (Synthesis of terminal phenolimide oligomer) Stirring device,
1, 11 with thermometer, cooling condenser, and Dean Stark water drain! 200.3 g (0.50 mol) of α,α゛-bis(4-aminophenyl)-m-diisopropylbenzene and 235.8 g of N-methylpyrrolidone were placed in a Yotsuro flask and dissolved at 70°C under a nitrogen atmosphere. , ASM 235.7 g (0.75 mol) were added in 4 portions over 1 hour, and stirring was continued for 2 hours. 54.6 g (0.50 mol) of meta-aminophenol and 73.8 g of xylene were added, and then heated at 160 to 1700 C for 24 hours.
Azeotropically dehydrated for hours. The amount of distilled water was 28.6 g.

It was diluted with 214.5 g of N-methylpyrrolidone to obtain a terminal phenolimide oligomer resin liquid.

100 g of this resin liquid was added to 400 J of methanol to perform precipitation, and the resulting precipitate was filtered out.
Washed twice with 0-. The precipitate was filtered off and dried under reduced pressure at 80°C to obtain 45.9 g of powdered product.

The number average molecular weight of the obtained product was determined by GPC to be 1850, and the phenolic hydroxyl equivalent by titration was 975 g/eq.

Example 3 Synthesize 37.4 g of bisphenol A epoxy resin (Sumi Epoxy ELA-128, manufactured by Sumitomo Chemical, epoxy equivalent 187 g/eq) in a 1F four-eye flask equipped with a stirrer, thermometer, and cooling condenser. The terminal phenolimide oligomer resin liquid prepared in Example 3 was
．． 3 g, ) Add 0.23 g of butylamine and add 15
The temperature was raised to 0°C, maintained for 24 hours, and then diluted with 619.7 g of N-methylpyrrolidone.

This resin liquid was added dropwise to 20,007 nl of methyl alcohol under high speed stirring to effect precipitation. The precipitate was separated by filtration and washed twice with methanol 150 (W). It was dried under reduced pressure at 80°C to obtain 170.5 g of a white powder product. GPC
The number average molecular weight of the obtained product was 12
．． It was 000.

Example 4 Bisphenol A epoxy resin (Sumi Epoxy [F] ESA-〇11 epoxy equivalent weight 526 g/eq, manufactured by Sumitomo Chemical Co., Ltd.) si, a g, synthesis Example 3
The terminal phenolimide oligomer resin liquid prepared in 2.
Add 35.8 g and 0.23 g of tributylamine to 150
The temperature was raised to °C, maintained for 24 hours, and then diluted with 743 g of N-methylpyrrolidone. This resin liquid was added dropwise to 2000 methanol under high speed stirring to perform precipitation. The precipitate was filtered off and washed twice with 150 fW of methanol. It was dried under reduced pressure at 80°C to obtain 170.5 g of a white powder product. As measured by GPC, the number average molecular weight of the obtained product was 10.500.

Synthesis Example 4 (Synthesis of terminal phenolimide oligomer) Stirring device,
In a II2 four-necked flask equipped with a thermometer, cooling condenser, and Dean-Stark water drainer, 140.2 g (0.35 mol) of α,α°-bis(4-aminophenyl)-m-diisopropylbenzene, N-methyl 184.5 g of pyrrolidone was charged and dissolved at 70°C under a nitrogen atmosphere, and 125.7 g (0.40 mol) of ASM was prepared.
The mixture was added in 4 portions over 1 hour, and stirring was continued for 2 hours. 10.9 g of meta-aminophenol (<0.10 mol) and 73.8 g of xylene were added, followed by azeotropic dehydration at 160 to 170°C for 40 hours. The amount of distilled water was 21.7 g. It was cooled to room temperature to obtain a terminal phenolimide oligomer resin liquid.

Add 10g of this resin liquid to 4007nl of methanol,
Precipitation is performed, the resulting precipitate is filtered, and methanol 4
Washed twice with 00-. The precipitate was filtered off and dried under reduced pressure at 80°C to obtain 7.0 g of powdered product. As measured by GPC, the number average molecular weight of the obtained product was 5100, and the phenolic hydroxyl equivalent by titration was 2700 g/
It was eq.

Example 5 43.2 g of bisphenol A epoxy resin (Sumitomo Chemical Co., Ltd. Sumiepoxy ESA-014 epoxy equivalent 1044 g/eq) was placed in an 11-fourth flask equipped with a stirrer, a temperature needle, and a cooling condenser, a synthesis example. 140. The terminal phenolimide oligomer resin liquid prepared in 4.
8 g, ) butylamine 0.34 g, and N-methylpyrrolidone 18.9 g were added and the temperature was raised to 150°C.
hold for an hour, then N-methylpyrrolidone 484.1
It was diluted in g.

This resin liquid was added dropwise to 2000 methanol under high speed stirring to effect precipitation. Separate the precipitate by filtration and add methanol 150
Washed twice with 07nl. Dry under reduced pressure at 80°C,
, 5 g of white powder product was obtained. As measured by GPC, the number average molecular weight of the obtained product was 15,000.

Comparative Example 1 In a 50 (W) four-piece flask equipped with a stirrer, thermometer, cooling condenser, and Dean-Stark water plate device, 2,
2-bis(4-aminophenoxyphenyl)propane 4
1.05 g (0.1 mol), mixed cresol 280
g, heated to 70°C under nitrogen atmosphere and dissolved.
31.42 g (0.1 mol) of ASM was added over several minutes, and after the addition, the mixture was kept at the same temperature for 4 hours. After keeping the temperature, 110 g of xylene was charged, the temperature was raised to 160 to 170°C, and azeotropic dehydration was performed for 14 hours. The distilled water is 3°3g
Met. After xylene was distilled off at 180° C., the resin solution was cooled to room temperature and added dropwise to 1400 methanol with high speed stirring to obtain a precipitate. This precipitate was separated by filtration, washed three times with 500 g of methanol, and further stirred and washed with 5007 nl of methanol under reflux for 1 hour.

The precipitate was filtered, washed with 100 methanol, filtered,
It was dried under reduced pressure at 0°C to obtain 64.2 g of a powdered product. G
As measured by PC, the number average molecular weight of the obtained product was 9.200.

Comparative Example 2 In Comparative Example 1, the amount of 2,2-bis(4-aminophenoxyphenyl)propane charged was 41.05 g (0,1
The reaction was carried out in exactly the same manner as in Synthesis Example 1 except that 59.11 g (0,144 mol) was changed, and 66 g (mol) of white powder was obtained.
．． 1g was obtained. The number average molecular weight of the product determined by GPC was 2.000.

Reference Examples 1 to 6 and Comparative Reference Examples 1 to 4 Among the components of the resin composition shown in Table 1, components other than the curing agent were removed at 120 to 150°C for 30 minutes while degassing under reduced pressure.
A uniform transparent resin composition was obtained by kneading for hours.

Next, the temperature is lowered to 60-80°C, a hardening agent is added, and the temperature is lowered to 60-80°C.
A resin composition was obtained by kneading at ~80°C. The resin composition was cured at 180° C. for 2 hours, and the performance of the cured product was evaluated. The evaluation results are shown in Table 1.

The physical properties were measured as follows.

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

・Bending strength, bending modulus and bending strain at break are JIS K-
6911.

- Strain energy release rate was based on ASTM B-399.

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

・ELMloo ・-triglycidyl-4-amino-
m-Cresol [Sumitomo Chemical (stock system Sumiepoxy)
ELM100], ・EPICLON 830 ・Diglycidyl bisphenol F [EPICLON■8 manufactured by Inu Nippon Ink Co., Ltd.
30]・4.4' D D S -4,4'-diaminodiphenylsulfone [Sumitomo Chemical Co., Ltd. (SumiCure ■S)], Polymer A ゛Imide polymer of Example 1, Polymer B °Example 2 Imide-based polymer,・
Polymer C--Imide polymer of Example 3, Polymer D--Imide polymer of Example 4, Polymer E
Imide polymer of Example 5, Polymer F Imide polymer of Comparative Example 1, Polymer G - Imide polymer of Comparative Example 2, Polymer H Polyether Sulfone 5003P manufactured by ICI

Claims (1)

[Claims] Having repeating structural units represented by the following formulas (I) and (IV), and having a number average molecular weight of 3,000 to 30,00
Polyimide phenoxy resin in the range of 0. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the above formula, A and R are aromatic residues, and B is a divalent group represented by the following formula (II) and/or formula (III). (N is an integer from 4 to 75.) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( IV) (R_1 in the above formula represents an aromatic residue.)