JPH04108829A - Polyimidesiloxane resin - Google Patents

Abstract

PURPOSE:To provide the subject resin having specific repeating structural units and a number-average mol.wt. in a specific range and gives excellent mechanical strengths, heat resistance. toughness, etc., when added to thermosetting resins to form cured products. CONSTITUTION:The objective resin having repeating structural units of formula I (A is aromatic residual group; B is divalent group of formula II and/or III) and IV [C is divalent group of formula V (R1, R2 are methyl, phenyl; R3 is 3-10C alkylene and/or aromatic residual group; (n) is 1-60)] and a number- average mol.wt. of 3000-30000 (preferably 5000-20000). The resin is synthesized by subjecting an aromatic diamine, a compound of formula II and/or a compound of formula III and an end-diamine silicone oligomer of formula V to an imidation reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to polyimide siloxane 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 the number of uses that require high toughness as structural materials has increased.

[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 new polyimide siloxane resin suitable for improving the toughness of thermosetting resins such as epoxy resins.

[Means to solve the problem]

The present invention has repeating structural units represented by the following formulas (Ia) and (Ib), and has a number average molecular weight of 3,000 to 3.
0.000 is provided.

云A −B+(I a ) 6C−B+(Ib) (wherein A is an aromatic residue, B is the following formula (n), and/
Alternatively, it is a divalent group represented by formula (III), and C is a divalent group represented by formula (IV). ) (wherein, R1,
R2 is a methyl group or phenyl group, R3 has 3 to 10 carbon atoms
alkylene group and/or aromatic residue, n is 1 to 6
Represents an integer of 0. ) Hereinafter, the present invention will be explained in detail.

A in the above formula (Ia) is a mononuclear or polynuclear divalent aromatic residue, and the aromatic ring may be substituted with a lower alkyl group, halogen, lower alkoxy group, etc. or unsubstituted. Contains things.

Specifically, A can include one or more aromatic diamine residues.

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-phenylenediamine, benzidine, 4,4°-diaminodiphenylsulfide, 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-ethylaniline), 3,3-dimethoxy-4,
4″-diaminobiphenyl, 3.3°-dimethyl-4,
4'-diaminobiphenyl, ■.

3-bis(4-aminophenoxy)benzene, 1,3-
Bis(3-aminophenoxy)benzene, 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)-p-diisopropylbenzene9.
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-xylylenediamine, p-xylylenediamine, 4,4'-diaminostilbene, 5-amino-1-(4'-aminophenyl-1
,3,3-trimethylindane,6-amino-1-(4
' -aminophenyl) 1.3.3-trimethylindane, 5-amino-6-methyl-1-(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-twomethyl-1-(4'
-amino-3゛-methylphenyl) -1,3,3-
Examples include trimethylindane, ~10), and the like.

Further, C in the above formula (Ib) represents the main chain structure of the terminal diamine silicone oligomer represented by the formula (IV), and the number average molecular weight of the silicone oligomer is 220 to 220.
5,000 is preferred, and 600 to 4,000 is particularly preferred.

The proportion of silicone oligomer in the polyimide siloxane resin is preferably 3 to 70% by weight. More preferably 5~
30% by weight, most preferably 5-20% by weight. 3
If it is less than 70% by weight, the effect of imparting toughness to the thermosetting resin will be small, and if it exceeds 70% by weight, the glass transition temperature will be lowered, which is not preferable.

The number average molecular weight of the polyimide siloxane resin needs to be in the range of 3.000 to 30.000. Furthermore, those having a number average molecular weight of 5.000 to 20.000 are more preferable in terms of handling properties and the effect of improving the toughness of the thermosetting resin.

The production of the polyimide siloxane resin of the present invention involves combining the above-mentioned aromatic diamine, a compound represented by the formula (n) and/or (m), and a terminal diamine silicone oligomer whose main chain structure is represented by (IV). Perform a normal imidization reaction,
Can be synthesized. The molecular weight can be adjusted by adjusting the molar ratio of the ingredients.

1fC-B in the polyimide siloxane resin of the present invention
The structure of the silicone oligomer has the above-mentioned formula (IV) as the main chain and both ends are amines, and the following formula (V) and/or (
VI) It can be synthesized by carrying out a conventional imidization reaction with a compound represented by the formula.

The molecular weight can be adjusted by adjusting the molar ratio of the charged materials, so it is best to appropriately determine the molar ratio of the charged materials so as to obtain a polyimide resin with a desired molecular weight. is designated as Bl, and its isomers are designated as X component and Y component, respectively.

B1 can be synthesized by a known method.

For example, α-methylstyrene and maleic anhydride,
It is obtained by reacting 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, the formula (
The acid anhydrides represented by V) and (VI) may be used in combination with some aromatic tetracarboxylic 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.

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-
Tetracarboxylic acids such as bis(4-(3,4-dicarboxyphenoxy)phenyl)propane, bis(3,4-dicarboxyphenoxy)diphenylsulfone, and 1,4-bis(2,3-dicarboxyphenoxy)benzene Dianhydrides and the like are exemplified, and one or more of these can be used.

The polyimide siloxane of the present invention is used by being added to a thermosetting resin, and examples of thermosetting resins include epoxy resin, bismaleimide resin, cyanate resin, unsaturated polyester resin, melamine resin, phenol resin,
Examples include urethane resins, which can be used alone or in combination of two or more.

To give an example of an epoxy resin that is particularly widely used, it is a compound that has two or more epoxy groups in the molecule, and the bifunctional type is excellent for improving flexibility, while the epoxy resin that has three or more epoxy groups is superior in terms of heat resistance. A polyfunctional type having a group is preferable, and in the present invention, one or more types of these are used.

Examples of epoxy resins having two epoxy groups in the molecule include dihydric phenols such as bisphenol A1 bisphenol F1 bisphenol AD, hydroquinone, and resorcinol, or halogenated bisphenol compounds such as tetrabromobisphenol A. diglycidyl ether compound derived from p
- Glycidyl ester compounds derived from aromatic carboxylic acids such as oxybenzoic acid, 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-bis(4-(2,3-epoxypropyl)
[cyclohexyl]furopane, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3
, 4-epoxycyclohexanecarboxylate, N,N-diglycidylaniline, etc., but are not limited to these.

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, 3,4i-diaminodiphenyl ether, 1,4bis(4-aminophenoxy)
Benzene, l,4-bis(3-aminophenoxy)benzene, l,3-bis(4-aminophenoxy)benzene, l,3-bis(3-aminophenoxy)benzene, 2
, 2-bis(4-aminophenoxyphenyl)propane, p-phenylenediamine, m-phenylenediamine,
2.4-4-toluene diamine, 2,6-toluene diamine, p-xylylene diamine, m-xylylene diamine,
1.4-cyclohexane-bis(methylamine), 1.
Amine-based epoxy resin derived from 3-cyclohexane-bis(methylamine) etc.; derived from novolak resin which is a reaction product of formaldehyde and phenol such as phenol, 0-cresol, m-cresol, p-cresol etc. Novolak epoxy resin, phloroglycine, tris-(4-hydroxyphenyl)methane,
1.1.2.2-Tetrakis(4-hydroxyphenyl)ethane, bis[α-(dihydroxyphenyl)-α-
There are glycidyl ether compounds derived from trivalent or higher phenols such as methyl ethyl benzene, triglycidyl isocyanurate, 2,4,6-driglycidyl-s-triazine, rubbers thereof, and urethane-modified compounds. , but not limited to these.

Further, cyanate resins include polyfunctional cyanate esters having two or more cyanate groups, and suitable cyanate esters have the general formula % (1) [where m is 2 or more, usually 5 R is an integer as shown below, 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, 1,3-1l, 4-1■, 6.1
．． 8-12,6- or 2,7-dicyanatonaphthalene, 1,3.6-1-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 cyanogenide. In addition to these, the special public
, Special Publication No. 44-4791, Special Publication No. 45-11712,
Japanese Patent Publication No. 46-41112 and Japanese Patent Publication No. 51-63149
Cyanic acid esters described in publications 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, and X 1 and X 2 are elementary, halogen,
Or it is an alkyl group and is an integer of n2 to 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', X2,
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 CH,0 1l -CH2-1-C-1-0-1- S -CH30 and Y may be the same or different and each represents a hydrogen atom, methyl, ethyl or isopropyl group), 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'-
Diaminodiphenylsulfide, 3,3″-diaminodiphenylsulfide, 4,4°-diaminodiphenylsulfoxide, 4,4°-diaminodiphenylsulfone, 3°3°-diaminobenzophenone, 4,4°
-Diaminobenzophenone, 3,4"-diaminobenzophenone, NIN'-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-amino'
Phenyl-3-aminobenzoate, 4°4°-diaminoazobenzene, 3,3°-diaminoazobenzene, bis(3-aminophenyl)diethylsilane, bis(4-
aminophenyl) phenylphosphine oxide, bis(4-aminophenyl)ethylphosphine oxide,
1,5-diaminonaphthalene, 2,6-diamitupyridine, 2,5-diamino-1,3,4-oxadiazole, m-xylylenediamine, p-xylylenediamine,
2,4(p-β-amino-tert-butylphenyl)ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl) ) Benzene, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 2,11-diaminododecane, l.

12-diaminooctadecane, 2,2-dimethylpropylenediamine, 2,5-dimethylhexamethylenediamine, 3-methylhexamethylenediamine, 2゜5-dimethylhbutamethylenediamine, 4,4-dimethylhexamethylenediamine , 5-methylnonamethylenediamine,
■, 4-diaminocyclohexane, bis(p-aminocyclohexyl)methane, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl)sulfide, N, N'
-bis(3-aminopropyl)methylamine and the like 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, N'-4,4'-)diphenylmethane bismaleimide, N, N'-2-methyl-1,3-phenylene bismaleimide, N , N'-4methyl-1
, 3-phenylene bismaleimide, NIN'-5-methyl-1,3-phenylene bismaleimide, N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-dodecamethylene bismaleimide etc.

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 general formula [wherein,
R1-R4 are hydrogen, lower alkyl, lower alkoxy, halogen, R5 and R6 are hydrogen, methyl, ethyl, trifluoromethyl, trichloromethyl, D, D2 has 2 carbon atoms
~24 organic groups are shown. ].

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, 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 ■-anilino2. , 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: [In the formula, X is a direct bond, -CH2--N=N-.

] Bis-orthoallylphenols represented by these may be combined. Specifically, CF.

etc. are exemplified.

The polyimide siloxane resin of the present invention is a thermosetting resin 1
10 to 100 parts by weight, preferably 2 parts by weight
0 to 80 parts by weight. If the amount is less than 10 parts by weight, sufficient toughness improvement effect will not be exhibited. Moreover, if it exceeds 100 parts by weight, the viscosity of the composition becomes too high, resulting in poor handling.
Processability decreases.

Particularly when processing prepregs for fiber-reinforced composite materials, there is the problem that it is difficult to impregnate fibers, and the prepregs manufactured by impregnating fibers with epoxy compositions lose their drapability and tackiness and can be molded into a predetermined shape. Problems such as difficulty arise.

Furthermore, a curing agent and a curing accelerator for the thermosetting resin are added as necessary.

In the case of epoxy resin, an epoxy curing agent is required,
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 novolak and cresol novolak, and acid anhydrides, dicyandiamide, and hydrazide compounds.

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-tris(dimethylaminomethyl)phenol, and 1,8-diazabicycloundecene, and 2-ethyl-4-methylimidazole. Examples include imidazole compounds and boron trifluoride amine complexes.

Furthermore, depending on the purpose of use, the resin composition containing the polyimidosiloxane resin of the present invention may contain 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 resin containing the polyimide siloxane resin of the present invention, fibers used as reinforcing materials include carbon fiber, graphite fiber, glass fiber,
Examples include organic and inorganic fibers such as silicon carbide fiber, alumina=28 fiber, titania fiber, aromatic polyamide fiber, aromatic polyester fiber, and polybenzimidazole fiber, 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 50 kg/mm.
As mentioned above, fibers having an elastic modulus of 5 t 7 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, 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〕

By adding the polyimide siloxane resin of the present invention to a thermosetting resin, it is possible to provide a cured product with excellent mechanical strength, heat resistance, and toughness.

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 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 chromatography (hereinafter abbreviated as GPC). The columns are Showa Denko AD-805/S and A.
D-803/S was used in conjunction, Liar's DMF solution of 0 and O1 mol/l was used as the solvent, and polyethylene glycol was used as the standard substance.

Example 1 An A S
84.0 g (0,267 mol) of M, 150 g of N-methylpyrrolidone, and 76 g of tetrahydrofuran were charged and dissolved at room temperature under a nitrogen atmosphere to give an amine equivalent of 650.
g/eQ diaminodimethyl silicone oligomer BY1
6-853 (molecular weight 1.300) (manufactured by Toshi/Dow Corning) 10.1 g in tetrahydrofuran 177
A solution dissolved in g was added dropwise over 30 minutes at room temperature, and stirring was continued for 1 hour.

2. 111.7 g (0,272 mol) of 2-bis(4-aminophenoxyphenyl)propane was dissolved in 165 g of N-
A solution of methylpyrrolidone and 61.5 g of tetrahydrofuran dissolved in a mixed solvent was added dropwise at room temperature, and stirring was continued for 1 hour. After raising the temperature to 70℃ and keeping it warm for 2 hours, it was heated to 160℃
The temperature rose to . At that time, when the internal temperature reached 100'C, distillation of tetrahydrofuran started and 247g was distilled out. Prepare 126g of xylene and heat to 160-170'C
and azeotropic dehydration for 30 hours. The distilled water is 20
, 4g. After xylene was distilled off at 180° C., the resin solution was cooled to room temperature and added dropwise to 200 Od of methyl alcohol under high speed stirring to obtain a precipitate.

This precipitate was filtered, and 200 ml of methyl alcohol (2
Washed twice. The precipitate was filtered and dried under reduced pressure at 80°C.
94 g of powdered product was obtained.

As measured by GPC, the number average molecular weight of the obtained product was 15,000, and the amine equivalent by titration was 7,300.
g/eq.

Example 2 The amount of ASM used in Example 1 was changed to 81.1 g (0,258 mol), 2.2-his(4-aminophenoxyphenyl)
The amount of propane charged was 104.7g (0,255 mol)
The reaction was carried out in the same manner as in Example 1 except that the amount of BY16-853 was changed to 19.5 g, and white powder 194
I got g.

As measured by GPC, the number average molecular weight of the obtained product was 15.000, and the amine equivalent by titration was 800.
It was 0g/eq.

Example 3 In Example 1, in place of BY 16-853, diaminodimethyl silicone oligomer BY 16-853C (molecular weight 770) with an amine equivalent of 385 g/eq (molecular weight 770) was used.
The reaction was carried out in exactly the same manner as in Example 1, except that the amount was changed to 9.7 g (manufactured by Dow Corning Co., Ltd.), and 195 g of a powder product was obtained.

As measured by GPC, the number average molecular weight of the polymer was 15.000, and the amine equivalent by titration was 7200.
g/eq.

Example 4 The amount of ASM prepared in Example 1 was changed to 84.0 g (0,26
Example 1 except that the amount of 2,2-bis(4-aminophenoxyphenyl)propane was changed to 104.4 g (0,254 mol) and the amount of BY 16-853 C was changed to 19.9 g. The reaction was carried out in exactly the same manner as above to obtain 194 g of white powder.

As measured by G P , C, the number average molecular weight of the obtained product was 15.000, and the amine equivalent weight by titration was 8000 g/eq.

Example 5 In place of BY 16-853 in Example, 20.7 g of diaminodimethyl silicone oligomer X-22-161B (molecular weight 3.200) (manufactured by Shin-Etsu Chemical Co., Ltd.) with an amine equivalent of 1600 g/eq, and A S M The amount of Og (0,267 mol) 2,2-bis(4-aminophenoxyphenyl)propane was 112.
The reaction was carried out in exactly the same manner as in Example 1, except that the amount was changed to 3 g, and 195 g of a powder product was obtained.

As measured by GPC, the number average molecular weight of the polymer was 15.000, and the amine equivalent by titration was 72oO
g/eq.

Example 6 The amount of ASM charged in Example 1 was 84.0 g (0,267 mo/l/), and the amount of 2,2-bis(4-aminephenoxyphenyl)propane charged was 113.7 g (0,277-
F-/l/), the amount of X-22-161B was 10.
The reaction was carried out in exactly the same manner as in Example 1 except that the amount was changed to 4 g, and 194 g of white powder was obtained.

As measured by GPC, the number average molecular weight of the obtained product was 13.0 OCI, and the amine equivalent by titration was 68.
It was 90g/eq.

Example 7 In Example 1, instead of BY 16-853, dianilinodimethyl silicone oligomer X-22-9023 (manufactured by Shin-Etsu Chemical Co., Ltd.) 2 with an amine equivalent of 1600 g/eq was used.
0.7g, the amount of ASM prepared is 84, Og (0,26
The reaction was carried out in exactly the same manner as in Example 1, except that the amount of 2゜2-his(4-aminophenoxyphenyl)propane charged was changed to 112.3 g, and 195 g of powder product was obtained.
I got it.

As measured by GPC, the number average molecular weight of the polymer was 15.000, and the amine equivalent by titration was 7200.
g/eq.

Comparative Example 1 In a 500 ml four-sided flask equipped with a stirrer, thermometer, cooling condenser, and Dean-Stark water plate device,
2,2-bis(4-aminophenoxyphenyl)propane 41.05 g (0.1 mol), mixed cresol 2
80 g of the solution was charged, heated to 70° C. under a nitrogen atmosphere, and dissolved. 31.42 g (0.1 mol) of ASM was added over several minutes, and the temperature was kept at the same temperature for 4 hours after the addition. 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 distilling off tosylene at 180° C., the resin solution was cooled to room temperature and added dropwise to 14,007 nl of methyl alcohol under high speed stirring to obtain a precipitate. This precipitate was filtered and washed three times with 5007 nl of methyl alcohol.
Further stirring and washing was carried out for 1 hour under reflux with 500% methyl alcohol. The precipitate was filtered, washed with 100% methyl alcohol, filtered, and dried under reduced pressure at 80°C to obtain 64.2 g of a powder product. As measured by GPC, the number average molecular weight of the obtained product was 9.200.

Comparative Example 2 In Comparative Example 1, the charged amount of 41.05 g (0.1 mol) of 2,2-bis(4-aminophenoxyphenyl)propane was changed to 59.0 g (0.1 mol). The reaction was carried out in exactly the same manner as in Example 1 except that the amount was changed to 1 g (0,144 mol), and white powder 66,
1g was obtained. The number average molecular weight of the product was 2000 as determined by GPC.

Reference Examples 1 to 7 and Comparative Reference Examples 1 to 3 Among the components of the resin composition shown in Table 3, the 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 uniform 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 1.

The physical properties were measured as follows.

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

・Bending strength, bending modulus and bending strain at break are JISK-6
911 compliant.

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

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

・ELMloo・”°・ Triglycidyl-4-amino-m-cresol [manufactured by Sumie Kagaku Kogyo ■ Sumiepoxy■
BLM100), EpIct, oNsao - diglycidyl bisphenol F [EPICLON 83 manufactured by Dainippon Ink ■
0], ・4,4°DDS-...4,4°diaminodiphenylsulf-38-one [SumiCure ■S manufactured by Sumitomo Chemical Co., Ltd.], ・Polymer A°''゛Imide polymer of Example 1・Polymer B...
Imide-based polymer/polymer C of Example 2 Imide-based polymer/polymer D of Example 3...°"Example 4
Imide polymer/polymer E...Imide polymer/polymer F° of Example 5...Imide polymer/polymer G of Example 6...°...Imide polymer/Polymer of Example 7 H”・Polymer/Polymer of Comparative Example 1■ Pa・Polymer/Polymer J of Comparative Example 2
・・I (Polyether sulfone 5003 manufactured by I company
P

Claims (1)

[Scope of Claims] Having repeating structural units represented by the following formulas (Ia) and (Ib), and having a number average molecular weight of 3,000 to 30,00
Polyimide siloxane resin in the range of 0. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I b) (In the formula, A is an aromatic residue, B is the following formula (II) and/or the formula It is a divalent group represented by (III), and C is a divalent group represented by formula (IV
) is a divalent group represented by ) ▲ 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) (In the formula, R_1 and R_2 are methyl groups or phenyl group, R
_3 represents an alkylene group and/or an aromatic residue having 3 to 10 carbon atoms, and n represents an integer of 1 to 60. )