JPH04114035A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition giving thermally cured products having excellent heat resistance, flexibility and dielectric characteristics, by compounding a specific molecular end-modified imide oligomer and a specified polyamine. CONSTITUTION:A composition comprises a molecular end-modified imide oligomer of formula I (Ar1 is divalent aromatic group; Ar2 is tetravalent aliphatic group or aromatic group; a is an integer of >=1; D, D' are organic groups having divalent unsaturated bonds) and a polyamine of formula II (Ar3 is >=2C aliphatic or aromatic group; b is an integer of >=2), H atoms bonded to at least one of the Ar1, Ar2 and Ar3 in the formulas I and II being partially or wholly substituted with fluorine atoms. The Ar1 and Ar3 are represented by formula III (Rf1 is -O-, etc.; X, Y are alkyl, etc.; n is 0 or 1; m is 0-4; l is 0-4).

Description

Detailed Description of the Invention (a) Industrial Application Field The present invention is used for manufacturing printed wiring boards or molded products that have excellent heat resistance, good workability, and excellent electrical properties. This invention relates to a thermosetting resin m paraboloid.

(b) Conventional technology In recent years, as electric and electronic devices have become larger in capacity, smaller and lighter, more reliable, and more dense, materials that are used in these devices are becoming more heat resistant and highly visible. Organic materials are required.

Conventionally, in the field of heat-resistant laminates, which require a high degree of heat resistance, through-hole adhesion reliability, dimensional stability, electrical properties, etc.
Polyamino bismaleimide resin (e.g. Japanese Patent Publication No. 46-2
Polyimide l'11Tlt+, which is described in Japanese Patent No. 3250 and is composed of dilN,N'-nophenylmethane bismaleimide and 4,4'-)7minonophenylmethane, has been used.

(c) Problems to be solved by the invention However, the above cured product has poor heat resistance, flexibility, and XW resistance.
There was good luck in declining sexuality.

Furthermore, the polyamide/bismaleimide resin mentioned above has poor solubility and is polar with an extremely high boiling point! g! Since it is only soluble in solvents, there are problems in the drying process and press processing when impregnating a base material to produce a prepreg.

In particular, with the recent development of large computers, reducing the dielectric constant of the substrate has become an essential issue in order to increase the signal transmission speed of computer computers, as is clear from the following equation.

Under these circumstances, polyimide resins and fluororesins are attracting attention because of their excellent heat resistance, visibility, and electrical properties.

However, the former substrate still has a dielectric constant! At a frequency of MHz, the dielectric constant is as high as 4 or more, and the latter substrate has a dielectric constant of about 2.5, which is a satisfactory characteristic value. It had the disadvantage of extremely poor chemical stability under high temperature conditions.

The present invention was completed in order to solve the above-mentioned technical RN, and by making a specific terminal-modified imide oligomer contain a specific polyamine and curing them through a heat reaction, heat resistance and visibility can be improved. , and has excellent workability,
Moreover, it is an object of the present invention to provide a thermosetting resin composition having low dielectric constant properties.

(d) Means for Solving the Problems In order to achieve the above objects, the thermosetting resin composition of the present invention employs the following technical configuration.

That is, the thermosetting resin composition of the present invention has the following general formula (1): an aliphatic group or an aromatic group, a is an integer of 1 or more, and D and D' represent an unsaturated bond of 21i1[i. D and D' may be the same or different. ) to the terminal-modified imide oligomer represented by the general formula (n) 8r→NH2 (Iri (however, Art is an aliphatic group or aromatic group having 2 or more carbon atoms, and b is an integer of 2 or more ), and one or more of Ar, , Ar2 or 1tArs in the above general formula (II) is such that some or all of the bonded hydrogen atoms are It is characterized by being substituted with 77 minions.

Further, in the thermosetting resin composition of the present invention, Ar, , Ar, in the above general formula (ff) is represented by a general formula, and in the general formula ([), R" is perfluoroalkylene. group or -〇-2X and Y are at least a group selected from the same or different alkyl groups and 7-odized alkyl groups, n is 0 or 1, and n is an integer of 0 to 4, ef
An integer between Jto and 4 is desirable.

Furthermore, in the thermosetting resin composition of the present invention, the general formula (
Ar in I) is preferably one selected from the following.

The present invention will be elaborated below.

The terminal-modified oligomer which is an essential component of the thermosetting M compound of the present invention is as described above! It is represented by the general formula (+).

In addition, A "1" in the general formula <1) is the general formula (
A fluorine-containing oligomer represented by I[l] is desirable.

Specific representative examples thereof include the following, and in the general formula, Rf is a perfluoroalkylene group, and Rf is a perfluoroalkylene group.

Further, it is preferable that Ar2 in the general formula (I) is ゛[δ''Rf.go1shi, and furthermore, in the general formula, Rf is a perfluoroalkylene group.

Specific representative examples of terminal-modified imide oligomers having repeating units represented by the above general formula (1) include maleimidized ones, such as [PI(4,4°-DOS, BPfl^maleimide 1°[PI(BAPP , 4BPF) maleimide].

[Pl(4,4'-DDE, BTD^)maleimide]?
[PI (3,3'-BAPS, 6FD^) Maleimide 1° [PI (B^^F, BPD^) Maleimide].

[PI (^TAF, 6FD^) Murray Do 1゜ [PI (BAPF, 3BPF) Murray ].

etc.

or, Other unsaturated bisui As a mido, for example, [PI(BAPF, 6FD^)maleimide].

[PI (DTFA, 6FD^) Maleimide 1° [PI (BAPF, 4BPF) maleimide 1° etc.

Furthermore, the terminal-modified imide oligomer of the present invention may be made into a terminal-modified cooligomer by using two or more diamine components or two or more acid components, or may be a mixture of two or more terminal-modified oligomers. .

That is, in the terminal-modified oligomer of the general formula <1), it is desirable that a be an integer of 1 or more from the viewpoint of heat resistance, visibility, and low dielectric properties of the cured product. However, it may also contain an aromatic bismaleimide in which a is 0.

In the present invention, the terminal amine imide oligomer, which is the precursor, is such that the terminal of the oligomer becomes an amine in the ratio of the diamine component (X moles) to the acid component (1 mole) consisting of a tetracarboxylic acid or a derivative thereof. From the viewpoint of synthesizing an oligomer with an appropriate degree of polymerization, α, the reaction is carried out in an organic solvent such that 1<x/y≦4, preferably 1<x/−y≦1.5. It is a terminal amine imide oligomer obtained by
(g/dl) or less, preferably 0.05 to 0.8
(g/dl), particularly preferably 0.1 to 0,
6 (g/dffi).

When the intrinsic viscosity exceeds 1 (g/dl), the viscosity is too high and the impregnation process into the reinforcing base material becomes extremely difficult.As a result, it becomes difficult to obtain a prepreg, and the terminal amine and unsaturated On the other hand, it is undesirable because the amount of unsaturated groups synthesized from the anhydride becomes very small, making it difficult for the unsaturated groups to react sufficiently and reducing solvent resistance.
If the intrinsic viscosity is less than 0.05 (g/dl), the cured product will have poor visibility, heat resistance, dimensional stability, and electrical properties, which is not preferable.

This intrinsic viscosity is calculated by the following formula, and the viscosity in the formula is measured by a capillary viscometer.

Among the above-mentioned tetracarboxylic acids or derivatives thereof as acid components, those without fluorine include butanetetracarboxylic acid, ethylenetetracarboxylic acid,
Propane tetracarboxylic acid, cyclobutanetetracarboxylic acid, cyclopenkunetetracarboxylic acid, cyclohexanetetracarboxylic acid, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,
Aliphatic tetracarboxylic acids such as 2-nocarboxylic acid, pyromellitic acid, benzo-71 nontetracarboxylic acid, 2.3
．． 6.7-S7talentetracarboxylic acid, 1°2.4.
5-su7talentetracarboxylic acid, 1,4゜5.8-su7talentetracarboxylic acid, 3,3°,4゜4゜-nophenyltetracarboxylic acid, 1.3.5.6-su7 Talentetracarboxylic acid, 2.2',3.3'-diphenyltetracarboxylic acid, 3.4,9.10-perylenetetracarboxylic acid, bis(3,4-dicarboxyphenyl)
Ether, decahyde asu7talene-1.4,5.8-
Tetracarboxylic acid, 4,8-dimethyl-1,2,3,5
,6,7-hexahydride asu7talene-1.2.5.6
-Tetracarboxylic acid, 2,6-cyclona7talene-1
．． 4.5.8-Tetracarboxylic acid, 2g7-dicaasu7talene-1゜4.5.8-Tetracarboxylic acid, 2.3
．． 6.7-Chitrachlorona 7talene-1.4.5.8-
Tetracarboxylic acid, 7-enanthrene-1.8.9.10
-tetracarboxylic acid, 2.3.4.5-pyrrolinonetetracarboxylic acid, 2.3.5.6-bilalanetetracarboxylic acid, 1,000-offenetetracarboxylic acid, 2.2-bis(3
, 4-dicarboxyphenyl)propane, 2.2-bis(2,3-)carboxy7enyl)propane, 1.1-
Bis(2,3-dicarboxy7enyl)ethane, 1.1
-bis(3,4-dicarboxy7enyl)ethane, bis(2,3-7carboxyphenyl)methane, bis(3,
4-1 carboxyphenyl)methane, bis(3,4-)
Examples include aromatic tetracarboxylic acids such as (carboxyphenyl) sulfone, and their acid dianhydrides, acid halides, monoesters, and noesters are used as derivatives.

In addition, among the above-mentioned tetracarboxylic acids, examples of fluorine-containing tetracarboxylic acids or derivatives thereof include tetracarboxylic acids having a fullylene group in which all the hydrogen atoms in the alkylene chain or the fullkyl group are replaced with 77 elementary atoms. used. For example, bis(3,4-dicarboxyphenyl)difluoromethane, 1,3-bis(3,4-dicarboxyphenyl)hexafluoropropane, 1,4-bis(3
,4-dicarboxyphenyl)octafluorobutane,
1,5-bis(3,4-dicarboxy7-yonyl)decafluoropentane, 1,6-bis(3,4-dicarboxyphenyl)dodecafluorohexane, 2,2-bis(3,
4-dicarboxyphenyl)hexafluoropropane,
2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)hexafluoropa-pan, 2,2-bis(
Examples include fluorine-containing aromatic tetracarboxylic acids and derivatives thereof such as 3-(3,4-dicarboxyphenoxy)phenyl-1hexafluora-propane. 4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(4-(3,4-
[Carboxyphenoxy) phenyl 1 hexafluoropropane, 2゜2-bis[3-(3,4-dicarboxy 7
e/xy) phenyl 1 hexafluoropropane and their acid dianhydrides, acid halides, monoesters,
No-esterification products are suitable.

On the other hand, as a diamino component to be reacted with the above acid component,
Examples of those without element 77 include 2,2-tmethylpropylene 7mine, 2,5-1 methylhex/tylennoamine, 2,5-tmethylhbutamethylene, and 4,4'-tmethylhbutamethylene. Diamine, 3-methylhbutamethylenediamine, 5-methyl7namethylenenoamine, 2.17-niifsadecylenediamine, 1,
4-di7mi/cyclohexane, 1,10-diamino-1
t10-Tmethyldecane, 2,11-diaminododecane, 1,12-diaminooctadecane, di7mi/propyltetramethylenediamine, 1,2-bis(3-amino/propoxy)ethane, 3-methoxyhexamethylenediamine, hexamethylene Aliphatic diamines such as diamines, heptamethylene diamine, octamethylene diamine, 7namelene diamine, decamethylene diamine, p-7z nylene diamine, -17 nylene diamine, diaminotoluene, 2,4-diaminotoluene, 4,4゛- Diaminodiphenylbroban, 4,4'-diami/di7enylmethane, benzunone, 3,3'-tumethylbenzinone, 3
．． 3'-dimethoxybentunone, 4,4'-diami7di7enyl sulfide, 4,4'-noamino diphenyl sulfone, 3,3'-noamino naphthalene, 3,3'-noamino diphenyl sulfone, 4゜4 '-Diami7 diphenyl ketone, 4,4'-diami7 diphenyl ether,
1f4-noaminonaphthalene, 1,5-sifminonaphthalene, 2,4-bis(β-amino-tcrt-butyl)
Toluene, bis(p-β-amino-tert-butylphenyl)ether, bis(p-β-methyl-Δ-aminophenyl)benzene, bis(plwl-dimethyl-t
ert 7minobentyl)benzene, 1-isopropyl-2,4-so-7enylenediamine, ■-xylenediamine, bis(4-7minophenyl)d,d'-p-xylenediamine, bis(4-(3-7minophenyl) )
7 enyl 1 sulfone, 2,2-bis[4-(4-7mi7
(phenoxy)phenyl-1-propane, etc., and in the present invention, these diamines modified into diisocyanates may be used.

Further, as the fluorine-containing diamino component, among the above-mentioned diamine components, a diamino having an alkyl group or an alkylene group in which all the hydrogen atoms in the alkyl group or alkylene chain are replaced with fluorine atoms is used. For example, 1,3
-bis(anilino)hexafluoropropane, 1,4-
Bis(aniso/)octafluorobutane, 1,5-bis(aniso/)decafluoropentane, 1,7-bis(7
=17/) Tetradecafluorohebutane, 2,2-bis(4-7minophenyl)hexafluoropropane, 2,
2-his(3-7minophenyl)hexafluoropropane, 2,2-bis(3-7minor-4-methylphenyl)
2, such as hexafluoropropane, 2,2-bis(4-7minor-3-methyl-7-ethyl)hexafluoropropane, etc.
Fluorine-containing aromatic diamine and 2,2-bis[4-
(4-Ami/7E/Xy) Phenyl 1 Hexafluoropropane, 2,2-Bis[4-(3-7E/Xy)
Phenyl 1 hexafluoropropane, 2,2-bis[4
-(2-7minophenoxy)phenyl 1hexafluoropropane, 2゜2-bis[4-(2-7minophenoxy)-3,5-tmethylphenyl 1hexafluoropropane, 2゜2-bis[4-(4 -ami/-2-)lifluoromethyl7eth/xy)phenyl1hexafluoropropane, 2,2-bis(3-(3-7mi/phenoxy)phenyl1hexafluoropropane, 1,3-bis[4 −(
4-7mi77enoxy)phenyl 1hexafluoropropane, 1.3-bis(4-(3-amino7eth/xy)phenyl 1hexafluoropropane, 1゜4-bis[4-
(4-ami7phenoxy)phenyl1octafluorobutane, 1,5-bis[4-(4-ami/phenoxy)phenyl1decafluoropentane, 1,5-bis[4-(
Examples include tetranuclear fluorine-containing aromatic diamines such as 4-7 minnow (2-trifluoromethylphenoxy) phenyl 1 hexafluoropentane.

Among these fluorine-containing aromatic diamines, 2,2-bis(4-(4-aminophenoxy)
Phenyl 1 hexafluoro σ propane, 2,2-bis(4
-7mi/phenyl)hexafluoropropane, 2.2-
(3-7-7-4-methylphenyl)hexafluoropropane and 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl-1hexafluoropropane are preferably used. The above diamine component may be used in place of Neusonanate, or two or more types may be used in combination.

Next, examples of the unsaturated nocarboxylic anhydride include (a) maleic anhydride or a derivative thereof, such as dimethyl maleic anhydride, noisobrovir maleic anhydride, nochloromaleic anhydride, and the like. (b) Tetrahydroheptacic anhydride or a derivative thereof, such as methyl tetrahydroheptalate, (e) Nanotsuccinic anhydride or a derivative thereof, such as methyl nadic anhydride, oxynadic anhydride, dimethoxynadic anhydride, hexachloronadic anhydride. There are acids, etc.

One type or two or more types of these unsaturated dicarbonate anhydrides can be used.

Examples of the organic polar solvent used in producing the terminal-modified imide oligomer used in the present invention include N,N-trimethylformamide, N,N-trimethylacetamide, and N-trimethylacetamide.
-Methyl-2-pyrrolidone (NMP), N-methylcaprolactam and other 7-amide solvents, trimethyl sulfoxide, hexamethyl 7-osphoramide, trimethyl sulfone,
Examples include solvents containing a sulfur atom such as tetramethylene sulfone and dimethyltetramethylene sulfone, phenolic solvents such as cresol and 7 ml, and other solvents such as pyridine, ethylene glycol, and tetramethyl urea8. The organic polar solvent used in the reaction can be used, and dioxane, methyl ethyl ketone (M E K
), monoglyme, diglyme, and other organic polar solvents having an oxygen atom in the molecule.

Furthermore, the organic polar solvent used in this invention may include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, solvent naphtha,
Other types of organic solvents such as benzonitrile, acetone, methanol can also be used in combination.

The terminal-modified imide oligomer of the present invention can be produced by reacting an acid component, a diamine component, and an unsaturated nocarboxylic acid anhydride in the above-mentioned organic polar solvent at a reaction temperature of about 100°C or lower, particularly 80°C or lower, to produce [amide- Oligomer with acid bond 1
and then adding an imidizing agent to the amide-acid oligomer (also referred to as amic acid oligomer) at a low temperature of about 0 to 140°C;
It can be obtained by a method of heating to a high temperature of 50° C. to cause dehydration and cyclization to produce a terminal-modified imide oligomer.

A particularly preferred method for producing the terminal-modified imide oligomer is to uniformly dissolve the acid component and the diamine component in the above-mentioned amide-based polar solvent having 1 to 60 °C.
After reacting with stirring for 180 minutes to produce 7mic acid oligomer, the reaction solution was heated to a temperature of 140-250'C, particularly preferably 140-180'C, and at that temperature 30-5000 The amic acid oligomer is stirred for ~500 minutes to undergo an imidization reaction to produce an imide oligomer, and then cooled to around room temperature. Next, an unsaturated nocarboxylic acid is added to this reaction solution, and the mixture is reacted at a reaction temperature of about 5 to 60°C for 1 to 180 minutes with stirring to produce a terminally unsaturated amyl-Y acid imide oligomer. Finally, the unsaturated amic acid obtained above is dehydrated and cyclized to produce an imide.
Known methods described in Japanese Patent Application No. 018,290, Japanese Patent No. 3.018292, and Japanese Patent No. 3,127,414 can be used.

For dehydration from unsaturated amic acids depleted by general formula NV), a tertiary amine (for example, triethylamine) is added in an amount of 1.05 to 1.5 mol per 1 mol of 7-amic acid groups, and As a catalyst, 0.0 per mole of amic acid group
It is suitable to carry out the reaction in the presence of 5 to 0.5 moles of nickel acetate using acetin as a solvent.

Same as general formula (IV). ) Further, in the present invention, the terminal-modified imide oligomer has the general formula (IT) ^r[HNO3)6 --- (If) (However, Ar=
is an aliphatic group or aromatic group having 2 or more carbon atoms, and b is an integer of 2 or more. ) It is characterized by containing a polyamine represented by:

In the present invention, at least one of Art, Arz, or Ari in the above-mentioned one general formula (II) is
It is required that some or all of the bonded hydrogen atoms be replaced with 77 element atoms.

Specific representative examples of the polyamines include, in addition to the diamines mentioned above, reaction products of aniline and formalin (polyamine compounds), 3,4,4'-)riaminodi7enylmethane, 3.3', 4.4 '-tetraamino7-enylmethane, )177mino-7enol, tris-(4
-7mi/phenyl) phos7yo-to and tris(4-7mi7
(phenyl)thiophosphate and the like are representative examples of polyamines that are particularly suitable for the thermosetting resin compositions of the present invention. It is also a particularly effective method in the present invention to use one or more of these polyamines as a mixture.

As the polyamine represented by the above general formula (n), the above fluorine-containing diamine is preferable from the viewpoint of lowering the dielectric constant.

Furthermore, in the present invention, although it is desirable to have a polyamine as an essential component, it is not necessarily necessary to add a polyamine to the terminal-modified imide oligomer.

10 regarding the curing conditions of the thermosetting resin composition of the present invention.
It may be heated at 0 to 350°C for about 1 minute to 48 hours, but
Depending on the purpose and use, the conditions are not particularly limited.

A polymerization initiator may be added to the thermosetting resin composition of the present invention for the purpose of completing curing by short-term heating. Such polymerization initiators include benzoyl peroxide, p-chlorobenzoyl peroxide, 2.4
-Nochlorobenzoyl peroxide, cabrylyl peroxide, latuloyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, tsucumyl peroxide, benzobinafur, bis(1-hydroxychlorohexyl peroxide), hydroxy Butyl peroxide, tertiary butyl hydroperoxide, p-menthane hydroperoxide, tertiary butyl perbenzoate, #IJ tertiary butyl peracetate, tertiary butyl peroctoate,
Organic peroxides such as tertiary butyl peroxyisobutyrate and no tertiary butyl per7thale are useful;
One type or two or more types thereof can be used.

In addition, as a 7-ion polymerization catalyst for terminally modified maleimide,
Basic catalysts such as tertiary amines, tertiary amine salts, quaternary ammonium salts, and imidazoles, and Lewis acid heptamine complex catalysts are used.

Examples of tertiary amines include pyridine, 2-chlorobilinone, 2.4.6-furinone, 2,6-nochlorobilinone,
a, β, γ-pyricone, 47znylpropylpyridine,
Bilinones such as 2-propylpyridine, 2゜6-lutidine, 2,4-lutidine, 2,5-lutidine, 3,4-lutidine, triethylamine, trilobylamine, tri〇octylamine, benoltzmethylamine,
Dimethylaminomethylphenol, F list methylamine/methylphenol, triethylenediamine, N,N
, N', N'-tetramethylethylenediamine,
Aliphatic tertiary amines such as tetramethylguanidine and heptamethylisoguanide, N,N-dimethylaniline,
N, N, N', N"-tetramethyldiaminodiphenylmethane, N, N, N", N'-tetramethyl-wa-phenylenediamine, N, N, N'
, N'-tetramethyl-p-phenylenediamine, N
and aromatic tertiary amines such as N-tumethyl-p-)luinone, triphenylphosphine, 1,8-noazabicyclo(5,4,0)undecene-7, and acid complexes thereof.

Examples of the above-mentioned tertiary amine salts include salts of the above-mentioned tertiary amines and triacetate or tribenzoate.

Examples of the quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, trimethylcetylammonium chloride, triethylcetylammonium bromide, ethylcetylammonium chloride, triethylacetylammonium bromide, and tetraethylammonium Examples include ioguido and the like.

The above imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimiguzole, 2-undecylimiguzole, 2-methylimidazole, 2,4-dimethylimidazole, 2-
Examples include isopropylimidazole or its 7-zine derivatives, trimellitic acid derivatives, and nitrile ethyl derivatives.

The Lewis acid amine complexes include B F ), ZnC
l2, A lc l,, S iC(1<, S nC1
4, Lewis acid such as FeCl, and monoethylamine, n
- Complexes of amine compounds such as hexylamine, benzylamine, triethylamine, aniline, piperinone and the like.

These basic catalysts can be used alone or in combination of two or more.

Furthermore, Brønsted acids and Lewis acids are used as acidic catalysts for the Michael addition reaction of polyamines to double bonds of terminally modified maleimides.

Brønsted acids include 7er7-el, cresol,
Fluorophenol, chloro7er/-l, aminophenol, nitrophenol, 2.4-dinitrophenol, 2.4.6-)dinitrophenol, benzenediol, 2,2-bis(4-hyF"j: Schiff xyl)propane, bis(4-hydroxyphenyl)methane,
Bis(4-hydroxy7enyl)sulfone, 2.2-
Phenols such as bis(4-hydroxyphenyl)hexafluoropropane, aliphatic carboxylic acids such as acetic acid, propionic acid, lauric acid, stearic acid, oleic acid, linoleic acid, 7-novic acid, decanoic acid, triphenyl, pentadecanoic acid, etc. Aromatic acids such as benzoic acid, toluic acid, fluorobenzoic acid, heptatalic acid, salicylic acid, 2,2-bis(4-carboxy7enyl)propane, 2,2-bis(4-carboxyphenyl)hexafluoropropane, etc. Examples include carboxylic acids.

Examples of Lewis acids include metal carboxylates such as aluminum chloride, iron chloride, titanium chloride, and tin octylate. These acidic catalysts can be used alone or in combination of two or more.

In the present invention, it is also possible to use known chain transfer agents such as mercaptans, sulfides, β-sonoketone metal chelates, and metal soaps in the above-mentioned polymerization catalyst. In addition, in order to improve the storage stability of the thermosetting composition at room temperature, for example, p-benzoquinone,
Quinones such as naphthoquine, 7-enanthraquinone, hydroquinone, p-tert-butylcatechol, 7-er7-ols such as 2,5゛-no-tertiary butylhydroquinone, nitro compounds, metals Known lanocal polymerization inhibitors such as salts can be used if desired.

Furthermore, various materials may be blended into the thermosetting resin composition of the present invention depending on its use. That is, for example, for use as a molding material, norphine oxide, silica, alumina, aluminum hydroxide, titania, zinc white, calcium carbonate, magnesite, clay, kaolin, talc, silica sand, glass, fused silica glass, asbeth Y, Inorganic fillers such as mica, various Uskar carbon blacks, graphite and molybdenum disulfide, mold release agents such as higher fatty acids and waxes, epoxy silanes, vinyl silanes, borane and alfoxy rapeseed F-based compounds, etc. A coupling agent such as this is blended. Further, flame retardant agents such as halogen-containing compounds, antimony oxide, and phosphorus compounds may be used as necessary.

It can also be used as a solution, such as varnish. The solvent used at that time is N-methyl-2-
Pyrrolidone, N,N-trimethylacetamide, N,N-
trimethylformamide, N.

N-methylformamide, N-methylformamide,
Noethyl sulfoxide, N,N-trimethylacetamide, N,N-dimethylmethquinacetamide, hexamethyl 7-osphoramide, birinone, trimethylsulfone,
Examples include tetramethylphorphone and dimethyltetramethylene sulfone, and examples of the 7-ethyl solvent group include 7-ethyl, cresol, xylene, and the like.

The following may be used alone or in combination of two or more.

Additionally, along with the aforementioned solvents, if necessary, other types of solvents such as aromatic hydrocarbon solvents such as benzene, toluene, xylene, alcoholic naphtha, benzonitrile, acetone, methyl ethyl ketone, diethyl ketone, chloroform, nooxane, methanol, etc. An organic solvent can also be used in combination.

In the thermosetting resin composition of the present invention, -
+)・A in (II) “1, Ar, is the general formula (Iff)
and in the general formula (III), R'
is a perfluoroalkylene group; Preferably an integer.

With this configuration, it is possible to obtain a 7-/element thermosetting resin composition that has excellent electrical properties, heat resistance, flexibility, and dimensional stability. A typical example is CF.

etc.

In the thermosetting resin composition of the present invention, it is desirable that the general formula is %, and in the -shell formula, Rf2 is a perfluoroalkylene group.

With this configuration, a fluorine-containing thermosetting resin composition can be obtained that has excellent electrical properties, heat resistance, flexibility, and dimensional stability.

(e) Function The thermosetting PA resin M composition of the present invention has the above structure, and the detailed reason why this cured product has a low dielectric constant, visibility, and excellent heat resistance is as follows. Although it is not clear, it is thought that by introducing 77-strand atoms into the molecule and increasing the fluorine content in the molecule, the electronic polarizability due to the C-F bond decreases, resulting in a decrease in the dielectric constant6. Ru.

In addition, the molecular main chain of this cured product has a specific repeating unit,
The zigzag structure of this repeating unit provides excellent visibility, and the introduction of 77 elementary atoms into the molecule weakens the interaction between molecules, which is thought to improve visibility. .

Furthermore, fluorine atoms are larger than hydrogen atoms, and the presence of fluorine atoms in molecules causes steric hindrance, which is thought to strengthen the three-dimensional crosslinked structure of the polymer and improve its heat resistance. .

In particular, the thermosetting resin composition of the present invention has good solubility in organic solvents, and therefore solutions such as varnishes can be obtained very easily. Then, by casting a solution such as this varnish onto a flat plate using an applicator or the like and then heating and curing it, a molded body can be obtained very easily, resulting in extremely excellent workability.

Furthermore, the thermosetting resin composition of the present invention has an imide skeleton and a three-dimensional frame ll1I! Since it is thermally cured to form a lI structure, this cured product has significantly superior dimensional stability compared to general-purpose cured products such as fluororesin and epoxy resin.

Since the laminate of the present invention is formed using the above thermosetting resin composition, it has a low dielectric constant and low dielectric loss,
Moreover, it has excellent heat resistance.

(f) Examples Next, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.

Example 1 2,2-bis(3,4-nocarpoxy7enyl)hexafluoropropanifi water li&1 (6F
DA) 88.8g (0,200IIot'), 212-
1:'
226*ol), N-methyl-2- and lolidone (NMP
) and stirred for 12 hours at room temperature below 30° C. in a nitrogen stream to obtain a terminal amine amic acid oligomer with a solid content concentration of 40.0% by weight.

Note that the intrinsic viscosity (in N-methyl-2-pyrrolidone, 0.
5g/d/concentration, 30°C, and the following intrinsic viscosity (under the same conditions) was 0.53 (g/d/+H).

Next, while heating this amic acid solution to 145°C,
The mixture was stirred for an hour and then at 160° C. for 3 hours to perform dehydration and ring-closing imidization to obtain an imide oligomer of terminal amine. The intrinsic viscosity is 0.26 (g/di), and this imide oligomer solution contains 0.045 sol of amide 7 groups (potentiometric titration analysis value with perchloric acid, theoretical value, 0.052 m
ol) Contained.

Maleic anhydride (MA
)25. 5g<0. 260moZ) was added and stirred for 12 hours at room temperature below 30°C in a nitrogen stream9.
Next, 3 g of p-)luenesulfonic acid hydrate (0,016
mof) and 200 g of toluene were added, and the mixture was stirred at 110° C. for 5 hours while removing the assemblage. After toluene was distilled off from the second solution under reduced pressure, it was added dropwise to water, and the precipitate precipitated was separated by filtration and dried under reduced pressure to obtain a terminal-modified imide oligomer (theoretical value of modified terminal group I: 0.052 mof).

Next, after dissolving this terminally modified imide oligomer in 300 g of NMP, 2.2-bis(4-(4-7 mino7
1/xy) phenyl 1 hexafluoropropane (BAP
F) Add 13.5g (0,026+*oN) to 180
The mixture was stirred at ℃ for 2 hours to form a prepolymer. This solution was cast on a glass plate and heated at 50 DEG C. for 2 hours and then at 250 DEG C. for 5 hours to obtain a film with a thickness of 80 .mu.m. The glass transition temperature of this film is 255°C,
The 5% weight dehumidification temperature was 440°C. In addition, the dielectric constant,
When the dielectric loss tangent was measured according to JIS C6481, it was 2.78 (IMHz), 0. O017 (IM
Hz).

Examples 2 to 5 Comparative Examples 1 and 2 Same as Example 1 except that diamine, acid dianhydride, and polyamine shown in Table 1 were used, and the amounts used were as shown in Table 1. and set the film to 91
I left it behind.

Comparative Example 3 N,N'-nophenylmethane bismaleimide (DAM-
M I ) and 4,4′-noaminonophenylmethane CD
A film was produced in the same manner as in Example 1 using a polyimide resin consisting of AM).

Table 1 shows the results of each of those characteristics.

(Blanks below) (g) Effects of the invention In the thermosetting resin composition of the present invention, a terminal-modified imide oligomer with a specific structure contains a polyamine with a specific structure, and this composition has good solubility and processability. is good,
Moreover, the molded body of the thermosetting d4 resin composition obtained by crosslinking and curing this by heat reaction has excellent heat resistance and flexibility, and has low dielectric constant and low dielectric loss characteristics. In addition, the molded product has particularly excellent heat resistance, through-hole adhesion reliability, dimensional stability, electrical properties, etc., and as a result, it can be used to further increase the capacity of electrical and electronic equipment and computers, make them smaller and lighter, or increase signal transmission speed and high performance. This has the effect of increasing reliability and increasing density.

Claims (3)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(I) (However, Ar_1 is a divalent aromatic group, Ar_2 is a tetravalent aliphatic group or aromatic group, a is an integer of 1 or more, and D and D' are divalent unsaturated bonds. (D and D' may be the same or different.) The terminal-modified imide oligomer represented by the general formula (II) ▲ has mathematical formulas, chemical formulas, tables, etc. ▼...・・・・・・
(II) (However, Ar_3 is an aliphatic group or aromatic group having 2 or more carbon atoms, and b is an integer of 2 or more.), and contains a polyamine represented by the above general formula (I) A thermosetting resin composition, wherein at least one of Ar_1, Ar_2, or Ar_3 in (II) is such that some or all of the bonded hydrogen atoms are replaced with fluorine atoms. (2) In the thermosetting resin composition of claim 1, Ar_1 and Ar_3 in general formulas (I) and (II) are represented by general formula (
III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・
...(III), and in the general formula (III), Rf_
1 is a perfluoroalkylene group, -O-, X and Y are the same or different alkyl groups, and at least one selected from fluorinated alkyl groups, n is 0 or 1, m is an integer of 0 to 4, and l is A thermosetting resin composition having an integer of 0 to 4. (3) In the thermosetting resin composition of claim 1, Ar_2 in the general formula (I) is ▲a mathematical formula, a chemical formula, a table, etc.▼, and in the general formula, Rf_2 is a perfluoroalkylene group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A type of thermosetting resin composition selected from.