JPS6069113A - Polyimide forming composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (9) Presentation of Related Applications This application is filed in U.S. Patent Application No. 459.
No. 442 (filed on January 20, 1983).

BACKGROUND OF THE INVENTION Bismaleimides, together with epoxy monomers and aromatic amines, have been used to form polyimide molding compositions with high heat distortion temperatures, such as in U.S. Pat.
No. 94.723 and No. 4,294,877. A particular disadvantage of these molding compositions is their slow curing rate, typically requiring about 115 to 2 hours to cure.

The rapid reaction of maleic anhydride with aliphatic vinyl ethers was demonstrated by Leonard Lii 'Vinyl
andDiene Monomers, VoL 2
4, Part 1, pp, 399-401
(=!L-yoke, Wi1ey engineering interscien
CE, 1970).

However, cured products obtained from maleimides and aliphatic vinyl ethers have low heat distortion temperatures (10) and are therefore not useful. Moreover, these aliphatic vinylic acids are liquid at room temperature and are not compatible with the formulation of solid molding compositions, making it difficult to process such compositions into final products.

The present invention was made based on the discovery that maleimide rapidly copolymerizes with aromatic vinyl ether. The resulting copolymers have high oxidative stability and high heat distortion temperatures, overcoming the shortcomings inherent in polyimide molding compositions known in the art.

Disclosure of the Invention The present invention provides a molding composition containing an aromatic vinyl ether and a maleimide.

A preferred molding composition comprises (A) an aromatic vinyl ether of the following formula: and a maleimide having -1 or more chemical bonding units of the following formula (11) and having a molecular weight in the range of 111 to about 5,000. wherein B*, R1, R4, R% and R are selected from the group consisting of hydrogen, halogen and alkyl groups having 1 to 8 carbon atoms, and R1 has 1 to 8 carbon atoms.
is an alkylene group selected from the group consisting of Gd-0-51 10-0- and mixtures thereof, and M is selected from the group of monovalent and polyvalent aromatic groups having from 6 to 130 carbon atoms. , n is an integer equal to 1-10.

Examples of maleimides suitable for use in the molding compositions of the present invention are described in the Holub et al. US Pat.

No. &55a741 and No. 478z439 (maleimide-substituted organoborisiloxy(12)san), No. 1652.71b and No. A 729.4
No. 46 (maleimide-substituted polyester), No. 1689,
No. 464 and No. 5764273 (maleimide-substituted polyamide) and No. 4574031 (maleimide-substituted organosilane). All of these patents have been assigned to the applicant.

Other suitable maleimides include bismaleimides of the formula: % formula % and monofunctional maleimides of the formula: 1 1 . wherein 16 and R. are selected from the group consisting of hydrogen, halogen, and alkyl groups having 1 to 8 carbon atoms;
5 divalent hydrocarbon group and the following divalent group of the formula (13): where 2 is a carbon atom number of 0
~15 hydrocarbon groups, -8-1-o-2-so2-1 are divalent groups, and R? ii a monovalent alkyl group having 1 to 6 carbon atoms, and Yij a monovalent hydrocarbon selected from the group consisting of an aliphatic group having 1 to 8 carbon atoms and an aromatic group having 6 to 20 carbon atoms; It is the basis.

To form a type of bismaleimide, 2M! 1! −
: A reaction between a diamino compound of XN (xFi in the formula, SY as defined above) and maleic anhydride is carried out to form maleamic acid. Maleamic acid is treated with a mixture of acetic anhydride and a catalyst composition such as nickel acetate and triethylamine to form the corresponding bismaleimide.

Certain monofunctional maleimides can be formed in a similar manner (14), using an amine of the formula NUt-Y (where Ytj is a monovalent group as described above) and maleic anhydride to form maleamic acid. do.

In addition to bismaleimides and monofunctional maleimides, maleimide oligomers of the following formula are also suitable for use in the molding compositions of the invention.

(15) Here, X%R5 and R6 are as defined above, and X' is I
selected from the same group of divalent organic groups as mFi1-10
is an integer.

K, which produces these oligomers, carries out a condensation reaction of bismaleimide with a diamine of the formula N-X'-NH, where X' is selected from the group of divalent groups described above.

A stoichiometrically insufficient amount of diamine is used to prevent complete polymerization of the bismaleimide.

The maleimide monomers and oligomers described above can be varied within a wide range, just as the organic groups represented by X, X' and Y present therein can be varied. ! Among the divalent groups represented by
The following divalent saturated alkylene groups include methylene, ethylene, propylene, butylene, impropylidene, hexylene, cyclohexylene, and neopentylene. Among the divalent groups X and X' are the formula -C3H@-CH
Snow-〇-OH, -OH, - divalent groups are included. Among the divalent aromatic groups within X and X' are, for example:
m-(16) phenylene, p-phenylene, 246-naphthylene, 2
-/thiru-1,3-phenylene, dichlorophenylene and diaryl groups, such as hap'-biphenylene, gm
'-biphenylene, diphenylene methylene, diphenylene oxide, diphenylene sulfone, diphenylene sulfide, ketobiphenylene, and the like. These diaryl groups may be attached to both nitrogens in the ortho, meta or para position.

Representative examples of bismaleimides Ktf which can be used in the molding compositions of the invention or which can be converted into oligomers include, for example:

\N'-1,2-ethylene-bismaleimide, N,
M'-methylene-bismaleimide, \N'-1,4-
Butylene-bismaleimide, \N'-1,6-hexamethylene-bismaleimide, N, N'-1,4-phenylene-bismaleimide, N,
N'-1,3-phenylene-bismaleimide, \N'-
2-methyl-1,3-phenylene-bismaleimide, (17) N, )l'-4,4'-cyphenylmethyl-bismaleimide, \n'-a,a'-diphenyl ether-bismaleimide, M, N'-4,4'-cyphenyls-hon-bismaleimide, M, N'-4,4'-diphenylsulfide-bismaleimide, zx'-a, a'-dicyclohexylmethane-bismaleimide, 11, M'- 1,3-xylene-bismaleimide, \I
'-4,4'-benzophenone-bismaleimide, \M'-(&!!'-dichloro464'-biphenylene)bismaleimide.

The bismaleimides listed above are typically prepared by reacting 1 mole of the corresponding diamino compound with the divalent group Xt- with 2 moles of maleic anhydride. Other anhydrides, such as substituted maleic anhydride, can also be used to produce bismaleimide (1B). For example, citraconic anhydride and pyrodinconic acid (also known as dimethylmaleic acid) anhydride? 4.4
'-Diaminodiphenylmethane used with bismaleimide, specifically ti3N'-4,4'-diphenylmethane-bis(methyllimide) and \N'-4,4
'-diphenylmethane-bis(dimethylyaleimide) can be formed. Mixtures of anhydrides and/or mixtures of diamino compounds can be used to prepare mixtures of bismaleimides. Mixtures of such bismaleimides are suitable for use in the molding compositions of the present invention and for producing oligomers suitable for use in the present invention. Halogenated bismaleimides, ie bismaleimides in which the halogen is present on the divalent radicals X and X' or on the monovalent radicals R11 and R6, can also be used without departing from the gist of the invention. For example, N, N'-(&3'
-diku o o -4,4'-diphenyloxy-bismaleimide), Bn'-(a3'-dibromo-4,4'-
Diphenylmethane)-bismaleimide and the like are suitable as the maleimide (19) used in the molding composition of the present invention.

Monofunctional maleimides can also vary within a wide range, depending on the organic groups present therein.

Particularly preferred among the monovalent groups represented by Y are monovalent saturated alkyl groups having 8 or less carbon atoms and having a straight or branched structure. Suitable alkyl groups include, for example, methyl, ethyl, propyl, butyl, isopropyl, pentyl, hexyl, and the like. The monovalent group represented by Y also includes an aromatic group having 6 to 20 carbon atoms. Included in the genus group are examples L id phenyl, 3-methylphenyl, naphthyl, bisphenyl, and the like.

The aromatic vinyl ethers of the molding compositions according to the invention can vary within a wide range, since a large number of different aromatic units can be present therein. Some of the vinyl ether monomers suitable for the molding compositions of the invention are
U.S. Pat.
) is defined in detail.

Aromatic polyvinyl ether monomer within the scope of the present invention (20
) The body parts are defined in detail as having the following: Aromatic vinyl ethers suitable for use in the present invention also include aromatic vinyl ethers having nine molecules t and t of the vinyl ether moiety.

Groups included within Formula 10A include polyvalent aromatic groups such as phenylene, tolylene, xylylene, naphthylene, biphenylyl (also known as xenyl), anthrylene, and diaryl groups of the formula: ζ where Q is selected from 10-5-S-11 and a divalent aromatic group of the formula: (21). Polyvalent aromatic groups also included within the scope of the term include those of the following formula.

Here, nTt is an integer from 1 to 10.

Monovalent aromatic groups within the scope of the formula include phenyl, naphthyl,
Included are xylyl and diaryl groups of the following formula: (wherein Q is the second as defined above).

A suitable aromatic vinyl ether is also vinylny(22) Varies with the groups present in the chill base.

Divalent groups included within R1 in Formula 1 are alkylene groups having from 1 to B carbon atoms, such as methylene, ethylene, trimethylene, tetramethylene, and the like. 'R2, Hm
and 'R4 are, for example, hydrogen, monovalent alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, etc., and halogen groups, such as chloro, bromo, etc.

Also included within the scope of the above-mentioned aromatic groups are chlorophenylene, bromotrilene, chlorophenyl, bromophenyl, and the like. Specific examples of aromatic polyvinyl ethers of Formula I include:

(23) T3a (24) 1 forming part of the aromatic vinyl ethers of formula I
One method is to condense an aryl hydroxide or an alkali metal salt of a carboxylic acid with a haloalkyl vinyl ether in the presence of dimethyl sulfoxide, as shown in the following reaction formula.

(25) Mu (GM)n+nBR"0O(R')-0(R")(R
”)-4 formula! Here, M, G, Pll, R1, R1
As defined above, 1 is a halogen group and R4 and n are an alkali metal ion.

Once the desired aromatic vinyl ether and maleimide compound have been obtained, the two-component tubes are melt-mixed at a temperature of about 110° C. or less to obtain a K-shaped molding composition. In addition to maleimide compounds and aromatic vinyl ethers,
The molding compositions may contain peroxides or azo catalysts to lower the required curing temperature or shorten the curing time. Typical organic peroxides suitable for obtaining catalytic action include, for example, ketone peroxides, peroxy acids, dibasic acid peroxides, aldehyde peroxides, alkyl peroxides, hydroperoxides, alkyl peroxy esters, dibeloryl peroxides, etc. Φcyto derivatives, specifically Fit-butyl peroxyvivalate,
2.4-Dichlorobenzoyl peroxide, cabrylyl peroxide, lauroyl peroxide, decanoyl peroxide, propionyl peroxide, acetyl peroxide (26), t-butyl peroxyisobutyrate, p-chlorobenzoyl peroxide, benzoyl peroxide, hydroxyhebutyl Peroxide, cyclohexanone peroxide, Z5-dimethylhexyl-2,5-cy(peroxybenzoate), di-t-butyl diberphthalate, t-butyl hydroperoxide, di-t-butyl peroxide, methyl ethyl ketone peroxide, p-methane hydroperoxide , cumene hydroperoxide,
These include 2,5-dimethylhexyl-2,5-dihydroperoxide, t-butyl-hydroperoxide, peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, and the like.

In addition to these organic peroxides, certain azo compounds are also suitable as catalysts for the molding compositions of the invention. Such azo compounds include azobisalkyl nitriles and azo compounds of the formula: (27); and quinones, such as Oct.

In addition to the catalyst, the molding composition may contain fillers, such as clay,
It may also contain silica, calcium carbonate, aluminum trihydrate, carbon black, talc, calcium sulfate, wollastonite, and the like.

(28) Suitable weight ratios of filler firing active ingredient range from 100 parts active ingredient 0 to 300 parts firing filler. These molding compositions may also contain other additives, such as antioxidants, flame retardants, impact modifiers, etc.

Once the paper molding composition has been prepared by melt mixing the aromatic vinyl ether and maleimide compound with the desired additives, the molding composition is cured by raising the temperature t from 140° to about 170°C. Application of such temperatures results in more rapid polymerization than K. This heat-activated polymerization is usually carried out in a mold under pressure. Such pressure is about 20
It can range from 0 to about 600 psi. Cure times range from about 1 to 4.5 minutes for typical GCti. Although this polymerization is rapid without catalyst and at relatively low temperatures,
The curing temperature or curing time of the above-mentioned peroxides can be lowered by adding an azo catalyst. Cure times for molding compositions containing such catalysts are typically reduced to a range of about 1 to 2 minutes. As a result, the polyimide molding composition of the present invention can be used as a photocurable coating and as a photoresist. Photoinitiated curing can be achieved by adding a conventional free radical photoinitiator, such as butyl benzoin ether* to a mixture of aromatic vinyl ether monomer and maleimide monomer. Photoinitiated curing can be accomplished for the butyl benzoin ether-containing mixtures by irradiating the molding composition from a mercury arc lamp for 30 seconds at a distance of 6 inches. If photoinitiated curing is desired, it is preferred to use a maleimide monomer with a low melting point to increase solubility with the aromatic vinyl ether at room temperature.

An alternative to the conventional mixing of the maleimide compound and the aromatic vinyl ether monomer described above is to mix both the aromatic vinyl ether monomer and the maleimide compound in a common organic solvent,
For example, it can be dissolved in acetone and impregnated with this solution on a fiber matrix, such as glass fiber cloth. Next, the organic solvent is removed from the single fiber matrix to obtain a dry fiber matrix impregnated with a maleimide compound and a vinyl ether monomer (hereinafter referred to as "preg (3f1) leg"). These prepregs are cut, stacked, and heated to initiate polymerization. Suitable curing temperatures range from about 140° to about 170°C. These prepregs have a curing temperature of about 400-600 ps.
It can be molded by pressing together for about 2 to 3 minutes at a pressure of

An alternative to curing a molten mixture consisting essentially of maleimide and aromatic vinyl ether is to granulate and pelletize the mixture to produce a solid thermoset composition for injection molding, compression molding and transfer molding. .

Optimum crosslinking density is obtained with a 1:1 molar ratio of maleimide, e.g. bismaleimide, having two or more electron-deficient groups to aromatic vinyl ether, e.g. aromatic bisvinyl ether, having two or more vinyl groups. It is from a molding composition. However, the stoichiometry of the molding composition can be varied within wide tolerances, and molding compositions in which the ratio of maleimide functional groups to vinyl groups of formula A suitably cured composition was obtained from the composition (31
) can be done.

The mechanical properties of the cured molding composition can be varied to desired values by varying the stoichiometry of the molding composition and by varying the components of the molding composition. For example, when high bending strength and elongation are desired,
Maleimide monomers and simalimide oligomers are preferred. Flexural strength, elongation and tensile strength can be varied by varying the stoichiometry.

Preferably, the curing temperature is in the range of about 1406°C to about 170°C. Higher temperatures of 0° C. are also suitable, but such high temperatures may lead to unwanted decomposition of the aromatic vinyl ether or additives present in the molding composition. Curing times at temperatures in the above range range from 1 to 4.5 minutes, depending on the presence or absence of a catalyst and the strength of the catalyst.

The cured molding composition typically has a high heat distortion temperature of about 220° C. and suitable engineering properties, such as percentage elongation, tensile strength, tensile modulus, flexural strength, and the like.

(32) The following experimental procedures were used to generate selected components of the specific thermoplastic compositions that make up the present invention. These procedures are presented to assist in practicing the invention and are not intended to limit the invention.

To produce \v'-4,4'-diphenylmethane bismaleimide, 4,4'-diaminodiphenylmethane and [15 moles of anhydrous maleic I! was added to 1 ton of A7 tons. A rapid reaction occurred to form a precipitate of bismaleamic acid. Next, α5 moles of triethylamine, 0.0
Add 2 moles of nickel acetate and 2.5 moles of acetic anhydride. After the mixture was refluxed for 5 hours, all of the bismaleamic acid had been dissolved, and the reaction mixture was poured into an equal volume of water. The product separated as an oil, which was crystallized in a water bath and purified by two recrystallizations from toluene. The yield before recrystallization was 65-80% of the theoretical value.

To produce the divinyl ether of the following formula: (33), 241 Na0il dissolved in 6&5f bisphenol A, 500 toluene, and 100 d of water were added to a 100-low flask. Add a paddle stirrer to the flask, a reflux condenser,
A Dean 8tark trap and nitrogen inlet tube were installed. The reaction mixture was heated to reflux;
The water produced was collected in a trap and removed from the reaction. Reflux was continued until no more water was collected, then the trap was replaced with a special Dean-Stark trap containing activated Molecule sieves. Refluxing was continued for 1 night to thoroughly dry the system. The reaction mixture was then filtered to recover bisphenol monosodium salt. 2000 yen of this salt
- Transferred to a flask and added 1 t of dimethyl sulfoxide. The reaction mixture was heated to about 60° C., 65 f0
2-Chloroethyl vinyl ether was added slowly. The reaction mixture was then stirred at −60° C. (34) for 1 hour, cooled, stirred for an additional 5 hours at room temperature, and then poured into 1000-501 MaOH. An oil separated and was collected. The oil was washed three more times with 50 liters of MaOH aqueous solution to remove unreacted bisphenol A. The washings were extracted with ether and the extract was added to the oil. Evaporation of the ether gave divinyl ether in a yield of 77t (yield 6q, e%).

To produce an aromatic divinyl ether of the formula: 652,
76 f (2 mol) of bisethoxylated bisphenol A (Dianol-22, manufactured by AKZO0Mm1J),! sOOa! l of toluene and 459.2 f
The reaction mixture of (6 moles) allyl chloride was stirred until the bisethoxymolated bisphenol was dissolved.

Next, 240 f (6 moles) of solid NaOH was added and stirring continued for 1 ft for 15 hours. Next i, 32f(α1(35
) Tetrabutylammonium bromide was added and stirring continued for 5 hours. The temperature of the reaction mixture was increased to 50
The temperature was slowly raised to 100°C, and since an exothermic reaction occurred, the reaction temperature rose to 100°C.

The temperature of the reaction mixture was brought to 75°C in a water bath and kept overnight (
16 hours) Stirred. The product was isolated from K by pouring the reaction mixture f2t into distilled water and separating the organic layer using a separatory funnel. After washing the organic layer three times with 500 g each of water, it was dried over solid sodium sulfate and the toluene was removed under vacuum to yield 690 t (86 t theoretical) of bisallyl ether product. .

Bisallyl ether of ethoxylated bisphenol 3
Rue/4 (PPhs') at 96.5F (1 mol)
sQ, 96 f (I Xl 0-smo') tm. The reaction mixture was soaked in a silicone oil bath (J) 120
℃ and held at this temperature for 1.5 hours. After cooling,
When the product was examined by nuclear magnetic resonance (KR'), it was found that it was completely isomerized to bispropenyl ether. The products are three bisproben(36) ether isomers (cia-cis, cis-tra
ns.

trans-trans).

The following examples are intended to specifically illustrate the present invention, but are not intended to limit the invention. All parts are parts by weight unless otherwise specified.

Example 1 This example specifically describes the production of one example of the molding composition of the present invention and its curing method.

The following materials were heated and mixed together at 80° C. until homogeneous.

46 parts t-butyl perbenzoate 2 parts The mixture was allowed to cool and solidify. Grind this to 100 (3
7) Combustion silica (emu 241, Combustion
! (manufactured by Engineering) and tri-blended.

This mixture was further mixed at 80° C. on a two-roll mill to obtain a solidified Kf. 12 tons Hu of solid molding compound
n Transfer molding press at 600 psi, 160
Transfer molding was performed at 9°C for 2 minutes. The resulting test material had a heat distortion temperature of 2001 at 264 psi:
The above has been shown. The mechanical properties are shown in Table 1.

25 &843 2.02X10・2.554 7.
f14X101150 &845 2.02X10'
2.027 ZO4X10”180 181B 2.0
2X10@2.077 7.5 x1os Example ■ This example specifically describes a method for manufacturing and curing a molding composition of the present invention.

The following materials were placed in a large beaker.

(38) 9.5 parts of CHa, 1 part of t-butyl perbenzoate The mixture was stirred at 80° C. until homogeneous, then 120 parts of silica (OIM 421) were added and the mixture was stirred until homogeneous. Continued until a blend was obtained. A molding compound (land) with a consistency similar to that of grain flour dough was obtained, which was described in Example I and transfer molded in the same manner as the hole.A bar and a disk were obtained, and the heating deformation temperature was 180. ℃
Met.

Example ■ This example specifically describes an alternative method for hardening one example of the molding composition of the present invention.

Example It--Repeated except for the silica filler.

(39) After making the mixture homogeneous by stirring at 80 °C,
This was used to impregnate glass cloth. 6 inches of impregnated cloth
The prepreg was made by cutting into 6 inch square pieces and stacking the 7 square pieces together. prepreg ftoar
The cured laminate was obtained after pressing in a ver press at 500 psi, 160° C., for 2 minutes.

Example W This example illustrates a method for producing and curing one example of the molding composition of the present invention.

The following ingredients were mixed at 80°C using the procedure of Example 1.

1 part t-butyl perbenzoate (40) The mixture was then mixed with 120 parts silica (011M 421)
The mixture was powder-blended and kneaded using a roll machine at 80°C. The hardened molding powder was then transfer molded as described in Example I to obtain a molded article.

The heating deformation temperature was 200°C or higher.

Example V This example illustrates the effect of various radical initiators on resin gelation time.

Using various radical initiators manufactured by Nijukei, molar amounts of the following materials were heated and mixed together at 150°C.

(a01%k) 0 0 Mixture of 5 types using radical initiators shown in Table ■ (41
) The gelation time for the samples was measured in a 5unshine Ge1 meter fitted with a constant temperature bath maintained at 150<0>C. The gelation time measurements and initiator half-life are shown in Table 2.

Table ■ Azoisobutyronitrile α40/100℃ 1.
0B Benzoyl peroxide 1.407100℃
2.90 Benzopinacol 4.5 Dt-butyl hydroperoxide 520/130°C
4.3mt-butylperbenzony) 18/100℃
50 Example ■ This example specifically describes a method for photocuring one example of the molding composition of the present invention.

158F ((101 mol) of N, PI'-bix-r
vimido-4,4'-diphenylmethane and 110
To f (101 mol) of bisphenol-bispropenyl ether was added (L13f (3 parts by weight) of N-p(42) methylbenzoin ether (benzoin n-butyl ether). The mixture was slightly warmed to form a homogeneous solution. The film was prepared and then spread as a 2 mil film on a glass plate using a drawer. The film was irradiated for 30 seconds from a medium pressure mercury arc lamp at a distance of 6 inches to obtain a crosslinked insoluble film. Before irradiation. Where the mask TL device was placed on the film, the film was washed with acetone after irradiation.
! l-, a negative image of the mask was obtained.

Although the embodiments described above illustrate various modifications of the present invention, it is clear that those skilled in the art can conceive of further modifications in accordance with the above teachings without departing from the gist of the invention.

(43) Procedural Amendment Interval 1, Indication of Case Patent Application No. 147719 of 1982, Title of Invention: Polyimide Molding Composition 3, Relationship with the Person Making the Amendment Applicant Address United States of America, 12305, New York State; Schenectaday, River Road 1 Name: General Electric Company Representative Samson Herzgott 4 Address: 1-14-14 Akasaka 1-14-3, Minato-ku, Tokyo 107
5 Kowa Building 4th floor Japan General Electric Co., Ltd. Far East Patent Department Telephone (588) 5200-5207 7. Contents of amendment (1) The scope of the claims is amended as shown in the attached sheet.

(2) r4.4'-J on page 33 line 7 of the specification is IQ, 2
5 moles of 4.4'-J.

Claim 1: A curable composition containing aromatic vinyl ether and maleimitotowo.

3. The photocurable composition according to claim 2, wherein the photocuring catalyst is N-butylbenzoin ether.

4. The molding composition according to claim 1, wherein the maleimide is a bismaleimide of the following formula: (in the formula, R5 and R6 are hydrogen) - rogene or a C4-8 alkyl group, X is a carbon atom selected from the group consisting of divalent hydrocarbon groups of numbers 1 to 35 and divalent groups of the following formula: (1), where 2 is a carbon atom number of 0
~15 hydrocarbon groups, -5-1-〇-1-so2-1O
HR' 111 is a divalent group selected from the group consisting of -O-1-N- and -R-, and R7 is a monovalent alkyl group having 1 to 6 carbon atoms).

5. The molding composition according to claim 1, wherein the divalent group X of the bismaleimide is bis6, and the maleimide is of the following formula: (2) (wherein R5 and R6 are hydrogen, halogen or at-S
The alkyl groups, X and X' are selected from the group consisting of divalent hydrocarbon groups having 1 to 35 carbon atoms and divalent groups of the formula
-15 divalent hydrocarbon group, -x-5-0-5 is a divalent group selected, R7 is a monovalent alkyl group having 1 to 2 carbon atoms, m is an integer of 1 to 1o ).

2. The molding product according to claim 1, wherein the maleimide is N, N'-4,4'-diphenylmethane bismaleimide or N, n/-6-methyl(3)-1,3-phenylene bismaleimide. Composition.

8. Claim 1 in which the molar ratio of maleimide to aromatic vinyl ether has a value within the range of about 0.25 to about 4.
The molding composition described in .

9(A) an aromatic vinyl ether of the following formula: and ω) having one or more chemical bonding units of the following formula: and a molecular weight of 111 to 50
A molding composition containing a maleimide in the range of 1 to 8 alk(4), G is selected from the group consisting of 10-11 -a-O- and mixtures thereof, and A is an alkyl group having 6 to 130 carbon atoms; and polyvalent aromatic groups, n being an integer equal to 1 to 10).

10. The molding composition according to claim 9, further comprising an effective amount of a thermosetting catalyst.

11. The molding composition according to claim 10, wherein the thermosetting catalyst is selected from the group consisting of organic peroxides and azo compounds.

12. The molding composition according to claim 10, wherein the thermosetting catalyst is selected from the organic peroxide group consisting of t-butyl perbenzoenite, t-butyl hydroperoxide, benzopinacol, and benzoyl peroxide. .

13. The aromatic group represented by the formula IOA is 7-enylene, tolylene, xylylene, naphthylene, biphenylyl, anthrylene, a diaryl group of the following formula: (5) and the following formula: OR.

R775E C1-C6 alkyl group selected from the group consisting of polyvalent aromatic groups from the group 75) and C1-C8 alkylene groups; The molding composition according to claim 9, wherein n' is an integer equal to 1 to 10.

(6) 14. The aromatic group A of formula I is bisphenol At15. The aromatic vinyl ether has the following formula: % formula % (a) The following formula: 3 1 A [G-R1-○-c-c ].

Contains a reactive composition containing an aromatic vinyl ether of I 4 R2 (7) and (b) a maleimide having one or more chemical bonding units of the following formula: and having a molecular weight in the range of 111 to about 5,000. A molding composition (in the formula, R1 is a carbon source 1 to
8 alkylene group, R2, R3, R4゜R5 and R6 are selected from the group consisting of hydrogen, and mixtures thereof, A is selected from the group of monovalent and polyvalent aromatic radicals having from 6 to 130 carbon atoms, and n is an integer equal to from 1 to 10).

1z The molding according to claim 16, wherein the filler is selected from the group consisting of clay, silica, cal(8)ium carbonate, aluminum trihydrate, carbon black, talc, calcium sulfate and wollastonite. Composition for use.

18. A molding composition according to claim 16, wherein the filler is in the form of a fibrous matrix.

19. A method for curing a film on a substrate, wherein the film further contains an effective amount of a photocuring catalyst in addition to aromatic vinyl ether and maleimide! A method comprising irradiating the film with ultraviolet light.

20 A method for curing a patterned mask on a substrate, wherein the mask is made of a composition containing aromatic vinyl ether, maleimide, and an effective amount of a photocuring catalyst, (
a) applying the composition on the substrate in an uncured state for about 2 times; (1+) partially exposing the composition to ultraviolet light for about 30 seconds or more; and (c) removing the uncured composition. A method that involves removing parts with a solvent.

1-11-1 death (9)

Claims (1)

[Claims] 1. A curable composition containing an aromatic vinyl ether and maleimide. 2. The molding composition according to claim 1, further comprising an effective amount of a photocuring catalyst. 5. The photocurable composition according to claim 2, wherein the photocuring catalyst is N-butylbenzoin ether. 4. The molding composition according to claim 1, wherein the maleimide is a bismaleimide of the following formula: (wherein 111 and R4 are hydrogen, halogen or t'j01-8.alkyl group, and X is carbon Number of atoms 1-3
selected from the group consisting of a divalent hydrocarbon group of 5 and a divalent group of the following formula: (1), and 2 has 0 carbon atoms.
-15 hydrocarbon group, -5-1-〇-1-801-1 divalent group, R? is an m alkyl group having 1 to 6 carbon atoms). 5. A molding composition according to claim 4, wherein the divalent group X of the bismaleimide is selected from the group consisting of bisphenol A and derivatives thereof. 6. The molding composition according to claim 1, wherein the maleimide is of the following formula: (2) (wherein R5 and R6 are hydrogen, halogen or at-S
The alkyl groups, X and X' are selected from the group consisting of divalent hydrocarbon groups having 1 to 35 carbon atoms and divalent groups of the formula:
~15 divalent hydrocarbon groups, -x-1-0-1 is a divalent group selected, R1 is a monovalent alkyl group having 1 to 6 carbon atoms, and %m is 1 to 1o. is an integer). 2 The above maleimide is N, N'-4,4'-diphenylmethane bismaleimide or 3M'-6-methyl (
3) The molding composition according to claim 1, which is -1,3-phenylene bismaleimide. a The molar ratio of maleimide to aromatic vinyl ether is approximately 1
A molding composition according to claim 1 having a value within the range of 25 to about 4. 9. France) An aromatic vinyl ether of the following formula: (B) 1 or more chemical bonding units +i of the following formula, and a molecular weight of 111 to 5
000 maleimide (in the formula, R1 has 1 to 8 carbon atoms)
ts Teh l), 'R', Ra, R4, R' $
'j HIR' is hydrogen, halogen and carbon atom number 1~
8, Al (4) is selected from the group consisting of 10-11, 10-0-0, and mixtures thereof, and M is a monovalent group having 6 to 130 carbon atoms. and polyvalent aromatic groups, n being an integer equal to 1 to 10). 10. The molding composition according to claim 9, further comprising an effective amount of a thermosetting catalyst. 11. The molding composition according to claim 10, wherein the thermosetting catalyst is selected from the group consisting of organic peroxides and azo compounds. 1Z The molding composition according to claim 10, wherein the thermosetting catalyst is selected from the group of organic peroxides consisting of t-butyl perbenzoate, t-butyl hydroperoxide, benzopinacol and benzoyl peroxide. 14 The aromatic group represented by A in formula I is a polyvalent aromatic group from the group consisting of phenylene, tolylene, xylylene, naphthylene, biphenylyl, anthrylene, a diaryl group of the following formula: (5) and a group consisting of the following formula: Hg. Q is selected from the group consisting of a divalent group of the following formula; -B-1-〇-1-e o, -1 and an alkylene group having 1 to 8 carbon atoms; 10. The molding composition according to claim 9, wherein the molding composition is an alkyl group having a number of 1 to 6, and n# is an integer between 1 and 10%. (6) 14. The molding composition according to claim 9, wherein the aromatic group of formula 1 is bisphenol A or a derivative thereof. 1. The molding composition according to claim 9, wherein the aromatic vinyl ether is selected from bisvinyl ethers of the following formula: 1/h (A) one or more fillers having a ratio of O to 60 and (g)) 40 to 100% of ra) an aromatic vinyl ether of the following formula: () and cb) a chemical bonding unit of the following formula ( - a molding composition containing a reactive composition containing at least one maleimide and a maleimide having a molecular weight within the range of 111 to about 5,000.
B is an alkylene group selected from the group consisting of R1,11,R4゜R1 and R11 hydrogen, halogen and an alkyl group having 1 to B carbon atoms, and G1 is -0-, -0-0- and mixtures thereof, m is selected from the group of monovalent and polyvalent aromatic radicals having from 6 to 130 carbon atoms, and n#' is an integer equal to 1 to 10). 1z The molding according to claim 16, wherein the filler is selected from the group consisting of clay, silica, cal(8)ium carbonate, aluminum trihydrate, carbon black, talc, calcium sulfate and wollastonite. Composition for use. 1a. A molding composition according to claim 16, wherein the filler is in the form of a fibrous matrix. 19. A method of curing a film on a substrate, the film comprising a composition containing aromatic vinyl ether, maleimide, and an effective amount of a photocuring catalyst, and comprising irradiating the skeleton film with ultraviolet light. 20. A method for curing a patterned mask on a substrate, wherein the mask is made of a composition containing aromatic vinyl ether, maleimide, and an effective amount of a photocuring catalyst, (
a) applying the composition in an uncured state onto the substrate for about 2-2 minutes, (1)) partially exposing the composition to ultraviolet light for about 30 seconds or more; A method that includes the step of removing uncured parts with a solvent.