JPS58125719A - Thermosetting resin composition and its prepolymer - Google Patents

Abstract

PURPOSE:A thermosetting resin composition, containing a dicyanamide compound and a polymerizable monomer, capable of giving heat-resistant cured articles, and utilizable for impregnation, casting, embedding, etc. CONSTITUTION:A thermosetting resin composition prepared by incorporating 100pts.wt. dicyanamide compound, e.g. 4,4'-dicyanamidodicyclohexylmethane, with 10-400pts.wt. polymerizable monomer, e.g. styrene. The resultant composition is then heated at 70-180 deg.C to give the aimed prepolymer. In obtaining cured articles, the composition is heated at 150-220 deg.C, and if necessary a curing catalyst, e.g. benzoyl peroxide, an inorganic filler, flame retardant, flexibilizer, pigment, etc. are incorporated with the composition. USE:For laminating, bonding, molding, prepregs and films.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a thermosetting resin composition that can be heat-cured to produce a cured product with excellent heat resistance and can be used as a solvent-free type for impregnating, casting, embedding, etc. Regarding "N" Shin 1 Crimer.

Addition-polymerized polyimides such as bismaleimide are well known as heat-resistant class H yuzu insulation materials. This maleimide is often used as a diamine or in combination with an epoxy resin, polyvalent carboxylic acid allyl ester, or the like. Additionally, according to US Pat. No. 4,043,986, cyanamide (NCNHz) is added to mono- or bisimide to improve heat resistance and chemical stability.
A composition that is cured by adding is proposed. but,
Even in these cases, the heat resistance of the cured product has not been sufficiently improved. Further, the curability of the composition is also not sufficient.

An object of the present invention is to provide a composition that can be cured into a heat-resistant resin equivalent to insulating material heat-resistant classification T44.

The thermosetting resin composition of the present invention comprises (a) dicyanamide represented by the general formula % (in formula (I), A represents a divalent organic group containing at least 2 carbon atoms); The percentage indicates that the compound contains a compound and (b) an i-combined integer.

In the present invention, the dicyanamide compound is cyclized or trimerized by heating to form an isomelamine ring represented by the following general formula [in formula (II), A is the same as in formula (I)]. to produce a cured product with

Simultaneously with this reaction, an addition reaction with the compound of component (b) present in the system occurs, for example, in the reaction with triallyl isocyanurate, the following general formula (in formula (m), A is the formula CI ) It is presumed that a prepolymer and a cured product having isomelaban rings in the network as shown in () are produced. During this reaction, it is effective to use a curing accelerator or catalyst such as an organic peroxide.

Examples of the dicyanamide compound represented by the above general formula in the present invention include 4,4'-dicyanamide dicyclohexylmethane, 1,4-dicyanamide cyclohexane, 2,
6-cyanamidophenyl, m-phenylene dicyanamide, p-phenylene dicyanamide, 4,4'-dicyanamidiphenylmethane, 2,2'-bis(4-cyanamidophenyl)propane, 4,4'-dicyanamidophenyl oxide, 4.4'-dicyanamidiphenylsulfone, bis(4-cyanamidophenyl)phosphine oxyto, bis(4-aminophenyl)phenylphosphine oxyto, bis(4-cyanamidophenyl)methylamine, 1.5-dicyanamidonaphthalene , m-xylylene dicyanamide, 1'+1-bis(p-cyanamidophenyl)furatane, p-xylylene dicyanamide, hexamethylene dicyanamide, 6.6 fudicyanamide 2,2'
-dipyridyl, 4.4'-dicyanamide benzophenone, 4.4'-dicyanamide azobenzene, bis(4-cyanamidophenyl)phenylmethane, 1.1-bis(4
-cyanamidophenyl)cyclohexane, 1,1-bis(4-cyanamidophenyl)-1,3,4
-Oxadiazole, 4.4'-dicyanamidiphenyl ether, 4.4'-bis(p-cyanamidophenyl)-2°2'-dithiazole, m-bis(4-p-cyanamidophenyl-2-thiazolyl)benzene , 4°4'
-Dicyanamide benzanilide, 4.4'-Cuciana 2-dophenylbenzoate, 2.2'-BisC4-(
4-cyanamidophenoxy)phenyl]propane, 2.
2'-bis[3-methyl-4-(4-cyanamidophenoxy)phenyl]propane, 2.2-bis[3-ethyl-4-(4-cyanamidophenoxy)phenyl]propane, 2゜2-bis[3 -Propyl-4-(4-cyanamidophenoxy)phenyl]propane, 2,2-bis(3
-1 sobrovir-4-(4-cyanamidophenoxy)phenyl]propane, bis(4-(4-cyanamidophenoxy)phenylmethane and a cyanamide terminal represented by the following formula (IV) CHs (n is 0 to 3) At least 111 sulfone ether oligomers are used. Prepolymers obtained by heating and polymerizing the above compounds are also useful.

In the present invention, examples of the polymerizable single compound used together with the dicyanamide compound include vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, vinylbenzene, and N-vinylpyrrolidone, triallyl trimellitate, diallyl terephthalate, diallyl Isophthalate, diallyl orthophthalate, triallyl isocyanurate, triallyl cyanurate, p, p'-diallyloxycarbonyl diphenyl ether, rn, p'-diallyloxycarbonyl diphenyl ether, 0゜p' -
-) allyloxycarbonyl diphenyl ether, nl,
Polyhydric carboxylic acid allyl esters such as m'-diallyloxycarponyl diphenyleder and diallyl chlorendate, methyl acrylate, ethyl acrylate, rope tyl acrylate, isobutyl acrylate, n-propyl acrylate, inpropyl acrylate, n-
Pentyl acrylate, n-hexyl acrylate, trimethylol propane triacrylate, 2-ethylhexyl acrylate-1, 2-hydroxyethyl acrylate, tetraethylene glycol diacrylate-1, hexa/diol diacrylate, neopentyl glycol Diacrylate, pentaerythritol triacrylate ester, methyl methacrylate, ethyl methacrylate, n-progel methacrylate, isoprogel methacrylate, -butyl methacrylate, inbutyl methacrylate, n-pentyl methacrylate, n-hexyl acrylate, trimethylolpropane trimethacrylate , ethylene dimethacrylate to l-, methacrylic acid esters such as diethylene dimethacrylate, tris(acryloyloxyethyl) isocyanurate, l.lis(methacryloyloxyethyl) isocyanurate, and the like. These compounds can also be used in combination of two or more. Furthermore, prepolymers obtained by pre-reacting these are also useful.

Even if the blending ratio of the dicyanamide compound and the polymerizable monomer in the composition of the present invention is changed over a wide range, a cured product having good heat resistance can be obtained. Generally, the former is $100 tt*, while the latter is 10 to 40
0 parts is appropriate. As the proportion of the dicyanamide compound increases, heat resistance improves, but viscosity tends to increase.

The inventive resin composition reacts and cures by heating. This reaction is preferably carried out by heating to about 150 to 220°C. 70-180C when obtaining a prepolymer
Heating may be stopped when the reaction reaches state B.

In addition, in the present invention, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, cumene hydroperoxide, dikushaributyl peroxide,
Common organic peroxides such as dicumyl peroxide, tertiary-butylcumyl peroxide, methyl ethyl ketone peroxide, and tertiary-butyl peroxybenzoate can be used as appropriate. The appropriate amount of electricity used by these curing catalysts is 0.1 to 5% by weight of the entire composition.

The resin composition of the present invention may contain known inorganic fillers, glass fibers, flame retardants, flexibility agents, pigments, coupling agents, mold release agents, and the like.

The resin composition of the present invention is useful as a solvent-free type for impregnation, lamination, adhesion, molding, prepreg, and film applications.

Example 1 4,4'-dicyanamidiphenylmethane 60fill
,) 40 parts of realyl isocyanurate), 1. O
A prepolymer was obtained by reacting at 0 to 130C for about 20 minutes. When the infrared absorption spectrum of this prepolymer was measured, absorption based on the wave number 1620 crn-'VC isomelamine ring was observed.

Next, 1 part by weight of dicumyl peroxide was added to this prepolymer and reacted at 170 to 200 C for 100 minutes to obtain an insoluble and infusible cured product.

Example 2 4.4'--dicyanamide diphenyl ether 50]i
-7 parts, 50 parts of triallyl trimellitate in 100-1
A prepolymer was obtained by reacting at 50''C for about 30 minutes.

2 parts by weight of dicumyl peroxide was added to this prepolymer and reacted at 170 to 200C for 180 minutes to obtain an insoluble and infusible cured product.

When the infrared absorption spectrum of this cured product was measured, it was found that the absorption of the anamide group at a wave number of 226On+-' almost disappeared, and a new absorption based on the isomelamine ring was observed at 1.620t:m-'.

Example 3 2'-bis[4-(4-cyanamidopheno(11)xy)phenyl]propane 55ffi 8Ll lyadyl isocyanurate-145 parts by weight were reacted at loo~150C for about 20 minutes to precipitate. A polymer was obtained.

As in Example 1, this prepolymer was confirmed to have absorption based on isomelamine rings using an infrared absorption spectrum.

Next, 1 part by weight of cumenohydrovar oxide was added to this prepolymer and reacted at 170 to 200C for about 100 minutes to obtain a cured product that was insoluble in -C and infusible.

Example 4 50 parts of 2.2'-bis[4-(4-cyanamidophenoxy)phenyl]frobuff, 50 parts of triallyl cyanurate
A prepolymer was obtained by reacting the mixture at 100-150C for about 20 minutes. 1 part by weight of di-tert-butyl peroxide was added to this prepolymer and reacted at 170 to 200 C for about 80 minutes to obtain an insoluble and infusible cured product. When the infrared absorption spectrum of this cured product was measured, the wave number 1
Absorption based on the isomelamine ring was observed at 620 rrn-' (12).

Example 5 4.4′-dicyanamidiphenylmethane 60 parts,
40 parts by weight of diallyl isophthalate at 100-130C
The mixture was reacted for about 30 minutes to obtain a prepolymer. When the infrared absorption spectrum of this prepolymer was measured, the wavenumber was 1.
Absorption based on the isomelamine ring was observed at 620 ryr −'.

Next, one layer of dicumyl peroxide was added to this prepolymer and reacted at 180 to 200'C for about 120 minutes to obtain an insoluble and infusible cured product.

Example 6 85 parts by weight of 4.4'-dicyanamidiphenylmethane,
A prepolymer was obtained by reacting styrene 15N indigo at 80 to 120C for about 30 minutes. To this prepolymer was added 1 part by weight of ditertiary butyl peroxide [1 part by weight]
The reaction was carried out at 70 to 200 C for about 80 minutes to obtain an insoluble and infusible cured product. When the infrared absorption spectrum of this cured product was measured, absorption (13) based on isomelamine rings was observed at a wave number of 1620 m-'.

Example 7 4.4′-dicyanamide diphenyl ether 80ffi
It part and 20 parts by weight of 2-ethylhexyl acrylate were reacted at 90 to 130C for about 30 minutes to obtain a prepolymer. One part by weight of ditertiary-butyl peroxide was added to this prepolymer and reacted at 170 to 200 C for about 80 minutes to obtain an insoluble and infusible cured product. When the infrared absorption spectrum of this cured product was measured, the wave number was 1620c.
Absorption based on the isomelamine ring was observed at rn-'.

A glass cloth treated with aminosilane having a thickness of 0.18 mm was impregnated with the prepolymer obtained in the above example to prepare a coated cloth having a resin content of approximately 40% by weight.

Next, stack 8 sheets of each coated cloth and apply a pressure of 10 to 40 kg.
/c1n' Laminated and bonded at a predetermined temperature, thickness approximately 1,
A 6 mm 8-layer plate was prepared.

As a conventional example, aminobismaleimide polymer (melting point 80-90C) was dissolved in the solvent N-methyl-2-pyrrolidone (boiling point 202tZ'), and (14) a face with a solid content of 50% by weight was created. . Next, the same glass cloth as above was impregnated and dried to prepare a two-coated cloth. Furthermore, stack 8 coated cloths at a time and apply a pressure of 80 kg.
/cnr2.180t? , hardened in 90 minutes, and
A laminate was prepared by post-curing at 220C for 180 minutes.

The results of measuring each characteristic of the resin and the laminate are shown in the table. The sound reduction at 500C is the reduction rate when it reaches 500t?The bending strength is the bending strength at 25C. The retention rate of the bending strength I carcass at each temperature with respect to the strength, and the retention rate of the bending strength with respect to the initial value after heating and deteriorating in air at 11.220C for a predetermined time at 91 degrees of bending after deterioration.The measurement temperature is room temperature (25C ).

(15) (16) 139

Claims (1)

[Claims] 1. (a) General formula NCI-IN-A-NH
A dicyanamide compound represented by CN (I) [in formula (I), A represents a divalent organic group containing at least 2 carbon atoms], and (b) a polymerizable compound. Thermosetting resin composition. 2.(a)m: A compound containing at least one compound selected from the group consisting of allyl polyvalent carboxylic acid ester, acrylic ester, and methacrylic ester as a synthetic compound. Thermosetting resin composition according to scope 1. 3. The thermosetting resin composition according to claims 1 and 2, to which an organic peroxide is added as a curing catalyst. 4, (a) General formula NCI-IN-A, -N
i-ICN (H [in formula (I), A represents a divalent organic group containing at least 2 carbon atoms 1′]), and (b) contains a polymerizable single compact. 5. The prepolymer according to claim 4, to which an organic peroxide is added as a curing catalyst.