JPS6026423B2 - Heat resistant resin composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to a heat-resistant resin composition.

Known heat-resistant resins include aromatic polyimide, polybenzimidazole, polyimide imidazopyrrolone, polyamideimide, and polyimide ester.

However, these resins are not only difficult to dissolve unless they are highly polar and have a high boiling point, but if they are applied to glass cloth to make pinned tape or B-stage prepreg tape, the following inconveniences occur: There is. That is, the solvent tends to remain, which tends to adversely affect the electrical characteristics, and since the resin coating is rigid, the processability of winding it around, for example, a gas conductor is poor, making it difficult to put it to practical use. Heat-resistant resin kneaded products containing alkenylphenol, maleimide, and furfuryl alcohol as components are also known. However, in the case of this resin composition, although the processability in the B-stage state (for wrapping around conductors, etc.) and the properties of the cured resin are good, it cannot be said to be fully satisfactory for practical use. That is, this heat-resistant resin has the disadvantage that it does not have sufficient adhesion to a substrate, and that when it is applied as a solution, the smoothness and flexibility of the coating film are poor. Therefore, the present invention aims to provide a resin composition that has heat resistance, has good workability even when used in an 8-stage state, and is easy to handle as an insulating material.

To explain the present invention in detail below, the present invention provides an imide group comprising W bismaleimide, at least one of polyvalent maleimides, alkenylphenol, at least one of alkenyl phenyl ethers, and furfuryl alcohol as reaction components. Containing polymer, 1 to 3% polyvinyl formal based on the total resin content,
q It is a heat-resistant resin composition comprising as an essential component 0.01 to 5% by weight of a fluorosurfactant based on the total resin content.

The imide group-containing polymer, which is one component in the present invention, can be easily obtained as follows. That is, bismaleimide, polyvalent maleimide, or a mixture thereof, alkenylphenol, alkenyl phenyl ether, or a mixture thereof, and furfuryl alcohol are made into a dioxane (solvent) solution, and reacted under 100 to 110 qo for about 3 hours. obtained by In the above reaction, the desired aggregate containing imide groups can also be obtained by first reacting the maleimide component with alkenylphenol, etc., and then adding and reacting the furfuryl alcohol component. It is well known to produce imide group-containing polymers by reacting polyvalent maleimides with alkenylphenols, etc., as can be seen, for example, in Japanese Unexamined Patent Publication No. 52-9.

In the present invention, furfuryl alcohol is further added for co-reaction. Furfuryl alcohol is incorporated into a polymer through an addition reaction between its unsaturated bonds and the unsaturated bonds of maleimide. In the present invention, the maleimide compound as one of the reaction components constituting the imide group-containing polymer includes the following compounds.

For example, N. N'-ethylene dimaleimide, N. N'-hexamethylene bismaleimide, N. N'dode'camethylene pismaleimide, N. N'-xylylene bismaleimide, N. N'-1,3-bismethylenecyclohexane bismaleimide, N. N'-1,4-bismethylenecyclohexane bismaleimide, NN'-2,4-tolylene bismaleimide, NN'-2,6-tolylene bismaleimide, N. N'-3,3'-diphenylmethane bismaleimide, N. N'-4,4'-diphenylmethane bismaleimide, 3,3-diphenylsulfone bismaleimide, 4,4'-diphenylsulfone bismaleimide, N. N'
-4,4'-diphenyl sulfide bismaleimide, N
．． N'-p-benzophenone bismaleimide, N. N'
- diphenylethane bismaleimide, N. N'-dipheni'reether bismaleimide, NN'-(methylene ditetrahydrophenyl) bismaleimide, N. N'-(3-ethyl)4,4'-diphenylmethane bismaleimide, NN'-(3,3-dimethyl)4,4'-diphenylmethane bismaleimide, N. N'-(3,3'-diethyl)diphenylmethane bismaleimide, N. N'-
(3,3'-dichloro)-4,4'-diphenylmethane bismaleimide, N. N'-tolidine bismaleimide,
N. N'1 p. p-diphenyldimethylsilyl bismaleimide, N. N'-benzophenone bismaleimide, N
．． N'-diphenylpro/gunpismaleimide, N. N
'-naphthalene bismaleimide, N. N'1P-phenylene pismaleimide, N. N'1m-phenylene bismaleimide, N. N'-4,4'-(1,1-diphenyl-cyclohexane)-bismaleimide, NN'-3,5
-(1,2,4-triazole)bismaleimide, N.
N'-pyridine-2,5-diylbismaleimide, N.
N'-5-methoxy 1,3-phenylenebismaleimide, 1,2-pis(2-maleimidoethoxy)-ethane, 1,3-bis(3-maleimidopropoxy)propane, N. N'-4,4'-diphenylmethane-bis-dimethylmaleimide, N. N'-hexamethylene-bis-dimethylmaleimide, NN'-4,4'-(diphenyl ether)-bis-dimethylmaleimide, N. N'-4,
4'-diphenylsulfone-bisdimethylmaleimide,
N. of 4,4'-diaminotriphenyl phosphate.
N'-bismaleimide, N. of 4,4'-diaminotriphenylthiophosphate. In addition to bifunctional maleimide compounds such as N'-bismaleimide, reaction products of aniline and formalin (polyamine compounds),
3.4. Polyfunctional maleimide compounds obtained by the reaction of 4'-triaminodiphenylmethane, triaminophenol, etc. with maleic anhydride, tris(4-aminophenyl) phosphate, tris(4-aminophenyl) thiophosphate, etc. A trifunctional maleimide compound obtained by reaction with maleic anhydride is a typical example of a polyvalent maleimide compound particularly suitable for the present invention. It is also a particularly effective method in the present invention to use one or more of these polyvalent maleimide compounds as a mixture. These maleimide compounds may be partially substituted with the following monomaleimide compounds. Examples of such monomaleimide compounds include the following. Maleimide, N-
Methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-allylmaleimide, N-phenylmaleimide, N-chlorophenylmaleimide, N- Tolylmaleimide, N-methoxyphenylmaleimide, N-penzylmaleimide, N-pyridylmaleimide, N-hydroxyphenylmaleimide,
N-acetoxyphenylmaleimide, N-dichlorophenylmaleimide, N-penzophenylmaleimide, N-
Diphenyl ether maleimide, N-cyclohexyl maleimide, N-methylene cyclohexane maleimide, N
-acetylphenylmaleimide, N-2-chlorophenylmaleimide, N-4-chlorophenylmaleimide. Although these monomaleimide compounds can be used as a mixture of one or more, the monomaleimide component preferably ranges from 5 to 8 weight percent of the total maleimide compound, and usually the monomaleimide content in the total maleimide is 15 to 6 weight percent. selected in a range of weight percentages.

Among alkenylphenols and alkenylphenol ethers, which are one of the reaction components forming the imide group-containing polymer in the present invention, the latter can be obtained by condensing allyl halide and various phenols using an alkaline catalyst.

In addition, this alkenyl phenyl ether is further added to 180
Alkenylphenol is obtained by heat treatment at ~200°C to cause the so-called Claisen rearrangement. - Generally, allylphenols, derivatives thereof, eugenol obtained by extraction from natural plants, and derivatives thereof can be mentioned. When allylfer/fers are obtained by synthesis, allyl chloride and allyl furomide are suitable as the allyl halide as a reaction component.

Phenols include phenol, resorcinol, cresol, thymol, chlorophenol, nitrophenol, dinitrophenol, picric acid, hydroquinone, pyrocatechol, pyrogallol, hydroxyhydroquinone, 2-methoxyphenol, 2,4-dibutoxyphenol, 2 , 5-dichlorophenol, 3-acetoxyphenol, aminophenol, 4,4'-dihydroxydiphenylproben, 4,4'-dihydroxydiphenylbentane, 4,4'-dihydroxydiphenylpro/gun, 4, 4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenyl methane, 4,
4'-dihydroxyphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-2,
2-dimethyl diphenyl ether, 4, page hydroxy diphenyl ethane, 4,4'-dihydroxy diphenyl ketone, 2-allylphenol, 2-allyl cresol, 2-allyl chloro'phenol, etc. can be used. These allylfers can be used alone or in a mixture of two or more types, but the type and mixing ratio are appropriately selected in consideration of various properties such as the desired heat resistance and viscosity of the resin.

Further, the composition of the allylphenol and the maleimide compound is preferably selected within a range in which the allyl group of the allylphenol is not in large excess with respect to the double bond of the maleimide compound. Generally, 0.0% per equivalent of maleimide double bond.
It is sufficient to select it within the range of 2 to 2 equivalents. In the present invention, furfuryl alcohol, which is a reactive component forming the imide group-containing polymer, contributes to the stability of the polymer produced by the reaction, and its composition ratio is 2.5 to 2.5 to the maleimide compound.
4% by weight (preferably 5 to 15% by weight).

In the present invention, the polyvinyl formal added to the above-mentioned imide group-containing polymer contributes to thickening when it is made into a solution, and has a molecular weight of about 20,000 to 100,000 and a formal conversion rate of about 40% or more (preferably a molecular weight of about 40% or more).
000 to 6,000 and a formalization rate of 80% or more), and the amount added is selected so that it accounts for about 1 to 3% by weight (preferably 3 to 15% by weight) of the total resin content.

Although this polyvinyl formal component may be added and blended later, it may also be added during the reaction production of the imide group-containing polymer and allowed to coexist in the reaction system. In the present invention, there are nonionic, cationic, and anionic fluorine-based surfactants that constitute an additional component together with the polyvinyl formal, such as Florard F.
C-430 Florado FC-134, Florado FC
-128 (both are trade names of Sumitomo 3M Co.), and the amount added is selected to be about 0.01 to 5% by weight.

The heat-resistant resin composition according to the present invention may be made of only three components, the above-mentioned imide group-containing polymer, polyvinyl formal, and fluorosurfactant, but it may further shorten the curing time and improve adhesion. Pond components can be added and blended. That is, as a curing catalyst, for example, a radical catalyst such as penzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, M old K-peroxide, t-butyl peroxybenzoate, azobisisobutyronitrile, or a secondary amine. , tertiary amines, quaternary ammonium salts, alkali metal compounds, transition metal acetylacetonates, or cationic polymerization catalysts such as boron trifluoride. In addition, to improve adhesion to substrates such as glass cloth,
A suitable silane coupling agent such as epoxylans, aminosilanes, pinylsilanes, and acrylic silanes may be added and blended. The resin composition according to the present invention is easily dissolved in dioxane, for example.

Therefore, it is generally preferable to use dioxane as a solution (in this case, the solvent is, for example, acetone, a ketone such as methyl ethyl ketone, an aromatic system such as toluene or xylene, an alcohol or dimethylformamide, and a dioxane system). There may be. As described above, the resin composition according to the present invention has an imide group-containing polymer as its main component, and further contains polyvinyl formal and a fluorine-containing surfactant as essential components.

However, when the polyvinyl formal component becomes a solution,
It contributes to the improvement of viscosity and allows a large amount of resin to be applied when applied to glass cloth, for example, and also imparts appropriate softness to the applied resin layer. In this way, for example, when a prepreg or B-stage tape is used and wound around a conductor for electrical equipment, taping can be easily performed due to the above-mentioned non-plasticity or durability, and breakage and work difficulties during the winding process are completely eliminated. Furthermore, by using a fluorosurfactant in combination, the coated resin layer maintains a good surface finish and fineness, contributing to excellent heat resistance and insulation. Furthermore, as mentioned above, this heat-resistant resin is insoluble in solvents with a boiling point of around 100° C., such as dioxane, so even when applied to the production of bripreg, the solvent can be easily removed without causing any deterioration of the resin content. Next, examples of the present invention will be described.

In the Examples, the composition ratio of each component is in parts by weight.
Bismaleimide diphenylmethane, polyvalent maleimide M2
0 (product name, manufactured by Mitsui Tosho Co., Ltd., maleimide dinuclear body 70-8
0% and 20 to 30% of 3-5 nuclear bodies), diaminodiphenylmethane maleimide, 0-methylphenylmaleimide, diallylbisphenol F, and furfuryl alcohol were selected in a predetermined composition ratio as shown in Table 1. Using dioxane as a solvent and using a flask equipped with a condenser and a rope strainer 1
1000C for 3 hours each to obtain a polymer containing an imide group.

Next, the temperature of the reaction system was lowered to about 50 oo, and polyvinyl formal and the fluorine surfactant Floral CF-
Five types of resin solutions were prepared by adding and blending predetermined amounts of 430 (fluorocarbon, detailed ingredients unknown), acrylic silane, dicumyl peroxide, methyl alcohol, etc.

Table 1 also shows the results of determining the resin nonvolatile content and viscosity (25° C.) for each of the prepared resin solutions. Table 1 The resin solutions prepared respectively above were applied to an aluminum plate on the 1st side of the thickness, and heat treated for 180 pm x 16 hours to form a cured resin film with a thickness of 0.1 mm.

Table 2 shows the results of measuring the volume resistivity ○ and dielectric positive saddle % at 25° C. and 180° C. of the coating film thus formed. Further, these resin solutions were applied to glass cloth and dried to prepare prepregs having a resin coating amount of about 3% by weight. Using this prepreg, heating temperature 1
80℃, pressure 50k9/mold, 180qo× after 1 hour molding
25qo, 18 for a laminate with a thickness of 1.6 ribs obtained after 16 hours or 200°C x 1 motherboard after-cue
The results of measuring the bending strength (kg/skin 2) at 0q○ and 240oo are also shown in Table 2. Table 2 The resin solution of Example 2 was applied to a glass cloth tape with a width of 20 capes and dried at 10500 for 10 minutes.The tape with a resin coating amount of about 3% by weight had sufficient flexibility as a prepreg tape. I was preparing for it.

Further, the resin solution of Example 3 was applied to a glass cloth tape to obtain a pinned tape having a resin coating amount of about 3% by weight, a thickness of 30.3 ribs, and a width of 19 legs.

When this tape was wrapped around a ring model specified in JISC2412 and evaluated, it was flexible and easy to wrap.
Moreover, the characteristic value according to the ring model test was 778k9. Further, the resin solution of Example 4 was applied to an aromatic nylon paper tape having a width of 15 mm and dried to obtain a prepreg tape with a resin coating amount of about 1% by weight. This prepreg tape has sufficient flexibility to wrap around rectangular copper wire.
When a half-wrapped electric wire was heat-treated for 18 C x 1 hour, the wrapped tape was strongly adhered to the surface of the electric wire. Furthermore, the resin solution of Example 5 was coated on a laminated mica paper having a thickness of 0.9 shipboard and dried at 11 pi for 15 minutes to obtain a prepreg sheet with a resin coating amount of about 1% by weight.

These sheets are laminated at a pressure of 50k9/ground and a temperature of 180k/ground.
A laminated mica plate having a thickness of 0.5 mm was formed by pressure molding for 1 hour. Next, this laminated mica board was subjected to post-curing of 20 pcs x 1 mater, and its bending strength was measured. It was 9/2 at 25°C and 2 at 180°C.
It exhibited excellent strength even at high temperatures at 1k9/ground and 18k9/ground under 24 and 0. In the above, the three components of bismaleimide, polyvalent maleimide, diallylbisphenol, and furfuryl alcohol were first reacted to obtain an imide group-containing polymer, and then the polypynyl formal component was added and blended, but the polypynyl formal component was added and blended. When the three components were reacted under 11 psi, similar results were observed when the polyvinyl formal component was allowed to coexist.

Claims (1)

[Claims] 1 (A) An imide group-containing polymer comprising at least one of bismaleimide and polyvalent maleimide, at least one of alkenyl phenols and alkenyl phenyl ethers, and furfuryl alcohol as reactive components; B) 1 to 30% by weight of the total resin content
of polyvinyl formal, and (C) 0.0% of the total resin content.
A heat-resistant resin composition comprising 1 to 5% by weight of a fluorine surfactant as an essential component.