Superconducting magnet coil and curable resin composition used therein

BACKGROUND OF THE INVENTION
(1) Field of the Invention
The present invention relates to a superconducting magnet coil, an insulating layer thereof and a curable resin composition used in the superconducting magnet coil.
(2) Description of the Prior Art
In a superconducting magnet coil used, by being dipped in liquid helium, in linear motor cars, superconducting electromagnetic propulsion vessels, nuclear fusion reactors, superconducting generators, MRI, pion applicators (for therapy), electron microscopes, energy storage apparatuses, etc., the superconducting wires contained in the coil cause a temperature increase incurred by frictional heat or the like when the superconducting wires are moved by an electromagnetic force or a mechanical force. As a result, the magnet may shift from a superconducting state to a state of normal conduction. This phenomenon is called a quench phenomenon. Hence, it is conducted in some cases to fill the gap between the wires of the coil with a resin such as epoxy resins or the like to fix the wires.
The resin, such as epoxy resins or the like, used for filling the coil gap usually has a thermal shrinkage factor of 1.8-3.0% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K. Meanwhile, the superconducting wires have a thermal shrinkage factor of about 0.3-0.4% under the same condition. As Y. Iwasa et al. describe in Cryogenics Vol. 25, pp. 304-326 (1985), when a superconducting magnet coil comprising superconducting wires and a resin used for filling the gap between the wires is cooled to a liquid helium temperature, i.e. 4.2K, a residual thermal stress appears due to the difference in thermal shrinkage factor between the superconducting wires and the resin. As a result, microcracks of several microns appear in the resin, a temperature increase of several degrees is induced at the peripheries of the microcracks due to the releasing energy of the residual thermal stress of the resin, and the superconducting wires show a sharp rise in resistance. Finally, the superconducting magnet coil shifts from a superconducting state to a state of normal conduction and causes an undesirable phenomenon called "quench". Further, at the liquid helium temperature (4.2K), the impregnant resin such as epoxy resins or the like gets very brittle and produces microcracks of several microns, due to an electromagnetic force or a mechanical force. The releasing energy from the microcracks gives rise to a temperature increase of several degrees at the peripheries of the microcracks. Thus, the superconducting wires show a sharp rise in resistance, the superconducting magnet coil shifts from a superconducting state to a state of normal conduction and disadvantageously causes quench.
SUMMARY OF THE INVENTION
The present invention has been made in view of the above situation. The objects of the present invention are to provide a superconducting magnet coil which is resistant to microcrack generation of impregnant resin and causes substantially no quench during operation; an insulating layer thereof; and a curable resin composition used in the superconducting magnet coil.
The objects of the present invention can be achieved by using, as a resin for impregnation of superconducting magnet coil, a curable resin composition capable of giving a cured product having a thermal shrinkage factor of 1.5-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K, particularly a cured product having a thermal shrinkage factor of 1.0-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K.
The present invention is briefly described as follows. The first aspect of the present invention relates to a superconducting magnet coil which is impregnated with a curable resin composition capable of giving a cured product having a thermal shrinkage factor of 1.5-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K, particularly a cured product having a thermal shrinkage factor of 1.0-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K.
The second aspect of the present invention relates to a resin used for impregnation of superconducting magnet coil, that is, a curable resin composition capable of giving a cured product having a thermal shrinkage factor of 1.5-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-4.5% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K, particularly a cured product having a thermal shrinkage factor of 1.0-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K.
The third aspect of the present invention relates to a process for producing a superconducting magnet coil which comprises a coil of superconducting wire and a cured product of a curable resin composition with which the coil has been impregnated, which process comprises the steps of:
(a) winding a superconducting wire to form a coil,
(b) filling the gap between the superconductors of the coil with a curable resin composition having a viscosity of 0.01-10 poises at the time of filling to obtain a curable-resin-composition-impregnated coil, and
(c) heating the curable-resin-composition-impregnated coil to cure the composition so as to give a cured product having a thermal shrinkage factor of 1.5-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K, particularly a cured product having a thermal shrinkage factor of 1.0-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K.
The fourth aspect of the present invention relates to an insulating layer of superconducting magnet coil, which is obtained by impregnation of a coil of superconducting wire with a curable resin composition and curing of the resin composition, said resin composition being capable of giving a cured product having a thermal shrinkage factor of 1.5-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-4.5% at 4.2K and a modulus of 500-1.000 kg/mm.sup.2 at 4.2K, particularly a cured product having a thermal shrinkage factor of 1.0-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-4.5% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K.
According to the present invention, there are provided:
a superconducting magnet coil which comprises a coil of superconducting wire and a cured product of a curable resin composition with which the coil has been impregnated, the cured product having a thermal shrinkage factor of 1.5-0.3% when cooled from the glass transition temperature to 4.2K, a bend-breaking strain of 2.9-3.9%, preferably 3.2-3.9% at 4.2K and a modulus of 500-1,000 Kg/mm.sup.2 at 4.2K;
a superconducting magnet coil which comprises a coil of superconducting wire and a cured product of a curable resin composition with which the coil has been impregnated, the cured product undergoing a thermal stress of 0-10 kg/mm.sup.2 when cooled from the glass transition temperature to 4.2K and being resistant to quench during superconducting operation;
a curable resin composition which gives a cured product having a thermal shrinkage factor of 1.5- 0.3%, preferably 1.0-0.3% when cooled from the glass transition temperature to 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K;
a process for producing the superconducting magnet coil which comprises the steps of:
(a) winding a superconducting wire to form a coil,
(b) impregnating the coil with a curable resin composition having a viscosity of 0.01-10 poises at the time of filling, for example, the curable resin composition comprising (i) at least one epoxy resin selected from the group consisting of diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F and diglycidyl ether of bisphenol AF, all having a number-average molecular weight of 350-1,000, (ii) a flexibilizer and (iii) a curing catalyst, so as to fill the gap between the superconductors of the coil with the curable resin composition to obtain a curable-resin-composition-impregnated coil, and
(c) heating the curable-resin-composition-impregnated coil to cure the composition to allow the cured product of the composition to have a thermal shrinkage factor of 1.5-0.3%, preferably 1.0-0.3% when cooled from the glass transition temperature to 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K,
preferably, the step (b) including the step of covering the outer surface of the coil with a release film or a perforated film, placing the film-covered coil in a mold, and effecting vacuum impregnation, and if necessary pressure impregnation, of the coil with the curable resin composition,
preferably, the step (c) including the step of curing the composition under pressure, and if necessary further comprising the step of clamping the curable-resin-composition-impregnated coil before the step of curing;
a superconducting magnet coil which comprises:
(a) a coil of a composite superconductor comprising a plurality of thin superconducting wires and a stabilizer selected from the group consisting of copper and aluminum which is thermally or electrically contacted with the wires, and
(b) a cured product of a curable resin composition with which the coil has been impregnated,
the cured product having a thermal shrinkage factor of 1.5-0.3% when cooled from the glass transition temperature to 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K;
a superconducting magnet coil which comprises:
(a) a coil of a composite superconductor comprising a plurality of thin superconducting wires and a stabilizer selected from the group consisting of copper and aluminum which is thermally or electrically contacted with the wires, and
(b) a cured product of a curable resin composition with which the coil has been impregnated,
the cured product undergoing a thermal stress of 0-10 kg/mm.sup.2 when cooled from the glass transition temperature to 4.2K and resistant to quench during superconducting operation;
a process for producing the superconducting magnet coil which comprises the steps of:
(a) winding a composite superconductor comprising a plurality of thin superconducting wires and a stabilizer selected from the group consisting of copper and aluminum which is thermally or electrically contacted with the wires to form a coil,
(b) filling the gap between the composite superconductors of the coil with a curable resin composition to obtain a curable-resin-composition-impregnated coil, and
(c) heating the curable-resin-composition-impregnated coil to cure the composition,
the step (a) including the step of subjecting the composite superconductor to surface treatment with a coupling agent before winding the composite superconductor; and
an insulating layer of a superconducting magnet coil which comprises:
(a) a coil of a composite superconductor comprising a plurality of thin superconducting wires and a stabilizer selected from the group consisting of copper and aluminum which is thermally or electrically contacted with the wires, and
(b) a cured product of a curable resin composition with which the coil has been impregnated,
the cured product having a thermal shrinkage factor of 1.5-0.3% when cooled from the glass transition temperature to 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K.

BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a race track-shaped superconducting magnet coil. The numeral 1 is a round superconducting magnet coil.
FIG. 2 is a cross-sectional view of the coil of FIG. 1 when cut at II--II' line.
FIG. 3 is a fragmentary enlarged view of FIG. 2 of a conventional race track-shaped superconducting magnet coil.
FIG. 4 is a perspective view of a saddle-shaped superconducting magnet coil.
FIG. 5 is a cross-sectional view of the coil of FIG. 4 when cut at a V--V' line.

DETAILED DESCRIPTION OF THE INVENTION
The curable resin composition according to the present invention can also be preferably used in switches for permanent current which are required in superconducting magnet coils for linear motor cars, MRI, energy storage and nuclear fusions.
The superconducting wire used in the present invention has no particular restriction and can be any wire as long as it has superconductivity. There can be mentioned, for example, alloy superconductors such as Nb--Ti and the like; intermetallic compound superconductors such as Nb.sub.3 Sn, Nb.sub.3 Al, V.sub.3 Ga and the like; and oxide superconductors such as LaBaCuO, YBaCuO and the like. Ordinarily, the superconducting wire has a composite structure comprising (a) the above superconductor and (2) a metal of normal conduction such as Cu, cupro-nickel (CuNi), CuNi--Cu, Al or the like. That is, the superconducting wire includes an ultrafine multiconductor wire obtained by embedding a large number of thin filament-like superconducting wires into a metal of normal conduction as a matrix, a straight twisted wire obtained by binding a large number of superconducting material wires into a straight bundle and twisting the bundle with the straightness being maintained, a straight wire obtained by embedding a straight superconducting material wire into a straight normal conductor, and an internal cooling type conductor having inside a passage for cooling medium.
The resin for impregnation of superconducting magnet coil, used in the present invention has no particular restriction and can be any resin as long as it can give a cured product having a thermal shrinkage factor of 1.5-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K, particularly a cured product having a thermal shrinkage factor of 1.0-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K.
When the cured product of the resin has a thermal shrinkage factor larger than 1.5% and a modulus larger than 1,000 kg/mm.sup.2, the stress applied to the superconducting magnet during the superconducting operation surpasses the strength of the cured product. As a result, the cured product generates cracks, and quench occurs due to the releasing energy of the stress. When the cured product has a thermal shrinkage factor smaller than 0.3%, the stress applied to the superconducting magnet during the superconducting operation surpasses the strength of the cured product due to the difference in thermal shrinkage factor between the cured product and the superconductor of the magnet. As a result, the cured product generates cracks, and quench tends to occur due to the releasing energy of the stress. When the modulus is smaller than 500 kg/mm.sup.2, the glass transition temperature tends to be lower than room temperature and, when the superconducting magnet has been returned to room temperature, the cured product generates cracks due to the low strength; when the magnet is recooled to 4.2K and reoperated, the cracks become a nucleus of further crack generation and the superconducting magnet causes quench. When the bend-breaking strain is smaller than 2.9%, the cured product has low adhesion to the superconductor and, after the cooling or during the operation of the superconducting magnet, peeling takes place between the superconductor and the cured product. As a result, thermal conductivity between them is reduced, even slight cracking invites temperature increase, and the superconducting magnet tends to incur quench.
As the method for increasing the bend-breaking strain of a thermosetting resin, that is, for toughening a thermosetting resin, there are a number of methods. In the case of an epoxy resin, for example, there are (1) a method of subjecting an epoxy resin to preliminary polymerization to obtain an epoxy resin having a higher molecular weight between crosslinked sites, (2) a method of adding a flexibilizer (e.g. polyol, phenoxy resin) to an epoxy resin to increase the specific volume of the latter, (3) a method of introducing a soft molecular skeleton into an epoxy resin by using a curing agent such as elastomer-modified epoxy resins, long-chain epoxy resins, long-chain amines, acid anhydrides, mercaptans or the like, (4) a method of using an internal plasticizer such as branched epoxy resins, polyamide-amines, dodecyl succinic anhydrides or the like, (5) a method of using, in combination with an epoxy resin, a monofunctional epoxy resin to give rise to internal plasticization, (6) a method of using an epoxy resin as a main component and a curing agent in proportions deviating from the stoichiometric amounts to give rise to internal plasticization, (7) a method of adding a plasticizer (e.g. phthalic acid ester) to give rise to external plasticization, (8) a method of dispersing butadiene rubber particles, silicone rubber particles or the like in an epoxy resin to form an islands-in-a-sea structure, (9) a method of introducing, into an epoxy resin, an acrylic resin, an urethane resin, a polycaprolactone, an unsaturated polyester or the like to form an interpenetrating network structure, i.e. an IPN structure, (10) a method of adding, to an epoxy resin, a polyether having a molecular weight of 1,000-5,000 to form a microvoid structure, and so forth. Of these methods, the methods (1) and (2) are preferable in view of the low thermal shrinkage and high toughness of the improved epoxy resin.
Specific examples of the improved epoxy resin obtained according to the above methods, are an epoxy resin obtained by curing an epoxy resin of high molecular weight with an acid anhydride, an epoxy resin obtained by curing an epoxy resin of high molecular weight with a catalyst alone, an epoxy resin obtained by adding a flexibilizer to an epoxy resin and curing the resin with an acid anhydride, an epoxy resin obtained by adding a flexibilizer to an epoxy resin and curing the resin with a catalyst alone, and a maleimide resin obtained by adding a flexibilizer.
The epoxy resin usable in the present invention can be any epoxy resin as long as it has at least two epoxy groups in the molecule. Such an epoxy resin includes, for example, bifunctional epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol AF, diglycidyl ether of bisphenol AD, diglycidyl ether of hydrogenated bisphenol A, diglycidyl ether of 2,2-(4-hydroxyphenyl)nonadecane, 4,4'-bis(2,3-epoxypropyl) diphenyl ether, 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, 4-(1,2-epoxypropyl)-1,2-epoxycyclohexane, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)-cyclohexane-m-dioxane, 3,4-epoxy-6-methylcyclohexylmethyl-4-epoxy-6-methylcyclohexanecarboxylate, butadiene-modified epoxy resin, urethane-modified epoxy resin, thiol-modified epoxy resin, diglycidyl ether of diethylene glycol, diglycidyl ether of triethylene glycol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, diglycidyl ether of 1,4-butanediol, diglycidyl ether of neopentyl glycol, diglycidyl ether of propylene oxide adduct of bisphenol A, diglycidyl ether of ethylene oxide adduct of bisphenol A, and the like; trifunctional epoxy resins such as tris[p-(2,3-epoxypropoxy)phenyl]methane, 1,1,3-tris[p-(2,3-epoxypopoxy)phenyl]butane and the like; and polyfunctional epoxy resins such as glycidylamine (e.g. tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidylamine, tetraglycidyl-m-xylylenediamine, tetraglycidyl-bisaminomethylcyclohexane), phenolic novolac type epoxy resin, cresol type epoxy resin and the like. It is also possible to use a polyfunctional epoxy resin obtained by reacting epichlorohydrin with at least two polyhydric phenols selected from (a) bis(4-hydroxyphenyl)methane, (b) bis(4-hydroxyphenyl)ethane, (c) bis(4-hydroxyphenyl)propane, (d) tris(4-hydroxyphenyl)alkane and (e) tetrakis(4-hydroxyphenyl)alkane, because the resin has a low viscosity before curing and gives easy working. Specific examples of tris(4-hydroxyphenyl)alkane are tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(4-hydroxyphenyl)hexane, tris(4-hydroxyphenyl)heptane, tris(4-hydroxyphenyl)octane, tris(4-hydroxyphenyl)nonane, etc. There can also be used tris(4-hydroxyphenyl)alkane derivatives such as tris(4-hydroxydimethylphenyl)methane and the like.
Specific examples of tetrakis(4-hydroxyphenyl)alkane are tetrakis(4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(4-hydroxyphenyl)propane, tetrakis(4-hydroxyphenyl)butane, tetrakis(4-hydroxyphenyl)hexane, tetrakis(4-hydroxyphenyl) heptane, tetrakis(4-hydroxyphenyl)octane, tetrakis(4-hydroxyphenyl)nonane and the like. It is also possible to use tetrakis(4-hydroxyphenyl)alkane derivatives such as tetrakis(4-hydroxydimethylphenyl)methane and the like. Of these, useful are diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol AF, diglycidyl ether of bisphenol AD, and diglycidyl ethers of higher-molecular-weight bisphenols A, F, AF and AD, because they have a low thermal shrinkage factor. Particularly preferable are diglycidyl ethers of higher-molecular-weight bisphenols A, F, AF and AD wherein the n of the repeating unit has a value of 2-18. The above polyfunctinal epoxy resins may be used in combination of two or more. If necessary, the polyfunctional epoxy resin may be mixed with a monofunctional epoxy resin such as butyl glycidyl ether, styrene oxide, phenyl glycidyl ether, allyl glycidyl ether or the like in order to obtain a lower viscosity. However, the amount of the monofunctional epoxy resin added should be small because, in general, the monofunctional epoxy resin has an effect for viscosity reduction but brings about increase in thermal shrinkage factor.
The acid anhydride used in the present invention has no particular restriction and can be any ordinary acid anhydride. Such an acid anhydride includes methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, dodecylsuccinic anhydride, succinic anhydride, octadecylsuccinic anhydride, maleic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bis(anhydrotrimellitate), glycerol tris(anhydrotrimellitate), etc. They can be used alone or in combination of two or more.
The maleimide used in the present invention can be any maleimide as long as it is an unsaturated imide containing in the molecule the group having the formula (I), ##STR1## wherein D is a bivalent group containing a carbon-carbon double bond. Such an unsaturated imide includes, for example, bifunctional maleimides such as N,N'-ethylene-bismaleimide, N,N'-hexamethylene-bis-maleimide, N,N'-dodecamethylene-bismaleimide, N,N'-m-xylylene-bismaleimide, N,N'-p-xylylene-bismaleimide, N,N'-1,3-bismethylenecyclohexane-bismaleimide. N,N'-1,4-bismethylenecyclohexane-bismaleimide, N,N'-2,4-tolylene-bismaleimide, N,N'-2,6-tolylene-bismaleimide, N,N'-3,3'-diphenylmethane-bismaleimide, N,N'-(3-ethyl)-3,3'-diphenylmethane-bismaleimide, N,N'-(3,3'-dimethyl)-3,3'-diphenylmethane-bismaleimide, N,N'-(3,3'-diethyl)-3,3'-diphenylmethane-bismaleimide, N,N'-(3,3'-dichloro)-3,3'-diphenylmethane-bismaleimide, N,N'-4,4'-diphenylmethane-bismaleimide, N,N'-(3-ethyl)-4,4'-diphenylmethane-bismaleimide, N,N'-(3,3'-dimethyl )-4,4'-diphenylmethane-bismaleimide, N,N'-(3,3'-diethyl )-4,4'-diphenylmethane-bismaleimide, N,N'-(3,3'-dichloro)-4,4'-diphenylmethane-bismaleimide, N,N'-3,3'-diphenylsulfone-bismaleimide, N,N'-4,4'-diphenylsulfone-bismaleimide, N,N'-3,3'-diphenylsulfide-bismaleimide, N,N'-4,4'-diphenylsulfide-bismaleimide, N,N'-p-benzophenone-bismaleimide, N,N'-4,4'-diphenylethane-bismaleimide, N,N'-4,4'-diphenylether-bismaleimide, N,N'-(methyleneditetrahydrophenyl)bismaleimide, N,N'-tolidine-bismaleimide, N,N'-isophorone-bismaleimide, N,N'-p-diphenyldimethylsilyl-bismaleimide, N,N'-4,4'-diphenylpropane-bismaleimide, N,N'-naphthalene-bismaleimide, N,N'-p-phenylene-bismaleimide, N,N'-m-phenylene-bismaleimide, N,N'-4,4'-(1,1'-diphenylcyclohexane)bismaleimide, N,N'-3,5-(1,2,4-triazole)bismaleimide, N,N'-pyridine-2,6-diyl-bismaleimide, N,N'-5-methoxy-1,3-phenylene-bismaleimide, 1,2-bis(2-maleimideethoxy)ethane, 1,3-bis(3-maleimidepropoxy)propane, N,N'-4,4'-diphenylmethane-bisdimethylmaleimide, N,N'-hexamethylene-bisdimethylmaleimide, N,N'-4,4'-(diphenylether)bisdimethylmaleimide, N,N'-4,4'-(diphenylsulfone)bisdimethylmaleimide, N,N'-bismaleimide of 4,4'-diaminotriphenyl phosphate, N,N'-bismaleimide of 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, N,N'-bismaleimide of 2,2'-bis[4-(4-aminophenoxy)phenylmethane, N,N'-bismaleimide of 2,2'-bis[4-(4-aminophenoxy)phenylethane and the like; polyfunctional maleimides obtained by reacting maleic anhydride with an aniline-formalin reaction product (a polyamine compound), 3,4,4'-triaminodiphenylmethane, triaminophenol or the like; monomaleimides such as phenylmaleimide, tolylmaleimide, xylylmaleimide and the like; various citraconimides; and various itaconimides. These unsaturated imides can be used by adding to an epoxy resin, or can be cured with a diallylphenol compound, an allylphenol compound or a diamine compound or with a catalyst alone.
The flexibilizer used in the present invention can be any flexibility-imparting agent as long as it can impart flexibility, toughness and adhesion. Such a flexibilizer includes, for example, diglycidyl ether of linoleic acid dimer, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, diglycinyl ether of alkylene oxide adduct of bisphenol A, urethane-modified epoxy resin, polybutadiene-modified epoxy resin, polyethylene glycol, polypropylene glycol, polyol (e.g. hydroxyl group-terminated polyester), polybutadiene, alkylene oxide adduct of bisphenol A, polythiol, urethane prepolymer, polycarboxyl compound, phenoxy resin and polycaprolactone. The flexibilizer may be a low viscosity compound such as caprolactone or the like, which is polymerized at the time of curing of the impregnant resin and thereby exhibits flexibility. Of the above flexibilizers, a polyol, a phenoxy resin or a polycaprolactone is preferable in view of the high toughness and low thermal expansion.
The catalyst used in the present invention has no particular restriction and can be any compound as long as it has an action of accelerating the reaction of an epoxy resin or a maleimide. Such a compound includes, for example, tertiary amines such as trimethylamine, triethylamine, tetramethylbutanediamine, triethylenediamine and the like; amines such as dimethylaminoethanol, dimethylaminopentanol, tris(dimethylaminomethyl)phenol, N-methylmorpholine and the like; quaternary ammonium salts such as cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, cetyltrimethyl-ammonium iodide, dodecyltrimethylammonium bromide, dodecyltri-methylammonium chloride, dodecyltrimethylammonium iodide, benzyldimethyltetradecylammonium chloride, benzyldimethyltetradecylammonium bromide, allyldodecyltrimethylammonium bromide, benzyldimethylstearylammonium bromide, stearyltrimethylammonium chloride, benzyldimethyltetradecylammonium acetylate and the like; imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-methyl-4-ethylimidazole, 1-butylimidazole, 1-propyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cycanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-azine-2-methylimidazole, 1-azine-2-undecylimidazole and the like; microcapsules of amines or imidazoles; metal salts between (a) an amine or imidazole and (b) zinc octanoate, cobalt or the like; 1,8-diaza-bicyclo[5.4.0]-undecene-7; N-methylpiperazine; tetramethylbutylguanidine; amine tetraphenyl borates such as triethylammonium tetraphenyl borate, 2-ethyl-4-methyltetraphenyl borate, 1,8-diazabicyclo[5.4.0]-undecene-7-tetraphenyl borate and the like; triphenylphosphine; triphenylphosphonium tetraphenyl borate; aluminum trialkylacetoacetates; aluminum trisacetylacetoacetate; aluminum alcoholates; aluminum acylates; sodium alcoholates; boron trifluoride; complexes between boron trifluoride and an amine or imidazole; diphenyliodonium salt of HAsF.sub.6 ; aliphatic sulfonium salts; amineimides obtained by reacting an alkyl monocarboxylate with a hydrazine and a monoepoxy compound; and metal (e.g. cobalt, manganese, iron) salts of octylic acid or naphthenic acid. Of these, particularly useful are quaternary ammonium salts, metal salts between (a) an amine or imidazole and (b) zinc octanoate, cobalt or the like, amine tetraphenyl borates, complexes between boron trifluoride and an amine or imidazole, diphenyliodonium salt of HAsF.sub.6, aliphatic sulfonium salts, amineimides, microcapsules of amines or imidazoles, etc. because they are relatively stable at room temperature but can cause a reaction easily at elevated temperatures, that is, they are latent curing catalysts. These curing agents are added ordinarily in an amount of 0.1-10% by weight based on the polyfunctional epoxy resin.
The stress which a superconducting magnet coil undergoes during operation of the superconducting magnet, includes a residual stress generated at the time of production, a thermal stress applied during cooling and an electromagnetic force applied during operation. First, description is made on the thermal stress applied to the cured resin of a superconducting magnet coil when the coil after production is cooled to a liquid helium temperature, i.e. 4.2K.
The thermal stress a applied to the cured resin of a superconducting magnet coil when the coil after production is cooled to a liquid helium temperature, i.e 4.2K, can be represented by the following formula: ##EQU1## wherein .alpha..sub.R is a thermal expansion coefficient of the cured resin; .alpha..sub.S is a thermal expansion coefficient of the superconducting wire of the coil; E is a modulus of the cured resin; and T is a curing temperature of the resin used for obtaining the cured resin. Since the modulus at temperatures above the glass transition temperature Tg of the cured resin is smaller by about two figures than the modulus at the glass transition temperature Tg or below, the thermal stress applied to the cured resin of superconducting magnet coil when the coil after production is cooled to 4.2K, can be substantially represented by the following formula (1) holding for when the coil after production is cooled from the glass transition temperature of the cured resin to 4.2K: ##EQU2##
Now, the thermal stress a applied to the cured resin of superconducting magnet coil when the coil after production is cured to 4.2K is roughly calculated from the above formula (1), using assumptions that the thermal shrinkage factor of the cured resin when cooled from the glass transition temperature Tg to 4.2K is 2.0%, the thermal shrinkage factor of the superconducting wire of coil when cooled under the same condition is 0.3% and the modulus of the cured resin be 1.000 kg/mm.sup.2 at 4.2K; the rough calculation gives a thermal stress .sigma. of about 17 kg/mm.sup.2. Meanwhile, cured epoxy resins ordinarily have a strength of 17-20 kg/mm.sup.2 at 4.2K. Accordingly, when the superconducting magnet coil after production is cooled to a liquid helium temperature, i.e. 4.2K, the thermal stress .sigma. plus the residual stress generated at the time of coil production allow the cured resin to form microcracks of several microns; the releasing energy of the stress of the cured resin gives rise to a temperature increase of several degrees at the peripheries of the microcracks; as a result, the resistance of the superconducting wire is increased rapidly and there occurs a transition from a superconducting state to a state of normal conduction, i.e. a so-called quench phenomenon. In superconducting magnet coils used in linear motor cars, MRI, etc., further an electromagnetic force of at least about 4 kg/mm.sup.2 is repeatedly applied during operation at 4.2K. This force plus the above-mentioned thermal stress and residual stress allow the cured resin to form cracks, and the releasing energy of the stress gives rise to a quench phenomenon.
The thermal stress a applied to the cured resin of superconducting magnet coil when the coil after production is cooled to 4.2K is roughly calculated from the formula (1), using a thermal shrinkage factor of the cured resin of 1.5% when cooled to 4.2K and a modulus of the cured resin of 1,000 kg/mm.sup.2 at 4.2K; the rough calculation gives a thermal stress a of about 12 kg/mm.sup.2. When an electromagnetic force of about 4 kg/mm.sup.2 is repeatedly applied to the above thermal stress during operation at 4.2K, the total stress becomes about 16 kg/mm.sup.2.
Meanwhile, cured epoxy resins ordinarily have a strength of 17-20 kg/mm.sup.2 at 4.2K. Therefore, on calculation, this strength can withstand the thermal stress applied to the cured resin of superconducting magnet coil when cooled to 4.2K and the electromagnetic force repeatedly applied to the cured resin during operation.
Various impregnant resins of different thermal shrinkage factors for superconducting magnet coil were actually tested. The test indicated that when there is used, as an impregnant resin for superconducting magnet coil, a curable resin composition giving a cured product having a thermal shrinkage factor of 1.5-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K, the cured resin composition of superconducting magnet coil generates no crack when cooled to a liquid helium temperature, i.e. 4.2K. The test also indicated that no quench appears even in a superconducting operation at 4.2K wherein an electromagnetic force is further applied.
When there is used, in particular, a thermosetting resin composition giving a cured product having a thermal shrinkage factor of 1.0-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-3.9% and a modulus of 500-1,000 kg/mm.sup.2, quench can be prevented with a large allowance even in a superconducting operation at 4.2K in which an electromagnetic force is applied.
The present invention is hereinafter described more specifically by way of Examples. However, the present invention is by no means restricted to these Examples.
The determination of thermal shrinkage was carried out with a thermal-mechanical analyzer (TMA) having a sample-system provided in a cryostat which can cool a sample to a very low temperature and a measurement-system containing a differential transformer with which the change of dimension of the sample detected by a detecting rod can be measured.
The determination of bending properties was carried out by immersing a sample in liquid helium using a conventional bend test apparatus equipped with a cryostat which can cool the sample to a very low temperature. The size of the sample is 80 mm.times.9 mm.times.5 mm. The conditions of the determination were:
length between supports: 60 mm
head speed: 2 mm/min
three-point bending.
In the Examples, the abbreviations used for polyfunctional epoxy resins, flexibilizers, curing catalysts and bismaleimides refer to the followings.
DER-332: diglycidyl ether of bisphenol A (epoxy equivalent: 175)
EP-825: diglycidyl ether of bisphenol A (epoxy equivalent: 178)
EP-827: diglycidyl ether of bisphenol A (epoxy equivalent: 185)
EP-828: diglycidyl ether of bisphenol A (epoxy equivalent: 189)
EP-1001: diglycidyl ether of bisphenol A (epoxy equivalent: 472)
EP-1002: diglycidyl ether of bisphenol A (epoxy equivalent: 636)
EP-1003: diglycidyl ether of bisphenol A (epoxy equivalent: 745)
EP-1055: diglycidyl ether of bisphenol A (epoxy equivalent: 865)
EP-1004AF: diglycidyl ether of bisphenol A (epoxy equivalent: 975)
EP-1007: diglycidyl ether of bisphenol A (epoxy equivalent: 2006)
EP-1009: diglycidyl ether of bisphenol A (epoxy equivalent: 2473)
EP-1010: diglycidyl ether of bisphenol A (epoxy equivalent: 2785)
EP-807: diglycidyl ether of bisphenol F (epoxy equivalent: 170)
PY-302-2: diglycidyl ether of bisphenol AF (epoxy equivalent: 175)
DGEBAD: diglycidyl ether of bisphenol AD (epoxy equivalent: 173)
HP-4032: 2,7-diglycidyl ether naphthalene (epoxy equivalent: 150)
TGADPM: tetraglycidylaminodiphenylmethane
TTGmAP: tetraglycidyl-m-xylylenediamine
TGpAP: triglycidyl-p-aminophenol
TGmAP: triglycidyl-m-aminophenol
CEL-2021: 3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexane carboxylate (epoxy equivalent: 138)
LS-108: bis-2,2'-{4,4'-[2-(2,3-epoxy)propoxy-3-butoxypropoxy]phenyl}propane (epoxy equivalent: 2100)
LS-402: bis-2,2'-{4,4'-[2-(2,3-epoxy)propoxy-3-butoxypropoxy]phenyl}propane (epoxy equivalent: 4600)
HN-5500: methylhexahydrophthalic anhydride (acid anhydride equivalent: 168)
HN-2200: methyltetrahydrophthalic anhydride (acid anhydride equivalent: 166)
iPA-Na: sodium isopropylate
BTPP-K: tetraphenylborate of triphenylbutylphosphine
2E4MZ-K: tetraphenylborate of 2-ethyl-4-methylimidazole
2E4MZ-CN-K: tetraphenylborate of 1-cyanoethyl-2-ethyl-4-methylimidazole
TEA-K: tetraphenylborate of triethylamine
TPP-K: tetraphenylborate of triphenylphosphine
TPP: triphenylphosphine
IOZ: salt between 2-ethyl-4-methylimidazole and zinc octanoate
DY063: alkyl alkoholate
YPH-201: an amineimide obtained by reacting an alkyl monocarboxylate with a hydrazine and a monoepoxy compound (YPH-201 manufactured by Yuka Shell Epoxy K.K.)
CP-66: an aliphatic sulfonium salt of a protonic acid (ADEKA OPTON CP-66 manufactured by ASAHI DENKA KOGYO K.K.)
PX-4BT: tetrabutylphosphonium benzotriazolate
BF.sub.3 -400: boron trifluoride salt of piperazine
BF.sub.3 -100: boron trifluoride salt of triethylamine
2E4MZ-CNS: trimellitic acid salt of 2-ethyl-4-methylimidazole
2E4MZ-OK: isocyanuric acid salt of 2-ethyl-4-methylimidazole
MC-C11Z-AZINE: microcapsule of 1-azine-2-undecylimidazole
2E4MZ-CN: 1-cycnoethyl-2-ethyl-4-methylimidazole
BDMTDAC: benzyldimethyltetradecylammonium chloride
BDMTDAI: benzyldimethyltetradecylammonium iodide
HMBMI: N,N'-hexamethylene-bismaleimide
BMI: N,N'-4,4'-diphenylmethane-bismaleimide
DMBMI: N,N'-(3,3'-dimethyl)-4,4'-diphepylmethane-bismaleimide
DAPPBMI: N,N'-bismaleimide of 2,2'-bis[4-(4-aminophenoxy)phenyl]propane
PMI: N,N'-polymaleimide of a reaction product (a polyamine compound) between aniline and formalin
DABPA: diallylbisphenol A
PPG: polypropylene glycol
KR: .epsilon.-caprolactone
DGEAOBA: diglycidyl ether of an alkylene oxide adduct of bisphenol A
PPO: phenoxy resin
CTBN: acrylonitrile-modified carboxyl group-terminated polybutadiene rubber
2PZCN: 1-cyanoethyl-2-phenylimidazole
LBO: lithium butoxide
PZ: pyridine
TEA: triethylamine
M2-100: benzylconium chloride
N-MM: N-methylmorpholine
MDI: 4,4'-diphenylmethane diisocyanate, equivalent: 125
LMDI: a mixture of MDI, an MDI derivative whose isocyanate group has been converted to carbodiimide and an MDI derivative whose isocyanate groups have been converted to carbodiimide, which mixture is liquid at room temperature, equivalent: about 140
TDI: a mixture of 80% of 2,4-tolylene diisocyanate and 20% of 2,6-tolylene diisocyanate, equivalent: 87
KR2019: a resin obtained by condensation polymerization of methylphenylsilicone
EXAMPLES 1-65 AND COMPARATIVE EXAMPLES 1-6
Each of the resin compositions shown in Tables 1-1 to 1-13 was thoroughly stirred, placed in a mold, and heat-cured under the curing conditions shown in Tables 1-1 to 1-13. Each of the resulting cured products was measured for thermal shrinkage factor when cooled from the glass transition temperature to 4.2K, and the results are shown in Tables 1-1 to 1-13. Each cured product was also measured for bending properties at 4.2K, and the bending strain and bending modulus are shown in Tables 1-1 to 1-13. All of the curable resin compositions of Examples 1-65 according to the present invention, when cured, had a thermal strinkage factor of 1.5-0.3% when cooled from the glass transition temperature to 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K.
EXAMPLE 66 AND COMPARATIVE EXAMPLE 7
Superconducting wires were wound to form coils of the same material and the same shape. The coils were impregnated with the curable resin compositions of Examples 1-65 and Comparative Examples 1-6, and the impregnated coils were heat-cured under given curing conditions to prepare small race track-shaped superconducting magnet coils. Switches for permanent current were also prepared by impregnation with each of the curable resin compositions of Examples 1-65 and Comparative Examples 1-6 and subsequent heat-curing under given curing conditions. FIG. 1 is a perspective view showing the superconducting magnet coils thus prepared. FIG. 2 is a cross-sectional view of the coil of FIG. 1 when cut at an II--II' line. In any of the coils, a cured product 3 of an curable resin composition was filled between the conductors 2 and any unfilled portion (e.g. void) was not observed. These coils were cooled to 4.2K. As shown in FIG. 3, in each of the coils impregnated with each of the curable resin compositions of Comparative Examples 1-6, cracks were generated in the cured resin composition 3; the cracks reached even the enamel insulating layer 5 of each conductor 2, which caused even the peeling 6 of the enamel insulating layer 5. Meanwhile, in the coils impregnated with each of the curable resin compositions of Examples 1-65, neither cracking of the cured resin composition nor peeling of the enamel insulating layer was observed.
EXAMPLE 67 AND COMPARATIVE EXAMPLE 8
Superconducting wires were wound to form coils of the same material and the same shape. The coils were impregnated with each of the curable resin compositions of examples 1-65 and Comparative Examples 1-6, and the impregnated coils were heat-cured under given curing conditions to prepare saddle-shaped superconducting magnet coils. FIG. 4 is a perpspective view showing the superconducting magnet coils thus prepared. FIG. 5 is a cross-sectional view of the coil of FIG. 4 when cut at V--V' line. These saddle-shaped superconducting magnet coils were .cooled to 4.2K. In the coils impregnated with each of the curable resin compositions of Comparative Examples 1-6, cracks were generated in the cured resin composition. Meanwhile, in the coils impregnated with each of the curable resin compositions of Examples 1-65, no crack was observed.
TABLE 1__________________________________________________________________________Thermal shrinkage factors of thermosetting resins__________________________________________________________________________ [Effect of repeating unit (molecular weight between crosslinked sites)] Thermal Bending Bending modulus shrinkage strain (Kg/mm.sup.2 Resin composition factor (%) (% at 4.2 K) at 4.2 K) Remarks__________________________________________________________________________Compara- DER332 100 1.73 2.3 650 n = 0.02tive HN-5500 92 BisphenolExample 1 PPG 15 A type 2E4MZ-CN 0.9Compara- EP-825 100 1.68 2.7 670 n = 0.06tive HN-5500 90 BisphenolExample 2 PPG 15 A type 2E4MZ-CN 0.95Compara- EP-828 100 1.65 2.9 690 n = 0.13tive HN-5500 85 BisphenolExample 3 PPG 15 A type 2E4MZ-CN 0.93Example 1 EP-1001 100 1.23 3.0 720 n = 2.13 HN-5500 34 Bisphenol PPG 15 A type 2E4MZ-CN 0.33Example 2 EP-1002 100 1.19 3.0 730 n = 3.28 HN-5500 25 Bisphenol PPG 15 A type 2E4MZ-CN 0.25Example 3 EP-1003 100 1.16 3.1 730 n = 4.05 HN-5500 22 Bisphenol PPG 15 A type 2E4MZ-CN 0.21Example 4 EP-1055 100 0.92 3.2 740 n = 4.89 HN-5500 19 Bisphenol PPG 15 A type 2E4MZ-CN 0.18Example 5 EP-1004AF 100 0.88 3.3 740 n = 5.67 HN-5500 17 Bisphenol PPG 15 A type iPA-Na 0.16Example 6 EP-1007 100 0.75 3.3 740 n = 12.93 HN-5500 8 Bisphenol PPG 15 A type iPA-Na 0.2Example 7 EP-1002 100 0.55 3.5 720 n = 16.21 HN-5500 7 Bisphenol PPG 15 A type iPA-Na 0.2Example 8 EP-1010 100 0.35 3.5 720 n = 18.42 HN-5500 6 Bisphenol PPG 15 A type iPA-Na 0.2Example 9 DER-332 50 1.15 3.0 705 n = 0.02 EP-1003 213 n = 4.05 HN-5500 85 Bisphenol PPG 15 A type 2E4MZ-CN 0.1Example 10 DER-332 50 1.10 3.1 710 n = 0.02 EP-1055 301 n = 4.89 HN-5500 85 Bisphenol PPG 15 A type 2E4MZ-CN 0.1Example 11 DER-332 50 1.00 3.1 710 n = 0.02 EP-1004AF 279 n = 5.67 HN-5500 85 Bisphenol PPG 5 A type 2E4MZ-CN 0.1Example 12 DER-332 50 0.95 3.1 710 n = 0.02 EP-1009 707 n = 16.21 HN-5500 85 Bisphenol PPG 15 A type 2E4MZ-CN 0.1Example 13 DER-332 50 0.90 3.2 710 n = 0.02 EP-1010 757 p = 18.42 HN-5500 85 Bisphenol PPG 15 A type 2E4MZ-CN 0.1Example 14 XB-4122 100 1.39 2.9 720 n = 0.2 HN-5500 46 2E4MZ-CN 0.1Example 15 LS-108 100 1.35 2.9 720 n = 5 HN-5500 8 2E4MZ-CN 0.1Example 16 LS-402 100 1.15 2.9 720 n = 10 HN-5500 4 2E4MZ-CN 0.1Example 17 PY-302-2 95 1.23 3.0 690 EP-1007 50 HN-5500 92 PPG 15 iPA-Na 0.2Example 18 DGEBAD 94 1.28 2.9 670 EP-1007 50 HN-5500 92 PPG 15 iPA-Na 0.2Example 19 TGADPM 80 1.25 2.9 690 EP-1075 50 HN-5500 92 PPG 15 iPA-Na 0.2Example 20 TTGmAP 80 1.23 3.0 700 EP-1007 50 HN-5500 92 PPG 15 iPA-Na 0.2Example 21 TGpAP 80 1.15 3.0 700 EP-1007 50 HN-5500 92 PPG 15 iPA-Na 0.2Example 22 TGmAP 80 1.20 2.9 730 EP-1007 50 HN-5500 92 PPG 15 iPA-Na 0.2Example 23 CEL-2021 76 1.20 3.2 740 EP-1055 50 HN-5500 92 PPG 15 iPA-Na 0.2Example 24 CEL-2021 76 1.10 3.3 740 EP-1004AF 100 HN-2200 91 PPG 15 iPA-Na 0.16Example 25 EP-807 100 1.28 3.0 735 PPG 10 BF.sub.3 -400 10Example 26 EP-807 100 1.18 3.2 720 PPG 15 BF.sub.3 -400 10Example 27 EP-807 100 1.09 3.2 720 PPG 20 BF.sub.3 -400 10Example 28 EP-807 100 1.28 3.1 725 PPG 10 BF.sub.3 -100 10Example 29 EP-807 100 1.25 2.9 740 PPG 10 CP-66 3Example 30 EP-807 100 1.20 3.1 732 PPG 10 PX-4BT 5Example 31 EP-807 100 1.10 3.3 720 PPG 10 YPH-201 5__________________________________________________________________________ Chemical structure of epoxy resin Curing conditions 100.degree. C./15h + 120.degree. C./15h
Thermal Bending Bending modulus shrinkage strain (Kg/mm.sup.2 Resin composition factor (%) (% at 4.2 K) at 4.2 K) Remarks__________________________________________________________________________Example 32 EP-807 100 1.15 3.1 705 PPG 10 IOZ 5Example 33 EP-807 100 1.10 3.2 700 PPG 15 TPP 5Example 34 EP-807 100 1.05 3.2 720 PPG 20 TPP-K 8Example 35 EP-807 100 1.20 3.1 700 PPG 10 TEA-K 8Example 36 EP-807 100 1.20 3.1 698 PPG 10 2ED4MZ-K 5Example 37 EP-807 100 1.15 3.2 700 PPG 10 BTPP-K 5Example 38 EP-807 100 1.10 3.2 700 PPG 10 iPA-Na 1.0__________________________________________________________________________ Curing conditions 90.degree. C./15h + 120.degree. C./15h
Thermal Bending Bending modulus shrinkage strain (Kg/mm.sup.2 Resin composition factor (%) (% at 4.2 K) at 4.2 K) Remarks__________________________________________________________________________Example 39 EP-807 100 1.20 2.9 710 PPG 10 2E4MZ-CN-K 5Example 40 EP-807 100 1.20 3.0 720 PPG 15 2E4MZ-CNS 5Example 41 EP-807 100 1.05 3.2 720 PPG 20 2E4MZ-OK 8Example 42 EP-807 100 1.20 2.9 720 PPG 10 2E4MZ-CN 2Example 43 EP-807 100 1.20 2.9 720 PPG 10 MC-C11Z-AZINE 5Example 44 EP-807 100 1.95 3.2 700 PPG 10 BDMTDAC 10Example 45 EP-807 100 0.96 3.2 700 PPG 10 BDMTDAI 10__________________________________________________________________________ Curing conditions 90.degree. C./15h + 120.degree. C./15h
Thermal Bending Bending modulus shrinkage strain (Kg/mm.sup.2 Resin composition factor (%) (% at 4.2 K) at 4.2 K) Remarks__________________________________________________________________________Example 44 PY-302-2 100 1.20 3.2 735 PPG 10 BF.sub.3 -400 10Example 45 PY-302-2 100 1.16 3.3 720 PPG 15 BF.sub.3 -400 10Example 46 PY-302-2 100 1.09 3.3 715 PPG 20 BF.sub.3 -400 10Example 47 EP-807 100 1.00 3.3 710 PPO 10 BF.sub.3 -400 10Example 48 EP-807 100 1.15 3.1 720 DGEAOBA 10 BF.sub.3 -400 10Example 49 EP-807 100 1.20 3.1 732 KR 10 BF.sub.3 -400 10Example 50 EP-807 100 1.30 2.9 750 CTBN 10 BF.sub.3 -400 10Example 52 EP-807 100 0.85 3.3 715 DABPA 20 DBMTDAC 5Example 53 EP-807 100 0.90 3. 4 710 DABPA 15 BDMTDAI 5Example 54 BMI 50 0.80 3.2 720 DABPA 50 KR 10 TPP-K 8Example 55 BMI 50 0.75 3.1 730 DABPA 50 PPG 10 TEA-K 8Example 56 DAPPBMI 100 0.75 3.1 710 DABPA 50 PPG 10 TEA-K 5Example 57 DAPPBMI 100 1.70 2.9 745 DABPA 20 PPG 10 TEA-K 5__________________________________________________________________________ Curing conditons 90.degree. C./15h + 120.degree. C./15h
Thermal Bending Bending modulus shrinkage strain (Kg/mm.sup.2 Resin composition factor (%) (% at 4.2 K) at 4.2 K) Remarks__________________________________________________________________________Example 58 DAPPBMI 100 0.90 3.2 730 DABPA 5 PPG 10 BDMTDAC 5Example 59 DAPPBMI 100 1.0 2.9 750 DABPA 0 DR 10 2E4MZ-OK 5Example 60 DMBMI 100 0.90 3.1 730 DABPA 50 KR 15 2E4MZ-OK 5Example 61 PMI 100 0.90 3.1 720 DABPA 50 KR 20 2E4MZ-OK 5Example 62 HMBMI 100 0.82 3.2 720 DABPA 50 KR 20 2E4MZ-OK 5Example 63 DAPPBMI 100 1.20 2.9 730 HMBMI 100 2E4MZ-OK 5__________________________________________________________________________ Curing conditions 100.degree. C./15h + 180.degree. C./15h
Thermal Bending Bending modulus shrinkage strain (Kg/mm.sup.2 Resin composition factor (%) (% at 4.2 K) at 4.2 K) Remarks__________________________________________________________________________Compara EP-1002 100 1.23 2.3 720tive HN-5500 25Example 4 PPG 0 2E4MZ-CN 0.25Compara- EP-1007 100 1.98 2.4 770tifve HN-5500 8Example 5 PPG 0 iPA-Na 0.2Compara- EP-807 100 1.20 2.2 790tive PPG 5Example 6 iPA-Na 1.0Example 64 DER-332 100 1.00 3.2 740 HN-5500 92 PPG 15 DAPPBMI 50 2E4MZ-CN 0.33Example 65 DER-332 100 0.98 3.2 760 HN-5500 92 DAPPBMI 50 DABPA 20 PPG 15 2E4MZ-CN 0.5__________________________________________________________________________ Curing conditions 100.degree. C./15h + 120.degree. C./15h
EXAMPLES 68-115
Each of the resin composition shown in Tables 2-1 to 2-11 was thoroughly stirred, placed in a mold, and heat-cured under the curing conditions shown in Tables 2-1 to 2-11. Each of the resulting cured products was measured for thermal shrinkage factor when cooled from the glass transition temperature to 4.2K, and the results are shown in Tables 2-1 to 2-11. Each cured product was also measured for bending properties at 4.2K, and the bending strain and bending modulus are shown in Tables 2-1 to 2-11. All of the curable resin compositions of Examples 68-115 according to the present invention, when cured, had a thermal shrinkage factor of 1.5-0.3% when cooled from the glass transition temperature to 4.2K, a bend-breaking strain of 3.5-4.5% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K.
TABLE 2__________________________________________________________________________Thermal shrinkage factors of thermosetting resins__________________________________________________________________________ Thermal Bending Bending modulus shrinkage strain (Kg/mm.sup.2 Resin composition factor (%) (% at 4.2 K) at 4.2 K) Remarks__________________________________________________________________________Example 68 DER332 100 1.49 3.5 650 n = 0.02 HN-5500 92 Bisphenol PPG 10 A type 2E4MZ-CN 0.9Example 69 EP-825 100 1.45 3.6 670 n = 0.06 HN-5500 90 Bisphenol PPG 10 A type 2E4MZ-CN 0.95Example 70 EP-828 100 1.46 3.6 690 n = 0.13 HN-5500 85 Bisphenol PPG 10 A type 2E4MZ-CN 0.93Example 71 EP-1001 100 1.48 3.6 720 n = 2.13 HN-5500 34 Bisphenol PPG 10 A type 2E4MZ-CN 0.33Example 72 EP-1002 100 1.19 3.7 730 n = 3.28 HN-5500 25 Bisphenol PPG 10 A type 2E4MZ-CN 0.25Example 73 EP-1003 100 1.16 3.7 730 n = 4.05 HN-5500 22 Bisphenol PPG 10 A type 2E4MZ-CN 0.21Example 74 EP-1055 100 0.92 3.8 740 n = 4.89 HN-5500 19 Bisphenol PPG 10 A type 2E4MZ-CN 0.18Example 75 EP-1004AF 100 0.88 3.7 740 n = 5.67 HN-5500 17 Bisphenol PPG 10 A type iPA-Na 0.16Example 76 EP-1007 100 0.75 3.6 740 n = 12.93 HN-5500 8 Bisphenol PPG 10 A type iPA-Na 0.2Example 77 EP-1009 100 0.55 3.6 720 n = 16.21 HN-5500 7 Bisphenol PPG 10 A type iPA-Na 0.2Example 78 EP-1010 100 0.55 3.6 720 n = 18.42 HN-5500 6 Bisphenol PPG 10 A type iPA-Na 0.2Example 79 DER-332 50 1.15 3.6 705 n = 0.02 EP-1003 213 n = 4.05 HN-5500 85 Bisphenol PPG 15 A type 2E4MZ-CN 0.1Example 80 DER-332 50 1.10 3.6 710 n = 0.02 EP-1055 301 n = 4.89 HN-5500 85 Bisphenol PPG 10 A type 2E4MZ-CN 0.1Example 81 DER-332 50 1.00 3.7 710 n = 0.02 EP-1004AF 279 n = 5.67 HN-5500 85 Bisphenol PPG 10 A type 2E4MZ-CN 0.1Example 82 DER-332 50 0.95 3.7 710 n = 0.02 EP-1009 707 n = 16.21 HN-5500 85 Bisphenol PPG 10 A type 2E4MZ-CN 0.1Example 83 DER-332 50 0.90 3.6 710 n = 0.02 EP-1010 757 p = 18.42 HN-5500 85 Bisphenol PPG 10 A type 2E4MZ-CN 0.1Example 84 LS-108 100 1.35 3.7 720 n = 5 HN-5500 8 2E4MZ-CN 0.1 PPG 10Example 85 LS-402 100 1.15 3.9 720 n = 10 HN-5500 4 2E4MZ-CN 0.1 PPG 10Example 86 PY-302-2 95 1.23 3.6 690 EP-1007 50 HN-5500 92 PPG 10 iPA-Na 0.2Example 87 DGEBAD 94 1.28 3.9 670 EP-1007 50 HN-5500 92 PPG 10 iPA Na 0.2Example 88 TGADPM 80 1.25 3.8 690 EP-1007 50 HN-5500 92 PPG 10 iPA-Na 0.2Example 89 TTGmAP 80 1.23 3.9 700 EP-1007 50 HN-5500 92 PPG 10 iPA-Na 0.2Example 90 TGpAP 80 1.15 3.6 700 EP-1007 50 HN-5500 92 PPG 10 iPA-Na 0.2Example 91 TGmAP 80 1.20 3.8 730 EP-1007 50 HN-5500 92 PPG 10 iPA Na 0.2Example 92 CEL-2021 76 1.20 3.9 740 EP-1055 50 HN-5500 92 PPG 15 iPA-Na 0.2Example 93 CEL-2021 76 1.10 3.8 740 EP-1004AF 100 HN-2200 91 PPG 15 iPA-Na 0.16Example 94 PY302.2 100 1.40 3.8 650 n = 0.02 HN-5500 94 Bisphenol PPG 10 A type 2E4MZ-CN 0.9Example 95 PY302.2 100 1.48 3.6 670 n = 0.06 HN-5500 94 Bisphenol PPG 10 A type DY063 0.1Example 96 PY302.2 100 1.35 3.6 690 n = 0.13 HN-5500 94 Bisphenol PPG 15 A type DY063 0.1Example 97 DER-332 100 1.48 3.6 720 n = 2.13 HN-5500 94 Bisphenol PPG 10 A type DY063 0.1Example 98 DER-332 100 1.31 3.6 720 n = 2.13 HN-5500 94 Bisphenol PPG 15 A type DY063 0.1Example 99 HP4032 100 1.50 3.8 650 n = 0.02 HN-5500 112 Bisphenol PPG 10 A type 2E4MZ-CN 0.9Example 100 HP4032 100 1.45 3.6 670 n = 0.06 HN-5500 112 Bisphenol PPG 10 A type DY063 0.1Example 101 HP4032 100 1.41 3.6 690 n = 0.13 HN-5500 112 Bisphenol PPG 15 A type DY063 0.1Example 102 DER-332 100 1.38 3.6 720 n = 2.13 HN-5500 94 Bisphenol PPG 10 A type TPP 0.1Example 103 DER-332 100 1.28 3.6 720 n = 2.13 HN-5500 94 Bisphenol PPG 10 A type BTPP-K 0.1Example 104 DER-332 100 1.38 3.8 650 n = 0.02 HN-5500 94 Bisphenol CTBN 10 A type 2E4MZ-CN 0.9Example 105 HP4032 100 1.48 3.7 670 n = 0.06 HN-5500 112 Bisphenol CTBN 10 A type DY063 0.1Example 106 DER-332 100 1.45 3.6 690 n = 0.13 HN-5500 94 Bisphenol CTBN 10 A type DY063 0.1Example 107 DY302, 2 100 1.28 3.6 720 n = 2.13 HN-5500 94 Bisphenol CTBN 10 A type DY063 0.1Example 108 DER-332 100 1.35 3.7 720 n = 2.13 HN-5500 94 Bisphenol CTBN 10 A type BTPP-K 0.1Example 109 DER-332 100 1.38 3.7 650 n = 0.02 HN-5500 94 Bisphenol CTBN 10 A type TEA-K 0.9Example 110 DER-332 100 1.28 3.6 670 n = 0.06 HN-5500 94 Bisphenol PPG 10 A type BF3-400 5Example 111 DER-332 100 1.17 3.6 690 n = 0.13 HN-5500 94 Bisphenol PPG 10 A type IOZ 0.9Example 112 PY302, 2 100 1.38 3.7 720 n = 2.13 HN-5500 94 Bisphenol PPG 10 A type 2E4MZ-K 0.1Example 113 DER-332 100 1.48 3.6 720 n = 2.13 HN-2200 94 Bisphenol PPG 10 A type DY063 0.1__________________________________________________________________________ Curing conditions 100.degree. C./15h + 120.degree. C./15h
Thermal Bending Bending modulus shrinkage strain (Kg/mm.sup.2 Resin composition factor (%) (% at 4.2 K) at 4.2 K) Remarks__________________________________________________________________________Example 114 PY302, 2 100 1.28 3.6 735 PPG 20 BF.sub.3 -400 10Example 115 DER-332 100 1.18 3.6 720 PPG 20 BF.sub.3 -400 10__________________________________________________________________________ Curing conditions 90.degree. C./15h + 120.degree. C./15h
As described above, in a superconducting magnet coil impregnated with a curable resin composition giving a cured product having a thermal shrinkage factor of 1.5-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K, particularly a cured product having a thermal shrinkage factor of 1.0-0.3% when cooled from the glass transition temperature to a liquid helium temperature, i.e. 4.2K, a bend-breaking strain of 2.9-3.9% at 4.2K and a modulus of 500-1,000 kg/mm.sup.2 at 4.2K, no microcrack is generated in the cured product when the superconducting magnet coil after production is cooled to a liquid helium temperature, i.e. 4.2K. Such a superconducting magnet coil causes substantially no quench even during its operation in which an electromagnetic force is applied.

Number	Name	Date
4595898	Shiraki	Jun 1986
5047741	Laskaris	Sep 1991
5168259	Takemura	Dec 1992
5177056	Hilti	Jan 1993

Number	Date	Country
0076887	Apr 1983	EPX
1441588	May 1966	FRX

Superconducting magnet coil and curable resin composition used therein

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Entry
Sahu "Chemistry of High T Superconductors II", ACS, 1988, Chapter 1.
Superconductors Materials Problems, Science Apr. 1, 1988, vol. 240, pp. 25-27.
"Superconducting Magnets," Wilson, Clarendon Press, Oxford 1983, pp. 310-330.
Patent Abstracts of Japan, vol. 11, No. 127 (E-501)(2574) Apr. 21, 1987 & Jp-61 272 902 (Hitachi Ltd) Dec. 3, 1986.
IEEE Transactions on Magnetics, vol. 17, No. 5, Sep. 1981, N.Y. US "Cause of Quenching in Epoxy Impregnated Coils", pp. 1799-1802.
Experimental and theoretical investigation of mechanical disturbances in epoxy-impregnated superconducting coils Bobrov et al--Cryogenic 1985 vol. 25, Jun. pp. 307-316.
"Stress-induced epoxy cracking and energy release at 4.2 K in epoxy-coated superconducting wires" Yasaka et al pp. 423-428 Cryogenics (Aug. 1984).
"Experimental study of energy release due to cracking of epoxy impregnated conductors" Yanagi et al pp. 753-757 Cryogenics 1989 vol. 29 Jul.