JPS6158486B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has excellent thermal stability, as well as adhesion and
The present invention relates to a curable resin composition that has significantly improved adhesion to a substrate and electrical properties. The fact that a resin with extremely excellent heat resistance can be obtained using maleimides, especially bismaleimide, is
It is already well known and used in many fields where heat resistance is required. Bismaleimide is obtained by the reaction of inexpensive maleic anhydride with diamines, and since it has a polymerizable unsaturated bond in the imide ring, it can be obtained by the reaction of aromatic tetracarboxylic dianhydride with diamines. Compared to existing wholly aromatic polyimides, it is easy to heat cure, has a relatively low melting point, has high fluidity, and has high solubility in solvents. Therefore, casting, impregnation, etc. are possible.
Attempts are being made to use it in a wide range of fields such as adhesives, laminated materials, and heat-resistant paints. As described above, bismaleimide has excellent performance among imide compounds, but it is still insufficient in terms of the performance required in these application fields, and various improvement methods are being investigated. has been done.
For example, when trying to use bismaleimides as constituent monomers of thermosetting resins in the electrical field such as laminated materials, the biggest problem is that sufficient electrical properties cannot be obtained. . On the other hand, cyanate esters or cyanate prepolymers cured alone have excellent electrical properties such as dielectric properties, but they have poor heat resistance, so they cannot be used in materials fields that are exposed to high temperatures for long periods of time. It was difficult to do so. Therefore, as a method for obtaining a resin with excellent electrical properties and heat resistance, a method has been attempted in which cyanate esters or a prepolymer thereof are blended with bismaleimides or a prepolymer thereof, and the mixture is cured together with an epoxy resin. The resin product obtained by blending and curing these three components does not substantially lose the excellent heat resistance of bismaleimides, and has improved electrical properties due to the coexistence of the cyanate ester component. ,
Furthermore, due to the effect of the epoxy resin, it has excellent adhesiveness and adhesion to the base material. However, curable resin compositions composed of bismaleimides, cyanate esters, and epoxy resins have serious drawbacks in practical use, and despite promising excellent performance, they have not yet been fully put into practical use. Not yet. In other words, this serious drawback is that it has low solubility in solvents and poor fluidity, so it is extremely difficult to attach the required amount of resin solids to the substrate by coating or impregnating, resulting in poor workability. This resin composition has a relatively high melting point and needs to be melted at high temperatures when used for paints, castings, etc. without solvents, but curing reactions begin at such high temperatures. Therefore, the degree of freedom of work is severely restricted, and the molded products obtained by curing and molding are generally brittle and have poor impact resistance, and other physical properties are also poor. The above-mentioned practical problems are mainly caused by bismaleimides, which are one of the raw material components of resins, and in order to improve this problem, diamines were added to bismaleimides. When a prepolymer is used, the solubility in a solvent and the softening point of the resulting resin composition are relatively improved, but the performance required from a practical standpoint cannot be met. The current improvement methods are:
This is merely a passive approach to reducing the amount of bismaleimides used, sacrificing heat resistance to some extent, and compensating for workability and other shortcomings. The present inventors have discovered that the cured product has excellent solubility in solvents, high fluidity, and excellent heat resistance. Electrical characteristics. For the purpose of obtaining a curable resin composition capable of imparting adhesive properties and mechanical strength,
As a result of various studies, (a) the maleimide component was selected from polymaleimides in which the average number of maleimide groups present in the molecule is greater than 2, a polymer of the polymaleimide, or a prepolymer of the polymaleimide and an amine. One or more compounds, (b) polycyanate having an average of two or more cyanate ester groups in the molecule as the cyanate ester component, a polymer of the polycyanate, or a combination of the polycyanate and amines. We have discovered that a curable resin composition comprising one or more compounds selected from prepolymers and (c) an epoxy compound can achieve the above object, and have completed the present invention. That is, in the curable resin composition of the present invention, by using a polymaleimide compound having more maleimide groups in the molecule than the normally used bismaleimide as the maleimide component,
The solubility and fluidity in solvents of the resulting curable resin composition can be significantly improved, the softening point and melting point are significantly lowered, and the impact resistance of the molded product obtained by curing is clearly improved. It became possible. The polymaleimide used in the curable resin composition of the present invention has the following properties: (1) The average number of maleimide groups present in the molecule is
There are no particular restrictions as long as it is larger than 2, but as a compound that specifically shows an excellent effect,
General formula () [In the formula, M is a maleimide group

[Formula] or maleimidomethyl group

[Formula] is the same or different, R is a divalent aliphatic/aromatic or aromatic aliphatic hydrocarbon group and is the same or different, R' is hydrogen, hydroxyl group, 1 valent aliphatic hydrocarbon group or alkoxy group, halogen atoms, the same or different, n is a number of 0 or more,
m represents an integer of 0 to 3 and may be the same or different, but the sum of m in the molecule is greater than 2. ] Compounds represented by: Furthermore, compounds included in the present invention have the general formula () (In the formula, each symbol has the same meaning as in the general formula ()) can also have a branched structure. Polymaleimide compounds represented by general formulas () and () include polymaleimides obtained from polymers obtained from aniline and formaldehyde, or aniline and acetaldehyde;
Polymaleimides of phenylene diamines, toluidines, xylidines, or anisidine reactants with formaldehyde, and polymaleimides of polyamines obtained by aminating soluble phenol formaldehyde resin, etc. Can be mentioned. Furthermore, a polymaleimide obtained by maleimidizing a high molecular weight amino compound obtained by reacting an aromatic amine with an aromatic aldehyde in the presence of an acid catalyst can also be used in the present invention. maleimidomethyl group

A compound having the formula is a mononuclear or polynuclear aromatic compound or a derivative thereof,
After halomethylation, it is treated with an aminating agent such as ammonia, and a polyamino compound can be produced by maleimidation. Further, a similar polyamino compound is produced by hydrogenating an aromatic polycyano compound obtained by ammoxidation of a polymethyl-substituted aromatic compound, and a polymaleimide can also be obtained by converting this into maleimide. Among polymaleimides, compounds showing particularly excellent effects are represented by the general formula (),
and poly(phenylmethylene) polymaleimide containing a branched structure represented by the general formula (). (In the formula, n' represents a number greater than 0) In the poly(phenylmethylene) polymaleimide described above, if the average number of N-phenylmaleimide residues in the molecule is greater than 2.0, it can be used as the maleimide component of the composition of the present invention.
Preferably, the number of N-phenylmaleimide residues is
It is desirable that poly(phenylmethylene) polymaleimide molecules of 4.0 or more are included. Poly(phenylmethylene) polymaleimides are
Compared to bismaleimide (N・N′-4・4′-diphenylmethane bismaleimide), the solubility in solvents is improved, the melting point is lower, and the fluidity is improved. This is due to the structure. Bismaleimide has a high molecular symmetry, and molecules of the same shape are arranged in a highly regular manner, so it is easily crystallized, its melting point increases, and its solubility decreases. However, poly(phenylmethylene) polymaleimide is not necessarily an aggregate of molecules with the same shape and chain length, and the regular arrangement seen in bismaleimides is difficult and has large irregularities. As a matter of course, the melting point decreases,
Improves solubility and fluidity. In particular, poly(phenylmethylene) polymaleimide with the number of N-phenylmaleimide groups in the molecule of 4.0 or more can have a branched structure in the molecule.
Regular arrangement of molecules becomes extremely difficult, and the effects of lowering the melting point and improving solubility and fluidity become significantly greater. That is, taking the case of a single compound as an example, if the N-phenylmaleimide residue is 2
Only a linear structure exists for N- and N-
A branched structure becomes possible only when the number of phenylmaleimide residues is 4 or more. Therefore, the presence of poly(phenylmethylene) polymaleimide with a branched structure is very effective, while other effects such as the molecular weight distribution of poly(phenylmethylene) polymaleimide may reduce the Because it can effectively improve solubility and fluidity,
It is not necessary that poly(phenylmethylene) polymaleimide having a branched structure be present. Such poly(phenylmethylene) polymaleimides include poly(phenylmethylene) polyamines obtained by reacting aniline with formaldehyde, and poly(phenylmethylene) polymaleamide acids obtained by reacting with maleic anhydride. It can be produced by cyclodehydration. Some of the poly(phenylmethylene) polyamines used as raw materials are commercially available as polyisocyanate raw materials; for example, Mitsui
MDA-150 (manufactured by Mitsui Toatsu Chemical Co., Ltd.) is a pale yellow viscous liquid with an amino group content of 15.5% by weight or more. (2) Furthermore, as the polymaleimide, a polymaleimide polymer obtained by further polymerizing the above-mentioned polymaleimides using a catalyst, heat, light, etc. can be used. The average molecular weight of the polymaleimide polymer that can be used in the present invention is 10,000 or less, preferably 3,000 or less. Polymaleimide polymers with an average molecular weight of 10,000 or more are insoluble in solvents and have almost no compatibility with other resins, so it is difficult to produce a uniform composition, and moreover, it is difficult to produce a uniform composition. Physical properties are significantly inferior. (3) Furthermore, as the polymaleimide, a prepolymer obtained by adding and modifying the above-mentioned polymaleimide with amines can also be used. The amines that can be used to obtain the prepolymer are not particularly limited as long as they are compounds having one or more amino groups in the molecule. That is, aliphatic amines, aromatic amines, aliphatic aromatic amines, etc., and amino compounds containing oxygen, halogens, sulfur, phosphorus, silicon, and various metal atoms in the molecule, etc. Also included in the above amines. As for the type of amine, primary and secondary amines are preferred, but there is no problem even if tertiary amines are present. Also,
Polyalkylene polyamines or polyarylene polyamines having two or more amino groups in the molecule, aromatic amines (e.g., aniline, toluidines, anisidines, xylidines, etc.) and aldehydes (e.g., formaldehyde, acetaldehyde) Polyamines obtained by the reaction of (e.g.) can also be used for this purpose. In particular, poly(phenylmethylene) polyamine obtained by the reaction of aniline and formaldehyde is industrially produced as a raw material for polyurethane, as mentioned above, such as Mitsui MDA-150 (manufactured by Mitsui Toatsu Chemical Co., Ltd.). It is commercially available as. When preparing prepolymers by reacting polymaleimides and amines, the ratio of the two used is:
The ratio of the total number of maleimide groups to the total number of amino groups,
That is, more specifically, the ratio represented by the formula () is 1 or more, preferably in the range of 1 to 50. (mi, ni/Mi)/(ma, na/Ma)≧1
() (In the formula, mi, ni and Mi represent the amount of polymaleimide used, the average value of the number of maleimide groups in the molecule, and the average molecular weight, respectively, and ma, na and Ma represent the amount of amines used, and the molecule (Indicates the average number of amino groups and average molecular weight.) Either these components can be reacted directly without the use of a solvent, or they can be reacted using an inert polar solvent such as N-methylpyrrolidone, dimethylformamide, or dimethylacetamide. The reaction can be carried out in the state of dissolution or suspension in .
The reaction is accomplished by heating to a temperature of 100-250°C for several hours. At this time, various catalysts may be used, but if a non-volatile catalyst is used, it is difficult to remove it from the prepolymer, and ultimately it remains in the resin after curing, resulting in the thermal stability of the resin. It is desirable not to use this type of catalyst because it impairs the properties of the catalyst and other physical properties. As the polycyanates used in the curable resin composition of the present invention, any organic compound having two or more cyanate ester groups in the molecule, particularly,
Aromatic compounds are preferred, and have the general formula () A(-O-C≡N)x () (where x is a number of 2 or more, A represents an organic group containing an aromatic ring, and the cyanate ester group is , which is assumed to be bonded to the aromatic ring of the organic group A). In the general formula (), the organic group A may be (i) an aromatic ring having 6 to 16 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring or a pyrene ring, or (ii) a plurality of aromatic rings. An organic group to which a hydrocarbon group is bonded directly or through a group, for example, the general formula () Ar ₁ (−R″) − _l Ar ₂ () (where Ar ₁ and Ar ₂ are aromatic hydrocarbon groups , which may be the same or different from each other, l represents a number of 0 or 1, and R″ is a divalent aliphatic, aromatic, or aromatic aliphatic hydrocarbon. group, oxygen atom, sulfur atom, carbonyl group, imino group, sulfonyl group, sulfinyl group, alkyleneoxyalkylene group,

【formula】

It may be an organic group represented by the divalent group represented by the formula (e.g., a divalent group such as (iii)) or a group derived from a novolac type phenolic resin (iii). The aromatic ring of these aromatic organic groups may be substituted with a substituent unrelated to the reaction, such as an alkyl group, an alkoxy group, a halogen atom, or a nitro group. Suitable examples of the organic group represented by the general formula () are biphenyl, diphenylmethane, α・α-dimethyldiphenylmethane, diphenyl ether,
It is a group derived from diphenyl dimethylene ether, diphenyl thioether, diphenyl ketone, diphenylamine, diphenyl sulfoxide, diphenyl sulfone, triphenyl phosphite, triphenyl phosphate, etc. These polycyanates are generally obtained by reacting the corresponding polyhydric phenols with cyanogen halides. Bisphenol A [2,2-bis(4'-
Hydroxyphenyl)propane], which is symmetrical and does not contain a condensed ring, and is obtained by the reaction of a cyanogen halide. Polycyanates obtained by reacting an initial condensate of phenol and formaldehyde with cyanogen halide can also be advantageously used. Further, as the polycyanates, in addition to using the above-mentioned polycyanate components as monomers, polymers thereof can also be used. Polycyanate polymers are obtained by polymerizing the above monomers in the presence of various catalysts. Catalysts that promote polymerization include mineral acids such as hydrochloric acid and sulfuric acid, Lewis acids such as Friedel-Crafts type catalysts, salts such as sodium carbonate and lithium chloride, and triethylamine.
amines, phosphines such as tributylphosphine, phosphites such as triethylphosphite, and sulfuric acid esters such as diethyl sulfate. The resulting polymer generally contains a triazine ring formed by trimerization of cyanate ester groups in the polycyanate. The average molecular weight of the polycyanate polymer that can be used in the present invention is within the range of 300 to 10,000, preferably
It is within the range of 400-6000. Furthermore, as the polycyanates used in the method of the present invention, prepolymers obtained by reacting polycyanates with amines can also be used.
The amines that can be used to obtain the prepolymer are not particularly limited as long as they are compounds having one or more amino groups in the molecule. That is, aliphatic amines, aromatic amines, aliphatic aromatic amines, etc., and amino compounds containing oxygen, halogens, sulfur, phosphorus, silicon, and various metal atoms in the molecule, etc. Also included in the above amines. As for the type of amine, primary and secondary amines are preferred, but there is no problem even if tertiary amines are present. In addition, polyalkylene polyamines or polyarylene polyamines having two or more amino groups in the molecule, aromatic amines (e.g., aniline, toluidines, anisidines, xylidines, etc.) and aldehydes (e.g., formaldehyde, Polyamines obtained by the reaction of acetaldehyde, etc.) can also be used for this purpose. When preparing a prepolymer by the reaction of polycyanate and amines, the ratio of the amounts of polycyanate and amines used is determined by the ratio of the total number of cyanate ester groups to the total number of amino groups, that is, more specifically, by the formula (). The ratio expressed is greater than or equal to 1, preferably in the range from 1 to 100. (mc, nc/Mc)/(m'a, n'a/M'a
)≧1() (where mc, nc and Mc represent the amount of polycyanate used, the average value of the number of cyanate ester groups in the molecule, and the average molecular weight, respectively, and m′a, n′a and M′a (indicates the amount of amine used, the average number of amino groups in the molecule, and the average molecular weight) These two components can be reacted directly without using a solvent, or dissolved or mixed in an organic solvent such as ketones. The reaction can be carried out in suspension. The reaction is accomplished by heating at a temperature of 0-150°C for 1 minute to several hours. A catalyst may be used to accelerate the reaction during this prepolymerization, but
Non-volatile catalysts are difficult to separate after the reaction and end up being contained in the cured resin, reducing the performance of the resin. It is recommended not to use it. Note that instead of using a prepolymer of polycyanate and amines as the polycyanate component of the curable resin composition, it is also possible to use polycyanate and free amines directly without using them as a prepolymer. As the epoxy compound used in the curable resin composition of the present invention, a polymer compound containing one or more epoxy groups, particularly two or more epoxy groups in the molecule is used. Generally, it is desirable that such an epoxy compound has an epoxy equivalent weight of 50 to 6000, particularly 150 to 4000, from the viewpoint of adhesion or adhesion of the final resin product. That is, most known epoxy resins can be used in the composition of the present invention, and typical examples include glycidyl ether type, glycidyl ester type, glycidyl amine type, linear aliphatic epoxide type, and alicyclic epoxide type. Epoxy resins contained in, for example, can be used. In particular, glycidyl ether type epoxy resins include bisphenol A type resins, polyhalogenated bisphenol A type resins, phenol novolak type or cresol novolak type resins obtained by glycidyl etherification of condensates of phenol or cresol and formaldehyde. These resins are easily available and exhibit performance suitable for the purpose of the present invention.
Further, a part of the epoxy resin used may be replaced with a monoepoxy compound such as phenyl glycidyl ether or butyl glycidyl ether.
In this case, although the heat resistance of the cured resin product tends to decrease slightly, the viscosity of the resin composition decreases, so the workability improves. Furthermore, epoxidized or epoxy-modified resins, such as acrylic resins having epoxy groups, alkyd resins, and epoxy-modified silicone resins, are also included in the epoxy compounds of the present invention. In the curable resin composition of the present invention, the composition ratios of the polymaleimide component, polycyanate component, and epoxy compound can be varied over a wide range, and there are no essential limitations. Therefore, the composition ratio can be adjusted to show the most excellent effect depending on the intended use of the cured product, particularly the required characteristics and the type of physical properties that require improvement. Typical embodiments implemented depending on the application and required performance are as follows. In the following description, the equivalents of polymaleimide, polycyanate, and epoxy resin are equivalents based on the maleimide group, cyanate ester group, and epoxy group, respectively. One preferred embodiment uses 0.01 to 0.85 equivalents, preferably 0.04 to 0.70 equivalents, of polycyanates and 0.05 to 4 equivalents, preferably 0.13 equivalents of epoxy compounds per equivalent of polymaleimide. According to this aspect, it is possible to obtain a resin product that has particularly excellent heat resistance and improved adhesiveness and electrical properties. Another preferred embodiment is polycyanates 1
0.01 to 0.85 equivalents of polymaleimide per equivalent,
Preferably, 0.04 to 0.70 equivalents are used, and the epoxy compound is used in an amount of 0.05 to 4 equivalents, preferably 0.1 to 3 equivalents. According to this embodiment, it is possible to obtain a cured product that has electrical properties such as excellent dielectric properties similar to cyanate ester resins, and has significantly improved properties such as heat resistance and adhesiveness. In yet another preferred embodiment, less than 1 equivalent of polycyanates, preferably from 0.34 to 1.0 equivalents, and less than 1.0 equivalents, preferably from 0.34 to 1.0 equivalents of polymaleimides are used per equivalent of epoxy compound. According to this embodiment, a cured product can be obtained which has excellent adhesive properties similar to those of epoxy resins, and which has significantly improved heat resistance and electrical properties. Although the composition of the present invention is not essentially limited in the composition ratio of the three components, it uses a large amount of polymaleimide and polycyanate relative to the epoxy compound, and moreover, Reacting polycyanates in approximately equal amounts tends to extremely shorten the gelation time of the resin composition, and as a result, tends to significantly reduce the physical properties of the cured product, so it is not a composition that should generally be used. . In the curable resin composition of the present invention, free amines can be present in addition to the above-mentioned amines used for prepolymerization of polymaleimides and polycyanates. Examples of these amines include triethylenediamine, imidazoles, imidazoles substituted with aliphatic groups, aromatic groups, araliphatic groups, cyanoethyl groups, etc., and trimellitic acid adducts of these imidazoles. The amount of these amines added in free form is 10% of the total compound.
% by weight or less, preferably in the range of 0.05 to 5% by weight. The curable resin composition of the present invention can be prepared from the above-mentioned polymaleimides, polyisocyanates, and epoxy compounds using a method that uses a solvent or a method that does not use a solvent. If a solvent is used, the three components should be mixed at a predetermined blending ratio in a common solvent for the three components.
A uniform solution of the resin composition can be obtained by dissolving the components all at once, or by dissolving each component in an optimal solvent and then mixing the respective solutions. In the latter method, for example, for polymaleimides, aprotic solvents such as N-methylpyrrolidone, N·N-dimethylformamide, N·N-dimethylacetamide, and dimethyl sulfoxide are used as the optimal solvent for each component. There are polar solvents and ketones such as acetone, and in contrast to polycyanates and epoxy resins, aromatic hydrocarbons such as toluene and xylene,
Ketones such as acetone and methyl ethyl ketone,
Esters such as ethyl acetate, ethers such as dibutyl ether, etc. are suitable, and solvents that dissolve polymaleimides such as N-methylpyrrolidone, N・N-dimethylformamide, N・N-dimethylacetamide, and dimethylsulfochloride are suitable. side,
It also dissolves easily. The mixed solution of the three components thus obtained is heated to a temperature between room temperature and the boiling point of the solvent,
It can be homogenized to form a solution-type curable resin composition. The curable resin composition prepared in this way can be stored stably, does not gel during storage, and can be used without problems in operations such as adhesion, painting, lamination, or molding. The solution may be a one-component composition in which the three components are mixed, or a two-component composition that is mixed before use, depending on the mutual reactivity of each component and additive, storage conditions, etc. are selected taking into consideration. Further, the concentration of the resin solid content in the solution is determined so as to obtain the most suitable workability depending on the individual application. Further, by distilling off the solvent under reduced pressure and/or heating from a solution in which the three components are uniformly dissolved, a solvent-free composition in which each component is uniformly mixed can be obtained. The curable resin composition thus obtained can be used for various purposes in the form of a dry powder, pellet, resin-impregnated product, or compound. On the other hand, when a solvent is not used, solid polymaleimides and solid polycyanates are pulverized and mixed, and then kneaded with an epoxy compound at room temperature or under heating to prepare a homogenized curable resin composition. can do. In addition, a composition obtained by pulverizing and mixing solid polymaleimides and polycyanates and adding an epoxy compound is heated to a temperature higher than the liquefaction temperature of this composition, then cooled to room temperature to solidify, and then pulverized. As a result, a more uniform powder composition can be prepared. At this time, it is desirable to carry out the melting homogenization operation at the lowest possible temperature and in the shortest possible time, but this is because each component reacts with itself or with each other during heating and melting, increasing the molecular weight and increasing the solubility in the solvent. This is because there is a risk of deterioration in workability such as a decrease in the temperature and a rise in the melting point. However, powdered compositions obtained by appropriate melting operations exhibit significantly superior physical properties, especially mechanical strength, after curing. These resin compositions can also be used in the form of emulsions or suspensions. In addition to the above-mentioned polymaleimides, polycyanates, and epoxy compounds, the following components can be added to the curable resin composition of the present invention. (1) This curable resin composition has the property that each component bonds with each other and forms a network when heated, forming a heat-resistant resin. Therefore, as a catalyst that promotes network formation,
For example, N.N-dimethylaniline tri-
Tertiary amines such as n-butylamine, pyridine, quinoline or triethylenediamine,
Imidazole and substituted imidazoles, phenols such as phenol and phloroglycin, organic metal salts such as lead naphthenate and lead stearate,
Friedel-Crafts metal chlorides such as SnCl ₄ , ZnCl ₂ , and AlCl ₃ , etc. The amount of these catalysts added varies depending on the type of catalyst, curing conditions, and use of the cured product, and generally , the amount may be 5% by weight or less based on the total resin solid components. In particular, high-boiling organic catalysts, non-volatile metal salts and inorganic catalysts are included in the cured product,
Since it deteriorates various physical properties, especially impact resistance and insulation, the amount used should be kept to the minimum necessary. (2) Powdered reinforcing agents and fillers, such as alumina, diatomaceous earth powder, magnesia, kaolin, calcium carbonate, magnesium carbonate, basic magnesium silicate, calcined clay, finely powdered silica,
Carbon black, boron nitride, etc., as well as fibrous reinforcing materials and fillers, such as glass fibers, rock wool, ceramic fibers, inorganic fibers such as asbestos, carbon fibers and semi-carbon fibers, paper, pulp, wood flour, linters, and These include various synthetic fibers such as polyimide fibers. The amount of these powder or fibrous reinforcing agents and fillers used varies depending on the application, but as laminated materials and molding materials,
It can be used up to 4 times the weight of the resin solid content. (3) Colorants and pigments, such as white pigments such as titanium dioxide, colored pigments such as yellow lead, carbon black, iron black, molybdenum red, navy blue, ultramarine blue, cadmium yellow, and cadmium red, or various organic dyes and pigments; In addition to coloring materials such as, when the resin composition of the present invention is used for paints, rust-preventing pigments such as zinc chromate, red lead, red iron, zinc white, and strontium chromate, and anti-sagging pigments such as aluminum stearate may be used. These are common paint compounding agents such as additives, dispersants, thickeners, film modifiers, and flame retardants. (4) Furthermore, for the purpose of improving the properties of the resin in the final coating film, adhesive layer, resin molded product, etc.
Blend with various natural/semi-finished products or synthetic resins. Such resins include, for example, oleoresins such as drying oils and semi-drying oils, rosins, silica, copal, oil-modified rosins, phenolic resins, alkyd resins, urea resins, melamine resins, polyester resins, vinyl butyral resins, and vinyl acetate. Examples include one or a combination of two or more of resins, vinyl chloride resins, acrylic resins, silicone resins, polybutadiene resins, diallyl(iso)phthalate resins, triallyl isocyanurate resins, diallyl ether resins, and allyl novolak resins. The amount of these resins used is within a range that does not impair the original properties of the polymaleimide-polycyanate-epoxy resin of the present invention, that is, 30% by weight or less of the total resin amount. The curing conditions for using the curable resin composition of the present invention as a cured product vary depending on whether or not a catalyst or curing agent is used, the type of resin actually used, and the form of the composition and the thickness of the coating film. Changes due to etc. Generally, the resin composition of the present invention is applied to a substrate as a coating film or adhesive layer, or formed or laminated as a powder, pellet, or even impregnated into a substrate, and then heated and cured. . The curing temperature is generally 0 to 300°C, preferably 100 to 300°C.
It is best to keep the temperature within 250℃. The heating time for curing is particularly influenced by the form, but generally a time sufficient for the resin component to be completely cured may be selected in the range of 30 seconds to 10 hours. moreover,
When used in the production of molded products, laminate products, adhesive structures, etc., it is desirable to apply pressure during heat curing, and the applied pressure may range from 1 to 100 Kg/cm ² . Methods for curing the curable resin composition of the present invention include, in addition to heating methods, curing methods using light (particularly ultraviolet rays) and ionizing radiation. In these methods, the curable resin composition of the present invention can be advantageously used particularly in the field of painting. In the photocuring method,
As a light source, a low-pressure or high-pressure mercury lamp, tungsten lamp, arc lamp, xenon lamp, halogen lamp, or sunlight is used. In addition, as a photosensitizer, for example, benzoin,
Organic carbonyl compounds such as benzoin alkyl ethers, benzanthrone, anthraquinone, and benzophenone, and combinations of sensitizing dyes such as eosin, erythrosine, and acridine with various amines are used in an amount of up to 5% by weight based on the resin solid content. Further, for curing with ionizing radiation, electron beams from various accelerators, gamma rays from isotopes such as cobalt-60, etc. can be used. The novel curable resin composition of the present invention has significantly improved solubility and fluidity in solvents, so it can provide excellent workability and productivity even when used in a variety of applications, and has a comparatively faster curing speed. It has the advantage of being able to be cured quickly and under relatively mild conditions. The cured product obtained by curing the novel curable resin composition of the present invention not only has excellent heat resistance, but also excellent electrical properties, adhesive properties, and adhesive properties, as well as mechanical properties and chemical resistance. It has high performance. Therefore, the curable resin composition of the present invention is useful for applications such as electrical insulation varnishes, adhesives, electrical insulation and other various laminated materials, heat-resistant, disaster prevention and other paints, and various molding resins. The present invention will be explained below using reference examples and examples. Reference example 1 32 parts of maleic anhydride was dissolved in 250 parts of acetone, and while stirring, the average number of aniline residues in the molecule was 2.8.
A solution of 30 parts of MDA-150 (manufactured by Mitsui Toatsu Chemical Co., Ltd.), a proprietary poly(phenylmethylene) polyamine, dissolved in 60 parts of acetone was gradually added to obtain a yellow precipitate. This precipitate was confirmed to be maleamic acid MDA-150 by infrared absorption spectrum (IR). To remove the above yellow precipitate, 1 part of cobalt acetate tetrahydrate, 6 parts of triethylamine, and 33 parts of acetic anhydride were added under stirring without separation, and after heating under reflux for 2 hours, most of the acetone was distilled off, and the remaining liquid was Injected into large amounts of water. A yellow-brown precipitate was formed, which was washed with water and dried to obtain 52 parts (yield: 98%) of a yellow-brown powder. This powder has an average of N-phenylmaleimide groups in its molecules, as determined by molecular weight measurements using nuclear magnetic resonance spectroscopy (NMR), IR, and VPO methods.
It was confirmed that it is poly(phenylmethylene) polymaleimide having 2.8 molecules. 52 parts of the poly(phenylmethylene) polymerimide thus obtained and 12 parts of MDA-150, which has an average of 2.8 aniline residues in the molecule, were mixed, heated to 150°C and reacted for 20 minutes, and the mixture A coherent prepolymer was obtained. When crushed after cooling, it becomes a yellowish brown powder, which is converted into polymaleimide prepolymer A.
shall be. Reference Example 2 35 parts of maleic anhydride was dissolved in 260 parts of acetone, and 33 parts of poly(phenylmethylene) polyamine, which has an average of 4.1 aniline residues in the molecule, dissolved in 70 parts of acetone was gradually added. A tan precipitate was obtained. This precipitate was confirmed by IR to have the structure of poly(phenylmethylene) polyamide. Without separating the yellow brown precipitate, add 1 part of cobalt acetate tetrahydrate and 7 parts of triethylamine while stirring.
After heating and refluxing for 3 hours, most of the acetone was distilled off and the residual liquid was poured into a large amount of water. A yellowish brown precipitate was formed, so it was washed with water and dried.57
(yield 97%) of a yellowish brown powder was obtained. This powder has an average N-phenylmaleimide group in the molecule, as determined by molecular weight measurements using NMR, IR, and VPO methods.
It was confirmed that it was poly(phenylmethylene)polymaleimide having 4.1 molecules. 57 parts of the poly(phenylmethylene) polymaleimide thus obtained and 13 parts of MDA-150, which has an average of 2.8 aniline residues in the molecule, were mixed, heated to 150°C, and reacted for 20 minutes with stirring. A viscous prepolymer was obtained. After cooling, it is ground into a yellow-brown powder, which is referred to as Polymaleimide Prepolymer B. Reference example 3 90 parts of N・N′-4・4′-diphenylmethane bismaleimide and 20 parts of 4・4′-diaminodiphenylmethane
The components were mixed and dissolved while heating, and reacted at 150°C for 15 minutes with stirring to obtain a prepolymer.
After cooling, it was crushed to obtain a yellow powder, which is referred to as bismaleimide prepolymer. Reference Example 4 90 parts of MDA-150 (manufactured by Mitsui Toatsu Chemical Co., Ltd.), which is a commercially available poly(phenylmethylene) polyamine,
% aqueous hydrochloric acid solution was added and sufficiently stirred to dissolve. Furthermore, while stirring this solution at room temperature,
13 parts of a 37% formaldehyde aqueous solution was gradually added dropwise, and after the addition was completed, stirring was continued at room temperature for 6 hours.
After the reaction was completed, 360 parts of a 10% aqueous sodium hydroxide solution was added and allowed to stand overnight at room temperature. The poly(phenylmethylene) polyamine produced was insoluble in the aqueous layer and precipitated in the lower layer. The precipitate was separated, further washed with 500 parts of water, and then dried under reduced pressure. The obtained poly(phenylmethylene)polyamine is a pale yellow waxy substance at room temperature, and has been analyzed by IR, NMR,
Determination of the amine value by titration and molecular weight measurement by the VPO method revealed that the molecule has an average of 5.6 aniline residues. Reference Example 5 126 parts of maleic anhydride was dissolved in 850 parts of acetone, and 120 parts of the poly(phenylmethylene) polyamine having an average of 5.6 aniline residues in the molecule obtained in Reference Example 4 was dissolved in 300 parts of acetone. A yellow precipitate was obtained by gradually adding the solution dissolved in . This precipitate is
It was confirmed by IR and NMR that it has the structure of poly(phenylmethylene)polymaleamic acid. While stirring without separating the above yellow precipitate,
2 parts of cobalt tetrahydrate, 10 parts of triethylamine,
After adding 131 parts of acetic anhydride and heating under reflux for 2 hours, most of the acetone was distilled off, and the remaining liquid was poured into a large amount of water. A yellow-brown precipitate was formed, which was separated, washed with water, and dried to obtain 198 parts (yield: 94%) of a yellow-brown powder. This powder was found to be poly(phenylmethylene) having an average of 5.6 N-phenylmaleimide residues in the molecule, as determined by NMR, IR, quantitative determination of imide groups by hydrogenated hydrogen iodide decomposition method, and molecular weight measurement by VPO method (solvent dioxane). ) It was confirmed that it was a polymaleimide, and this was called Polymaleimide C. Reference Example 6 18.7 parts of maleic anhydride was dissolved in 90 parts of acetone, and while cooling the liquid temperature to 40°C or lower, a dioxane solution of 14 parts of aminomethylated diphenyl ether containing an average of 3.8 aminomethyl groups in the molecule was prepared. 120
was gradually added dropwise to obtain a yellow precipitate. This precipitate is found to have a polymaleamic acid structure by IR
and confirmed by NMR. To 30 parts of this polymaleamic acid, 85 parts of acetic anhydride, 0.3 parts of cobalt acetate tetrahydrate, and 1.2 parts of triethylamine were added, and the mixture was heated to 85°C.
After reacting for 3 hours, acetic anhydride and acetic acid were distilled off under reduced pressure, and the residue was cooled to obtain a solid.
This was finely ground, washed five times with 100 c.c. of water, and dried to obtain a brown powder. This powder can be used to quantify imide groups using NMR, IR, and hydrogenated hydrogen iodide decomposition methods.
Molecular weight measurement using the VPO method (solvent dioxane) revealed that the average number of maleimidomethyl groups in the molecule was 3.8.
It was confirmed that the poly(maleimidomethyl)-substituted diphenyl ether was a polymaleimide D, which is called polymaleimide D. Examples 1 to 3 Polymaleimide prepolymer A obtained in Reference Example 1, cyanic acid ester KU-6573 of bisphenol A manufactured by West German Bayer Co., Ltd., and epoxy resin DER542 (diglysic acid ester of tetrabromo bisphenol A manufactured by Dow Chemical Company, USA) ether, epoxy equivalent
325-375) in the proportions shown in Table 1 to form a homogeneous mixture, N-methyl-2-
Pyrrolidone-methyl ethyl ketone (volume ratio 35/
65) and obtained the results shown in Table 1. Comparative Example 1 Polymaleimide The solubility was examined under the same conditions as in Example 1, except that the bismaleimide prepolymer obtained in Reference Example 3 was used instead of prepolymer A, and the results are shown in Table 1. .

[Table] Examples 4 to 6 Polymaleimide Prepolymer B obtained in Reference Example 2, cyanate ester of bisphenol A KU-6573 manufactured by West German Bayer, and epoxy resin Ebicoat 1001 manufactured by Schiel Chemical (bisphenol type, epoxy 450 to 500) were thoroughly mixed in the ratio shown in Table 2 to form a homogeneous mixture, a portion was placed in a micro test tube with an inner diameter of 5 mm to a height of 8 to 10 mm, and placed in an oil bath. The temperature at which the solids in the contents completely melted was measured and shown in Table 2. Comparative Example 2 The melting end temperature was measured under the same conditions as Examples 4 to 6, except that the bismaleimide prepolymer obtained in Reference Example 3 was used instead of Polymaleimide Prepolymer B, and the results are shown in Table 2. Indicated.

[Table] Example 7 To the sample of Example 2 (N-methyl-2-pyrrolidone-methyl ethyl ketone solution containing 11% of polymaleimide prepolymer A, 78% of KU6573, and 11% of DER542), 3% by weight of 2- ethyl-4
- After adding methylimidazole, B
I made prepreg for the stage. A laminate was made by stacking multiple sheets of prepreg and then layering copper foil under a pressure of 35 kg/cm ² for 3 hours at 180°C. The plate is dark red, has a glass transition temperature of 220℃, a copper foil peel strength of 2.3Kg/cm, and a dielectric constant of 4.7 (IMHz).
Moreover, it was a copper-clad laminate with self-extinguishing properties. Example 8 Sample of Example 4 (polymaleimide prepolymer B, 77%, KU-6573 6%, Epicote 1001 17
%) was added with 0.5% of 2-ethyl-4-methylimidazole, heated and melted, solidified by cooling, and further pulverized to obtain a powdery composition.
The above powder composition is uniformly adhered to a grounded electrolytic copper foil with a thickness of 35μ by a fluid immersion electrostatic coating method using an applied voltage of 60KV DC, further covered with glass cloth, and heated at 125℃ for 10 minutes. A B-stage metal foil prepreg was manufactured using the following method. The two metal foil prepregs obtained in this way were stacked so that each copper foil was on the outside,
A laminate plate with copper cladding on both sides was obtained by lamination molding at 170°C for 2 hours at a pressure of 30 kg/cm ² . The peel strength of the copper foil of this laminate is 20Kg/cm, and 260
No change was observed even after holding at ℃ for 10 hours, and the weight loss was less than 2%. Example 9 Polymaleimide C13 part obtained in Reference Example 5 was
- 18 parts of a cyanate ester resin prepared from bisphenol A and cyanogen chloride dissolved in 30 parts of methyl-2-pyrrolitone, 27 parts of Dow Chemical's epoxy resin DER-542, 2-ethyl-4-methylimidazole 0.5 part was added to make a homogeneous solution, which was impregnated and coated on a glass cloth, and heated at 110°C for 30 minutes to produce a B-stage prepreg. A laminate was produced by stacking six sheets of prepreg and then stacking copper foil at 180°C for 3 hours at a pressure of 40Kg/cm ² . The peel strength of the copper foil was 2.5 kg/cm, and the soldering heat resistance was 120 seconds or more at 280°C. Example 10 12 parts of Polymaleimide D obtained in Reference Example 6, 28 parts of cyanate ester resin produced from bisphenol A and cyanogen chloride, 10 parts of epoxy resin Epicoat 1001 manufactured by Ciel Chemical Co., and 2-ethyl-4-methyl 0.3 parts of imidazole in N-methyl-
After dissolving in 55 parts of 2-pyrrolidone to obtain a uniform solution, a laminate was prepared under the same conditions as in Example 9.
Copper foil peel strength 1.7Kg/cm, dielectric constant 5.5 (1MHZ)
It was a copper-clad laminate with self-extinguishing properties. Example 11 45 parts of poly(phenylmethylene) polymaleimide having an average of 2.8 N-phenylmaleimide groups in the molecule shown in Reference Example 1, 15 parts of epoxy resin Epicoat 1001 manufactured by Ciel Chemical Co., and 2.
2'-bis(4-cyanatophenyl)propane
Prepolymer 40 obtained by heating at 155℃ for 3 hours
Grind and mix 1 part and then diallyl isophthalate
20 parts of zinc octylate, 0.1 part of zinc octylate, and 0.1 part of triethylenediamine were mixed and stirred, kneaded with rolls at 80°C, pulverized, and pressed at 170°C for 10 minutes. The obtained sample was heated using the TMA method (penetration method) at a heating rate of 25℃/mi.
Glass transition temperature measured by n, He50c.c./min)
275°C was obtained.

Claims (1)

[Claims] 1 (a) One or more types selected from a polymaleimide in which the average number of maleimide groups present in the molecule is greater than 2, a polymer of the polymaleimide, or a prepolymer of the polymaleimide and an amine. one or two types selected from a compound and (b) a polycyanate having an average of two or more cyanate ester groups in the molecule, a polymer of the polycyanate, or a prepolymer of the polycyanate and an amine. A curable resin composition comprising the above compound and (c) an epoxy compound.