JPS5889619A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain titled composition with adequate heat resistance, usable under solvent-free condition, comprising an aliphatic maleimide having a specific structure, a multivalent maleimide compound, an amino compound, etc. CONSTITUTION:The objective composition comprising (A) at least one sort of an ether bond-contg. aliphatic maleimide of formulaI(R1 is H, 1-20C hydrocarbon, halogen R2O, R2CO, R2CONH, OH, CN, or nitro; Q is l-valent aliphatic ether; l>=1), (e.g., N-2,2'-hydroxyethoxyethyl maleimide). (B) a multivalent maleimide compound of formula II (0.01<=n<=15), (C) an amino compound of formula III (e.g., ethylamine), and, if required, (D) an epoxy resin (e.g., bisphenol A), a catalyst (e.g., triethylamine), etc. In addition, the above composition may be incorporated with a prepolymer derived from at least two of the components (A), (B), and (C). Using the composition, a cured product can be obtained through a pressure molding.

Description

Detailed Description of the Invention The present invention provides a heat-resistant curable resin composition that has higher performance than conventional heat-resistant resins such as polymaleimide resins in terms of curability and workability, and can be used without a solvent. relating to things.

Polyimide resin is the most well-known electrical insulating material with excellent heat resistance, but it has difficulties in processability, so it is generally not molded or processed in the form of its precursor, polyamic acid. It is necessary to perform an imidization reaction to cure it.

The process becomes complicated, and problems such as foaming and blistering occur due to ice produced as a by-product in the imidization reaction process. An amine compound-modified bismaleimide resin is a material that has improved on these problems, but this resin is difficult to dissolve in general-purpose organic solvents, and when used as a solution-impregnated varnish, it is particularly difficult to use it because of its high boiling point and strong hygroscopic polarity. Organic solvents N,N-dimethylformamide, N,N-dimethylacetamide, N
-Needs to be dissolved in methyl-2-pyrrolidone or the like.

Moreover, these solvents have a high permeability through the skin, making them unfavorable in terms of safety and hygiene.Furthermore, these solvents have a strong affinity with bismaleimide resins, making them difficult to remove from the resin, and are expensive and economical. It is also disadvantageous. On the other hand, in recent years, for the purpose of saving energy and improving workability, it has been attempted to produce a solvent-free face, and a combination of bismaleimide resin and epoxy resin has been adopted. However, these two have poor compatibility, and bismaleimide precipitates, and high temperatures are required to obtain a homogeneous liquid, resulting in a short pot life, which limits the scope of their application.

The present invention provides a composition having a low melting point and a long pot life, which is composed of an aliphatic maleimide having an ether bond, a polyvalent aromatic maleimide compound, and an amine compound, which eliminates the various drawbacks found in the above-mentioned bismaleimide resins. It provides:

That is, the present invention has the following formula: Number of carbon atoms: 1~
20 hydrocarbon groups or a group substituted with halogen), Q represents a monovalent aliphatic ether group, and t represents an integer of 1 or more. (b) at least one aliphatic maleimide represented by the general formula [wherein R1 is the same or different, each being a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms;

A hydroxyl group, a cyano group, or a nitro group (wherein R2 represents a hydrocarbon group having 1 to 20 carbon atoms or a group substituted with a halogen thereof), and n is 0.01 to 15
Indicates the number of ranges. This is a curable resin composition comprising a polyvalent maleimide compound represented by the following formula and (C) an amino compound, and optionally further contains (d) an epoxy resin.

The aliphatic maleimide and polyvalent maleimide compounds used in the composition of the present invention have a lower melting point than ordinary bismaleimide resins, and have significantly superior solubility in organic solvents. has the advantage of providing a highly flexible cured product since it does not have a benzene ring. Therefore, it is not necessarily necessary to use polar organic solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide, which are required for normal bismaleimide resins from the standpoint of safety, health, and work environment. , general-purpose low-boiling point organic solvents can be used. As a result, workability has been improved, and the solvent has become easier to remove from products such as laminates, making it possible to produce cured products with significantly improved quality and no voids.

Furthermore, the low melting point and long pot life characteristic of the composition of the present invention enable the composition to be used in a solvent-free form, and since the aliphatic maleimide of the present invention has an ether bond, the present invention It is also expected to improve the adhesion ability between the resin and various base materials.

The aliphatic maleimide used in the present invention has a maleimide residue having the formula % (% formula %) (wherein, R+ 21R'+ 21 R″1□, R′7□
and R13 may be the same or different and may be a linear or branched mono- to trivalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or it is substituted with an alkoxy group, a hydroxy group, or a halogen. a, b, C1
X, y and 2 represent numbers of 1 or more. ) is a compound that is an aliphatic ether group and has the structure shown below. A very typical example of such aliphatic maleimide is N
-2゜2'-hydroxyethoxyethylmaleimito, N
-1-methoxymethylpropylmaleimide, N-1-ethoxymethylpropylmaleimide, N-1-methoxymethylbutylmaleimide, N.

N'-4,7-thioxadecane-1,10-bismaleimide, N, N'-3,6,9-trioxaoundegan-1,11-bismaleimide, N.

N'-4,9-dioxadodecane-1,12-bismaleimide, N,N'-4,7,10-)dioxatridecane-1,13-bismaleimide, N,N'-7-methyl -4,10-dioxatridecane-1,13-bismaleimide, N,N'-3,6,9,12-tetraoxatetradecane-1,14-bismaleimide, N,N'-3
,6゜9 12 15-pentaoxaheptadecane-1
, 17-bismaleimide, bis(3-N-maleimidopropyl)polytetrahydrofuran, U

υ (where a is 2, 6, 5.6 or 33.1
It is. ) (In the formula, the sum of a and C is R7, b is about 13
5 to 1 (in the formula, the sum of X, y and 2 is about 53). Furthermore, compounds in which the hydrogen atom bonded to the unsaturated carbon atom in the maleimide group of the above aliphatic maleimi P is substituted with a chlorine atom, a bromine atom, a methyl group, a phenyl group, etc. may also be used. Further, the aliphatic maleimides of general formula (I) can be used alone or in combination of two or more.

The polyvalent maleimide compound used in the present invention is an Ibi compound represented by the above general formula (11) II, in which the maleimide residue is composed of aniline and formaldehyde (in the formula, n has the same meaning as above). It means the structure shown, but can further include a branched structure represented by H2-.

Some of the aniline-formaldehyde resins are manufactured on an industrial scale as polyisocyanate raw materials.For example, MDA-150 (trademark: manufactured by Mitsui Toatsu Chemical Co., Ltd.) is a pale yellow viscous liquid, and its amine group content is is 15.5% by weight or more.

Since the amine group of this resin can be easily converted into maleimide by reaction with maleic anhydride, it is advantageous for producing the polyvalent maleimide compound having the structure of the general formula used in the present invention.

- As an example of the above compound where n = 1, N-2,4-bis(47N/-maleimidobenzyl)phenylmaleimide can be mentioned, but as the above polyvalent maleimide compound, the unsaturated carbon atom in the maleimide group Compounds in which bonded hydrogen atoms are appropriately substituted with chlorine atoms, bromine atoms, methyl groups, ethyl groups, phenyl groups, etc. can also be used. In general, a value in the range of 0.01 to 15 can be used for n, but in practice it is 0.05 to 9.0 from the viewpoint of low melting point and heat resistance.
A range of 0.1 to 5 degrees is particularly preferred.

In the composition of the present invention, there is no particular limitation on the ratio of the aliphatic maleimide of general formula (1) and the polyvalent maleimide compound of general formula (II), but generally the former is
2 to 99% by weight, preferably 5 to 99% by weight, based on the total amount of the latter
It is 95% by weight. If the amount of the former exceeds the above range, the heat resistance of the resulting cured product will decrease, while if it falls below the above range, the curability and flexibility of the composition will deteriorate.

The amine compound used for the purpose of imparting a homogeneous and dense structure, toughness, and mechanical strength to the cured product of the present invention is expressed by the following formula (% formula %) (wherein 2 is a carbon atom number of 1 to 150). .

It is an n-valent organic group that can contain atoms such as hydrogen, oxygen, sulfur, halogen, nitrogen, I77, silicon, etc.
is an integer of 1 or more), typical examples of which are ethylamine, propylamine,
Hexylamine, aniline, p-(m or 0-)toluy, dine, p-(m or 0-)methoxyaniline.

p-(m or o-) chloroaniline, 3,5-dichloroaniline, p-(m or θ-) hydroxyaniline + p (m or δ-) carboxyaniline, p-(m
or 0-) vinylaniline + I' (m or O-
) allylaniline gp-(isopropenylaniline, 2
-Methyl-4-isoprope and luanili/, 4-aminopyridine 2 (4/-hydroxyphenyl)-2-(
4"-aminophenyl)propane, 2 (4'-hydroxyphenyl)-2-(f-methyl-eaminophenyl)propane, benzylamine, 1-aminonaphthalene, 2-aminonaphthalene, 2,2'-hydroxyethoxy Ethylamine, l-methoxymethylpropylamine, 1-ethoxymethylpropylamine, l-methoxymethylbutylamine, ethylenediamine, trimethylenediamine, hexamethylenediamine, decamethylenediamine, octamethylenediamine, 2,2.4-)limethylhexane Methylenediamine, oxydipropylenediamine, ethylenedioxydiethylenediamine, 4,7-
Thioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine, 4,7゜10-)dioxatridecane-1,13-diamine, 7-methyl-
4,10-dioxatridecane-1,13-diami/,
bis(3-aminopropyl)polytetrahydrofuran,
p-(or m-)phenylenediamine, 1,4-diaminocyclohexane, 2,4-diaminotoluene, 4,
4'-diaminodiphenylmethane, 3゜4'-cyaminodiphenylmethane, 2,2-bis(4'-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4
'-Diamino diphenyl sulfone, 3.3'-diaminodiphenylsulfone, 4.・4'-diaminodicyclohexylmethane, p-(or m-)xylylenediamine, his(4-aminophenyl)diphenylsilane, bis(4-aminophenyl)methylphosphine oxide,
Bis(3-chloro-4-aminophenyl)methane, 2,
2-bis(4'-aminophenoxyphenyl)propane, 1,4-bis(p-aminophenoxy)benzene, 1゜4-diaminonaphthalene, 2,4-diaminopyridine, 4-methyl-2,4-bis (p-aminophenyl)pentane, 4-mef-2,4-bis(p-7minophenyl)-1-pentene.

4-)Tyl-2,4-bis(p-7minophenyl)-2
- pentene, tris(4-aminophenyl) phosphate, tris(4-aminophenyl) thiophosphate,
2,4.6-tris(4'-aminophenoxy)-S-
) riazine, 5(or 6)-amino-1-(4'-aminophenyl)-1,3,3-1-limethylindane, and even (wherein a is about 2.6, 5.6 or 33 .1 is 7?
1) (In the formula, the sum of a and C is approximately 3.5, and b is approximately 13.
5 to 45.5. ) (In the formula, the sum of x, y and 2 is approximately 5.3.) (These amine compounds are commercially available from Mikata Texaco Chemical Company under the trade name Chefamine.) , trimer or higher polymers of vinylanilines or isopropenylanilines, aromatic amines (
Polyamines obtained by the reaction of aldehydes (e.g. formaldehyde, paraform, acetaldehyde) with aldehydes (e.g. aniline, toluidines), especially poly(phenylenemethylene)polyamines obtained by the reaction of aniline with formaldehyde (e.g. the above-mentioned MDA). -150)
and alicyclic polyamines obtained by hydrogenating the polyamine. These amine compounds alone have 2
It can also be used as a mixture of more than one species.

There is no particular limitation on the amount of these amine compounds used in the composition of the present invention, but aliphatic maleimide and/or
Alternatively, the ratio of the total number of amine groups in the amino compound to the total number of maleimide groups in the maleimide component of the polyvalent maleimide compound [general formula (goods)] is preferably 1 or less, and more preferably in the range of 0.01 to 1. .

(In the formula, mi, ni, and Mi represent the amount of the maleimide compound 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 the amine compound used, and the number of amine groups in the molecule, respectively. (The average value and average molecular weight are shown.) The prepolymer of an amine compound and an aliphatic maleimide and/or a polyvalent maleimide compound (both are abbreviated as maleimide compounds) or a prepolymer of a maleimide compound depends on the specific reaction method. There are no restrictions, but each component may be directly and uniformly mixed and reacted without a solvent at a reaction temperature of 0 to 200°C9 and a reaction time of 5 minutes to 20 hours, or each component may be reacted using a solvent. It is a preliminary reaction product obtained by reacting as a homogeneous solution or suspension state.

The composition of the present invention is used not only as a mere mixture but also in a form containing the above-mentioned prepolymers.

If the amount of the amine compound used exceeds the above range, the heat resistance of the cured product will decrease, while if it falls below the above range, the adhesive strength will decrease and the mechanical strength of the cured product will tend to decrease.

On the other hand, the epoxy resin used for the purpose of improving adhesive strength and adjusting viscosity as necessary may be any known solid or liquid product. Typical examples include bisphenol^ type epoxy resin, bisphenol F type epoxy resin, etc. resin,
Heterocyclic epoxy resins such as halogenated bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolak type epoxy resins, alicyclic epoxy resins, triglycidyl cyanurate, triglycidyl isocyanurate or hydantoin epoxy,
Hydrogenated bisphenol A type epoxy resin, aliphatic epoxy resin such as propylene glycol diglycidyl ether and pentaerythritol polyglycidyl ether, epoxy resin obtained by reaction with aliphatic or aromatic carboxylic acid tobichlorohydrin, spiro ring The containing epoxy resin, a chrycidyl ether type epoxy resin which is a reaction product of an orthoarylphenol novolac compound and epichlorohydrin, P represented by the following molecular formula,
P'-N, N, N', N'-tetraglycidyldiaminodiphenylmethane or triglycidyl-p- represented by the following molecular formula
Epoxy resins obtained by reacting aliphatic or aromatic amines such as amine phenol with epichlorohydrin, epoxy resins in which part of the above epoxy resins are ring-opening polymerized, and epoxidized or epoxy-modified resins (e.g., epoxy resins with epoxy groups). acrylic resins, 1,2-polybutadiene or alkyd resins, and epoxy-modified silicone resins).

In the present invention, epoxy resins can be used alone or in combination of two or more, and a monofunctional so-called reactive diluent may be partially included. There is no particular limitation on the amount of epoxy resin used, but in order not to impair the heat resistance of the cured product obtained from the composition of the present invention.

Preferably, the amount is 50% or less of the total weight of the composition.

A catalyst is not necessarily required for the curing reaction of the composition of the present invention, but one or more catalysts can be used depending on the situation. In this case, the amount used is within a range that does not interfere with the excellent effects of the composition of the present invention and improves its performance, and is practically 5% by weight or less based on the total weight of the composition. Catalysts used for purposes such as improving workability and adjusting curing speed depending on the form of use of the composition include boron trifluoride amines such as boron trifluoride monoethylamine complexes and boron trifluoride piperidine complexes. Complexes, tertiary amines such as triethylamine, N,N-dimethylbenzylamine, hexamethylenetetramine, N,N-dimethylaniline, quaternary ammonium salts such as tetramethylammonium bromide, triphenyl porate, tricresyl porate, etc. imidazole compounds such as porate compounds, N-methylimidazole, and N-phenylimidazole.

Metal compounds such as zinc acetate, sodium acetate, titanium acetylacetonate, sodium metalahetate, aluminum chloride, zinc chloride, tin chloride, manganese nanthenate, cobalt naphthenate, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride Acids, acid anhydrides such as nadic anhydride, benzophenone tetracarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, maleic anhydride, peroxides such as dicumyl peroxide, t-butyl perbenzoate, methyl ethyl ketone peroxide , azo compounds such as azobisin butyronitrile.

The composition of the present invention can be used in a cold solvent type by simply mixing uniformly and heating by taking advantage of its characteristics such as a low melting point and a long pot life, but it can also be used in the form of a solution because it is easily soluble in organic solvents. . In the case of a solution, there are no restrictions on the organic solvent used, but preferred specific examples include ketones such as acetone, methyl ethyl ketone, and cyclohexane.

Hydrocarbons such as n-hexane and cyclohexane, diethyl ether, ethyl celerol, methyl cellosolve,
1. Ethers such as 4-dioxane and tetrahydrofuran, methylene chloride chloroform, trichloroethane,
Chlorine compounds such as carbon tetrachloride, aromatic hydrocarbons such as benzene, xylene, and mesitylene, alcohols such as methanol, ethanol, isopropyl alcohol, phenol, and cresol, nitriles such as acetonitrile, methyl acetate, ethyl acetate, 2- Examples include esters such as ethoxyethyl acetate. N again.

Of course, a solution composition can be obtained by using N-dimethylformamide, N-methyl-2-prolidone, etc., but these solvents have the drawbacks mentioned above, so they cannot be used for special purposes. It is preferable to refrain from using it for other purposes.

If necessary, the curable resin composition of the present invention may contain powder within a range that does not inhibit the effects of the present invention.

Granular or fibrous reinforcing agents, fillers and thickeners.

Addition of mold release agents, coupling agents such as vinyltriethoxysilane, flame retardants, flame retardants, pigments and coloring agents, and other auxiliary agents.

The curable resin composition of the present invention can be used for impregnation, prepreg, coating and lamination varnishes, molding powders, paints, adhesives,
It has a wide range of uses such as sealants and rubber chemicals, and the curing conditions for forming a cured product vary depending on the composition and the form of the cured product. Generally, the composition of the present invention is applied to a substrate as an adhesive layer or coating, or is impregnated into a substrate such as a powder, pellet, or glass cloth, molded or laminated, and then cured by heating. . The curing temperature is generally in the range of 0 to 350°C, preferably 50 to 300°C.

Curing time depends on the form of the cured product, but is generally 30
A sufficient time for the resin component to be completely cured may be selected from a range of seconds to 20 hours. Furthermore, when used for manufacturing molded products, laminate products, or adhesive structures, it is desirable to apply pressure during heat curing, and the applied pressure range is 1 to 1.
50 yen is enough. In addition, as a method for curing the composition of the present invention, it is also possible to use electromagnetic waves such as visible light, ultraviolet rays, X-rays, and γ-rays.

Although there are no particular restrictions on the specific embodiments of carrying out the present invention, preparation examples of impregnating varnishes, prepregs, and laminates are shown below as examples of embodiments.

A homogeneous liquid consisting of an aliphatic maleimide and a polyvalent maleimide compound or a homogeneous solution containing an organic solvent is prepared. When a solvent is used, the concentration of the composition of the present invention in the solution is preferably in the range of 10 to 80% by weight. A curing catalyst, a silane coupling agent, a flame retardant, etc. are added to this homogeneous liquid or solution as necessary, and the mixture is uniformly mixed to form a varnish. After impregnating a glass cloth with the varnish and air-drying it for a certain period of time,
Pre-cure in the open of 'C' to obtain prepreg. Prepreg is often used as it is as various insulating materials, such as prepreg mic tape, etc.8 Prepreg obtained from varnish prepared using the composition of the present invention does not cause separation of components or foaming, and It has favorable dryness to the touch, can be stored stably for a long period of time even at room temperature, and maintains its flexibility. Next, for example, after stacking multiple prepreg sheets made of glass cloth, copper foil is layered on one or both sides of the prepreg sheets, and a compression molding machine is used to heat the sheets to 10°C.
A laminate for a wiring board can be obtained by performing pressure molding at a pressure of 0 to 300' C1 and a pressure of 10 to 150 yen.

The present invention will be explained below using practical examples and comparative examples.
The present invention is not limited to the following examples. In the examples, parts and %&-1 are based on weight unless otherwise specified. Further, various measurement methods in Examples are as follows.

Thermogravimetric analysis: Measured using DTG-30M manufactured by Toritsu Seisakusho at a heating rate of 10°C/min in a nitrogen stream. Gel time: Approximately 1511 samples were placed on a stainless steel hot plate heated to 180°C. The sample was kneaded with a spatula at a rotational speed of 1 rotation per minute, and the time required for the sample to start stringing was measured.

Soldering heat resistance: According to JrS C-6481K, the temperature of the solder bath was set to 3°00°C, and the time required until blistering or peeling occurred on the copper foil surface was measured. Copper foil peel strength: According to JIS C-6481. Ta.

Bending strength: According to JIS C-6481.

Impact resistance: 50% for a circular shape, 1 layer thick cured product!
A spherical bronze piece No. 9 was dropped from a height of 60 cm and the degree of cracking at that time was observed according to the following criteria.

O: Not cracked, "△: Cracks appear. ×: Broken into pieces.

Example 1 Poly(phenylenemethylene)polymaleimide 18 of the formula
After fully mixing 0 parts of 4,4'-diaminodiphenylmethane and 25 parts of 4,4'-diaminodiphenylmethane, a melt reaction was carried out at 130°C for 10 minutes to produce a prepolymer.

Next, this prepolymer and N,N'74.7-thioxadecane-1,10-bis-reimide were sufficiently mixed in the formulation shown in Table 1 to obtain a resin composition, and the gel time was measured on a portion of the resin composition. Further, this composition was filled into a mold coated with a mold release agent, pressure molded at a temperature of 180°C and a pressure of 50% for 1 hour, and then after-cured at 200°C for 3 hours to form a mold with a size of 50 dragons x 4 m. A cured product (test piece) was prepared, the impact resistance of this cured product was examined, and thermogravimetric analysis was performed.

Examples 2-12 N,N'-4,7-thioxadecane-1,10-bismaleimide, Shefamine D-230 and D-400
Bismaleimide (Chefamine is polyoxypropylene amine, a product of Mitsui Texaco Chemical Company);
N,N'-4゜9-dioxadodecane-1,12-bismaleimide, poly(/phenylene methylene) of Example 1
Polymaleimide, poly(phenylene methylene) of the formula
Polymaleimide, 4.4′-diaminodiphenylmethane, 4,7-thioxadecane-1,10-diamine, 4°9-dioxadodecane-1,12-diamine, Chefamine D-230,
A composition shown in Table 2 was thoroughly mixed using Chefamine D-400, hexamethylene diamino, and MDA-150 (aromatic polyamine, a product manufactured by Mitsui Toatsu Chemical Co., Ltd.), and then cured in the same manner as in Example 1. A specimen (test piece) was obtained.

Comparative Example 1,2 N,N'-4,7-thioxadecane-1,10-bismaleimide and the poly(phenylene methylene) of Example 1
The gel time of each individual polymaleimide was measured, and a cured product was obtained in the same manner as in Example 1. But poly(
The cured product of polymaleimide (phenylene methylene) did not have a circular shape and was broken into pieces, and the impact resistance was measured by selecting sufficiently large pieces.

Table 2 shows the compositions of Examples 2 to 12 and Comparative Examples 1 and 2 together with the gel time, impact resistance of the cured product, and thermogravimetric analysis.

Example 13 30 parts of N,N'-4,7-thioxadecane-1,10-decane-bismaleimide, 60 parts of the poly(phenylenemethylene)polymaleimide of Example 1, and 10 parts of 4,4'-diaminodiphenylmethane were sufficiently added. After mixing, a melt reaction was performed at a reaction temperature of 120° C. for 10 minutes to produce a prepolymer. 90 parts of this prepolymer, Epicoat 828
(Bisphenol-based epoxy resin manufactured by Shell Chemical Co., Ltd.) 10
An impregnated varnish was prepared by dissolving 33 parts of trimellitic anhydride and 110 parts of 1,4-dioxane. Next, glass cloth (thickness 0.18 mm) was treated with aminosilane.
The prepreg was impregnated with water, air-dried, and then dried at 160°C for 10 minutes to obtain a prepreg. 9 sheets of this prepreg were stacked, one sheet of copper foil was placed on top of it, and the press pressure was set to 75 to 180℃ using a heat press machine.
A copper clad laminate was obtained by compression for 0 minutes. Thereafter, this laminate was after-cured for 8 hours in an open environment at 200°C.

Examples 14-22 N,N'-4,7-thioxadecane-1.,10-bismaleimide, Chefamine D-230 and D as described above
-400 bismaleimide, N.

N'-7-methyl-4,10-dioxatridecane-1
, 13-bismaleimide, the poly(phenylene methylene) polymaleimide of Example 1, N-2,4-bis(4/
N/-maleimidobenzyl) phenylmaleimide, 4
, 4'-diaminodiphenylmethane, 4,7-thioxadecane-1,10-cyane, Shefamine D-230
, -,j-Famine D-400, MDA-1 as described above
50, Epicote 828, DEN431 (manufactured by Dowkej Cal, Borac-based epoxy resin), 2-ethylimidazole, trimellitic anhydride, 1,4-dio-san, tetrahydrofuran and methyl ethyl ketone were melted or dissolved in the formulation shown in Table 3. A impregnated varnish was prepared. A copper-clad laminate was obtained in the same manner as in Example 13 except for the above.

Comparative Example 3 50 parts of the poly(phenylene methylene/)polymaleimide used in Example 1 was dissolved in 50 parts of 1,4-dioxane to prepare an impregnating varnish, and a copper-clad laminate was obtained in the same manner as in Example 13.

The solder heat resistance, peel strength and bending strength of the copper foil of the copper-clad laminates obtained in Examples 14 to 22 and Comparative Example 3 were measured,
The results are shown in Table 3.

Example 23 After thoroughly mixing 30 parts of N,N'-4,7-thioxadecane-1,10-bismaleimide, 70 parts of the poly(phenylene methylene) polymaleimide used in Example 1, and 10 parts of MDA-150, A prepolymer was produced by performing a melt reaction at ℃ for 20 minutes. Next, 90 parts of this prepolymer,
10 parts of Epicor) 828, 33 parts of trimellitic anhydride, 120 parts of natural graphite, and 2.5 parts of calcium stearate as a mold release agent were kneaded for 30 minutes in a pressure kneader at a temperature of 130°C. Then, this composition was heated to a mold temperature of 250°C.

Pressure molding was carried out for 2 hours at a pressure of 120~. The bending strength of this molded product measured according to JIS K-6911 was 18.2 kg/lit at 25°C, and t5. after heating at 250°C for 500 hours. s kgAd, and showed satisfactory heat deterioration resistance.

In addition, the symbols in the table below represent the following compounds. (Aliphatic maleimide) BM-AN, N'-4, 7-thiokidecane-1,
10-bismaleimide BM-B In the following formula, a 2.6 (Chefamine D-230 bismaleimide) BM-C In the following formula, a J-5,6 (Chefamine D
-400 bismaleimide) BM-D N , N'-4,9-dioxadodecane-
1,12-bismaleimide BM-EN, N'-7-methyl-4,10-dioxatridecane-1,13-bismaleimide (polyvalent maleimide compound).

PM-A Poly(i,enylenemethylene)polymaleimide of Example 1 PM-BN-2,4-bis(4'-N'-maleimidobenzyl)phenylmaleimide (amine compound) AM-A Poly( phenylenemethylene) polyamine AM-H4,7-thioxade f)7-1,10-diamine AM-C4,9-dioxadodecane-1゜12-diamine AM-D In the following formula, 26 (chefamine D) in a
-230) AM-E In the following formula, 5.6 (chefamine
D-400) ') AM-F Hexamethylene diamine AM-G MDA-150 (represented by the following formula)0
．． 5 AM-H44'-Diaminodiphenylmethane Table 1 Table 2 (Continued) [Note] In Examples 13, 15, 20, and 21 marked with an umbrella, the aliphatic maleimide, polyvalent maleimide compound, and amine compound are not just a mixture; This is a three-component prepolymer.

However, all the production was carried out under the conditions described in Example 13.

Claims (1)

[Claims] ill (a) General formula [In the formula, R1 is the same or different and each has four groups (However, R2 is a hydrocarbon group having 1 to 20 carbon atoms or a group substituted with a halogen thereof) ), and Q is t
aliphatic ether group, t represents an integer of 1 or more. ] At least one aliphatic maleimide represented by (b) the general formula [wherein R1 is the same or different, each nitro group (however, R2 is a hydrocarbon group having 1 to 20 carbon atoms or its... (representing a group substituted with rogene),
n represents a number in the range of 0.01 to 15. A curable resin composition comprising a polyvalent maleimide compound represented by the following formula and (C) an amino compound. (2) The curable resin composition according to claim 1, further comprising (d) an epoxy resin in the (a), (b), and (C) as required. (3) Any two-component prepolymer selected from the above (a), (b) and (C), or (a),
The curable resin composition according to claim 1, which contains a three-component prepolymer (b) and (C).