JPS58132010A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:A thermosetting resin composition excellent in heat resistance and rapid curability and suitable as a material for electrical devices and appliances, etc., prepared by mixing an N-(alkenylphenyl)maleimide derivative or its dimer or polymer and an aliphatic maleimide. CONSTITUTION:The purpose thermosetting resin composition is prepared by mixing a maleimide compound selected from the group consisting of an N-(alkenylphenyl)maleimide derivative of the formula (wherein R1-R6 are each H, a halogen, a 1-10C alkyl, phenyl or a like group, X is H, a halogen, carboxyl, hydroxyl or like group, m1, m2 and m3 are each 0-4, and m1+m2+m3=5), e.g., N-(o-vinylphenyl)maleimide, and its dimer and polymer, with an aliphatic maleimide (e.g., N-2,2'-hydroxyethoxyethylmaleimide) and, if necessary, an amino compound (e.g., ethylamine) and an epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel external thermosetting resin composition having excellent heat resistance and fast curing properties.

Various heat-resistant resins are available as insulating materials to meet the demands for larger capacity, smaller size, lighter weight, and higher reliability of electronic equipment, as well as for greater stability, longer life, and maintenance-free electrical equipment.

Addition polymerization type imide resins such as bismaleimide resins or bismalei iP-aromatic diane modified resins are well known as such heat-resistant resins. However, although the bismaleimide resin has excellent heat resistance, it has a high melting point, slow curing speed, is soluble in general-purpose organic solvents such as methyl ethyl ketone and tetrahydrofuran, and is soluble in N-methyl-2-pyrrolid ν N .

It has the disadvantage of being soluble only in high boiling point polar organic solvents such as N-dimethylformamide, N,N-dimethylacetamide, and dimethylsulfoxide. Dera K
When preparing a face of bismaleipod-based resin using these polar organic solvents, impregnating it into a base material to make a prepreg, and then thermally compressing the KB-staged prepreg on a sand field to produce a laminate, it is necessary to It is extremely difficult to completely remove the solvent from the drying and manufacturing process of laminates, and the solvent remains, causing cracks in the laminate and deteriorating its quality and performance, and especially in copper-clad laminates, causing swelling of the copper foil. , or caused peeling, which was unsatisfactory. Furthermore, the polar organic solvents described above have permeability through the human body and are highly toxic (their use is undesirable from the viewpoint of environmental health and safety).

On the other hand, in recent years, attempts have been made to develop impregnated varnishes using general-purpose organic solvents with low boiling points or solvent-free fests for the purpose of saving energy and improving workability, and a combination of bismaleimide resin and epoxy resin has been adopted. However, these two have poor compatibility, and bisfreide precipitates, and high temperatures are required to obtain a uniform liquid, resulting in a short pot life, which limits the scope of their application.

The present invention is directed to an N-(alkenylphenyl)maleimide derivative, or a multimer thereof (hereinafter referred to as a group of these compounds, kN-(alkenylphenyl)maleimide), which eliminates the various drawbacks found in the above-mentioned bismaleimide resins. ) and an aliphatic maleimide having a needle bond is a thermosetting resin composition that optionally contains a tetraamino compound, has a low melting point, and has excellent solubility in organic solvents. The present invention also provides a fast-curing composition.

The present invention is based on the general formula (1) (where TIRI to R are mutually the same or true hydrogen atoms,
Halogen atom, number of carbon atoms that may be branched: 1 to 10
an alkyl group, a phenyl group or an alkyl group having 1 to 10 carbon atoms which may be branched, an alkyl group, Rt
It is an O-substituted phenyl group, and each of R4, R1, and R- may be the same or different when there is a plurality of them, and xRl is a carbon atom that may be branched. Indicates an alkyl group of number 1 to 10, a phenyl group, an optionally branched alkyl group having 1 to 5 carbon atoms, or a phenyl group substituted with a halogen atom, and when there are multiple groups, they are the same or different. Good too. ), a group consisting of N-(alkenylphenyl)maleimide derivatives, their dimeric forms and their multimers; and B: at least one aliphatic maleimide. A curable resin composition, and a thermosetting resin composition comprising the above A: maleimide compound, B: aliphatic maleimide and C niamino compound, and if necessary, these compositions may be added with a resin. It is a thermosetting resin composition containing.

The N-(alkenylphenyl)maleimide su; taz used in the composition of the present invention has significantly better solubility in solvents than the malei Z yarn compound, and it N-methyl-2-
The purpose can be sufficiently achieved using ordinary general-purpose organic solvents with relatively low boiling points without using polar organic solvents such as pyrrolidone, N,N-dimethylformade, etc., and it has a relatively fast curing property. It becomes possible to B-stage at low temperatures, and in terms of workability, it is also easy to remove solvents from products such as paper laminates, making it possible to greatly improve the quality of nine difficult products.

On the other hand, since aliphatic maleimide does not have a benzene ring in its molecule, it has the advantage of providing a highly flexible cured product.Also, when an aliphatic maleimide having an ether bond is used, It is also expected that the adhesive ability between the resin of the present invention and various base materials will be improved.

Examples of N-(flukenylphenyl)maleimide derivatives represented by general formula 111 which are component A of the present invention
, N-(o-vinylphenyl)maleimide, N-(m
-vinylphenyl)maleimide, N-(p-vinylphenyl)maleimide, N-(o-impropenylphenyl)-rreimide, N-(m-isopropenylphenyl)
male(j-do, N-(p-(:/propenylphenyl)maleimide, N-(vinyltolyl)maleimide (including all isomers), N-C impropenyltolyl) male(
f (including all isomers), N-(p-α-ethylvinylphenyl)maleimide, N-(P-α-phenylvinylphenyl)malej)', N-(6-vinylphenyl)dichloromaleimide , N-(m-vinylphenyl)di/Oamaleimide, N-Cp-vinylphenyl)
dichloromaleimide, N-Cp-isopropenylphenyl)dichloromaleimide, N-(m-iso7''obenylphenyl)dichloromaleimide, N-(·-impropenylphenyl)cyclomaleimide, 2-hydroxyphenyl)maleimide, N-(
4-vinyl-3-hydroxyphenyl)maleimide, N
-(4-1)! Rhynyl-2-acetoxyphenyl)maleimide, N-(4-inzolo(nyl-3-acetoxyphenyl)maleimide, N-(4-vinyl-3-cyanophenyl)maleimide, N-(4-vinyl-2-cyanophenyl) ) maleimide, N-(4-impropenyl-3
-cyanophenyl)male(j-do, N-(4-impropenyl-2-cyanophenyl)maleimide, N, N'-(
1-vinyl-2,4-phenylene) bismaleimide, N
, N'-(1-vinyl-3゜5-phenylene)bisfurei2do, N,N'cy(l-isodebenyl-2.4-7ethylene)bismaleimide, N,N'-(1-isopvs4 Nilu 3.5
-phenylene)bismale4N)", N-(p-vinylphenyl)-di-butylmaleide, N-(P-isopropenylphenyl)diisopropylmaleide, N-
(p-α-(p/-cyanophenyl)vinylphenyl]maleimide, N-[p-α-(m'-chlorophenyl)vinylphenylcomaleimide, 2-4 soderopenyl-4-N-maleimide-4'- Chlorobi phenyl, 2-
Vinyl-4-N-maleimido-4'-methyldi' pphenyl, 3-isozolo(nyl-4-N-maleimido-3'-methoxybiphenyl, 3-vinyl-3-N-maleimido-4'-hydroxybiphenyl, 3-isoglopenyl-4-N-maleimido-4'-acetylbiphenyl, 2-N-maleimido-4-impropenyl-4'-
Examples include cyanobiphenyl, N-(p-infurobenylphenyl)-p-10rophenylmaleimide, and the like.

In the present invention, the above-mentioned 0N-(alkenylphenyl)maleimide dimer and multimer thereof can be used.

An example of a dimer of N-(alkenylphenyl)maleimide is a dimer of N-(P-impropenylphenyl)maleimide represented by the formula 1), t-1tf. The polymer of N-(alkenylphenyl)maleimide is not particularly limited, but it is preferably one with a molecular weight of 10,000 or less.In the present invention, the above compounds are used alone or in a mixture of two or more. Is possible.

This 1nbN-(alkenylphe,nyl)maleimide derivative is disclosed in, for example, JP-A-55-129266 and JP-A-56-1.
31566 and Japanese Patent Application Laid-Open No. 56-145272.

The aliphatic maleimide which is the B component of the present invention has a maleimide residue having the formula % formula %) (wherein, R1s R@', HsIf, R@# and R
ot: may be the same or different and have a carbon atom number of 1 to
10 linear or branched mono- to trivalent aliphatic hydrocarbon groups or those substituted with cadalkoxy groups, hydroxy groups or halogens, a, b, e%X%y
and 2 indicates a number of 1 or more. ) Compounds having an aliphatic ether group having a structure represented by:

Very typical examples of such aliphatic maleimides include N-2,2'-hydroxyethoxyethylmaleimide, N-1-methoxymethylpropylmaleimide, 'N
-1-ethoxymethylderovyl malei, mido, N-1-
Methoxymethylbutylmaleimide, 'N, N'-
3゜6-thioxaoctane-1,8-bismaleimide,
N,N'-4,7-thioxadecane-1,10-bismaleimide, N,N'-3゜6.9-)dioxaundecane-1,11-bismaleimide, N,N'-4,9- Dioxadodecane-1,12-bismaleimide N.

N'-4,7,10-)lioxatri rkan-1.13
-Bismalei is do, N, N'-7-methyl-4,1O-
Dioxatridecane-1,13-bismaleimide, N,
N'-3゜6.9.12-tetraoxatetradecane-
1,14-bismaleimide, N, N', -3°6, 9
For example,
0 (where a is 2.6.5.6 or 3
It is 3.1. )1 (wherein, the sum of I%y and 2 is about 5.3).

Furthermore, compounds in which the hydrogen atom bonded to the unsaturated chlorine atom in the maleimide group of the above aliphatic maleimides are appropriately substituted with a fluorine atom, a bromine atom, a methyl group, an ethyl group, a phenyl group, etc. can also be used. Further, aliphatic maleimides can be used alone or in combination of two or more types.

In the composition of the present invention, there is no particular limitation on the proportion of both the N-(alkenylphenyl)maleimide a of general formula (11) and the aliphatic maleimide used, but generally the former is 2% of the total amount of both components. -99 weight, preferably 5-9
5 I am very disappointed. If the amount of the former is less than the above range, the heat resistance of the cured product obtained will decrease, and if it exceeds the above range, the curability and flexibility of the composition will deteriorate.

The amino compound used as necessary for the purpose of imparting a homogeneous and dense structure to the cured product according to the present invention and imparting toughness and mechanical strength is expressed by the following formula (%) (in the formula, zFi has 1 carbon atom) It is a monovalent organic group that can contain atoms of hydrogen, oxygen, sulfur, halogen, nitrogen, phosphorus, and silicon, and t is an integer of 1 or more. , typical examples thereof are ethylamine, propylamine, hexylamine, aniline, p-(m or .-)toluidine, p-(
rm or ◎-) methoxyaniline, 1)-(!II or .-) clouaniline, 3,5-dichloroaniline, p-(wa or -) hydroxyaniline, p-(
mtdaId o-) Cal? xyaniline, p-(mataha・-)vinylaniline, p-(mt?,:ti・
-) Allylaniline, p-1 nderopenylaniline, 2
-Methyl-4-ingropenylaniline, 4-aζnoviridine, '2-(4'-hydroxyphenyl)-2-(
4"-7j/phenyl)pro/f, 2-(4'-hydroxyphenyl)-2-(3"-methyl-41-71
Nophenyl) 10 nobun, benzylamine,! -aminonaphthalene, 2-aminonaphthalene, ethylene diamine, trimethylene cyanide, hexamethylene diamine, r
Camethylene diamine, octamethylene diamine, 2,2
゜4-Trimethylhexylylene diamine, p-(or --> phenylene diamine, 114-diaminocyclohexane, 2.4-diaminotoluene, 4.4'-diaminodiphenylmethane, 3.4'-diaminodiphenylmethane, 2.2 -bis(4'-7minophenyl)fo pan, 4.4'-diamyidiphenyl ether, 4.
4'-thia ζ methyl sulfide, 4.4'-diaminodiphenylsulfone, 3.3'-N aminodiphenyl sulfone, 4.4'-diaminodicyclohexylmethane, p-(or m-)xylylenediamine, bis( 4
-71nophenyl)diphenylsilane, bis(4-aminophenyl)methylphosphine oxide, bis(3-chlorot1-4-inophenyl)methane, 2,2-bis(
4/-4#-aminophenoxyphenyl)fronoman, l.

4-bis(p-aponophenoxy)benzene, 1.4-
Diaminonaphthalene, 2.4-LuaZnoviridine, 4-
Methyl-2,4-bisCP-'7inophenyl)pentane, 4-methyl-2,4τbis(,-aminophenyl)
-1-pentene, 4-methyl-2,4-bis(p-aminophenyl)-2-pentene, tris(4-aminophenyl)phosphate, tris(4-7Znophenyl)thiophosphate, 2,4.6- Tris(4'-aminophenoxy)-a-triazine, 5(or 6)-amino-1-(4'-aminophenyl)-1,3,3-)limethylindane, or vinylanilines, or iso! Trimers or higher polymers of robenil ani + 7 silanes, 1-reamis compounds obtained by the reaction of aromatic amines IM (e.g., aniline, toluidine) and aldehydes Ia (e.g., formaldehyde, paraform, acetaldehyde), especially aniline. Poly(phenylene methylene) boriaone obtained by reaction with formaldehyde (for example, M
Examples include DA-150 (trade name, manufactured by Mitsui Toatsu Chemical Co., Ltd.) and alicyclic group I ria-Z in which hydrogenated [/diamino]. These amino compounds can be used alone or as a mixture of two or more.

The amount of these amino compounds used in the composition of the present invention is not particularly limited, but N-(alkenylphenyl)
The ratio of the total number of amino groups in the amino compound to the total number of maleimide groups in the maleimide component of maleimide derivatives and aliphatic maleimides (general formula (I)) is! It is preferably less than or equal to 0.01! The range is more preferable.

(In the formula, mi, ni, and Mi represent the amount of maleimide compound used, the average value of the number of maleimide groups in the molecule, and the average molecular weight, respectively; ma%na and Ma represent the amount of amino compound used, and h the number of amino groups in the calf. If the amount of the amino 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 decrease. It tends to come off.

The thermosetting resin composition of the present invention comprises components A, B and 1'
Pre/IJ-v- means A:N-(alkenylphenyl)! It may be a simple mixture of component C depending on the composition, or it may be a composition containing at least one part of these pre-4 remers. Ray Z-dos, B: Intended two components selected from aliphatic maleimide and C-nia compound or tlA
, is a preliminary reaction product obtained by reacting the three components B and C, and although there are no restrictions on the specific reaction method, the reaction temperature is in the range of 0 to 200 ° C and the reaction time is 5 minutes to 10 hours. The components can be reacted by directly and uniformly mixing them without a solvent, or by using a solvent as a homogeneous solution or S oil state of each component.

In addition, the D:4 resin used for the purpose of improving adhesive strength, adjusting viscosity, etc. according to the present invention may be any known solid or liquid product, representative examples of which include bisphenol resin. Heterocyclic epoxy resins such as type epoxy 11&, bisphenol F type epoxy resin, halogenated bisphenol A type epoxy resin, phenol type I resin, cresol type I lac type amerate or hydantoin type I, hydrogenated bisphenol. Type A epoxy resins, aliphatic engineered I-oxy resins such as globylene glycol diglycidyl ether and pentaerythritol 4-liglycidyl ether, aliphatic or aromatic carboxylic resins, etc. Epoxy resins obtained by the reaction of hydrochloric acid and epichlorohydrin, spia*-containing s-z* resins, glycidyl ether type epoxy resins in which orthoarylphenol is the reaction product of lac compounds and epichlorohydrin, with the following molecular formula: expressed. p, p'-N, N.

NI, N/-tetraglycidyldiaminodiphenylmethane or triglycidyl-p- represented by the following molecular formula
Polyoxy resins obtained by reacting aliphatic or aromatic amines such as aminophenols with epichlorohydrin, polyoxy resins obtained by ring-opening polymerization of a portion of the above epoxy resins, and epoxidized or epoxy-modified resins ( Examples include acrylic resins having epoxy groups, 1,2-polybutadiene or alkyd resins, and epoxy-modified silicone resins.

In the present invention, the epoxy resin can be used alone or in combination of two or more, and of course, a monofunctional so-called reactive diluent may be partially included. The amount of epoxy resin to be used is not particularly limited, but it is preferably 50% or less of the total weight of the composition so as not to impair the heat resistance of the cured product obtained from the composition of the present invention.

In the curing reaction of the thermosetting resin composition of the present invention, catalysts are not necessarily abundant, 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 in fact is 5 tatami or less based on the total weight of the composition. Catalysts used for purposes such as improving workability and adjusting curing speed σ), depending on the usage type of the composition, include boron trifluoride such as boron trifluoride monoethylamine complex and boron trifluoride piperidine complex. Amine complex, triethylamine, N,N-dimethylbenzylamine, hexamethylenetetramine, N.

Tertiary amines such as N-dimethylanili7, IIE quaternary ammonium salts such as tetramethylammonium bromide, ester compounds such as triphenyl ester and tricresyl ester, imidazoles such as N-methyl imidazole and N-phenyl imidazole. Compounds, metal compounds such as zinc acetate, sodium acetate, titanium acetylacetonate, sodium methylate, aluminum chloride, zinc chloride, zinc chloride, manganese naphthenate, cobalt naphthenate, phthalic anhydride, tetrahydrophthalic anhydride, methyl anhydride Acid anhydrides such as tetrahydrophthalic acid, nanotsuccic anhydride, benzophenone tetracarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, maleic anhydride, peroxides such as tsucumyl peroxide, t-butyl perbenzoate, methyl ethyl ketone peroxide, etc. Examples include oxides and azo compounds such as azobisisobutyronitrile.

The composition of the present invention contains an aliphatic maleimide, which is a low-melting liquid maleimide, and takes advantage of the characteristics such as 1 to obtain a homogeneous mixture. However, since it is easily soluble in organic bath agents, it can also be used in the form of a solution. In the case of a bath liquid, there are no restrictions on the organic solvent to be used, but specific preferred examples include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, hydrocarbons such as n-hexane and cyclohexane, diethyl ether, ethyl cellosolve, and methyl. Ethers such as 4-dioxane and tetrahydrofuran, chlorine compounds such as methylene chloride, chloroform, trichloroethane, and carbon tetrachloride, benzene, xylene, mectylene, aromatic hydrocarbons, methanol, ethanol, isopropyl alcohol, phenol, cresol, etc. alcohols, nitriles such as acetonitrile, and esters such as methyl acetate, ethyl acetate, and 2-ethoxyethyl acetate. N again.

Of course, a bath liquid composition can be obtained by using N-dimethylformamide, N-methyl-2-pyrrolidone, etc., but these solvents have the drawbacks mentioned above, so they should not be used for any purpose other than special purposes. It is better to refrain.

The curable resin composition of the present invention may optionally contain powder, granular or fibrous reinforcing agents, fillers, thickeners, mold release agents, vinyltriethoxysilane, etc., as long as they do not inhibit the effects of the present invention. That's cool! By adding ring agents, flame retardants, flame retardants, pigments, coloring agents, and other auxiliaries, we can produce preg, coating and laminating varnishes, molding powders, paints, adhesives, sealants, and rubber agents. It has a wide range of uses.

The curing conditions for producing a cured product vary depending on the composition and the form of the cured product. Generally, the composition of the present invention can be used as an adhesive layer or coating.
It is applied to a substrate, or is molded or laminated in a state in which it is impregnated into a substrate such as a powder, pellet, or glass cloth, and then heated and cured. Curing temperature is generally θ~3
50C, preferably in the range of 50 to 300C. Although the curing time depends on the form of the cured product, it is generally sufficient to select a time in the range of 30 seconds to 20 hours that is sufficient for the resin component to be completely cured. 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 l-
150 Ke/cd is sufficient. It is also possible to use electromagnetic waves such as visible light, ultraviolet rays, XIm, and γ rays as a method for curing the composition of the present invention.

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 N-(alkenylphenyl)maleimide and aliphatic maleimide or a homogeneous dispersion WX containing an organic solvent is prepared.

When using a solvent, 1? ! The concentration of the composition of the present invention in the liquid is preferably within the range of 10 to 801 kg. A curing catalyst, a silane coupling agent, a flame retardant, etc. are added to this uniform liquid or uniform bath liquid as required, 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,
A prepreg is obtained by pre-curing in an open air at 00°C. Prepreg is often used in its original form as various insulating materials, such as prepreg mic tape.

The prepreg obtained from the varnish prepared from the composition of the present invention does not cause component separation or foaming, has favorable dryness to the touch, can be stored stably for a long period of time even in a room, and Maintains flexibility.

Next, for example, after stacking a plurality of prepreg sheets made of glass cloth, copper foil is layered on one side or both sides, and pressure molding is performed using a compression molding machine at a temperature of 100~300°C and a pressure of 10~150 kg/cd. A laminate for wiring boards can be obtained.

The present invention will be explained below with reference to Examples and Comparative Examples.
The present invention is not limited to the following examples. In addition, parts and parts in the examples are based on weight unless 4I is given.

Further, various measurement methods in Examples are as follows.

Thermogravimetric analysis: Measurement was carried out using DTG-30M manufactured by Shimadzu Corporation at a heating rate of 10 c/min in a nitrogen stream.

Time: A sample of about 1.5 f was placed on a stainless steel hot plate heated to 180°C, kneaded with a sno-knuckle at a rotation speed of once per minute, and folded until the sample began to string. The time was measured.

Soldering heat resistance: According to JI8 C-6481, the temperature of the solder bath was set to 300°C, and the time required until blistering or peeling occurred on the copper foil surface was measured.

Steel foil peel strength: According to JI8 C-6481.

Bending strength: According to JIS C-fi481.

Impact Resistance A 50f spherical bronze was dropped onto a cured product having a circular shape and a thickness of 1 cm from a height of 60cI11, and the degree of cracking at that time was observed according to the following criteria.

01 not broken, Δ: Hipi enters , X: Breaks into pieces.

Example 1 4-Methyl-2,4-bis (p-N-maleimidophenyl 1-1-pentene 6.0 g + so is produced as shown in Production Example 1 below) and NUN' -4,7
-dioxadecane-l.

40 parts of lO-bismaleimide were thoroughly mixed, and the r time was measured using a portion thereof. Next, 100g of the mixture
Prepare a varnish by dissolving 100 g of 1.4-dioxane in a bath at 30°C. Apply a release agent to an aluminum container with a smooth bottom and an inner diameter of 60 cm and a depth of 14 cm. ), heated to 500K on a hot plate under a nitrogen stream, held for 2 hours, gradually raised the temperature to 130C over 30 minutes, held at this temperature for 3 hours, and then heated to 200C over 1 hour. Gradually raise the temperature 1. It was held at this temperature for 2 hours and cured at °C. Thereafter, after-curing was carried out for 2 hours at 250 UK to produce a brown cured product (test piece), and the impact resistance of this cured product was examined and thermogravimetric analysis was performed.

Production Example 1 4-Methyl-2,4-bis(p-N-maleimidophenyl 1-1-pentene ap: anhydrous maleic I!!108
Dissolve M in 500 parts of acetone, maintain this solution at 20C, and dissolve l4-lf syl-,4-di(p-aminophenyl).
133 parts of -1-payyn was gradually added without stirring. After the addition was completed, the reaction solution was continued to be stirred at a temperature of 20° C. for 2.5 hours. The reaction liquid was a yellow slurry. Next, this slurry reaction solution - 1.25 parts of cobalt acetate tetrahydrate,
25 parts of triethylamine and 123 parts of acetic anhydride were added, and the temperature of the reaction solution was raised to 600 °C.

Thereafter, the reaction solution was maintained at 60° C. and stirring was continued for 13 hours.

Next, the reaction solution was cooled to room temperature, 25 parts of methanol was added, and the mixture was gradually added dropwise into 1,500 parts of thoroughly stirred water to obtain 1 precipitate. This precipitate was separated in a furnace, poured into water, added with a sodium carbonate water bath solution to make pns, s, separated by F and washed with water several times, thoroughly washed with water, and finally washed and purified with 1 oos of methanol. The mixture was dried under reduced pressure at a temperature of 50°C to obtain 1,194 parts of 4-methyl-2°4-bis1p-N-maleimidophenyl)-1-pentene (melting point 148-150°C).

Note that N-p-(sozolopenylphenylmaleimide, 4-
Methyl-2,4-bis(p-N-maleimidophenyl)
-2-bentene and N-(p-iaflopenylphenyl)maleimide oligomers are the starting materials p-ingropenylaniline, 4-methyl-2,4-diTp-aminophenyl)-2-pentene and p- Isopropenylaniline oligomer (composition: monomer 3.2, 2-1
body 76.9. trimer 8.2.4 g # body or more 11.7 division)
It was produced in the same manner as above.

Implementation @2-13 N,N'-4,7-thioxadecane-1,10-bismaleimide, N,N'-4,9- as aliphatic maleimide
Geogisadodecane-1,12-bismaleimide, N, N
'-7-lfk-4, IO-dioxatridecane-1
13-Bismaleimide, Shefamine D-230 and D-400T Shefamine are polyoxypropylene amines in three-piece Texaco.

It is a product of Michal ■. ) bismaleimide, N-(alkenylphenyl)maleimide, N-p-ingropenylphenylmaleimide, 4-methyl-2,4-bis(p-N-maleimidophenyl)-2-pentene, m as an amine compound -7 enylensoamine, 4゜4'~diaminosophenyl ether, 4-4'~diaminodiphenylmethane, and 1,4-dioxane and methyl ethyl ketone as solvents were thoroughly mixed at the compounding ratio shown in Table 1K, and the procedure was repeated in the same manner as in Example 1. The glue time value and cured product were obtained.

Comparative Example 1.2 4-Methyl-2,4-bis(p-N-maleimidophenyl 1-1-pentene and N.

The time of individual N'-4,7-thioxadecane-1,10-bismaleimide was measured, and the mixture was pressed in the same manner as in Example 1 to obtain a cured product. However, 4-methyl-2,
4-bis(p-N-maleimidophenyl+ -1--1
! The cured product did not have a circular shape and was broken into pieces, and the impact resistance was measured by selecting sufficiently large pieces.

For the compositions of Example 9111-13 and Comparative fl11.2, the blending, Kr time, impact resistance of the cured product, and thermogravimetric analysis are collectively shown in Tables 1&f.

Implementation fl114 N-jp-isopropenylphenyl) maleimide oligomer (composition: monomer 3.1%, dimer 76.5%, 31
1 body 8.3 people, 411 bodies or more 12.1 fights 1501M! and N,N'-7-methyl-4,to-sooxatridecane-1゜13-bismaleimide (50 parts) and 11.4-dioxane (100 parts Km) to prepare an impregnated varnish viIl.Next, aminosilane treatment was performed. Glass cloth (thickness: 1
8) After impregnating with K and air drying, it was dried at 150°C for 9 minutes to obtain a prepreg.

Nine sheets of this prepreg were stacked, one sheet of steel foil was placed on top of the sheet, and the sheet was compressed using a hot press at a pressure of 75 Ke/cd at 1180° C. for 30 minutes to obtain a copper-clad laminate. Thereafter, this laminate was after-cured in an oven at 200°C for 8 hours.

Example 15 N, N'-4,7-dioxadecane-l.

After thoroughly mixing 82 parts of lO-bismaleimide and 24 parts of 4,4'-noaminosophenylmethane, a melt reaction was performed at a reaction temperature of 120°C for 20 minutes to produce a prepolymer. 30 parts of this brepolymer and N -+p-impropenylfer) maleimide oligomer (composition: 170 parts of the same as in Example 14 and 50 parts of 1,4-dioxane! II
and 50 parts of methyl ethyl ketone in a mixed bath additive!
An impregnating varnish was prepared. Thereafter, a copper-clad laminate was obtained in the same manner as in Example 14 and after-cured.

Examples 16-24 N~(alkenylphenyl)maleimide and LCN-(P
-isopropenylphenyl)maleimide, N-(p-vinylphenyl)maleimide, N-(p-isopropenylphenyl)sochloromaleimide, 4-methyl-2,4-
bis(p-N-maleimidophenyl)-1-pentene,
4-Methyl-2,4-bistp-N-maleimidophenyl)-2-pentene, [EltaN-(p-isopropenylphenyl)maleimide oligomer, N,N'-4,7-thioxadecane as aliphatic maleimide l.

10-Bismaleimide, Chefamine D-23 described above
0, D-400 and D-2000 bismaleind;
As an amino compound, 4゜4'-diaminodiphenylmethane, 4,4'-cyabanodiphenyl ether, the above-mentioned MD Mu-150, as an epoxy resin Epico) 828
(trade name of bisphenol-based epoxy resin manufactured by Shell Chemical Company), DEN431 (trade name of novolac-based epoxy resin manufactured by Dow Chemical Company), 2-ethylimidazole as a catalyst, trimellitic anhydride, and 1 as a solvent.

4-dioxane and methyl ethyl ketone were melted or bath-dissolved in the formulation shown in Table 2 to prepare 1-impregnation varnish V. Other than that, a copper-clad laminate was obtained which was after-cured using Example 14 and ljJ's KL.

Comparative Example 3 70 parts of N,N'-(methylenedi-p-phenylene)bismaleimide and 30s of N,N'-4°7-sooxadecane-1.10-bismaleimide were dissolved in 1009 parts of N,N-dimethylformamide. An impregnating varnish was prepared, and a copper-clad laminate was obtained in the same manner as Meishi-114. The surface of the resin-containing glass cloth after air-drying is KN, N'-(methylene di-p).
-phenylene) bismaleimide precipitated, and a good prepreg could not be obtained.

The solder heat resistance, copper foil peel strength, and bending strength of the copper-clad laminates obtained in Examples 14 to 24 and Comparative Example 3 were measured, and the results are shown in Table 2.

Example 25 111 50m, N,N'-4,7-thioxadecane-1,10-bismaleimi), 25M:td and MDA-150, 15ffl of the above-mentioned N-(p-ingropenylphenyl)maleimide oligomer were sufficiently added. After mixing with −1
A melting reaction was carried out at 20C for 20 minutes to produce pre-4 remer.

Next, this prepolymer 90s1 Epicoat 828, l
Oll, m water) IJ metate acid 3.3%.

Natural graphite 120 @ and calcium stearate 2.5 sV 100 C at pressure knee IP-3
The mixture was kneaded for o minutes. This composition was then heated to a mold temperature of 200 C.
, pressure molding was carried out for 1 hour at a pressure of 1201111/-. The bending strength of this molded product measured according to JI8 K-6911 was 18.7 Kp/j at 25°C, and after heating at 250°C for 500 hours, it was 16. It was OKf/sJ and showed satisfactory heat deterioration resistance.

1j The symbols in the table represent the compound of F. AB
M-ABM-A N-1)-inoglopenylphenylmaleimide ABM-BBM
-B 4-methyl-2,4-bis(p-N-maleimidophenyl)-1-pentene ABM-CBM-
C4-Methyl-2,4-bis(p-N-maleimidophenyl)-2-pentene ABM-DBM-
DN-1p-isoglobenylphenyl) maleimide 9 oligomer (composition: monomer 3.1, dimer ABM-E76.
5 excellent, trimer 8.3, tetramer or higher 12.1) BM-E N-1p-vinylphenyl)ma ABM-
F Reimide BM-I N-1p-isopropenylphenyl)duchlormaleimide N, N'-4,7-nooxadecane-1, 10-bismaleimide N, N'-4,9-sooxadodecane-1,12-bis1 Reimide N, N'-7-Methyl-4゜10-Soxatridecane-1, tQ-bismaleimide In the following formula, 2.6 in a (bis 1 of Duefamine D-230 Reimide) In the following formula, ``[in a] 5.6 (Bis-1 Reimide of Soefamine D-400) In the following formula, 33.I I Bismaleimide of Soe-7 Aden D-2000) AM-A m-phenylenediamine AM-B 4.4'-diamino Diphenyl ether AM-04,4'-Diaminodiphenylmethane AM-D MDA-150 (represented by the following formula) Note *) Example 15.20.22.23 and 24, 1 is N-(alkenylphenyl)maleimide and/or Alternatively, the aliphatic maleimide and the amino compound are not a mere mixture, but a prepolymer of the two or three components.However, all 70 preparations were made in accordance with Example 15.

Example 20: Prepolymer of ABM-A and AM-D Example 22: Prepolymer of ABM-D and AM-C Example 23.24: Three-component Grebori

Claims (1)

[Scope of Claims] <1) General formula (11) (wherein R1 to R@ are the same or different and each represents a hydrogen atom, a halogen atom, or an optionally branched alkyl group having 1 to 10 carbon atoms. , is a phenyl group or a phenyl group substituted with a carbon group or a cyano group which may be branched, and each of R4, RI and R. when there are a plurality of these, may be the same or different from each other. Also, X is a hydrogen atom, a halogen atom, a car-xyl group, a hydroxyl group, an ano group, and when there are two or more, they may be the same or different.
s"1, ml and ms are each in the range of 0 to 4, ml+ms+ms=5, and R is an alkyl group having 1 to 10 carbon atoms which may be branched, a phenyl group, or a phenyl group which may be branched. At least one maleimide compound selected from the group consisting of a good alkyl group having 1 to 5 carbon atoms or a multimer thereof, and B: at least III aliphatic maleimide. Thermosetting resin composition. (2) General formula A+11 (wherein R1 to R- are the same or different and each represents a hydrogen atom, a halogen atom, or an optionally branched alkyl group having 1 to 10 carbon atoms) , a phenyl group, an alkyl group having 1 to 10 carbon atoms which may be branched, a phenyl group substituted with a halogen radical or a cyano group, and R4,
Each of R- and R. may be the same or different when there is a plurality of them, x is a hydrogen image or a cyano group, and when there are several of them, they may be the same <1111, ml and ms are respectively O~
4, ml + ml + ms = 5, and R1 is an optionally branched alkyl group having 1 to 10 carbon atoms, a phenyl group, an optionally branched alkyl group having 1 to 5 carbon atoms, or halodane. It represents a phenyl group substituted by an atom, and when there is more than one phenyl group, they may be the same or different from each other. B:
A thermosetting resin composition comprising at least one aliphatic maleimide and a C-niamino compound. 13) The above A: maleimide compound and B: aliphatic maleimide are further combined with D: The curable resin composition according to claim 1, which contains an xylene resin. (4) The curable resin composition according to claim 2, further comprising A: a maleimide compound, B: an aliphatic maleimide, and a C niamino compound, and D: an engineered 4-oxy resin. (5) Any two components or curable resin composition of the components A, B and C.