JPH0411649A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. having a low m.p., an increased solubility in an org. solvent, and improved fast curing properties by compounding a specific maleimide compd., an aliph. maleimide having an ether bond, and an amino compd. CONSTITUTION:A maleimide mixture comprising 2-99wt.% maleimide compd. selected from the group consisting of an N-alkenylphenylmaleimide of formula I[wherein R1 to R6 are each H, halogen, (branched) 1-10C alkyl, phenyl, R7O-, formula II or III, OH, or cyanated phenyl; X is H, halogen, COOH, OH, R7O-, formula II or III, or cyano; m1 to m4 are each 0-4 provided that m1+m2+m3=5; and R7 is (branched) 1-5C alkyl or halogenated phenyl], a dimer thereof, and a polymer thereof and 98-1wt.% aliph. maleimide having an ether bond is compounded with an amino compd. in a ratio of the number of maleimide groups in the mixture to the amino groups of the amino compd. (shown by formula IV) of 1 or lower.

Description

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

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

Addition polymerization type imide resins such as bismaleimide resins or vinylimide aromatic diamine 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, a slow curing speed, and is poorly soluble in general-purpose organic solvents such as methyl ethyl ketone and tetrahydrofuran. N.

It has the disadvantage that it is only soluble in high boiling point polar organic solvents such as N-trimethylformamide, N,N-trimethylacetamide, and dimethyl sulfoxide. In the case where a bismaleimide resin phenol is prepared using these polar organic solvents, impregnated onto a base material to form a prepreg, and then heated and compressed from the B-staged prepreg to tabulate a laminate. It is extremely difficult to completely remove the solvent from the prepreg drying and laminate manufacturing process, and the solvent remains and causes voids in the laminate, reducing its quality and performance. This was not satisfactory as it caused swelling or peeling. Furthermore, the above-mentioned polar organic solvents are permeable through the human body and highly toxic, so their use is undesirable from the standpoint of environmental health and safety.

On the other hand, in recent years, for the purpose of saving energy and improving workability, attempts have been made to produce impregnated varnishes or solvent-free fests using general-purpose organic solvents with low boiling points, 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 uniform liquid, resulting in a short pot life, which limits the scope of their application.

The present invention is directed to N-(alkenylphenyl)maleimide derivatives, dimers thereof, or multimers thereof (hereinafter referred to as these compound groups 2N-(alkenylphenyl)maleimides), which eliminate the various drawbacks found in the above-mentioned bismaleimide resins. ) and aliphatic maleimide with an ether bond, and if necessary, an amine compound? 711, which has a low melting point, excellent solubility in organic bath agents, and is fast curing.

According to the present invention, A knee maximum (I) (wherein R and %R6 are the same or different, hydrogen atom, halogen atom, optionally branched alkyl group having 1 to 10 carbon atoms, phenyl group, or branched optional alkyl group having 1 to 10 carbon atoms, halogen i atom, R7
0-substituted phenyl group, and R 4 , RS
and R6 may be the same or different when there is a plurality of them; An alkyl group having 1 to 5 carbon atoms or a phenyl group substituted with a halogen atom.When there is more than one group, they may be the same or different from each other. ), at least one maleimide compound selected from the group consisting of N-(alkenylphenyl)maleimide derivatives, their 2it forms and multimers thereof, and B: at least one type of aliphatic maleimide; It is a thermosetting resin composition consisting of a resin composition and the above-mentioned A: maleimide compound, B: aliphatic maleimide, and C: amine compound, and if necessary, a thermosetting resin composition that entirely contains an epoxy resin in these compositions. It is a resin composition.

The N-(alkenylphenyl)maleimide that can be used in the composition of the present invention has significantly better solubility in bath additives than conventional maleimide compounds, and has been conventionally used in compositions containing maleimide compounds. The purpose can be sufficiently achieved using a general-purpose organic solvent with a relatively low boiling point, without using polar organic solvents such as N-methyl-2-pyroIJton, N,N-methylformamide, and the like. Since it has curability, it can be B-staged at relatively low temperatures, which not only improves workability but also makes it easier to remove solvents from products such as laminates, which can greatly improve product quality.

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, and when an aliphatic maleimide having an ether bond is used, the resin of the present invention It is also expected to improve the adhesion ability with various base materials.

Examples of N-(alkenylphenyl)maleimide derivatives represented by general 201 which are component A of the present invention include N-
(o-vinylphenyl)maleimide, N-(m-vinylphenyl)maleimide, N-(p-vinylphenyl)maleimide, N-(o-impropenylphenyl)maleimide, N-(m-isopro4nylphenyl)maleimide, N-(p-inpronylphenyl)maleimide, N
-(vinyl + full) maleimide (including all isomer sounds), N-(impropenyltolyl) maleimide (including all isomers), N-(p-α-ethylvinylphenyl)maleimide, N-(p -α-phenylvinylphenyl)maleimide, N-(o-vinylphenyl)dichloromaleimide, N-(tn-vinylphenyl)dichloromaleimide, N-(p-vinylphenyl)dichloromaleimide, N-(1)-yne propenylphenyl) dichloromaleimide, N-(rn-impropenylphenyl)
Dichloromaleimide, N-(o-impropenylphenyl)cyclomaleimir, N-(4-bi-2-hydroquinphenyl)maleimide N-(4-vinyl-3-humanCxyphenyl)? Vim) e, N (4-impro-enyl-2-acetoxyphenyl)maleimide, N
-(4-inoproynyl-3-acetoxyphenyl)maleimide, N-(4-vinyl-3-cyanophenyl)maleimide, N-(4-vinyl-2-cyanophenyl)maleimide, N-C4-impronyl-3 -cyanophenyl)maleimide, N-(4-improbenyl-2-cyanoneenyl)maleimide, N,N'-(1-vinyl-
2,4-7 enylene) bismaleimide, N, N'-(
1-vinyl-3゜5-phenylene) bismaleimide, N
, N'-(X-improynyl-2,4-phenylene)
Bismaleimide, N, N'-(1-isopropyl-3
,5-phenylene)bismaleimide, N-(p-vinylphenyl)-not-t-butylmaleimide, N-(J)-
(soderobenylphenyl)diisopropylmaleimide,
N-[p-α-(p'-cyanophenyl)vinylphenyl simaleimide, N-[p-α-(m'-chlorophenyl)vinylphenyl simaleimide, 2-isoprotonyl-4-N-maleimide-4 '-chlorobiphenyl, 2-
Vinyl-4-N-maleimido-47-methylCbiphenyl, 3-improzenyl-4-N-maleimido-37-medoxybiphenyl, 3-vinyl-5-N-maleimido-4'-hydroxybiphenyl, 3-impro4nyl-4-N-maleimido-47-acetylbiphenyl, 2-N-maleimido-4-isozorobenyl-4'-
Examples include cyanobiphenyl, N-(1)-impropenylphenyl)-p-chlorophenylmaleimide, and the like.

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

An example of a dimer of N-(alkenylphenyl)maleimide is 2iC1 of N-(p-isopronylphenyl)maleimide, which is represented by the FII formula. There are no particular restrictions on the polymer of phenyl)maleimide, but it is preferable that it has a molecular weight of 10,000 or less.In the present invention, the above compounds can be used alone or in a mixture of two or more. be.

These N-(alkenylphenyl)maleimide derivatives include, for example, JP-A-55-129266 and JP-A-56-131.
566 and JP-A-56-145272.

The aliphatic maleimide which is the B component of the present invention has maleimide residues of the formula % (wherein R8, R8', R8", R811! and R9
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, hydroxy group or ]. aSb, C1X, y and 2 each represent 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'-hydroquinethoxyethylmaleimide, N-1-methoxymethylpropylmaleimide, N-1
-ethoxymethylpropylmaleimide, N-1-methoxymethylbutylmaleimide, N,N'-3゜6-thioxaoctane-1,8-bismaleimide, N,N'-4,
7-thioxadecane-1,10-bismaleimide, N,
N'-3゜6.9-) rioxaundecan-1.11-
Bismaleimide, N, N'-4,9-dioxato"decane-1,12-bismaleimide, N.

N'-4,7,10-) rioxatridecane-1.1
3-bismaleimide, N,N,'-7-methyl-4.1
0-dioxatri-rcan-1,13-bismaleimide,
N, N'-3゜6.9.12-tetraoxatetradecane-1,14-bismaleimide, N, N'-36,9,
12,15-inkoxaheptadecane-1,17-bismaleimide, bis(3-N-maleimide flovir) 7
I? Examples of Ritetrahydrofuran and Zara K include (In the formula, a is 26.5.6 or 331.) (In the formula, the sum of % 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 maleimide is appropriately substituted with a chlorine atom, bromine atom, methyl group, ethyl group, phenyl group, etc. may 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 N-(alkenylphenyl)maleimide and aliphatic maleimide used, but generally the former is 2 to 2 to 99 weight type or 5 to 95 weight type. 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 amine compound used as necessary for the purpose of imparting a homogeneous and dense structure to the cured product of the present invention and imparting toughness and mechanical strength is expressed by the following formula (%) (where Z is the number of carbon atoms) It is a tetravalent organic group consisting of 1 to 150 atoms and can contain atoms of hydrogen, oxygen, sulfur, ), nitrogen, and silicon phosphorus, and t is an integer of 1 or more. ), typical examples of which are ethylamine, propylamine, and hexylamine.
Aniline p-(m or.-) Toluidine, p-(m
or 0-) methoxyaniline, p-(m or Ir!-
o-) chloroaniline, 3,5-dichloroaniline, p-(m or tri o-)hydroxyaniline,
p-(mariIt'1o-)carboxyaniline, p-
(rn or 0-) vinylaniline, p-(m or 0
-) Allylaniline, p-impropenylaniline, 2
-Methyl-4-isopronylated aniline, 4-aminopyridine, 2-(4'hydroxyphenyl) -2-(4
″-aminophenyl)pronozone, 2-(4′-hi)
'Oxyphenyl)-2-(3'-methyl-4'aminophenyl) f-lonozone, benzylamine, 1-aminonaphthalene, 2-aminonaphthalene ethylenenoamine,
trimethylenezamine, hexamethylenediamine, rcamethylenenoamine octamethylenezamine, 2,2゜4-trimethylhexamethylenediamine
m -) Phenylenenoamine 14-diaminocyclohexane 2,4-noaminotoluene, 4.4'-noaminophenylmethane, 3.4'-noaminodiphenylmethane, 2,2-bis(4'-aminophenyl ) id, 4.4'-diaminodiphenylsulfone 3.3'
-diaminodiphenylsulfone, 4,4'-diaminodicyclohexylmethane, p-(or m-)xylylenediamine, bis(4-7minophenyl)diphenylsilane, bis(4-7minophenyl)methylphosphine oxide, bis(3- chloro-4-aminophenyl)methane, 2,2-bis(4'-4''-aminophenoxyphenyl)pro/zone, ■.

4-bis(p-aminophenoxy)benzene 1,4-diaminonaphthalene, 2,4-diaminopyridine, 4-methyl-2,4-bis(p-aminophenyl)intane,
4-methyl-2,4-bis(p-aminophenyl)-1
4-methyl-2,4-bis(p-7minophenyl)-2--''silane, tris(4-aminophenyl)phosphate, tris(4-aminophenyl)thiophosphate, 2,4.6 −) Squirrel (4'
-Ami) phenoxy)-S-triazine, 5
(or 6)-amino-1-(4'-7 minophenyl)
- Trimer or higher polymers of 1,3,3-1-limethylindane, vinylanilines, or isopronylated anilines, aromatic amines (e.g., aniline, toluidine) and aldehydes (e.g., formaldehyde) ) Polyamines obtained by the reaction with aniline and formaldehyde (e.g., MDA-150, subproduct name manufactured by Mitsui Toatsu Chemical Co., Ltd.) and the polyamines obtained by the reaction of aniline with formaldehyde. Examples include hydrogenated alicyclic polyamines. These amine compounds can be used alone or as a mixture of two or more.

The amount of these amine compounds that can be used in the composition of the present invention is not particularly limited, but N-(alkenylphenyl)
The ratio (-maximum) 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 is preferably 1 or less, and is in the range of 0.01 to 1. More preferred.

(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 Mac represent the amount of the amine compound used, and the average value of the number of amine groups in the molecule, respectively. and the average molecular weight.) 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 UP, the adhesive strength will decrease and the mechanical strength of the cured product will tend to decrease. It is in.

The thermosetting resin composition of the present invention may be a simple mixture of components A, B, and optionally component C, or may be a composition containing at least a part of these prepolymers. Prepolymer and HA: N-(alkenylphenyl)maleimides, B: Aliphatic maleimide and C:
It is a preliminary reaction product obtained by reacting any two components selected from amine compounds or three components A, B, and C. There are no restrictions on the specific reaction method, but if the reaction temperature is 0.
In the range of ~200℃ and reaction time in the range of 5 minutes to 10 hours, each component can be directly mixed and reacted uniformly without a solvent, or the components can be reacted as a homogeneous solution or suspension using all solvents. source.

Further, in the present invention, the epoxy resin D used for the purpose of improving adhesive strength, adjusting viscosity, etc. may be any known solid or liquid product, and typical examples thereof include bisphenol A type epoxy resin, Bisphenol F
type epoxy resins, halogenated bisphenol A type epoxy resins, phenol novolak type epoxy resins, heterocyclic epoxy resins such as cresol novolac type epoxy resins, hydrogenated bisphenol A type epoxy resins, propylene glycol diglycidyl ether, pentaerythritol polyglycidyl ether, etc. Aliphatic epoxy resins, epoxy resins obtained by reaction with aliphatic or aromatic carboxylic acid tobichlorohydrin, spiro ring-containing epoxy resins, glycidyl ethers that are reaction products of orn arylphenol novolanc compounds and epichlorohydrin. The type epoxy resin is represented by the following molecular formula. p,
p'-N, NN/, N/-tetraglycinol-p-, which is represented by the following molecular formula:
Epoxy resins obtained by reacting aliphatic or aromatic amines such as aminophenol with epichlorohydrin, epoxy resins obtained by ring-opening polymerization of a portion of the above epoxy resins, and epoxidized or epoxy-modified resins (e.g.
Examples include acrylic resins having epoxy groups, polybutadiene or alkyd resins, and epoxy-modified silicone resins.

In the present invention, the epoxy resin can be used alone or in a mixture of two or more types, and of course, a monofunctional so-called reactive diluent may also be partially included. The amount of epoxy resin to be used is not particularly limited, but it is preferably at most 50 parts 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.

Although a catalyst is not necessarily required for the force curing reaction of the curable resin composition of the present invention, one or more catalysts may be used depending on the situation. In this case, the amount used is determined according to the invention. The amount should be within a range that does not interfere with the excellent effects of the composition and improves its performance, and in fact it is 5 or less based on the total weight of the composition. Catalysts used for the purpose of improvement, curing rate Q) adjustment, etc. include boron trifluoride monoethylamine complex,
boron trifluoride amine complex with a non-complex coated with boron tsuride, triethylamine, N,N-trimethylpennolamine,
Hexamethylenetetramine, N.

Tertiary imines such as N-trimethylaniline, quaternary ammonium salts such as tetramethylammonium bromide, borate compounds such as triphenylborate and triphrenorborate, imidazoles such as N-methylimidazole and N-phenylimidazole. Compounds, metal compounds such as acetic acid titanate, storium acetate, titanium acetylacetonate, sodium methylate, aluminum chloride, zinc chloride, tin chloride, manganese naphthenate, cobalt naphthenate, phthalic anhydride, detrahydrophthalic anhydride, Methyltetrahydronotaric anhydride, Nanotsuciic anhydride,
Anhydrous//Acid anhydrides such as phenotetracarboxylic acid, pyromellitic anhydride, trimellitic anhydride, and maleic anhydride; peroxides such as nocumyl-oxide, t-butylnomobenzoate, and methyl ethyl ketone/e-oxide. , azobisisobutyronitrile and other ab compounds.

The composition of the present invention utilizes characteristics such as containing aliphatic maleimide, which is a liquid maleimide with a low melting point, so that a uniform mixture can be obtained. Although it can be used in the form of a solution, it is easily soluble in organic bath agents. When bathing, there are restrictions on the organic solvent used, but specific examples include acetone, methyl ethyl ketone,
Ketone Q such as nclohexano 7, n-hexane, hydrocarbons such as /chlor\xa/nato, noethyl ether, ethyl celonorb, methyl celonorb, 14-nooxano, tetrahydrofuran, etc. J) ni 7'-ru a, Chlorine compounds such as methylene chloride, chloroform, trichloroethane, carbon tetrachloride, benzene, xylene, mesitylene natono aromatic Fr hydrogen hydride, alcohols such as methanol, ethanol, impropyl alcohol, phenonope cresol, nitriles such as acetonitrile and esters such as methyl acetate, ethyl acetate, and 2-ethoxyethyl acetate. N again.

Of course, a solution composition can be obtained by using N-trimethylformamide, N-methyl-2pyroIJton, etc., but these solvents have the drawbacks mentioned above, so they cannot be used for special purposes (7). It is preferable to refrain from using it for any other purpose.

The curable resin composition of the present invention may optionally contain powder, granular or fibrous reinforcing agents, fillers, thickeners, mold release agents, vinyl triethoquinosilane, etc., as long as they do not inhibit the effects of the present invention. Coupling agents, flame retardants, flame retardants, pigments and coloring agents and other auxiliary agents can be added for gray, coating and laminating varnishes, molding powders, paints, adhesives, sealants, rubber. It has a wide range of uses including medicine.

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 formed or laminated after being impregnated with a substrate such as a powder, a coating, or a glass cloth, and then cured by heating. let Curing temperature is generally 0-3
500°C, preferably in the range of 50 to 300°C. The curing time depends on the form δ of the cured product, but generally f
The time Vζ sufficient for the resin component to be completely cured may be selected within the range of 30 seconds = 20 hours. In addition, molded products, laminate products,
When used for manufacturing adhesive structures, etc., it is desirable to apply pressure during heating and hardening, and the applied pressure may range from 1 to 150 to 9/crA. It is also possible to use electromagnetic waves such as visible light, ultraviolet rays, X-rays, and γ-rays as a method for curing the composition of the present invention.

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

A homogeneous liquid comprising an N-(alkenylphenyl)maleimide and an aliphatic maleimide or a homogeneous bath 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 polymerizing agent, a flame retardant, etc. are added to this uniform liquid or uniform bath liquid as necessary, and the mixture is uniformly blended to form a varnish. After impregnating a glass cloth with the varnish and air-drying it for a certain period of time,
The prepreg is obtained by precuring in an oven at ℃. Prepreg σ) is often used as it is 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 separation of components or foaming, has favorable dryness to the touch, can be stored stably for a long period of time even at room temperature, and has a high level of stability. Flexibility is maintained.

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 to 300°C and a pressure of lO to 150 to /eMI. 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 examples below. Note that the necropsy and measurements in Example 1 were based on weight unless otherwise specified. Further, the various methods in the Examples are as follows.

Thermogravimetric analysis: 1. In a nitrogen stream using DT G-30M manufactured by Takasha Seisakusho. Measured by heating rate of Oc/min.

Place a sample of f1.52 on a stainless steel hot plate heated to 180°C, knead with a spatula at a rotation speed of once per minute, and measure the time it takes for the sample to start stringing. did.

Solder heat resistance: According to JIS 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.

Copper foil peel strength: According to JrS C-6481.

bending strength Impact resistance: According to JIS C-6481 Ta.

Cured product with circular shape and thickness of 1cm 502 spherical bronze 60α At seven o'clock, it was dropped from a height of Check the degree of cracking using the following criteria. I guessed it.

01 not cracked, △: cracked ×: Breaks into pieces.

Example 1 4-Methyl-2,4-bis(p-N-maleimidophenyl 1-1-pentene 60 w (the production method of s is as in Production Example 1 below) and N,N'-4,7- 40 parts of duoxadecane-1゜10-bismaleimide were thoroughly mixed, and the time was measured using a portion of the mixture.Next, 100 parts of the mixture was added to 100 parts of 1.4-soxane at 30°C.
A varnish was prepared by dissolving it.

A predetermined amount of this varnish (equivalent to resin content of about 59) was applied to an aluminum container with a smooth bottom and an inner diameter of 60 mm and a depth of 14 Wa after applying a mold release agent, and heated to 80CVC7x+ on a moving plate under a nitrogen stream and held for 2 hours. After that, the temperature was gradually raised to 130°C in the shade for 30 minutes, maintained at this temperature for 3 hours, and then heated to 200°C for 1 hour (the temperature was gradually raised and held at this temperature for 2 hours to cure. After-curing was performed at 250 CFr°C for 2 hours 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--'? Manufacture of maleic anhydride 108
4 methyl-2,4-no(p-aminophenyl)-
133 parts of 1-pentene were gradually added with 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, 1.25 parts of cobalt acetate tetrahydrate, 25 parts of ethylamine, and 123 parts of acetic anhydride were added to this slurry reaction g, and the temperature of this reaction solution was raised to 60°C.

Thereafter, the reaction solution was kept at 60° C. and stirring was continued for 3 hours. Next, the reaction solution was cooled to room temperature, 25 parts of methanol was added, and the mixture was gradually dropped into 1500 parts of thoroughly stirred water to obtain a precipitate. This precipitate was taken from house to house, poured into industrial water, and carbonated) After adding an aqueous IJum solution to adjust the pH to 8.5, the precipitate was thoroughly washed by washing several times at each house, and finally washed and purified with 100 parts of methanol. 4-Methyl-2°4-bis(p-N-maleimidophenyl)-1-pentene (melting point 148-150°C) was dried at a temperature of 50°C under reduced pressure.
194 copies were obtained.

tx ON-p~impropenylphenylmaleimide, 4-methyl-2,4-bisCP-N-maleimidophenyl 1-2-bentenyl and N-[p-impronylphenyl)maleimide oligomers are the starting materials p
-impropenylaniline, 4-methyl-2,4-no(
p-7 minophenyl+-2--5 nteno and p-1
Nylaniline oligomer (composition, monomer 3.
Dimer, dimer 76. 9. Trimer 8. 2. Quaternary or more 11
．． 7%) was used, and the same method as above was used.

Examples 2 to I3 Aliphatic maleimide to N,N'-4,7-nooxadecane-1 to bismaleimide, N,N'-4,9
-Nooxadodecane-1 12-bismaleimide, N
, N'-7-methyl-4,10-dioxatridecane-
1゜13-Bismaleimide, Noefamine D-230 and D-400 (Soefamine is a polyoxypropylene amine, a product of Mitsui Texaco Chemical), Bismaleimide, N-(alkenylphenyl)maleimide" (N-p -i noglobenylphenylmaleimide,
4-methyl-2,4-bisjp-N-maleimidophenyl 1-2-pentene, 1m-phenyleneduamine as an amino compound, 4゜4'-noaminonophenyl ether,
4-4'-noaminonophenyl meta/, as a solvent 1.
Table 1 using 4-nooxane 6 and methyl ethyl ketone
(The mixture was sufficiently mixed at the compounding ratio shown in ()) and the cure time value and cured product were obtained in the same manner as in Example 1.

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

Glutime of each individual N'-4,7-nooxadecane-1,10-bismaleimide was measured, and a cured product was obtained in the same manner as in Example (2). However, 4-methyl-2,
The cured product of 4-bis(p-N-maleimidophenyl+-t--s) did not have a circular shape and was broken into pieces, and the impact resistance was measured by selecting sufficiently large pieces. Ta.

Table 1 shows the compositions of Examples 1 to 13 and Comparative Example 1.2 together with the measurement results of glue time, impact resistance of cured products, and thermogravimetric analysis.

Example 14 N-+p-j'/f-nylphenyl)maleimide oligomer (composition monomer 3.+4.2mer 76.5%, 3
8.3% of tetramer, 50 parts of tetramer (section 12.1) and 50 parts of N,N'-7-methyl-4,10-duoxatridecane-113-1:"sufreimide. A glass cloth (thickness 0-18+
++ml was impregnated, air-dried, and then dried at 150° C. for 9 minutes to obtain a prepreg.

Stack 9 sheets of this prepreg, place one sheet of copper foil on top, and use a hot press machine to press at 75 to 9/ctd at 1180°C.
The material was compressed for 30 minutes to obtain a copper-clad laminate. This laminate was then after-cured in an oven at 200°C for 8 hours.

Example 15 After thoroughly mixing 82 parts of N,N'-4,7-nooxadecane-IIO-bismaleimide and 24 parts of 4,4'-noa≧tunophenylmethane, the mixture was heated at a reaction temperature of 120°C for 20 minutes.
A bath melting reaction was carried out for a minute to produce pre-JP IJ mom.

30 parts of this prepolymer and N-1p-isopronylphenyl)maleimide oligomer (composition: Example 14)
An impregnating varnish was prepared by dissolving 70 parts of 1,4-duoxa (same as above) in a mixed solvent of 750 parts of 1,4-duoxa and 50 parts of methyl ethyl ketone. Thereafter, a copper-clad laminate was obtained which was subjected to after-curing in the same manner as in Example 14.

Examples 16-24 N-(p
-impropenylphenyl)maleimide, N-(p-vinylphenyl)maleimide, N-(p-isopronylphenyl)nochloromaleimide, 4-methyl-2,4bis(p-N-maleimidophenyl 1-1-intene) , 4
-Methyl-2,4-bis(pN-maleimidophenyl)-2--s silane, N-(p-impronilphenyl)maleimide oligomer N,N'-4,7-nooxadecano as aliphatic maleimide 1°10-
Bismaleimide, Noefamine D-230, D as described above
-400 and D-2000 bismaleimide, 4゜4'-noaminonophenylmethane as amine compound, 4
, 4' noaminophenyl ether, MDA-
150, Epicote 828 (trade name of bisphenol-based epoxy resin manufactured by Gel Kagaku Co., Ltd.) as an epoxy resin, D
EN431 (trade name of novolac epoxy resin manufactured by Dow Chemical Company), 2-ethylimidazole and trimellitic anhydride as a catalyst, and 1°4-duoxane and methyl ethyl ketone as a solvent were melted or dissolved in the composition shown in Table 2 and impregnated with varnish. was prepared. Other than that, Example 14
A copper-clad laminate that was after-cured was obtained in the same manner as above.

Comparative Example 3 70 parts of N,N'-1methyleneno-p-phenylene)bismaleimide and 30 parts of N,N'-4°7-nooxadecanol,10-bismaleimide were dissolved in 100 parts of N,N-tmethylformamide. An impregnated varnish was prepared, and a copper-clad laminate was obtained in the same manner as in Example 14. After the lice dry, the surface of the resin-containing glass cloth is coated with N, N' (methylene resin).
(phenylene) bismaleimide was precipitated, and a good silipreg could not be obtained.

The heat resistance, silver foil peel strength, and bending strength of the copper-clad laminates obtained in Examples F1114-24 and Comparative Example 3 were measured, and the results are shown in Table 2.

Example 25 The above N-(p-isopropenylphenyl)maleimide oligomer 509, N,N'-4,7-thioxadecane-1. 25 parts of to-bismaleimide and MDA-1
After thoroughly mixing 50.15 parts, a melt reaction was carried out at 120° C. for 20 minutes to produce a prepolymer.

Next, 90 parts of this prepolymer, Epicoat 828,
10 parts, anhydrous tori meri note yen depreciation
3387, 120 parts of natural graphite and 2.59" of suderic acid were kneaded for 30 minutes in a force pressure niegu at a temperature of 2100 C.Then, this composition was kneaded under the conditions of a mold temperature of 200 C and a pressure of 120 KQ/-. The molded product had a bending strength of 18.7 Ky/i at 25C measured according to JIS K-6911.
, 16.0 after heating for 500 hours at a temperature of 250°C.
Kq/mj, and showed satisfactory heat deterioration resistance.

In addition, the symbol in the table:・Engineer F? represents a compound of

BM-A 8M 8M 8M 8M-E 8M-F ltJ-p-inozoloinylpheny lumaleimide 4-methyl-2,4-bis(p N-maleimidophenyl 1 d 4-methyl-2,4-bis(p -N-maleimidophenyl) 2-Entertainment N-(p-impropenylphenyl maleimide oligomer ( Composition: 3.1 units of monomer, 3.1 units of monomer, dimer 76.5 units, trimer 8.3%, 4 units 12.1%) N-1p-vinylphenyl) Reimi Do N-tp-inopro-nilphenylphene nil) nochlormaleimide B.M. BM-B BM-C BM-D BM-E N,N'-4,7-nooxa Deka-110-Bismale imide N,N'-4,9-nooxa Dodecane-1,12-bisma Reimi Do N, N'-7-methyl-4° 10-Noxatridecane 1.13 ~ Bismaleimide In the following formula, a 2.6 (Noe Famin D-230 screw 7 Reimi Do) In the following equation, 5, 6 (shelf) in a Fumin D-400 screw 7 Reimi Do) BM-F In the following formula, a x 33.1f Bi of Efamine D-2000 sumaleimide) M M M- M m-phenylenenoamine 4.4'-Noaminonophenyl ether 4.4'-Noaminonophenyl methane MDA-150 + Expressed by the following formula ) It is a molecular prepolymer. However, the product All constructions were carried out in accordance with the full15 experiment.

Example 20: Prepolymer of ABM-A and AM-DExample 22: Prepolymer of ABM-D and AM-CExample 23, 24: Three-component polyester Example 15.20.22 .23 and 24, the N-(alkenylphenyl)maleimide and/or aliphatic maleimide and the amine compound are not just a mixture, but the amended two-component or three-component procedure dated December 28, 1990, Commissioner of the Japan Patent Office Matsu Ue Toshi Tono Akira Specification Name of the invention Thermosetting resin composition Claims (1) 8-Maximum (I) 1. Indication of the case 42-531-2 (', 1 Heisei
Patent application filed on November 30, 2017 (1) 2, Name of the invention Thermosetting resin composition 3, Relationship with the case of the person making the amendment Patent applicant name (312) Mitsui Toatsu Chemical Co., Ltd. 4, Agent Person: 105 ff103 (431) 1831 Address: 40 Mori Building, Toranomon 5-13-1, Minato-ku, Tokyo Name (6538) Patent attorney Minoru Yamashita
Heijo 7 - Full text of the specification (x) Ir12 (wherein R1-R6 are the same or different, each a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 10 carbon atoms, or 1 to IO carbon atoms which may be phenyl or branched
alkyl group, halogen atom, Rho- group, R, C-
R4, R5 and R6 may be the same or different when a plurality of them are present, and X is a hydrogen atom. , halogen atom, carboxyl group,
Hydroxyl ○ O group, R70- group, R7C- group, R7C0- group, or cyano group, and when multiple X exist, they may be the same or different, and m2, m2 and m2 are They are 0 to 4, respectively, m and +m.

+ m z = 5, and R7 is an optionally branched alkyl group having 1 to 10 carbon atoms or a phenyl group, or an optionally branched alkyl group having 1 to 5 carbon atoms N-(alkenylphenyl)maleimide derivatives, their double bodies, and A thermosetting material characterized by containing at least one maleimide compound selected from the group consisting of multimers thereof, B: at least one aliphatic maleimide having an ether bond, and C: at least one amino compound. Resin composition.

(2) The thermosetting resin composition according to claim 1, which contains at least a portion of any two-component or three-component prepolymer of the components A, B, and C.

3. Detailed Description of the Invention The present invention relates to a novel thermosetting resin composition having excellent heat resistance and fast curing properties.

Various heat-resistant resins are available as insulating materials that meet the demands for larger capacity, smaller size, lighter weight, and higher reliability of electronic equipment, as well as thermal stability, longer life, and maintenance-free electrical equipment. As such heat-resistant resins, addition polymerization type imide resins,
For example, bismaleimide resin or bismaleimide
Aromatic diamine modified resins are well known. However, the bismaleimide resin does not provide excellent heat resistance, but has a high melting point, a slow curing rate, and is poorly soluble in general-purpose organic solvents such as methyl ethyl ketone and tetrahydrofuran. , N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and the like have the disadvantage of being soluble only in high boiling point polar organic solvents. Furthermore, when preparing a bismaleimide resin varnish using these polar organic solvents and impregnating it into a base material to form a prepreg, the B-staged prepreg is then heated and compressed to produce a laminate. Since it is extremely difficult to completely remove the solvent from the drying and manufacturing processes of laminates, the solvent remains and causes voids in the laminate, reducing its quality and performance. This was not satisfactory as it caused the foil to swell or peel. In addition, the above-mentioned polar organic solvents are permeable through the skin and are highly toxic, so their use is undesirable from the standpoint of environmental health and safety.

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

The present invention is directed to N-(alkenylphenyl)maleimide derivatives, dimers thereof, or multimers thereof (hereinafter these compounds are referred to as N-(alkenylphenyl)maleimides), which eliminate the various drawbacks found in the above-mentioned bismaleimide resins. ), a thermosetting resin composition containing an aliphatic maleimide having an ether bond and an amino compound, which has a low melting point, excellent solubility in organic solvents, and fast curing. It is something that provides something.

The thermosetting resin composition of the present invention has the following characteristics: A, -maximum (I) (wherein R5-R6 are the same or different, and each has a hydrogen atom, a halogen atom, and the number of optionally branched carbon atoms) 1-10 alkyl groups or phenyl groups, or 1-10 carbon atoms which may be branched
alkyl group, 10gen atom, R, O- group, R7C
- group, R7Co- group, hydroxyl group, or phenyl group substituted with cyano group, each of Rh, R5 and R6 may be the same or different when a plurality of them are present, and X is hydrogen atom, halogen atom, carboxyl group, hydroxyl group, R, O- group, R7C- group, R7Co- group, or cyano group, and when multiple Xs are present, they may be the same or different, ml, m2 and m are each 0 to 4, m + + m is 10 m, = 5, and R7 is an optionally branched alkyl group having 1 to 10 carbon atoms or phenyl 1 to 5 carbon atoms, which may be a group or branched
N-(alkenylphenyl)maleimide derivative represented by a phenyl group substituted with an alkyl group or a nor\rogen atom, and when multiple R7s are present, they may be the same or different , at least one maleimide compound selected from the group consisting of a duplex thereof and a multimer thereof; B: at least one aliphatic maleimide having an ether bond; and C: at least one amino compound. Features.

The N-(alkenylphenyl)maleimides used in the composition of the present invention have significantly better solubility in solvents than ordinary maleimide compounds, and have been conventionally used in compositions containing maleimide compounds. The objective can be fully achieved using ordinary general-purpose organic solvents with relatively low boiling points without using polar organic solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide, and it is fast curing. This makes it possible to B-stage at relatively low temperatures, which not only improves workability but also makes it easier to remove solvents from products such as laminates, greatly improving product quality. can.

On the other hand, aliphatic maleimide having an ether bond has the advantage of providing a highly flexible cured product since there is no benzene ring in the molecule, and since it has an ether bond, it is compatible with the resin of the present invention and various base materials. It is also expected to improve adhesive ability.

Examples of the N-(alkenylphenyl)maleimide derivative represented by the general formula (I), which is component A of the present invention, include N-
-(o-vinylphenyl)maleimide, N-(m-vinylphenyl)maleimide, N-(p-vinylphenyl)maleimide, N(0-isopropenylphenyl)maleimide, N-(m-isopropenylphenyl)maleimide, N-(p-isopropenylphenyl)maleimide,
N-(vinyltolyl)maleimide (including all isomers), N-(isopropenyltolyl)maleimide (including all isomers), N-(p-αethylvinylphenyl)
maleimide, N-(p-α-phenylvinylphenyl)
Maleimide, N(0-vinylphenyl)dichloromaleimide, N-(m-vinylphenyl)dichloromaleimide, N-(1)-vinylphenyl)dichloromaleimide, N-(p-isopropenylphenyl)dichloromaleimide, N-( m-isopropenylphenyl)dichloromaleimide, N-(o-isopropenylphenyl)dichloromaleimide, N-(4hinyl-2-hydroxyphenyl)maleimide, N-(4-hinyl-3-hydroxyphenyl)maleimide, N-(4 -isopropenyl-2
acetoxyphenyl)maleimide, N-(4isopropenyl-3-acetoxyphenyl)maleimide, N-(4
-vinyl-3-cyanophenyl)maleimide, N-(4
-vinyl-2-cyanophenyl)maleimide, N-(4
-isopropenyl-3-cyanophenyl)maleimide,
N-(4-itubropenyl-2-cyanophenyl)maleimide, N,N'-(1-vinyl-2,4-)ecocine)hismaleimide, N,N'-(1-vinyl35-phenylene)bismaleimide , NN'-(1-isopropenyl-2,4-phenylene) bismaleimide, N, N'
-(1-isopropenyl-3,5-phenylene)hismaleimide, N-(p-vinylphenyl)-di-t-butylmaleimide, N-(p-isopropenylphenyl)diisopropylmaleimide, N-(p~α -(p-cyanophenyl)vinylphenylcomaleimide, N-Cp-
α-(m'-chlorophenyl)vinylphenylcomaleimide, 2-isopropenyl-4-N-maleimide-4'
-chlorobiphenyl, 2-vinyl-4-N-maleimido-4'-methylbiphenyl, 3-isopropenyl-4-
N~maleimido-3'-methoxybiphenyl, 3-vinyl-5-N-maleimido-4'-hydroxybiphenyl, 3-isopropenyl-4-N-maleimido-4'-acetylbiphenyl, 2-N-maleimido-4 -isopropenyl-4'-cyanobiphenyl, N~(p-isopropenylphenyl)-p-talolophenylmaleimito, and the like.

In the present invention, the above N-(alkenylphenyl)maleimide dimer and its multimer can be used. N
An example of the -(alkenylphenyl)maleimide dimer is a N-(p-isopropenylphenyl)maleimide dimer represented by the formula.

Further, there are no particular restrictions on the polymer of N-(alkenylphenyl)maleimide, and it is preferable that the polymer has a molecular weight of 10,000 or less. In the present invention, the above compounds can be used alone or in combination of two or more.

These N-(alkenylphenyl)maleimide derivatives include, for example, JP-A-55-129266 and JP-A-56-131.
566 and JP-A-56-145272.

The aliphatic maleimide having an ether bond, which is component B of the present invention, is a maleimide residue having the formula % (wherein R*, Re', RIN Re'' and R3
may be the same or different, each being a linear or branched mono- to trivalent aliphatic hydrocarbon group having 1 to ]O carbon atoms, or an alkoxy group, hydrocoxyl group, or a halogen; is substituted with aSb
, cSx, y and Z each represent 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-methoxymethylbutylmaleimide, and N-1-
Nitoxymethylpropylmaleimide, N-1-methoxymethylbutylmaleimide, N,N'-3,6-thioxaoctane-1,8-bismaleimide, N,N'-4,7
-Shioxadecane-1,10-hismaleimide, N.

N'-3,6,9-trioxaundecane-111-hismaleimide, N,N'-4,9-dioxadodecane-
1,12-bismaleimide, N.

N'-4,7,10-trioxatridecane-I, 13
-Bismaleimide, N,N'-7-methyl-4,IO-
Dioxatridecane-1,13-hismaleimide, N,
N' ~3.6,9.12-tetraoxatetradecane-1,14-bismaleimide, N, N' -3,6
,9,12,15-pentaoxahebtadecane-1,1
7-pismaleimito, bis(3-N-maleimidopropyl)polytetrahydrofuran, and further, for example, (wherein a is 2.6.5.6 or 33.1), (wherein the sum of a and C is (wherein, the sum of x, y and Z is about 5.3).

Furthermore, compounds in which the hydrogen atom bonded to the unsaturated carbon atom in the maleimide group of the above aliphatic maleimide is appropriately substituted with a chlorine atom, bromine atom, methyl group, ethyl group, phenyl group, etc. may also be used. In addition to using aliphatic maleimide alone, it is also possible to use a mixture of two or more types.

In the composition of the present invention, there are no particular regulations regarding the proportions of both the N-(alkenylphenyl)maleimide of general formula (I) and the aliphatic maleimide, and generally the former is used relative to the total amount of both components. 2-99% by weight, preferably 5-9%
It is 5% by weight. 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 for the purpose of imparting a homogeneous and dense structure and imparting toughness and mechanical strength to the cured product according to the present invention is expressed by the following formula (%) (in the formula, Z has 1 to 150 carbon atoms) It is a monovalent organic group that can contain atoms of hydrogen, oxygen, sulfur, halogen, nitrogen, phosphorus, and silicon, and 1 is an integer of 1 or more. Specific examples include ethylamine, propylamine, hexylamine,
Aniline, p-(m- or o-)toluidine, p-(
m or 0-)methoxyaniline, p-(m or.

) chloroaniline, 3,5-dichloroaniline, p-(
m or 0-) hydroxyaniline, p-(m or 0
-) carphokidianiline, p-(m or 0-) vinylaniline, p-(m or 0-) allylaniline, p-
Isopropenylaniline, 2-methyl-4-isopropenylaniline, 4-aminopyridine, 2-(4'-hydroxyphenyl)-2-(4''-aminophenyl)propane, 2-(4'-hydroxyphenyl)- 2 (3
"~methyl-4"-aminophenyl) propane, pencylamine, 1-aminonaphthalene, 2-aminonaphthalene, ethyleneamine, trimethylenediamine, hexamethylenediamine, decamethylenediamine, octamethylenediamine, 2.2.4 -trimethylhexamethylenediamine, p-(or m-)phenyleneamine, 1
．． 4-diaminocyclohexane, 2,4-aminotoluene, 4,4'-diaminodiphenylmethane, 3,4'
-Diaminodiphenylmethane, 22-bis(4'-aminophenyl)pronone, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4°4'-diaminodiphenyl sulfone, 3,3'diaminodiphenyl enylsulfone, 4,4'-diaminodicyclohexylmethane, p-(or m-)xylylenediamine, bis(4-aminophenyl)diphenylsilane,
Bis(4-aminophenyl)methylphosphine oxide, his(3-chloro-4-aminophenyl)methane, 2
．． 2-bis(4',4"-aminophenoxyphenyl)
Propane, 1,4-bis(p-aminophenoxy)benzene, 1,4-diaminonaphthalene, 2,4diaminopyridine, 4-methyl-2,4-bis(p-aminophenyl)pentane, 4-methyl2. 4-bis(p-aminophenyl)-1-pentene, 4-methyl-2,4-bis(
p-aminophenyl)-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
-4-trimethylindane, or trimer or higher polymers of vinylanilines or isopropenylanilines, aromatic amines (e.g. aniline, toluidine)
and polyamines obtained by the reaction with aldehydes (e.g., formaldehyde, paraform, acetaldehyde), especially poly(phenylene methylene) polyamines obtained by the reaction of aniline with formaldehyde (e.g., MDA-150, a product manufactured by Mitsui Toatsu Chemical Co., Ltd.) (name) and alicyclic polyamines obtained by hydrogenating the polyamine. These amino compounds can be used alone or as a mixture of two or more.

There is no particular limitation on the amount of these amino compounds used in the composition of the present invention, or 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 maleimide (formula (■) below) is preferably 1 or less, and preferably in the range of 0.01 to 1. More preferred: (In the formula, mi, ni and Mi each represent the usage amount of the maleimide compound, the average value of the number of maleimide groups in the molecule, and the average molecular weight, and ma, na and Ma respectively represent the usage amount of the amino compound, and the average value of the number of maleimide groups in the molecule. (The average value of the base number and the average molecular weight are shown.)

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

The thermosetting resin composition of the present invention may be a simple mixture of component A, component B, and component C, or may be a composition containing at least a portion of these prepolymers. Prepolymer is a preliminary reaction obtained by reacting any two components selected from A (N-(alkenylphenyl)maleimides), B (aliphatic maleimides), and C (amino compounds) or three components (A, B, and C). product, and are there any restrictions on the specific reaction method? Each component can be directly and uniformly mixed without a solvent at a reaction temperature of 0 to 200°C and a reaction time of 5 minutes to 10 hours. The reaction may be carried out, or the components may be reacted as a homogeneous solution or suspension using a solvent.

A catalyst is not necessarily required for the curing reaction of the thermosetting resin composition of the present invention, but one or more catalysts may 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 actually 5% 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 monoethylamine complexes, boron trifluoride amine complexes, and boron trifluoride piperidine complexes. Tertiary amines such as nitriethylamine, N,N-dimethylbenzylamine, hexamethylenetetramine, N,N-dimethylaniline, quaternary ammonium salts with tetramethylammonium bromide, triphenylborate, tricresylborate, etc. phorate compound with,
Imidazole compounds such as N-methylimidazole and N-phenylimidazole, zinc acetate, sodium acetate,
Titanium acetylacetonate, sodium methylate,
Metal compounds such as aluminum chloride, zinc chloride, tin chloride, manganese naphthenate, cobalt naphthenate, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, benzophenonetetracarboxylic anhydride, pyromellitic anhydride Examples include acids, acid anhydrides such as trimellitic anhydride and maleic anhydride, peroxides such as dicumyl peroxide, t-butyl perbenzoate, and methyl ethyl ketone peroxide, and azo compounds such as azobisisobutyronitrile. I can do it.

The composition of the present invention takes advantage of the fact that it contains aliphatic maleimide, which is a low-melting liquid maleimide, and can obtain a homogeneous mixture, so that the homogeneous mixture can be cured without any solvent by simply heating it. It can be used in the form of a type, or it can be used in the form of a solution as it is easily soluble in organic solvents. In the case of a solution, there are no restrictions on the organic solvent used. Specific preferred examples include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, hydrocarbons such as n-hexane and isoclohexane, diethyl ether, ethyl cellosolve, Ethers such as methyl cellosolve, 1,4-dioxane and tetrahydrofuran, chlorine compounds such as methylene chloride, chloroform, trichloroethane and carbon tetrachloride, aromatic hydrocarbons such as Hensen, xylene and mesitylene, methanol, ethanol, Examples include alcohols such as isopropyl alcohol, phenol, and cresol, nitriles such as acetonitrile, and esters such as methyl acetate, ethyl acetate, and 2-ethoxyethyl acetate. Also, even if N,N-dimethylformamide, N-methyl-2-pyrrolidone, etc. are used, it is of course possible to obtain a solution-like composition, but since these solvents have the drawbacks mentioned above, it is difficult to use them for special purposes. It is recommended that you refrain from using it for any other purpose.

The curable resin composition of the present invention may optionally contain reinforcing agents in the form of powder, particles, or fibers, fillers, thickeners, mold release agents, vinyltriethoxysilane, etc., as long as they do not inhibit the effects of the present invention. Coupling agents, flame retardants, flame retardants, pigments and coloring agents, and other auxiliary agents can be added.

The curable resin composition of the present invention has a wide range of uses including impregnation, prepreg, coating and laminating varnishes, molding powders, paints, adhesives, sealants, and rubber chemicals.

Curing conditions for forming a cured product vary depending on the composition and the form of the cured product. In general, 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 powder, pellets, or glass cloth, molded or laminated, and then cured by heating. . Curing temperature is generally 0-3
50°C, preferably in the range of 50 to 300°C. The curing time depends on the form of the cured product, but is generally in the range of 30 seconds to 20 hours, which is sufficient time to completely cure the resin component. In addition, molded products, laminate products,
When used for manufacturing adhesive structures, it is preferable to apply pressure during heat curing, and the applied pressure may range from 1 to 150 kg/crl.

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.

There are no particular restrictions on the specific mode of carrying out the present invention, and examples of preparation of impregnating varnish, prepreg, and laminate are shown below as examples of the mode.

A homogeneous liquid comprising an N-(alkenylphenyl)maleimide, an aliphatic maleimide, and an amine 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,
A prepreg is obtained by precuring in an open air at °C.

Prepreg is often used as a variety of 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 at room temperature, and is Flexible or sustained.

Next, for example, after stacking a plurality of 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 at a temperature of 100 to 300°C and a pressure of 10 to 150 kg/al.
A laminate for a wiring board can be obtained by pressure molding.

Hereinafter, the present invention will be explained with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. Note that parts and percentages in the examples are by weight unless otherwise specified. Further, various measurement methods in Examples are as follows.

Thermogravimetric analysis: Measured using DTG-30M manufactured by Koguruma Seisakusho in a nitrogen stream at a heating rate of 10°C/min.

KEL TIME: Place approximately 1.5 g of the sample on a stainless steel hot plate heated to 180°C, knead with a spatula at a rotation speed of once per minute, and measure the time required for the sample to tighten. did.

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

Copper foil peel strength: According to JIS C-6481.

Bending strength: According to JIS C-6481.

Impact resistance: A 50 g spherical bronze was dropped from a height of 60 cm onto a circular, one-thick cured product, and the degree of cracking was observed according to the following criteria: O: No cracks, △: A baboon can fit, , breaks into pieces.

Production Example 1 Production of 4-methyl-2,4-bis(p-N-maleimidophenyl)-1-pentene.

Dissolve 108 parts of maleic anhydride in 500 parts of acetone,
This solution was kept at 20°C and 4-methyl 2,4-di(
133 parts of p-aminophenyl)-1-pentene were gradually added with stirring. After the addition is complete, the reaction solution is heated to a temperature of 2.
Stirring was continued for 2.5 hours at 0°C. The reaction solution was a yellow slurry. Next, 1.25 parts of cobalt acetate tetrahydrate, 25 parts of triethylamine, and 123 parts of acetic anhydride were added to this slurry reaction solution, and the temperature of this reaction solution was raised to 60°C. Thereafter, the reaction solution was maintained at 60°C and stirring was continued for 3 hours. Next, the reaction solution was cooled to room temperature, 25 parts of methanol was added, and the mixture was gradually dropped into 1,500 parts of thoroughly stirred water to obtain a precipitate.

This precipitate was separated and poured into water, and after adjusting the pH to 8.5 by adding an aqueous sodium carbonate solution, the separation and washing with water were repeated several times to thoroughly wash the precipitate, and finally, the precipitate was purified by washing with 100 parts of methanol. 4-Methyl-
194 parts of 2,4-bis(p-N-maleimidophenyl)-]-pentene (melting point 148-150°C) were obtained.

In addition, N-p-isopropenylphenylmaleide, 4-methyl-2,4-his(p-N-maleimidophenyl)-
2-pentene and N(p-isopropenylphenyl)maleimide oligomers are the starting materials p-isopropenylaniline, 4methyl-2,li-di(p-aminophenyl)-2=pentene and p-isopropenylaniline oligomers, respectively. -(composition, monomer 3.2%, dimer 76.9
%, trimer: 8.2%, weight: 11.7%).

Examples 1 to 6 N-(alkenylphenyl)maleimide of the type and amount shown in Table 1, an aliphatic maleimide having an ether bond of the type and amount shown in Table 1, and an amino compound of the type and amount shown in Table 1 were sufficiently prepared. The mixture was mixed and the gel time was measured on a portion thereof. Next, 100 parts of the mixture was dissolved in 100 parts of i4-dioxane or methyl ethyl ketone at 30°C to prepare a varnish. Apply this varnish to the smooth inner diameter 6
Pour a predetermined amount of mold release agent (equivalent to approximately 5 g of resin) into a 14 mm deep aluminum container, heat it to 80'C on a hot plate under a nitrogen stream, hold for 2 hours, and then heat to 130°C. 30
Gradually raise the temperature over a period of minutes, hold at this temperature for 3 hours,
Next, the temperature was gradually raised to 200°C over 1 hour, and this temperature was maintained for 2 hours to cure. After that, after-cure was performed at 250°C for 2 hours, and the brown cured product (test piece)
The impact resistance of this cured product was investigated and thermogravimetric analysis was conducted.

Comparative Example 1.2 The gel time of each of 4-methyl-2,4-bis(p-N-maleimidophenyl)-1-pentene and N,N'4,7-thioxadecane-1,10-bismaleimide was measured, Furthermore, cured products were obtained in the same manner as in Examples 1 to 6. However, the cured product of 4-methyl-2,4-bis(p-N-maleimidophenyl)-1-pentene did not have a circular shape and broke into pieces, so the impact resistance measurement was sufficiently large. I chose a piece and went.

For the compositions of Examples 1 to 6 and Comparative Examples 1 to 2, the formulations as well as the measurement results of gel time, impact resistance of cured products, and thermogravimetric analysis are shown in Table 1.

Example 7 After thoroughly mixing 82 parts of N,N'-4,7-thioxadecane-1,10-bismaleimide and 24 parts of 4,4'-diaminodiphenylmethane, 2
A melt reaction was performed for 0 minutes to produce a prepolymer. An impregnated varnish was prepared by dissolving 30 parts of this prepolymer and 70 parts of N-(p-isopropenylphenyl)maleimide oligomer in a mixed solvent of 50 parts of 1,4-dioxane and 50 parts of methyl ethyl ketone. Next, a glass cloth (thickness: 0.18 mm) treated with aminosilane was impregnated, air-dried, and then dried at 150° C. for 9 minutes to obtain a prepreg. Stack nine sheets of this prepreg, place one sheet of copper foil on top, and use a heat press to press at a pressure of 75 kg/aI! The material was compressed at 180°C for 30 minutes to obtain a copper-clad laminate. The laminate was then after-cured in an oven at 200°C for 8 hours.

Example 8 N-(alkenylphenyl)maleimide of the type and amount shown in Table 2, aliphatic maleimide having an ether bond of the type and amount shown in Table 2, amino compound of the type and amount shown in Table 2, and amino compound shown in Table 2 An impregnated varnish was prepared by blending different types and amounts of solvents and melting or dissolving them. Other than that, a copper-clad laminate was obtained which was subjected to after-curing in the same manner as in Example 7.

Comparative Example 3 70 parts of N,N'-(methylenedi-p-phenylene)bismaleimide and 30 parts of N,N'-4,7-thioxadecane-1,10-bismaleimide were dissolved in 100 parts of N,N-dimethylformamide. An impregnated varnish was prepared, and a copper-clad laminate was obtained in the same manner as in Example 7. Note that N,N'-(methylenedi-p-phenylene)bismaleimide was precipitated on the surface of the resin-containing glass cloth after air drying, and a good prepreg could not be obtained.

The solder heat resistance, peel strength and bending strength of the copper foil of the copper-clad laminates obtained in Examples 7 to 8 and Comparative Example 3 were measured. The results are shown in Table 2.

The symbols in the table represent the following compounds.

N-(alkenylphenyl)maleimides BM-A
N-p-isopropenylphenylmaleimide BM-84-Methyl-2,4-his(p-N-maleimidophenyl)-1-penteneBM-C4-methyl-2,4-his(p-Nmaleimidophenyl)- 2-Pentene BM-DN-(p-isopropenylphenyl)maleimide oligomer (composition).

Monomer 3.1%, dimer 76.5%, trimer 8.3%,
12.1% of tetramer or more) Aliphatic maleimide ABM-A N,N'-4,7-thioxadecane-1
．． 10-Bismaleimide ABM-B N,N'-4,9-dioxadodecane-
1,12-bismaleimide ABM-CN, N'-7-methyl-4,10ABM-D -dioxatridecane-1,13 monobismaleimide In the following formula, a″=F2.6 (Chefamine D-230
Hismaleimide) ABM-E In the following formula, a ~ 5.6 (Hismaleimide of Shefamine D-400 ABM-F) In the following formula, a = 33.1 (Bismaleimide of Shefamine D-2000) Amino compound M- A M-B M-C m-phenylenediamine 4.4'-diaminodiphenyl ether 4.4'-diaminodiphenyl meta

Claims (5)

[Claims] (1) A: General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 to R_6 are the same or different, hydrogen atom, halogen atom, carbon atom that may be branched) There are alkyl groups of 1 to 10, phenyl groups, alkyl groups of 1 to 10 carbon atoms that may be branched, halogen atoms, R_7O- groups, ▲numerical formulas, chemical formulas, tables, etc.▼
There are groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups, phenyl groups substituted with hydroxyl groups or cyano groups, and each of R_4, R_5 and R_6 may be the same or different when there are multiple of them. X may be a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, an R_7O- group, a ▲numeric formula, a chemical formula, a table, etc.▼ group,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ groups or cyano groups, and when there are multiple groups, they may be the same or different, m_1, m_2 and m_3
are respectively 0 to 4, and m_1+m_2+m_3=5, and R_7 is an optionally branched alkyl group having about 1 to 10 carbon atoms, a phenyl group, and an optionally branched alkyl group having about 1 to 5 carbon atoms. Alternatively, it represents a phenyl group substituted with a halogen atom, and when there is a plurality of phenyl groups, they may be the same or different from each other. )
At least one maleimide compound selected from the group consisting of N-(alkenylphenyl)maleimide derivatives, dimers thereof and multimers thereof, and B: at least one aliphatic maleimide. Thermosetting resin composition. (2) A: General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 to R_6 are the same or different, hydrogen atom, halogen atom, carbon atom that may be branched) Alkyl groups with numbers 1 to 10, phenyl groups or alkyl groups with 1 to 10 carbon atoms that may be branched, halogen atoms, R_7O- groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ A phenyl group substituted with a hydroxyl group or a cyano group, and each of R_4, R_5 and R_6 may be the same or different if there are multiple of them. X can be a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, an R_7O- group, ▲a mathematical formula, a chemical formula, a table, etc.▼
There are groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups or cyano groups, and when there are multiple values, they may be the same or different. m_1, m_2 and m
Each of _3 is 0 to 4, and m_1+m_2+m_3=5, and R_7 is an optionally branched alkyl group having 1 to 10 carbon atoms, a phenyl group, or an optionally branched alkyl group having 1 to 5 carbon atoms. Alternatively, it represents a phenyl group substituted with a halogen atom, and when there is a plurality of phenyl groups, they may be the same or different from each other. ); B: at least one aliphatic maleimide; and C: an amino compound. A thermosetting resin composition comprising: (3) The curable resin composition according to claim 1, further comprising A: a maleimide compound, B: an aliphatic maleimide, and D: an epoxy resin. (4) The curable resin composition according to claim 2, further comprising A: a maleimide compound, B: an aliphatic maleimide, and C: an amino compound, and D: an epoxy resin. (5) The thermosetting resin composition according to claim 2, which contains at least one part of a prepolymer of any two or three components of the components A, B, and C.