JPH0152420B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has excellent flexibility, adhesion, etc., and has heat resistance and
This invention relates to a resin composition with excellent chemical resistance, electrical properties, etc. Polyfunctional cyanate esters are an essential component,
A curable resin composition containing an appropriate polyfunctional maleimide and further an epoxy resin ()
is published in Japanese Patent Publication No. 41-1928 (component a), No. 46-
41112 (composition of a + c), No. 54-30440 (composition of a + b), No. 52-31279 (composition of a + b + c), and others, and has excellent heat resistance, mechanical strength, chemical resistance, and moisture resistance. However, in terms of flexibility and flexibility, although some improvement has been made by introducing aliphatic long-chain organic groups into the monomers used, it is still insufficient. Ta. In addition, it was difficult to use in applications that required adhesiveness and tackiness. As a result of research on improving the above-mentioned drawbacks, the present inventors have developed an unsaturated acid anhydride-added acrylonitrile-butadiene copolymer obtained by adding an unsaturated acid anhydride at its unsaturated carbon-carbon bond as a modifier. By using the polymer (), bendability, flexibility, etc. can be greatly improved, and tackiness can be further imparted, and conversely, the heat resistance of the unsaturated acid anhydride-added acrylonitrile-butadiene copolymer can be improved. We also discovered that a resin composition containing polyfunctional cyanate esters as an essential component and optionally polyfunctional maleimide and further epoxy resin is extremely effective as a modifier for chemical resistance, etc., and we have published this book. Completed the invention. That is, the present invention provides a. a. a polyfunctional cyanate ester, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine, or a. and b. a polyfunctional maleimide, the maleimide prepolymer, or the maleimide. An acrylonitrile-butadiene copolymer obtained by adding an unsaturated acid anhydride at the unsaturated bond in a cyanate ester-based curable resin composition () consisting of a prepolymer of and an amine or c. an epoxy resin. A curable resin composition containing (), preferably containing 5 to 95% of the component () in the composition.
Weight%, component () is selected from the range of 95 to 5% by weight, flexibility, adhesion, heat resistance, electrical properties,
It is possible to obtain a cured product with excellent chemical resistance. The configuration of the present invention will be explained below. First, the cyanate ester-based curable resin composition () of the present invention has a cyanate group (-O
-C≡N), preferably two or more, or a prepolymer thereof alone, or a resin composition containing these components as essential components.
What is polyfunctional cyanate ester, which is an essential component?2
It is an organic compound having at least 1 cyanate ester group, and a suitable cyanate ester has the following general formula R ¹ (-O-C≡N)m...(1) [m in the formula is usually 2 or more and 5 or less is an integer of
R ¹ is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group R ¹ . Specific examples include 1,3- or 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3
-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene, 1,3,6
-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis(4-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis(3,5-dichloro-4-cyanatophenyl) ) propane, 2,2-bis(3,
5-dibromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl) ether, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, tris(4-cyanatophenyl)
-cyanatophenyl) phosphite, tris(4
-cyanatophenyl) phosphites, and cyanic acid esters obtained by the reaction of novolacs with cyanogen halides. In addition to these, Tokuko Sho 41-1928, Tokko Sho 44-4791, Tokko Sho 45-
11712, JP 46-41112 and JP 51-63149
Cyanic acid esters described in et al. may also be used. Further, a prepolymer obtained by polymerizing the above-mentioned polyfunctional cyanate ester in the presence of a catalyst such as a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, or a phosphate ester such as tributylphosphine. It can be used as These prepolymers are symylamines formed by trimerization of the cyanide groups in the cyanate ester.
- Generally has a triazine ring in the molecule.
In the present invention, it is preferable to use the prepolymer having an average molecular weight of 400 to 6,000. Next, the components constituting the cyanate ester resin composition in combination with the above cyanate esters will be explained. The maleimide preferably used is a compound having one maleimide group, preferably two or more maleimide groups, which is used to form a resin composition with excellent heat resistance and moisture resistance. The polyfunctional maleimide suitably used in the present invention has the following general formula: [In the formula, R ² is an aromatic or alicyclic organic group having a valence of 2 or more and usually 5 or less, X ¹ and X ² are hydrogen, halogen, or an alkyl group, and n is 2 or more,
It is an integer less than or equal to 5. ] It is a compound represented by The maleimides represented by the above formula are mixed with maleic anhydride and 2 or more, usually 5
It can be produced by a method known per se in which maleamic acid is prepared by reacting it with an amine having up to 10 amino groups, and then the maleamic acid is cyclodehydrated. It is preferable that the polyvalent amines used are aromatic amines in terms of the heat resistance of the final resin, but if flexibility and flexibility of the resin are desired,
Alicyclic amines may be used alone or in combination. Furthermore, it is particularly desirable that the polyvalent amines be primary amines in terms of reactivity, but secondary amines can also be used. Suitable amines include meta- or paraphenylenediamine, meta- or paraxylylenediamine, 1,4- or 1,3-cyclohexanediamine, hexahydroxylylenediamine, 4,4'-diaminobiphenyl, bis( 4
-Aminophenyl)methane, bis(4-aminophenyl) ether, bis(4-aminophenyl)
Sulfone, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-aminophenyl)cyclohexane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-amino-3-methylphenyl)propane, bis(4-amino-3-chlorophenyl)methane, 2,2-bis(3,5-dibromo-4-aminophenyl)propane, bis(4- Aminophenyl) phenylmethane, 3,4-diaminophenyl-4'-aminophenylmethane, 1,1-bis(4-aminophenyl)-1-phenylethane, and melamine having an s-triazine ring, aniline and formalin. Examples include polyamines in which benzene rings are linked with methylene bonds through reaction. In the present invention, the above-mentioned polyfunctional maleimide can also be used in the form of a prepolymer instead of in the form of a so-called monomer. The epoxy resin is used as necessary to improve adhesive strength, adjust viscosity, etc., and is a compound having two or more epoxy groups in the molecule and a prepolymer thereof. For example,
Polyol, polyhydroxybenzene, bisphenol, low molecular weight novolak type phenolic resin, hydroxyl group-containing silicone resin, aniline, 3,5
These include polyglycidyl compounds obtained by the reaction of -diaminophenol etc. with epihalohydrin, and polyepoxy compounds in which the double bond of butadiene, pentadiene, vinylcyclohexane, dicyclopentyl ether is epoxidized. Furthermore, other components include esters of (meth)acrylic acid such as esters of (meth)acrylic acid, epoxy esters of (meth)acrylic acid, alkenyl esters of (meth)acrylic acid, and prepolymers thereof; diallyl phthalate. , polyalkenyl compounds such as divinylbenzene, diallylbenzene, and trialkenyl isocyanurate, and their prepolymers; dicyclopentadiene and their prepolymers; phenolic resins; polyvinyl acetal resins, such as polyvinyl formal, polyvinyl acetal, and polyvinyl butyral;
Acrylic resin with CH group or COOH group,
Silicone resin, alkyd resin; liquid-clastic rubbers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, butadiene-styrene copolymer, polyisoprene, butyl rubber, natural rubber, polyimide polymers, etc. be. Next, an unsaturated acid anhydride-added acrylonitrile-butadiene copolymer () (hereinafter, unsaturated acid anhydride The term "addition acrylonitrile-butadiene copolymer" refers to a so-called acrylonitrile-butadiene copolymer to which an unsaturated acid anhydride is added at its unsaturated carbon-carbon bond. The raw material used, acrylonitrile-butadiene copolymer, has a number average molecular weight of 900 to 100,000,
Preferred is an acrylonitrile-butadiene copolymer of 1,000 to 5,000, which is produced by a generally known method. During production, it is preferable to select a catalyst system and conditions that produce many C═C unsaturated bonds in the side chains. An unsaturated acid anhydride is a compound having an olefinic unsaturated bond and an acid anhydride group in the molecule,
Preferred examples include those of the following formula. The unsaturated acid anhydride-modified acrylonitrile-butadiene copolymer contains 0.1 to 100 g of the unsaturated acid anhydride per 100 g of the acrylonitrile-butadiene copolymer.
By adding 3.0 mol, preferably 0.2-2.0 mol. As the addition reaction conditions, conventionally known methods are used. That is, in a solvent in which the unsaturated acid anhydride and the acrylonitrile-butadiene copolymer are soluble or in a molten state, the temperature is 50 to 300°C, preferably 100 to 250°C.
The reaction is carried out at ℃ by adding a small amount of anti-gelling agent such as phenylene diamine, pyrogallol or naphthol as necessary. The usage ratio of the resin components of the above-mentioned curable resin composition of the present invention is not particularly limited, but when used as a heat-resistant resin, it is a suitable component constituting the cyanate ester resin composition. A cyanate ester resin composition containing a certain cyanate ester and/or maleimide as a main component
95 wt%, 5 to 50 wt% of acid anhydride-added acrylonitrile-butadiene copolymer, more preferably
It is preferable to use the cyanate ester resin composition in an amount of 10 to 45 wt%, and conversely, to improve the heat resistance of the latter, it is preferable to use the former cyanate ester resin composition in an amount of 5 to 50 wt%. The resin composition of the present invention itself has the property of becoming a heat-resistant resin by being bonded and reticulated by heating, but in order to promote crosslinking and reticulation, it is usually used in the form of a catalyst. Such a catalyst is
2-Methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1
-cyanoethyl-2-methylimidazole, 1-
Imidazoles exemplified by cyanoethyl-2ethyl-4methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanaminoethyl-2-methylimidazole, and further, these imidazoles such as trimellitic acid adducts; N,N-dimethylbenzylamine, N,N-
Dimethylaniline, N,N-dimethyltoluidine, N,N-dimethyl-p-anisidine, p-halogeno-N,N-dimethylaniline, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, Tertiary amines such as N-methylmorpholine, triethanolamine, triethylenediamine, N,N,N',N'-tetramethylbutanediamine, N-methylpiperidine; phenol, cresol, xylenol, resorcin, phloroglucin, etc. Phenols: lead naphthenate, lead stearate, zinc naphthenate,
Organic metal salts such as zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate;
Inorganic metal salts such as SnCl ₄ , ZnCl ₂ , AlCl ₂ ; benzoyl peroxide, lauroyl peroxide, caprylyl peroxide, acetyl peroxide,
Examples include peroxides such as parachlorobenzoyl peroxide and di-tertiary butyl di-perphthalate, as well as azobisnitriles. In addition, those generally known as curing agents or catalysts for epoxy resins, such as acid anhydrides such as pyromellitic anhydride and phthalic anhydride, can also be used in combination. Moreover, those used as cross-flowing agents for rubber can also be used in combination. The composition of the present invention may contain various additives as desired, as long as the original properties of the composition are not impaired. These additives include natural or synthetic resins for imparting new properties to the composition of the present invention; fibrous reinforcing materials; fillers; dyes and pigments; coupling agents; thickeners; lubricants; flame retardants. ;
Contains various known additives such as rubber anti-aging agents,
They may be used in appropriate combinations as desired. The temperature for curing the resin composition of the present invention varies depending on the presence or absence of a curing agent and catalyst, the types of composition components, etc., but is usually 90 to 350°C, preferably
It may be selected within the range of 100 to 300°C. When used in the production of laminates, adhesive structures, etc., it is preferable to apply pressure during heat curing, and generally speaking, the pressure is appropriately selected within the range of 0.1 to 200 kg/cm ² . Moreover, ultraviolet rays, radiation, etc. can also be used for curing. The cured resin obtained by curing the resin composition of the present invention described in detail above has a desirable combination of various properties such as flexibility, adhesion, heat resistance, and electrical properties. It also has excellent chemical resistance. Although the crosslinking and reticulation reaction mechanism of the resin composition of the present invention described in detail above has not been proven, it is possible that the reaction of the cyanato groups of polyfunctional cyanate esters and the reaction of polyfunctional maleimides. The reaction of the maleimide group is estimated as follows. Furthermore, the reaction mechanisms of epoxy groups in epoxy resins with hydroxyl groups, carboxyl groups, amino groups, acid anhydride groups, etc. are known. (1) Reaction of polyfunctional cyanate ester. (2) Reaction of polyfunctional maleimide. From the above, in the composition of the present invention, in addition to the reactions that are presumed to occur in the composition consisting of the known polyfunctional cyanate esters and polyfunctional maleimides, as well as the epoxy resin, there is a new reaction. It is presumed that a reaction occurs between the acid anhydride group in the unsaturated acid anhydride-added acrylonitrile-butadiene copolymer () added as a component and the cyanato group or maleimide group. It is presumed that reactions with saturated double bonds also occur. However, it is inconceivable that all the components react in proportion to the amount of functional groups based on the reaction mechanism inferred above. Different functional groups have different reaction temperatures, rates, selectivities, catalyst types, etc., so the mutual reactions between the functional groups in each component described above are mainly due to the affinity between the different components. It is also inferred that this contributes to the improvement of (compatibility) and realizes a finer dispersion state. This will be explained in detail below using Examples and Comparative Examples. Note that parts represent parts by weight. Example 1 Butadiene-acrylonitrile copolymer (acrylonitrile component 15.4%, average molecular weight 2000, butadiene 1,2-bond 14%) 1000g, maleic anhydride 200g, Antigen 3C (gelling inhibitor, manufactured by Sumitomo Chemical Industries, Ltd.) 2 g and 10 g of xylene were placed in a separable flask (No. 3) equipped with a reflux condenser, and after purging the system with nitrogen, a maleation reaction was carried out at 198° C. for 4 hours. After the reaction was completed, the solvent and unreacted substances were distilled off under reduced pressure to obtain a maleated butadiene-acrylonitrile copolymer. To 200 parts of this maleated butadiene-acrylonitrile copolymer, 500 parts of 2,2-bis(4-cyanatophenyl)propane pre-reacted at 150°C for 450 minutes was added, and both were further reacted at 150°C for 20 minutes.
Pre-react for 1 minute. This contains 0.1 zinc octylate.
1 part and 0.1 part of triethylenediamine were added, and these were dissolved in a mixed solvent of methyl ethyl ketone and N,N-dimethylformamide. This solution is impregnated into a carbon fiber woven fabric and dried to create a B-stage prepreg, which is layered one on top of the other.
A 35μ electrolytic copper foil was inserted and press molded at 175°C and 40Kg/cm ² for 140 minutes. The performance of this copper-clad laminate is
Shown in the table. Example 2 900 parts of 2,2-bis(4-cyanatophenyl)propane and 100 parts of bis(4-maleimidophenyl)methane were pre-reacted at 140°C for 150 minutes, and then an epoxy resin (ECN-1273, manufactured by Ciba Geigy) was added. )
200 parts, 400 parts of the maleated acrylonitrile-butadiene copolymer obtained in Example 1, 0.1 part of zinc octylate, 5.0 parts of N,N-dimethylbenzylamine, and 2.0 parts of di-tertiary butyl peroxide as catalysts, These were dissolved in methyl ethyl ketone. A glass woven fabric was impregnated with this solution and dried to produce a B-stage prepreg.
Use one sheet of this and put 35μ electrolytic copper foil on the top and bottom.
A good copper-clad laminate was obtained by press molding at 175° C. and 40 kg/cm ² for 120 minutes. The performance of this board is shown in Table 1. Comparative Examples 1 and 2 Copper-clad laminates were produced in the same manner as in Examples 1 and 2, except that the maleated acrylonitrile-butadiene copolymer was not used. The properties of this plate are shown in Table 1.

【table】

【table】

Claims (1)

[Claims] 1 a. A polyfunctional cyanate ester, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine, or a and b. A polyfunctional maleimide, the maleimide prepolymer, or A prepolymer of the maleimide and an amine or
c. A cyanate ester-based curable resin composition () consisting of an epoxy resin is blended with an acrylonitrile-butadiene copolymer () obtained by adding an unsaturated acid anhydride at its unsaturated bond. Curable resin composition. 2. The curable resin composition according to claim 1, wherein the component () in the composition is 5 to 95% by weight, and the component () is 95 to 5% by weight.