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    • 专利摘要:
    1496725 Laminates SUMITOMO BAKELITE CO Ltd 2 May 1975 [3 June 1974] 18539/75 Heading B5N [Also in Divisions C3 and D1] Prepregs are laminated by hot-pressing to each other and/or to Cu, Al or nichrome foil, and these laminates may themselves be further laminated to form a multilayer printed-circuit board, the prepregs having been made by impregnating cloth or paper of glass, asbestos, and/or carbon fibres, pretreated with a coupling agent, with a solution of a composition comprising by weight: 100 parts (I) polyamino bismaleimide, 10-300 parts (II) polyepoxide, and 5-150 parts (III) copolymer(s) of aromatic vinyl compound(s) with (a) maleic anhydride and/or (b) alkyl maleate(s), or a partial alkyl ester of the copolymer with (a). (III) has number average M.W. 1000-60,000. (II) may have epoxy equivalent 100-4000. The coupling agent may be y-glycidoxypropyltriethoxysilane, or γ-aminopropyltriethoxysilane. Reference has been directed by the Comptroller to Specifications 1,276,646 and 1,190,718.
    公开号:SU1169545A3
    申请号:SU752134769
    申请日:1975-05-05
    公开日:1985-07-23
    发明作者:Ватанабе Цутому；Ямаока Сигенори
    申请人:Сумитомо Бейклайт Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

    oh o
    CL 11 The invention relates to a floor of heat resistant materials that are suitable for making multilayer boards for printed circuits, laminated plastics. Laminated materials of phenolic and epoxy resins are most often used as materials for the manufacture of printed wiring boards in electronic equipment. However, at present, the requirements for the operation of the equipment, its high reliability and high wiring density have increased significantly, so that these materials no longer satisfy these requirements, the laminates of phenolic resin were unsatisfactory in terms of electrical properties and heat resistance so that they can be used as functional elements in large integrated circuits. In addition, due to the low glass transition temperature, the epoxy resin laminate noticeably changes in size due to processing when forming a circuit or circuit, epoxy resin printing circuits at elevated temperatures deteriorate the electrical and mechanical characteristics, which leads to a decrease in electronic equipment reliability. Multilayer boards, typical boards for printed circuits of high density are assembled using layers of copper coating, epoxy resin glass and conversation from the same materials. However, when producing large printed circuit boards for computers or very dense multilayer boards for printed circuits (eight or more layers) in experimental structures made of conventional laminated copper coatings — epoxy resin glass — the reproducibility of the conductor model is small, and the exact layout of the circuit impossible due to unacceptably large size changes in the frontal direction as a result of heat treatment of the circuit and heat and pressure used in the process of forming the mounted layers. The holes in the shield are damaged as a result of deformation and twisting, the through holes are easily damaged due to thermal shock. Because of the relatively large linear expansion ratio in the thickness direction of the polyamino-Suc laminate, the low-imide resin resins are known as heat-resistant thermosetting resins obtained by the addition of N, N-5t / c-maleimide to diamine, have excellent mechanical properties at high temperature, resistance to deterioration under the action of heat and a very low linear expansion coefficient, they are preferred as a material for the manufacture of multilayer SHIT with high precision printed circuits. However, polyamino-5- / c maleimide resin does not cure poorly under the molding conditions of a conventional layered material and therefore requires long pressing at a temperature of at least 200 s or bakelization at and above for a long time after pressing at 170–200 s. In addition, the polyamino-o-c-maleimide resin has a poor flow property during the pressing process, is prone to including voids between the layers of base materials and is characterized by a low bond strength between the layers of base materials. Therefore, when drilling a laminate or forming an external shape, a crack is formed in the layers. The resin also exhibits a very weak adhesion to the copper foil and, especially, the adhesion to the prepreg of the copper foil in the inner layer of the circuit, which is a very important requirement for multilayer boards for printed circuits. Such a defective board (shield) does not meet the requirements of processing and installation, which causes great difficulties during operation. Polyamino-5 isomeimide resin contains reactive groups in its molecule that contain active amine hydrogen, and it can be used in conjunction with epoxy resin to improve curing ability, molding ability, and adhesion strength to a certain degree. use in laminates containing a layer of copper coating. The inclusion of a large amount of epoxy resin, however, leads to a decrease in heat resistance with insufficient adhesion of the inner layers of the multilayer board for printed circuits. A suitable for practical application of adhesion force cannot be achieved even with the mechanical or chemical treatment of the surface of the copper foil.
    A glass bonding agent is known, including a polyamino-5x / C-male imide based on 5 "C-imid selected from the group consisting of N, N, 4,4-diphenylmethane-isomelate, S, K-m- phenylene-5us-maleimide and N, N-hexamethylene g (s-maleimide, and a diamine selected from the group consisting of 4,4 diaminodiphenylmethane, 4,4-diaminodiphenyl ether and 4,4-diaminodicyclohexane, epoxy dianoyl or epoxy-newol pitch l.
    However, the combination of polyamino-3-smaleimide with epoxy resin leads to a significant decrease in heat resistance, respectively, taking the amount of epoxy resin into polyamine o-5k with -lime. The high heat resistance, inherent in the polyamino-S acmaleimide, is significantly deteriorated. In addition, the grip of the proposed composition with copper foil is not enough.
    The purpose of the invention is to increase the heat resistance of the material.
    This goal is achieved by the fact that a binder for fiberglass, including polyamino-SKC-maleimide on the basis of St / c -mide, selected from the group consisting of N, N, 4,4-diphenmemethane-5chs-maleimide, Y, Y-m-phenylene -bas-maleimide and N, N-hexamethylene Bis-maleimide, and diamine selected from the group including 4,4-diaminodiphenylmethane, 4,4-diaminodiphenyl ether and 4,4-diaminodicyclohexane and epoxy resin, additionally contains a copolymer selected from the group, including copolymer of styrene or its methyl derivatives with maleic anhydride, incomplete Gj-C alkyl; ester of a copolymer of styrene or its methyl derivative with maleic anhydride, a copolymer of isobutyl maleate with dimethylstyrene and a styrene copolymer of maleic anhydride with mono-N-pentylmapeate, in the following ratio of components, by weight:
    Polyamino bis-maleimide 100
    Epoxy resin 10-300
    Copolymer 5-150
    The polymer composition can, if necessary, be mixed with a small amount of hardeners of epoxy resins.
    low molecular weight epoxy resins, flame retardants, fillers and dyes.
    The addition of a copolymer leads to an improvement in the adhesion properties between the polyaminox-maleimido epoxy composition and the metal foil,. in particular copper. The strength of adhesion to the inner copper foil is achieved immediately by a sufficient practical level, as is required for a multilayer board for the printed circuit, allowing for harsh processing conditions.
    To obtain a layered material using a composition, a lacquer concentration of 20-50% by weight is prepared by dissolving the polymer composition in an inert solvent, for example amide, for example, for N, N-metalformamide. In N, N-dimethyl acetamide, in lactones, e.g. methyl-2-pyrrolidone, gamma-butyrolactone, lactams, e.g. caprolactam, or in mixtures of solvent and aromatic hydrocarbon or ketone.
    Fibrous base material, such as fiberglass, glass paper, asbestos paper, carbon fiber cloth, etc., treated with an appropriate binding agent, is impregnated with the obtained varnish using a cover-drying machine and dried at 130-140 ° C for 1-ZOm. nepetpeB B-stages with a resin content of 30–60 wt.%. One or several sheets of prepreg are applied one on top of the other to a predetermined size from O, 1 mm to several millimeters and, if necessary, metal foil, for example from copper, aluminum, nichrome, etc., is placed on one or both sides of the package.
    The resulting laminate or bag is heated under pressure by means of a press (hot plate) and a laminate is obtained with a metallic coating (metallic cloth).
    Heating under pressure is carried out at 120-250 0 and pressure of 5-200 kg / cm for 15-240 minutes. Due to the higher curing ability of the composition, the molding of the laminate can be carried out at lower temperatures than when forming a conventional polyamide resin or a single polyamino5 maleimide resin, for example, at 150-180 ° C for 30-180 minutes. The molded laminate has satisfactory properties without further bakelization.
    However, to reduce the tension formed during the molding process, the molded laminate is baked to 180-250 ° C from a few hours to 20 hours to improve the dimensional stabilization.
    Multi-layer shield for printed circuits can be prepared in the following way. The shield with the internal printed circuit is formed using a laminated material with a double-sided copper coating of a material with a base of fiberglass and, if necessary, subjected to chemical or mechanical surface treatment. The prepreg floor is placed between several sheets of the inner circuit board and between the inner circuit and the shield side of the laminated material with a one-sided copper coating with the surface circuit and the position of the prepreg, the inner circuit board and the laminate material of the surface circuit are brought to the required exact position using a metal plate ( plates) with a guide pin, and the resulting bag is pressed in the form between hot plates using heat and pressure to form a multilayer upiTa.
    The surface circuits and the through holes (cavities) form to obtain a finished or finished multi-layer printed circuit board.
    The layered material and the laminated material with a copper coating exhibit some deterioration in flexural strength, flexural modulus and adhesion strength at elevated temperatures in excess of 150 ° C and mechanical properties and adhesion strength when used or operated at elevated temperatures up to 150-200s for for a long time and are therefore materials of high strength for the manufacture of electronic parts. This laminate, at a temperature of 150 ° C, has a linear coefficient of expansion equal to one half or one third of the coefficient
    ordinary epoxy resin and fiberglass. Therefore, the size change in the facade direction as a result of heat treatment when crawling the printed circuit board and forming a multilayer package is small. Such high dimensional stability facilitates the production of printed circuits with a grid size of 1.27 mm and the production of ultra-dense printed circuit boards in eight or more layers, made difficult by using epoxy resin and glass fabric materials. Since the linear expansion coefficient in the thickness direction of the multilayer shield is small, the defects caused by the difference in thermal expansion and contraction between the copper-coated layer in the hollow part and the shield during thermal shock are small, and as a result, the strength of electronic equipment, such as a computer, increases.
    The multilayer printed circuit board is amenable to drilling, moisture resistant, heat resistant when soldering, possesses high electrical properties required for a multilayer printed circuit board, it can be made fire resistant. The proposed polymer composition has great advantages in terms of accuracy, yield, cost and strength of adhesion to copper foil (initial adhesion, adhesion when heated, change in adhesion with time and between the inner layers), which is a mutual factor for printed circuit boards.
    The proposed composition is particularly effective for use in multilayer boards of printed circuits of high technology and quality, it can be used in the manufacture of heat-resistant parts of tele equipment, in aviation, in electric cars, in automobiles, in obtaining printed circuits in functional parts of electronic communication equipment, in home electrical appliances.
    The introduction of the filler allows it to be used as a heat-resistant molding material.
    Example 1. A varnish containing 45% by weight of a polymer composition is obtained by dissolving 100 wt.h. in N-methyl-2-pyrrolidone. polyamido and α-maleimide, obtained by reacting 1 mole of N, N-4,4-diphenylmethane-Siuc-maleimide with 1 mole of 4,4-diaminodiphenyl ethane in the molten state at 150 ° C for 30 minutes, 10.0 wt. SttC-phenol-A diglycidyl ether with an epoxy equivalent of 450 to 500 (Epicot 1001 from Shell Chemical Corp.), 10 math., styrene copolymer — male and anhydride, containing 50 molecular units of maleic anhydride. A 0.1 mm thick fiberglass sheet is treated with gamma-glycidoxypropyl-triethoxysilane, impregnated with this varnish and dried for 7 minutes at 130 ° C using a coating-drying machine and a B-stage prepreg sheet is obtained with 40% by weight resin (polymer) content. Sixteen layers of prepreg are placed one above the other and on both sides of the resulting bag is placed a foil of electrolytic copper 35 microns thick, and the bag thus obtained is placed between two stainless steel sheets and heated for 2 hours at 170 C under a pressure of 50 kg / cm These (heated) plates and get a laminate with double-sided copper-i coating with a thickness of 1.6 mm. The test results of the performance characteristics of the laminate with a coating are given in Table. 1, where the ability to cure is expressed in terms of the time (period) of gelatinization when the varnish obtained in this way is heated on a hot plate at 150 C. As shown in Table 1. 1, in comparison with the known polymer compositions based on polyamino-5 US-maleimide, the proposed composition has the ability to cure at low temperature, and the copper-coated laminates obtained from it have high mechanical properties and adhesion strength at elevated temperatures, that even after a prolonged heat treatment, the reduction or deterioration of these properties is insignificant. This copper-clad laminate, however, has a coefficient of thermal expansion of between half and a third of a similar coefficient for conventional epoxy resin laminates, has a significantly higher heat resistance when soldering and other properties necessary for heat-resistant laminate, even in the absence of heat post-molding treatments. As follows from the table. 1, when bakelizing a laminate with a copper coating for 24 hours, its thermal properties slightly improve, but with only a slight difference between them before and after bakelization. Example 2 (comparative). The same polyamino-B is-maleimide as in Example 1 is dissolved in N-methyl-2-pyrrolidone and a lacquer containing 50% by weight of resin is obtained. In the same way as in Primer 1, a sheet of glass cloth with a thickness of 0 mm, treated with gammaglycidoxypropyltriethoxysilane, is impregnated with this varnish and dried for 10 minutes at 150 ° C and a prepreg sheet of stage B is obtained with a 40% resin content. The obtained prepreg sheets are mounted as described in Example 1 and heated for 2.5 hours at 100 kg / cm and a laminate with a double-sided copper coating of 1.6 mm is obtained. Covered with copper laminate, obtained in this way, after bakelizatsni within 24 h at 200 C detects, as follows from the table. 1, high mechanical properties at elevated temperatures and a high thermal expansion coefficient, however, with a very weak adhesion force between the copper foil and, and therefore, are not used in multilayer boards of printed circuits. The polyamine o-fwc-maleimide lacquer obtained by the above method has a markedly prolonged gelation time, and the oxidation reaction is weak. Therefore, it cannot be imparted to sufficient properties only by the said molding under pressure, and, in particular, the ciina of its adhesion to the copper foil prior to bakelization is 0.3 kg / cm. Therefore, this laminate cannot be used for practical purposes.
    PRI me R 3 (comparative). Varnish containing 30 wt.% Polymer composition, dissolving 100 May, h. diglycidyl ester of Suc-phenol-A with an epoxy equivalent of 450 to 500 (Epicot 1001) and 12 ma.h, of methane diamine in methyl ethyl ketone.
    Analogously to example 1, a sheet of fiberglass with a thickness of 0.1 mm, treated with gamma-glycidoxypropyltriethoxysilane, is impregnated with the obtained varnish, then dried for 7 minutes at 30 ° C to obtain a prepreg sheet of stage B with 40% by weight resin content.
    Similarly to the example, 1 pack of prepreg sheets is subjected to heat and pressure using a press with hot (heated) plates at 170 C and 70 kg / cm for h and get a laminate with a double-sided copper plate 1.6 mm thick.
    Crawled laminate with copper lining, as can be seen from the table. 1, worse in terms of mechanical strength and strength of adhesion to copper foil at elevated temperatures, deteriorates noticeably during heat treatment at elevated temperatures and is not satisfactory in heat resistance when soldering. Therefore, such a laminate with copper lining can not be used in practice as a heat-resistant laminate. Further, the laminate has a linear (thermal) expansion ratio that is too large to be used in high-density multilayer printed circuit boards. .
    PRI me R 4 (comparative). A varnish containing 45% by weight of the polymer composition is obtained by dissolving 100 wt.h. the same polyamino-fetJC maleimide as in example 1, and. 100 ma.ch. diglycidyl ether 5 (c-phenol-A e with an epoxy equivalent from 450 to 500 (Epicot 1001) in 1-meter -1-2-pyrrolidone.
    Analogously to example 1, a 1-mm-thick fiberglass sheet, treated with gamma-glycido-co-propyltriethoxy-silane, is impregnated with the obtained varnish, then dried for 5 minutes with and a prepreg sheet of stage B is obtained. with. 40% by weight resin content. Similar to Example 1, a set or package of prepreg sheets (prepared in this way) is exposed to heat and pressure using a press with heated plates at and 50 kg / cm for
    2.5 hours and get a laminate with double-sided copper lining thickness
    ., 6mm.
    The performance properties of this laminate with copper cladding are presented in Table. 1, Although this laminate exhibits relatively good heat resistance and without bakelization, however, the heat resistance of polyamino Snc-maleimide is not completely dyed. After bakelization for 24 hours at 200 ° C, the laminate shows some improvement in mechanical properties at elevated temperatures and an improved linear expansion coefficient, but still not satisfactory for heat resistant laminate.
    Compared to the laminate, which uses one polyamino-5 umaleimide, the adhesion force between the copper foil and the shield (cardboard) in the copper-coated laminate is slightly better in terms of the initial value, but not sufficient for a multi-layer printed circuit board, which will have to cope with laminate processing and operation.
    The gel time of the specified lacquer is significantly reduced by adding a polyepoxy derivative as compared to a lacquer containing one polyamino-8k (α-maleimide, but not enough compared to a lacquer containing the proposed polymer composition.
    Example 5. A lacquer containing 40% by weight of a polymer composition is obtained by dissolving 100 wt.h. in dimethylformamide. polyamino 6 ac-m of apeimide obtained by reacting 1.5 mol of N, M-4,4-diphenipmetan-ismaleimide with 1 mol of N, N-diaminodiphenylmethane in the molten state at 0.5 h, 200 wt.h. brominated diglycidyl ether Site-phenol-A e with epoxy equivalent 450-500 (Epicot 1045 from Shell Chemikap Corp.) and 50 wt.h. styrene isobutyl polyether copolymer - maleic ana-
    hydride containing 50 mol.% maleovog anhydride.
    Analogously to example 1, a sheet of fiberglass with a thickness of 0.1 mm, treated with gamma-aminopropyltriethoxiscan, is impregnated with varnish, dried for 5 minutes at 140 ° C and a prepreg sheet of stage B containing 45% by weight of the polymer composition is obtained.
    Analogously to example 1, a set of prepreg sheets prepared by the method described above is exposed to heat and pressure using a press and heated plates at 170 ° C and 40 kg / cm for 2 hours and a laminate with a double-sided copper plate with a thickness of 1.6 mm is obtained.
    As can be seen from the table. 1, this laminate is characterized by high mechanical properties at elevated temperature, linear expansion coefficient and heat resistance during soldering, and high adhesive force between the copper foil and the shield at the initial stage at elevated temperature and after prolonged heat treatment. Therefore, it is heat-resistant and has a high fire resistance (UZ class V-0, in accordance with the test method for vertical combustion),
    Prim fish-12. Analogously to example 1, a series of lacquers based on various polymer compositions is prepared by dissolving various combinations of polyamino-5'-c-maleimides, polyepoxy derivatives and acid-type copolymers in a mixture of methyl-2-pyrrolidone and methyl ethyl ketone solvents. A glass fiber sheet manufactured by Asahi Schwebel Co., treated for polyamide laminate with a thickness of 1 mm, is impregnated with varnish and dried for 510 minutes at 130-150 ° C and a prepreg is obtained with 35-50 wt.% Resin content. The prepared prepreg is heated under pressure together with electrolytic copper foil with a thickness of 35 μm using a press with heated plates at 160-180s and 4080 kg / cm for 1.5-2.5 hours and get a laminate with double-sided copper lining with a thickness of 1, 6 mm.
    The formulation of the approximate composition is presented in table. 2, and the gelatinization time and the performance characteristics of the laminate with copper
    facing - in table. 3. As follows from the table. 3, the proposed polymer composition exhibits, in a wide range of formulations, high heat resistance, in particular, the ability to cure at low temperature, and adhesion to copper foil compared to conventional polyimide based compositions.
    Example 13. A fiberglass sheet of thickness O, 1 mm is impregnated with the polymer composition of Example 1 and dried Analogously to Example 1, the prepreg kit and copper foil are exposed to heat and pressure using a press with heated plates to form a laminate with double-sided copper facing (copper foil thickness 7 µm) 0.2 mm thick An internal circuit board is formed from a laminate for testing high-density configuration. A 2 Mt-f multilayer shield is made of three sheets of inner board (cardboard), a circuit, two sheets of laminate with a copper face and a thickness of 35 µm foil (on one side) and several prepreg sheets of thickness O, 1 mm, prepared using the polymer composition of Example 1. The resulting multilayer board is further processed to form a surface circuit and openings, and a finished eight layer printed circuit board is obtained. The main operational characteristics of the shield are presented in table. four.
    For comparison, multilayer boards of printed circuits are obtained from a single polyamino-ois-maleimide resin, epoxy resin, and a composition of polyamine 0-S "c-small emide a and epoxy resin, respectively, as in Examples 1.5 and 6, and their properties are compared.
    As can be seen from the table. 4, the proposed polymer composition exhibits excellent properties under the harsh conditions of processing and processing of an eight-layer printed circuit board, in particular, adhesion with an internal copper foil and dimensional stability required for high-precision printed circuit boards.
    In contrast, when using a conventional polymer composition, the adhesion force with the inner copper foil I is unsatisfactory, and there is a noticeable deterioration in the processing of heat.
    scrap and moisture, size is bad. shield shielding — all of this does not meet the high accuracy requirements of multilayer printed circuit boards.
    Example 8 p 14. A lacquer with a 50 wt.% Resin content is obtained by dissolving 100 parts by weight in a mixture of dimethylformamide and toluene. polyamino-isaleimide from example 1, 50 weight.h. of a polyether type diglycidyl compound obtained by the reaction of epichlorohydride and a dihydric alcohol obtained by the reaction of bis-phenol-A with propylene oxide (Adeka rez EP-4000 Asahi Denk Kogyo ko), and 10 weight parts. copolymer of maleic anhydride - alphametstistirol (45:55 mol.%).
    A carbon fiber cloth sheet with a thickness of 0.3 mm, treated with gammaaminopropyltriethoxysilane, is impregnated with varnish and dried for 5 minutes at 150 ° C and a prepreg is obtained with 40% by weight resin content.
    A set of seven sheets of prepreg is exposed to heat and pressure in a press with heated plates for 2 hours at 170 ° C and 80 kg / cm and a laminate is obtained on the basis of carbon fiber 2 mm thick. The bending strength of the laminate is 58 kg / cm at room temperature and 43 kg / cm at 200 C. It is suitable for use in heat-resistant parts.
    PRI me R 15. Varnish with 55 wt.% - Noah content of the polymer composition is obtained by dissolving 100 parts by weight in N, N-metkp-2 pyrrolidone 100 parts by weight. polyaminoSuc-maleimide from example 6, 30 weight.h. diglycidyl ether of brominated oas-phenol-Ac with epoxy equivalent 450-500 (Epicot 1045) and 30 parts by weight a copolymer of maleic anhydride - alpha-methyl - /) - isopropylstyrene containing 30 mol.% maleic anhydride.
    A sheet of glass-asbestos paper with a thickness of 0.3 mm is impregnated with varnish and dried for 10 minutes while a prepreg sheet containing 60% by weight of the polymer composition is obtained.
    A set of six sheets of prepreg with a 0.1 mm thick nichrome foil placed on one side of the set is exposed to heat and a laminate with a single-sided or chrome lining 1.6 mm thick is obtained. The resulting laminate has a heat distortion temperature, specific volume resistance A. equal to 210 Si cm and 5.-10 Si cm (C-96/40/90 and fire resistance according to UL class V-0 by the VL method when tested by vertical burning. Laminate is suitable for use in heat-resistant shields for resistance circuits, heater shields, and the like.
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    x / 4 Also Separation angle 90 ° Immersion in the NSS; Halogen: 1/1 with a comfortably heated temperature for 7 min. Changing the size of a vanilla scheme -0.01 shield,% Parallel After heat treatment laminate -0.02 Е-0.5 / 170 After a temperature cycle x / 5-0.03
    TableA
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    -0.02
    -0.04
    -0.06 out of opacity 0.01 -0.03 0.03 -0.08 0.05 -0.10 Below Tg Coefficient Perpendicular to the laminate Above Tg linear expansion shield board () Remarks
    Continuation of Table 4 e: x / 1. In comparative example 1, polyamine o-Juc-maleimide was used. X / 2. In comparative example 2, epoxy resin was used .... . x / z. In comparative example 3, polyamino-8-maleimide / epoxy resin was used. x / 4.-60 ° 10 min.: 20 cycles. x / 5.-65 ° 0.5 h — 25 ° 15 min — 125 ° 0.5 h —- 25 15 min: 5 cycles. 3, 5.10 6.6-10 4-10 1.4. 1.5-1SG 3.110 1.8-U
    权利要求:
    Claims (1)
    [1]
    Binder for fiberglass, including polyamino-8us-maleimide based on b "c-imide selected from the group consisting of Ν, Ν 4,4-diphenylmethane-8is-maleimide, Ν, Ν * -Μ-phenylene-Sue-male yimide and Ν, Ν * —hexamethyl en-NDS-maleimide, and a diamine selected from the group consisting of 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether and 4,4′-diaminodicyclohexane, epoxy diane or epoxy novolac resin, characterized in that, in order to increase heat resistance, it further comprises a copolymer selected from the group comprising a styrene copolymer or its a methyl derivative with maleic anhydride, an incomplete C2 ~ C ^ -alkyl ester of a styrene copolymer or its methyl derivative with maleic anhydride, a copolymer of isobutyl maleate with dimethyl styrene and a styrene copolymer of maleic anhydride with mono-H-pentyl malate, which has the following ratio:
    Polyamino-5ns-mapeimide Epoxy resin Copolymer component 100
    10-300
    5-150
    1 1169545 2
    类似技术:
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    同族专利:
    公开号 | 公开日
    DE2559417C3|1979-05-03|
    CA1056541A|1979-06-12|
    DE2559417B2|1978-09-07|
    DE2519950B2|1977-01-20|
    FR2279818B1|1977-04-15|
    JPS535920B2|1978-03-02|
    FR2279818A1|1976-02-20|
    US3985928A|1976-10-12|
    DE2519950A1|1975-12-04|
    HK31482A|1982-07-16|
    JPS50153098A|1975-12-09|
    GB1496725A|1977-12-30|
    DE2559417A1|1976-08-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP6185574A|JPS535920B2|1974-06-03|1974-06-03|
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