CN115960437A - Novel halogen-free copper-clad plate and preparation method thereof - Google Patents
Novel halogen-free copper-clad plate and preparation method thereof Download PDFInfo
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Abstract
The invention provides a halogen-free copper-clad plate which comprises, by mass, 90-110 parts of epoxy resin, 100-300 parts of phosphorus-containing amine bismaleimide curing agent, 0.5-5 parts of accelerator, 300-700 parts of solvent and 150-400 parts of inorganic filler. The halogen-free copper-clad plate with the specific formula and the specific composition, provided by the invention, contains the phosphoric amine bismaleimide curing agent with the specific structure and the specific composition, the curing agent takes amino as an active group, the nitrogen element content is high, the synergistic flame retardant effect with phosphorus is better, and the nitrogen element has better compatibility and stability on the main chain of a long-chain curing agent. Furthermore, the curing agent contains maleimide groups, so that a cured product has excellent heat resistance. The halogen-free copper-clad plate with more excellent heat resistance and comprehensive performance is obtained by matching other simple raw material formulas and a specific pressing process.
Description
Technical Field
The invention belongs to the technical field of halogen-free copper-clad plates, relates to a halogen-free copper-clad plate and a preparation method thereof, and particularly relates to a novel halogen-free copper-clad plate and a preparation method thereof.
Background
A Copper Clad Laminate (CCL) is a plate-like material, which is simply called a Copper Clad Laminate, prepared by impregnating electronic glass cloth or other reinforcing materials with resin, coating Copper foil on one or both surfaces, and hot-pressing. Various printed circuit boards with different forms and different functions are manufactured into different printed circuits by selectively carrying out the working procedures of processing, etching, drilling, copper plating and the like on a copper-clad plate. The copper clad laminate mainly plays the roles of interconnection conduction, insulation and support for the printed circuit board, and has great influence on the transmission speed, energy loss, characteristic impedance and the like of signals in a circuit, so that the performance, quality, processability in manufacturing, manufacturing level, manufacturing cost, long-term reliability and stability of the printed circuit board are greatly dependent on the copper clad laminate.
Copper-clad plates can be classified into rigid copper-clad plates and flexible copper-clad plates, wherein the rigid copper-clad plates are classified into organic resin copper-clad plates, metal-based (core) copper-clad plates and ceramic-based copper-clad plates according to insulating materials and structures thereof. The adopted insulating resin can be divided into an epoxy resin copper clad laminate, a polyester resin copper clad laminate, a cyanate ester resin copper clad laminate and the like, and the epoxy resin copper clad laminate is an important component in the copper clad laminate. The epoxy copper clad laminate is a hard copper clad laminate formed by soaking glass fiber cloth or wood pulp paper with epoxy resin, coating copper foil on one side or two sides and hot pressing, is a main base material for producing printed circuit boards in civil electric appliances, and generally has strict requirements on flame retardance.
In the conventional epoxy resin flame retardant technology, halogen compounds (tetrabromobisphenol a) are widely used for electronic materials requiring flame retardant property due to their excellent flame retardancy, but corrosive and toxic carcinogenic substances such as hydrogen bromide, tetrabromobiphenyl dioxine and tetrabromobisphenol benzofuran, etc., which are released during the combustion using halogen flame retardants, are forbidden by environmental regulations, and currently, phosphorus flame retardants are preferred in flame retardant systems in view of environmental protection.
In the prior art, phosphate esters or 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) compounds are used as phosphorus flame retardants. When the epoxy resin copper-clad plate curing agent is used comprehensively, dicyandiamide (Dicy) curing agent is needed to be added to prepare epoxy resin glue solution, so that a phosphorus-containing flame-retardant epoxy resin copper-clad plate system is obtained. And the phenolic aldehyde or modified phenolic resin is reacted with DOPO or DOPO compounds to obtain hydroxyl-containing compounds, and hydroxyl is used as an active group to react with epoxy resin during curing to obtain the reticular cross-linked resin. However, the method has influence on the comprehensive performance of the prepared epoxy resin copper-clad plate.
Therefore, how to find a more suitable flame retardant curing agent to further ensure or improve the comprehensive performance of the epoxy resin copper-clad plate has become one of the problems to be solved urgently by a plurality of front-line researchers and scientific research enterprises in the field.
Disclosure of Invention
The invention provides a halogen-free copper-clad plate and a preparation method thereof, in particular to a novel halogen-free copper-clad plate. The halogen-free copper-clad plate provided by the invention contains the specific phosphorus-containing amine heat-resistant epoxy curing agent, the amino group is used as an active group, the nitrogen element content is high, the synergistic flame-retardant effect with phosphorus is good, the compatibility and the stability are better, the heat resistance can be effectively improved, and the comprehensive performance of the epoxy resin copper-clad plate is further improved; and the preparation method is simple, mild in condition and good in controllability, and is more beneficial to industrial scale production, popularization and application.
The invention provides a halogen-free copper-clad plate which comprises the following raw materials in parts by weight:
preferably, the phosphorus-containing amine bismaleimide curing agent has a structure shown in formula (I):
wherein R is selected from
Said R is 1 Is selected from
Said R is 2 Is selected from
/>
The epoxy resin comprises one or more of bisphenol A epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin and bisphenol F epoxy resin;
the accelerator comprises one or more of 2-methylimidazole, imidazole, 2-ethyl-4-methylimidazole and 2, 4-dimethylimidazole;
the solvent comprises one or more of DMF, cyclohexanone, acetone, butanone and propylene glycol methyl ether;
the inorganic filler comprises one or more of silicon dioxide, silicon micropowder, mica powder, magnesium hydroxide, aluminum hydroxide and magnesium hydroxide;
the phosphorus amine-containing bismaleimide curing agent comprises a phosphorus amine phenolic curing agent.
Preferably, the active group of the phosphorus-containing amine bismaleimide curing agent comprises an amine group;
the phosphorus-containing amine bismaleimide curing agent comprises a bismaleimide structure;
the raw materials also comprise glass fiber cloth;
the phosphorus-containing amine bismaleimide curing agent is a curing agent for epoxy resin;
the Tg of the cured epoxy resin prepared from the phosphorus-containing amine bismaleimide curing agent is more than 200 ℃;
the raw materials do not contain other amine curing agents;
the phosphorus-containing amine bismaleimide curing agent is a phosphorus-containing amine bismaleimide curing agent with a flame retardant effect;
the flame retardant effect is specifically a nitrogen-phosphorus synergistic flame retardant effect.
Preferably, the preparation method of the phosphorus-containing amine bismaleimide curing agent comprises the following steps:
1) Mixing a DOPO organic solution, a catalyst, isocyanate and an organic solvent, and reacting to obtain an intermediate solution;
2) Reacting the intermediate solution obtained in the step with diamine again to obtain a reaction solution;
3) And carrying out reflux reaction on the reaction liquid obtained in the step and a bismaleimide compound to obtain the phosphorus-containing amine bismaleimide curing agent.
Preferably, the solvent of the DOPO organic solution comprises one or more of toluene, methyl isobutyl ketone, xylene, propylene glycol methyl ether, diethylene glycol dimethyl ether and cyclohexanone;
the catalyst comprises one or more of imidazole compounds, quaternary ammonium salt compounds and triphenylphosphine compounds;
the isocyanate comprises one or more of diphenylmethane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate and isophorone diisocyanate;
the organic solvent comprises one or more of toluene, methyl isobutyl ketone, xylene, propylene glycol methyl ether, diethylene glycol dimethyl ether and cyclohexanone;
the catalyst accounts for 0.05 to 0.2 weight percent of the total mass of the DOPO and the isocyanate;
the molar ratio of DOPO to isocyanate is (0.8-1.2): 1.
preferably, the catalyst comprises tetrabutylammonium bromide;
the reaction temperature is 150-190 ℃;
the reaction time is 2-3 h;
the mixing mode is specifically that a catalyst and isocyanate are premixed to obtain a solution, and then the DOPO organic solution is dripped into the solution for mixing;
the dripping time is 1-3 h;
the dropping temperature is 150-190 ℃;
the molar ratio of DOPO to diamine is (0.8-1.2): 1;
the diamine includes one or more of phenylenediamine, 4' -diamino-3, 3' -dimethylbiphenyl, diaminodiphenylmethane, diaminodiphenylsulfone, bisphenol A type diether diamine, and 3,3' -dimethyl-5, 5' -diethyl-4, 4' -diaminodiphenylmethane.
Preferably, the temperature of the secondary reaction is 110-130 ℃;
the secondary reaction time is 4-6 h;
the molar ratio of the DOPO to the bismaleimide compound is (0.8-1.2): 1;
the bismaleimide compound comprises one or more of DDM modified bismaleimide, DDS modified bismaleimide, 4' -diamino-3, 3' -dimethyl biphenyl modified bismaleimide, 3' -dimethyl-5, 5' -diethyl-4, 4' -diaminodiphenylmethane modified bismaleimide and bisphenol A type diether diamine modified bismaleimide;
the temperature of the reflux reaction is 110-140 ℃;
the time of the reflux reaction is 1 to 4 hours;
and heating to remove the solvent and/or dissolving after the reflux reaction.
The invention provides a preparation method of a halogen-free copper-clad plate, which comprises the following steps:
a) Mixing epoxy resin, a phosphorus-containing amine bismaleimide curing agent, an accelerator and a solvent, adding an inorganic filler, and continuously mixing to obtain a glue solution;
b) Soaking glass fiber cloth in the glue solution obtained in the step, and drying to obtain a prepreg;
c) And (3) laminating the prepregs obtained in the step, laminating the prepregs with copper foil, and pressing to obtain the halogen-free copper-clad plate.
Preferably, the rotating speed of the mixing is 400-1000 r/min;
the rotating speed of the continuous mixing is 400-1000 r/min;
the time for continuously mixing is 1-4 h;
the drying temperature is 100-250 ℃.
Preferably, the pressing pressure is 20 to 30kg/cm 2 ；
The pressing is gradient pressing;
the first gradient of the gradient pressing is that the temperature is increased to 220 ℃ from 85 ℃, and the time of the first gradient is 30min;
the heat preservation temperature of the second gradient of the gradient pressing is 220 ℃, and the heat preservation time of the second gradient is 120min;
the third gradient of the gradient pressing is that the temperature is reduced to 130 ℃ at 220 ℃, and the time of the third gradient is 30min.
The invention provides a halogen-free copper-clad plate which comprises, by mass, 90-110 parts of epoxy resin, 100-300 parts of phosphorus-containing amine bismaleimide curing agent, 0.5-5 parts of accelerator, 300-700 parts of solvent and 150-400 parts of inorganic filler. Compared with the prior art, the invention is based on the problem that the conventional epoxy resin halogen-free copper-clad plate adopts a phosphorus flame-retardant curing agent to influence the comprehensive performance of an epoxy resin system, researches show that although the flame-retardant effect is improved by adopting the synergistic effect of nitrogen and phosphorus, the comprehensive performance of the epoxy resin system can be ensured and improved, for example, dicy and the like are added, and then, in patent CN103755925, a phosphorus-containing phenolic curing agent is obtained by reacting phenolic resin after etherification with DOPO, and nitrogen-containing additives such as melamine or acetoguanamine and the like are added in the reaction process, so that nitrogen elements are introduced. However, the invention considers that the introduction mode of additionally adding the nitrogen-containing compound has the problems of complicated process, limited addition amount of the addition mode, low nitrogen element proportion and limited improvement of comprehensive effect, and the small-molecule nitrogen-containing compound also has defects in the aspects of compatibility, stability and the like.
Based on the above, the invention especially designs a halogen-free copper-clad plate with a specific formula and composition, wherein the halogen-free copper-clad plate contains a phosphorus-containing amine bismaleimide curing agent with a specific structure and composition, and the halogen-free copper-clad plate is a novel long-chain phosphorus-containing amine bismaleimide epoxy curing agent. The synthetic curing agent takes amido as an active group, has high nitrogen content, has better flame retardant effect with phosphorus, has better compatibility and stability because the nitrogen is in the main chain of the long-chain curing agent, and simultaneously contains maleimide group, so that a cured substance has excellent heat resistance, the comprehensive properties such as the heat resistance of the epoxy resin during application are further improved, and the halogen-free copper-clad plate with excellent flame retardant property and comprehensive property is obtained.
The novel phosphorus-amine-containing bismaleimide resin is used as an epoxy resin curing agent, the halogen-free flame-retardant copper-clad plate material is obtained on the premise of simplifying a resin formula, and the comprehensive performance, particularly the heat resistance, of the copper-clad plate is further improved on the basis of ensuring the excellent flame-retardant effect of the conventional flame-retardant copper-clad plate formula.
The invention makes DOPO combine in resin more easily by reacting isocyanate as initial raw material with DOPO to obtain phosphorus-containing aldehyde compound, then reacts with diamine to obtain phosphorus-containing amine curing agent, and then reacts with modified bismaleimide again to obtain heat-resistant curing agent containing phosphorus amine and modified bismaleimide groups. According to the invention, the heat-resistant epoxy curing agent containing phosphorus amine, which has excellent heat resistance and takes amino as an active group, is obtained by introducing nitrogen element with the assistance of isocyanato after the reaction of DOPO and isocyanate and further introducing a bismaleimide structure. The invention changes the prior phosphorus-containing curing agent that all hydroxyl groups are used as active groups, but amino groups are introduced as epoxy curing groups; the curing agent phosphorus is not easy to separate out and has excellent compatibility with epoxy resin; meanwhile, the curing agent contains amino, no amine curing agent needs to be additionally added when the curing agent is cured with epoxy resin, and the nitrogen element is fixed on the long chain, so that the curing agent is more stable and has better compatibility. Furthermore, the curing agent contains maleimide groups, so that a cured product has excellent heat resistance. The invention improves the proportion of nitrogen element in nitrogen and phosphorus curing agent, has better nitrogen and phosphorus synergistic effect in flame retardance, better realizes the nitrogen and phosphorus blending flame retardant effect of an epoxy curing system, and more importantly, the prepared halogen-free flame retardant copper-clad plate has excellent performances in the main performances of soldering resistance, glass transition temperature, peeling strength, thermal weight loss and the like, especially heat resistance and higher glass transition temperature.
The phosphorus-containing amine bismaleimide heat-resistant epoxy curing agent provided by the invention takes amino as an active group, has high nitrogen content and good synergistic flame-retardant effect with phosphorus, and the prepared halogen-free flame-retardant copper-clad plate remarkably improves the heat-resistant performance of the system and has excellent comprehensive performances such as soldering tin resistance, peel strength, thermal weight loss and the like; meanwhile, the preparation method is simple, mild in condition and good in controllability, and is more beneficial to industrial scale production, popularization and application. The novel halogen-free copper-clad plate provided by the invention directly uses the phosphorus-containing amine curing agent, simplifies the formula of the resin glue solution, and is matched with other simple raw material formulas and a specific pressing process, so that the halogen-free copper-clad plate with more excellent flame retardant property and comprehensive property is obtained.
Experimental results show that the halogen-free flame-retardant copper-clad plate adopting the phosphorus-containing amine bismaleimide heat-resistant epoxy curing agent has the flame-retardant effect reaching UL-94V-0 level, and the main performances of the plate, such as soldering resistance, peeling strength, thermal weight loss and the like, reach or exceed the level of products sold in the market, particularly the glass transition temperature T g ≥210℃。
Detailed Description
In order to further understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All raw materials of the invention are not particularly limited in purity, and the invention preferably adopts the purity of the conventional raw materials in the field of analytical purification or copper-clad plate preparation.
The invention provides a halogen-free copper-clad plate which comprises the following raw materials in parts by weight:
in the present invention, the epoxy resin may be added in an amount of 90 to 110 parts by weight, 94 to 106 parts by weight, and preferably 98 to 102 parts by weight.
In the present invention, the amount of the phosphoric amine bismaleimide curing agent added is 100 to 300 parts by weight, and may be 140 to 260 parts by weight, and preferably 180 to 220 parts by weight.
In the present invention, the amount of the accelerator added is 0.5 to 5 parts by weight, and may be 1.5 to 4 parts by weight, and preferably 2.5 to 3 parts by weight.
In the present invention, the solvent may be added in an amount of 300 to 700 parts by weight, 350 to 650 parts by weight, preferably 400 to 600 parts by weight, and more preferably 450 to 550 parts by weight.
In the present invention, the inorganic filler may be added in an amount of 150 to 400 parts by weight, 200 to 350 parts by weight, and preferably 250 to 300 parts by weight.
In the present invention, the molar ratio of active hydrogen (hydrogen atom bonded to N) to epoxy group in the phosphorus-containing amine bismaleimide curing agent is preferably (0.95 to 1.2): 1, more preferably (1.00 to 1.15): 1, more preferably (1.05 to 1.10): 1.
in the present invention, the amount of the accelerator is preferably 0.05wt% to 0.2wt%, more preferably 0.07wt% to 0.18wt%, and still more preferably 0.1wt% to 0.15wt% of the total weight of the resin system.
In the present invention, the mass ratio of the inorganic filler to the resin system is preferably (0.2 to 0.4): 1, more preferably (0.23 to 0.38): 1, more preferably (0.25 to 0.35): 1.
in the present invention, the solvent is preferably used in an amount such that the solid content of the raw material slurry is between 55% and 65%, more preferably between 57% and 63%, and still more preferably between 59% and 61%.
In the invention, the resin system preferably comprises epoxy resin, auxiliaries (curing agent and accelerator) and filler, does not comprise solvent, does not comprise fiber relative to the final epoxy resin copper-clad plate, and is the sum of the resin system and the solvent.
In the present invention, the epoxy resin preferably includes one or more of bisphenol a type epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, and bisphenol F epoxy resin, and more preferably bisphenol a type epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, or bisphenol F epoxy resin. Specifically, the epoxy resin of the present invention may be a novolac epoxy resin.
In the present invention, the accelerator preferably includes one or more of 2-methylimidazole, imidazole, 2-ethyl-4-methylimidazole and 2, 4-dimethylimidazole, and more preferably 2-methylimidazole, imidazole, 2-ethyl-4-methylimidazole or 2, 4-dimethylimidazole.
In the present invention, the solvent preferably includes one or more of DMF, cyclohexanone, acetone, butanone, and propylene glycol methyl ether, more preferably DMF, cyclohexanone, acetone, butanone, or propylene glycol methyl ether.
In the present invention, the inorganic filler preferably includes one or more of silica, fine silica powder, mica powder, magnesium hydroxide, aluminum hydroxide, and magnesium hydroxide, and more preferably silica, fine silica powder, mica powder, magnesium hydroxide, aluminum hydroxide, or magnesium hydroxide.
In the present invention, the phosphorus amine-containing bismaleimide curing agent preferably comprises a phosphorus amine-containing phenolic curing agent.
In the present invention, the reactive group of the phosphoric amine-containing bismaleimide curing agent preferably includes an amine group.
In the present invention, the raw material preferably further includes a glass fiber cloth.
In the present invention, the phosphoric amine-containing bismaleimide curing agent preferably comprises a bismaleimide structure.
In the present invention, the phosphoric amine-containing bismaleimide curing agent is preferably a curing agent for epoxy resin.
In the present invention, the raw materials preferably do not contain other amine-based curing agents.
In the present invention, the Tg of the cured epoxy resin prepared from the phosphorus amine-containing bismaleimide curing agent is preferably greater than 200 ℃, more preferably greater than 210 ℃, and more preferably greater than 220 ℃.
In the present invention, the phosphoric amine-containing bismaleimide curing agent is preferably a phosphoric amine-containing bismaleimide curing agent having a flame retardant effect.
In the invention, the flame retardant effect is particularly preferably a nitrogen-phosphorus synergistic flame retardant effect.
In the present invention, the curing agent preferably has a structure represented by formula (I):
wherein R is selected from
Said R is 1 Is selected from
/>
The R is 2 Is selected from
In the present invention, the preparation method of the phosphoric amine bismaleimide curing agent preferably comprises the following steps:
1) Mixing a DOPO organic solution, a catalyst, isocyanate and an organic solvent, and reacting to obtain an intermediate solution;
2) Reacting the intermediate solution obtained in the step with diamine again to obtain a reaction solution;
3) And carrying out reflux reaction on the reaction liquid obtained in the step and a bismaleimide compound to obtain the phosphorus-containing amine curing agent.
The DOPO organic solution, the catalyst, the isocyanate and the organic solvent are mixed and then react to obtain the intermediate solution.
In the present invention, the solvent of the DOPO organic solution preferably includes one or more of toluene, methyl isobutyl ketone, xylene, propylene glycol methyl ether, diethylene glycol dimethyl ether and cyclohexanone, and more preferably toluene, methyl isobutyl ketone, xylene, propylene glycol methyl ether, diethylene glycol dimethyl ether or cyclohexanone.
In the present invention, the catalyst preferably includes one or more of imidazole compounds, quaternary ammonium salt compounds and triphenylphosphine compounds, and more preferably imidazole compounds, quaternary ammonium salt compounds or triphenylphosphine compounds.
In the present invention, the isocyanate preferably includes one or more of diphenylmethane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and isophorone diisocyanate, and more preferably diphenylmethane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, or isophorone diisocyanate.
In the present invention, the organic solvent preferably includes one or more of toluene, methyl isobutyl ketone, xylene, propylene glycol methyl ether, diethylene glycol dimethyl ether and cyclohexanone, and more preferably toluene, methyl isobutyl ketone, xylene, propylene glycol methyl ether, diethylene glycol dimethyl ether or cyclohexanone.
In the present invention, the proportion of the catalyst to the total mass of the DOPO and the isocyanate is preferably 0.05 to 0.2wt%, more preferably 0.08 to 0.17wt%, and still more preferably 0.11 to 0.14wt%.
In the present invention, the molar ratio of DOPO to isocyanate is preferably (0.8 to 1.2): 1, more preferably (0.85 to 1.15): 1, more preferably (0.9 to 1.1): 1, more preferably (0.95 to 1.05): 1.
in the present invention, the reaction temperature is preferably 150 to 190 ℃, more preferably 155 to 185 ℃, more preferably 160 to 180 ℃, and more preferably 165 to 175 ℃, so that the self-polymerization of isocyanate is more preferably inhibited.
In the present invention, the reaction time is preferably 2 to 3 hours, more preferably 2.2 to 2.8 hours, and still more preferably 2.4 to 2.6 hours.
In the present invention, the mixing mode is specifically preferably that the catalyst and the isocyanate are premixed to obtain a solution, and then the DOPO organic solution is added dropwise to the solution to mix.
In the present invention, the dropping time is preferably 1 to 3 hours, more preferably 1.4 to 2.6 hours, and still more preferably 1.8 to 2.2 hours.
In the present invention, the dropping is preferably performed at the reaction temperature. That is, the temperature for the dropwise addition is preferably 150 to 190 ℃, more preferably 155 to 185 ℃, more preferably 160 to 180 ℃, and more preferably 165 to 175 ℃.
The invention further reacts the intermediate solution obtained in the step with diamine to obtain reaction liquid.
In the present invention, the diamine preferably includes one or more of phenylenediamine, 4 '-diamino-3, 3' -dimethylbiphenyl, diaminodiphenylmethane, diaminodiphenylsulfone, bisphenol a type diether diamine, and 3,3 '-dimethyl-5, 5' -diethyl-4, 4 '-diaminodiphenylmethane, and more preferably phenylenediamine, 4' -diamino-3, 3 '-dimethylbiphenyl, diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), bisphenol a type diether diamine, or 3,3' -dimethyl-5, 5 '-diethyl-4, 4' -diaminodiphenylmethane.
In the present invention, the molar ratio of DOPO to diamine is preferably (0.8 to 1.2): 1, more preferably (0.85 to 1.15): 1, more preferably (0.9 to 1.1): 1, more preferably (0.95 to 1.05): 1.
in the present invention, the temperature of the re-reaction is preferably 110 to 130 ℃, more preferably 115 to 125 ℃, and still more preferably 119 to 121 ℃.
In the present invention, the time for the re-reaction is preferably 4 to 6 hours, more preferably 4.4 to 5.6 hours, and still more preferably 4.8 to 5.2 hours.
Finally, carrying out reflux reaction on the reaction liquid obtained in the step and a bismaleimide compound to obtain the phosphorus-containing amine curing agent.
In the present invention, the molar ratio of DOPO to bismaleimide compound is preferably (0.8 to 1.2): 1, more preferably (0.85 to 1.15): 1, more preferably (0.9 to 1.1): 1, more preferably (0.95 to 1.05): 1.1
In the present invention, the bismaleimide-based compound preferably includes one or more of DDM-modified bismaleimide (DDM-BMI), DDS-modified bismaleimide (DDS-BMI), 4 '-diamino-3, 3' -dimethylbiphenyl-modified bismaleimide, 3 '-dimethyl-5, 5' -diethyl-4, 4 '-diaminodiphenylmethane-modified bismaleimide, and bisphenol a-type diether diamine-modified bismaleimide, and more preferably, DDM-modified bismaleimide, DDS-modified bismaleimide, 4' -diamino-3, 3 '-dimethylbiphenyl-modified bismaleimide, 3' -dimethyl-5, 5 '-diethyl-4, 4' -diaminodiphenylmethane-modified bismaleimide, or bisphenol a-type diether diamine-modified bismaleimide.
In the present invention, the temperature of the reflux reaction is preferably 110 to 140 ℃, more preferably 115 to 135 ℃, and more preferably 120 to 130 ℃.
In the present invention, the time of the reflux reaction is preferably 1 to 4 hours, more preferably 1.5 to 3.5 hours, and still more preferably 2 to 3 hours.
In the present invention, the reflux reaction preferably further comprises a temperature-raising solvent-removing and/or dissolving step, and more preferably a temperature-raising solvent-removing or dissolving step.
The invention is a complete and detailed integral technical scheme, further ensures the structure and the composition of the phosphorus-containing amine curing agent, better improves the flame retardant property, the curing effect and the system stability of the phosphorus-containing amine curing agent, and better improves the comprehensive properties such as the heat resistance and the like of a subsequent epoxy resin system, and the phosphorus-containing amine curing agent and the preparation method thereof preferably comprise the following contents:
the novel phosphorus-containing amine phenolic curing agent synthesized by the invention has an amino active group and contains a bismaleimide structure.
1. DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) reacts with isocyanate to give DOPO-R-CHO.
The DOPO/toluene solution is dropped into the isocyanate (or isocyanate solution) containing the catalyst at a certain temperature.
Specifically, the isocyanate includes, but is not limited to, diphenylmethane diisocyanate (MDI), toluene Diisocyanate (TDI), naphthalene Diisocyanate (NDI), hexamethylene Diisocyanate (HDI), m-xylylene isocyanate (XDI), isophorone diisocyanate (IPDI), preferably MDI.
Specifically, the catalyst commonly comprises imidazoles, quaternary ammonium salts and triphenylphosphine compounds, and preferably quaternary ammonium salt compounds, namely tetrabutylammonium bromide.
The reaction formula of the above steps is shown as follows:
2. DOPO-R-CHO reacts with diamine to synthesize the amine curing agent containing phosphorus.
Specifically, the diamine includes, but is not limited to, phenylenediamine, 4' -diamino-3, 3' -dimethylbiphenyl, diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), bisphenol a type diether diamine, and 3,3' -dimethyl-5, 5' -diethyl-4, 4' -diaminodiphenylmethane, and more preferably 4,4' -diamino-3, 3' -dimethylbiphenyl. Among them, amines having a methyl group or an ethyl group in the benzene ring contribute to improvement of dielectric properties of the resin. .
The reaction formula of the above step is shown as follows:
3. the Bismaleimide (BMI) is introduced, and the bismaleimide structure can further improve the glass transition temperature of a cured resin and improve the heat resistance of the plate. The bismaleimide can be DDM-BMI, DDS-BMI and other bismaleimide compounds containing benzene rings or heterocyclic rings.
The reaction formula of the above steps is shown as follows:
the specially designed diamine-containing epoxy curing agent with a specific structure and composition is a novel diamine-containing epoxy curing agent, the diamine-containing epoxy curing agent takes an amine group as an active group, has high nitrogen content and better flame retardant effect in cooperation with phosphorus, has better compatibility and stability due to the fact that the nitrogen is in the main chain of a long-chain curing agent, and contains a maleimide group, so that a cured product has excellent heat resistance, the comprehensive performance of an epoxy resin halogen-free copper-clad plate is further improved, the problem that the existing copper-clad plate has the effects of halogen-free flame retardant effect and high Tg (glass transition temperature) is effectively solved, and the special epoxy resin containing a high heat-resistant group is usually matched with the phosphorus-containing curing agent for use.
According to the invention, nitrogen is introduced through the assistance of isocyanic acid radicals after the reaction of DOPO and isocyanate, and a bismaleimide structure is further introduced, so that the phosphorus-containing amine heat-resistant epoxy curing agent with excellent heat resistance and taking an amino group as an active group is obtained. The invention changes the prior phosphorus-containing curing agent that all hydroxyl groups are used as active groups, but amino groups are introduced as epoxy curing groups; the curing agent phosphorus is not easy to separate out and has excellent compatibility with epoxy resin; meanwhile, the curing agent contains amino, so that an amine curing agent is not required to be additionally added when the curing agent is cured with epoxy resin, and the nitrogen element is fixed on the long chain, so that the curing agent is more stable and has better compatibility. Furthermore, the compound contains bismaleimide groups, so that a cured product has excellent heat resistance. The invention improves the proportion of nitrogen element in nitrogen and phosphorus curing agent, has better nitrogen and phosphorus synergistic effect in flame retardance, better realizes the nitrogen and phosphorus blending flame retardant effect of the epoxy resin halogen-free copper-clad plate, and more importantly, the prepared epoxy resin halogen-free copper-clad plate has excellent performances in the main performances of soldering resistance, peeling strength, thermal weight loss and the like, especially heat resistance and higher glass transition temperature.
The invention provides a preparation method of a halogen-free copper-clad plate, which comprises the following steps:
a) Mixing epoxy resin, a phosphorus-containing amine bismaleimide curing agent, an accelerator and a solvent, adding an inorganic filler, and continuously mixing to obtain a glue solution;
b) Soaking glass fiber cloth in the glue solution obtained in the step, and drying to obtain a prepreg;
c) And (3) laminating the prepregs obtained in the step, laminating the prepregs with copper foil, and pressing to obtain the halogen-free copper-clad plate.
The invention firstly mixes the epoxy resin, the phosphoric amine bismaleimide curing agent, the accelerant and the solvent, then adds the inorganic filler and continuously mixes to obtain the glue solution.
In the present invention, the rotation speed of the mixing is preferably 400 to 1000 rpm, more preferably 500 to 900 rpm, and still more preferably 600 to 800 rpm.
In the present invention, the rotation speed of the continuous mixing is preferably 400 to 1000 rpm, more preferably 500 to 900 rpm, and still more preferably 600 to 800 rpm.
In the present invention, the time for the continuous mixing is preferably 1 to 4 hours, more preferably 1.5 to 3.5 hours, and still more preferably 2 to 3 hours.
And then, soaking the glass fiber cloth in the glue solution obtained in the step, and drying to obtain the prepreg.
In the present invention, the temperature for drying is preferably 100 to 250 ℃, more preferably 130 to 220 ℃, and more preferably 160 to 190 ℃.
And finally, laminating the prepregs obtained in the step, laminating the prepregs with copper foil, and pressing to obtain the halogen-free copper-clad plate.
In the present invention, the pressure of the pressing is preferably 20 to 30kg/cm 2 More preferably 22 to 28kg/cm 2 More preferably 24 to 26kg/cm 2 。
In the present invention, the pressing is preferably gradient pressing.
In the present invention, the first gradient of the gradient pressing is preferably increased from 85 ℃ to 220 ℃, and the time of the first gradient is preferably 30min.
In the present invention, the holding temperature of the second gradient of the gradient compaction is preferably 220 ℃, and the holding time of the second gradient is preferably 120min.
In the present invention, the third gradient of the gradient pressing is preferably cooled to 130 ℃ from 220 ℃, and the time of the third gradient is preferably 30min.
The invention is a complete and refined integral technical scheme, further ensures the flame retardant property, the curing effect and the system stability of the phosphoric amine bismaleimide curing agent, and better improves the flame retardant property, the stability and the heat resistance of the copper-clad plate, and the preparation method of the novel halogen-free copper-clad plate preferably comprises the following steps:
the epoxy resin, the novel phosphorus-containing amine bismaleimide curing agent, the accelerator and the solvent are stirred at a high speed at a rotating speed of 400-1000 rpm to be dissolved, and then the inorganic filler is added to continue stirring for 2 hours. And soaking the glass fiber cloth in the glue solution, and drying at 100-250 ℃ to obtain the prepreg. And (5) cutting the prepreg, and overlapping 8 prepregs with the copper foil for pressing.
The pressing conditions are as follows: the pressure is 25kg/cm 2 The temperature rise program is 85 ℃→ 220 → 220 ℃→ 130 ℃, the temperature rise time is 30min,120min,30min.
The invention provides a novel halogen-free copper-clad plate and a preparation method thereof, the halogen-free copper-clad plate with a specific formula and a specific composition contains a phosphoric amine bismaleimide curing agent with a specific structure and a specific composition, and the novel long-chain phosphoric amine bismaleimide epoxy curing agent is a novel long-chain phosphoric amine bismaleimide epoxy curing agent. The synthetic curing agent takes amido as an active group, has high nitrogen content, has better flame retardant effect with phosphorus, has better compatibility and stability because the nitrogen is in the main chain of the long-chain curing agent, and simultaneously contains maleimide group, so that a cured substance has excellent heat resistance, the comprehensive properties such as the heat resistance of the epoxy resin during application are further improved, and the halogen-free copper-clad plate with excellent flame retardant property and comprehensive property is obtained.
The novel phosphorus-amine-containing bismaleimide resin is used as an epoxy resin curing agent, the halogen-free flame-retardant copper-clad plate material is obtained on the premise of simplifying a resin formula, and the comprehensive performance, particularly the heat resistance, of the copper-clad plate is further improved on the basis of ensuring the excellent flame-retardant effect of the conventional flame-retardant copper-clad plate formula.
The invention makes DOPO easier to combine in resin by using isocyanate as an initial raw material to react with DOPO so as to obtain a phosphorus-containing aldehyde compound, then the phosphorus-containing aldehyde compound reacts with diamine so as to obtain a phosphorus-containing amine curing agent, and then the phosphorus-containing amine curing agent reacts with modified bismaleimide again so as to obtain a heat-resistant curing agent containing phosphorus amine and modified bismaleimide groups. According to the invention, the heat-resistant epoxy curing agent containing phosphorus amine, which has excellent heat resistance and takes amino as an active group, is obtained by introducing nitrogen element with the assistance of isocyanato after the reaction of DOPO and isocyanate and further introducing a bismaleimide structure. The invention changes the prior phosphorus-containing curing agent that all hydroxyl groups are used as active groups, but amino groups are introduced as epoxy curing groups; the curing agent phosphorus is not easy to separate out and has excellent compatibility with epoxy resin; meanwhile, the curing agent contains amino, so that an amine curing agent is not required to be additionally added when the curing agent is cured with epoxy resin, and the nitrogen element is fixed on the long chain, so that the curing agent is more stable and has better compatibility. Furthermore, the curing agent contains maleimide groups, so that a cured product has excellent heat resistance. The invention improves the proportion of nitrogen element in nitrogen and phosphorus curing agent, has better nitrogen and phosphorus synergistic effect in flame retardance, better realizes the nitrogen and phosphorus blending flame retardant effect of an epoxy curing system, and more importantly, the prepared halogen-free flame retardant copper-clad plate has excellent performances in the main performances of soldering resistance, glass transition temperature, peeling strength, thermal weight loss and the like, especially heat resistance and higher glass transition temperature.
The phosphorus-containing amine bismaleimide heat-resistant epoxy curing agent provided by the invention takes amino as an active group, has high nitrogen content and good synergistic flame-retardant effect with phosphorus, and the prepared halogen-free flame-retardant copper-clad plate remarkably improves the heat-resistant performance of the system and has excellent comprehensive performances such as soldering tin resistance, peel strength, thermal weight loss and the like; meanwhile, the preparation method is simple, mild in condition and good in controllability, and is more beneficial to industrial scale production, popularization and application. The novel halogen-free copper-clad plate provided by the invention directly uses the phosphorus-containing amine curing agent, simplifies the formula of the resin glue solution, and is matched with other simple raw material formulas and a specific pressing process, so that the halogen-free copper-clad plate with more excellent flame retardant property and comprehensive property is obtained.
Experimental results show that the halogen-free flame-retardant copper-clad plate adopting the phosphorus-containing amine bismaleimide heat-resistant epoxy curing agent has the flame-retardant effect reaching UL-94V-0 level, and the main performances of the plate, such as soldering resistance, peeling strength, thermal weight loss and the like, reach or exceed the level of products sold in the market, particularly the glass transition temperature T g ≥210℃。
For further illustration of the present invention, the following will describe in detail a halogen-free copper-clad plate and a preparation method thereof provided by the present invention with reference to examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, which are only for further illustration of the features and advantages of the present invention, but not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Examples
The epoxy resin, the phosphorus-containing amine bismaleimide curing agent, the accelerator and the solvent are stirred at a high speed at a rotating speed of 400-1000 rpm to be dissolved, and then the inorganic filler is added to continue stirring for 2 hours. And soaking the glass fiber cloth in the glue solution, and drying at 100-250 ℃ to obtain the prepreg. And after the prepreg is cut, one group of 8 prepregs are superposed with copper foil for pressing.
The pressing conditions were: the pressure is 25kg/cm 2 The temperature rise program is 85 ℃→ 220 → 220 ℃→ 130 ℃, the temperature rise time is 30min,120min,30min.
And (3) blending the resin glue solution according to the proportion in the table 1 to finally obtain the copper clad plate material and testing the performance. Wherein the halogen-free curing agent of the comparison group is an XZ-92741 product produced by Dow.
The structure of the curing agent used in the examples is as follows:
referring to table 1, table 1 shows the formula of copper clad plate material prepared in the examples and comparative examples of the present invention, the process parameters and the performance test results.
TABLE 1
As can be seen from Table 1, the diamine-containing curing agent synthesized by the method of the present invention has excellent flame retardancy as well as the commercial phosphorus-containing curing agent, and can reach UL-94V-0 grade. And the Tg of the solidified phosphorus-containing amine phenolic curing agent containing the bismaleimide structure is far higher than that of a conventional high-Tg product, so that the heat resistance of the copper-clad plate can be improved to a great extent.
1. Gel time: 0.2mg of the prepreg powder was weighed and placed on a hot plate at =170 ℃, and the time required for gelation was recorded.
2. Interlayer bonding force: according to IPC-TM-650-2.4.8C method.
3. Thermal weight loss Td5%: the TGA test was used, and the determination was made according to the TGA test method as defined in IPC-TM-650.4.24.6.
Solder tin resistance and heat resistance at 4.288 ℃ (2 hours via PCT pressure cooker)
The testing method comprises immersing the pressure cooker test piece in a solder tin furnace at 288 deg.C, and recording the time required for explosion and delamination of the test piece; the evaluation was concluded when the substrate had not blistered or delaminated in the tin oven for more than 5 minutes.
5. Glass transition Temperature (Temperature of glass transition) test:
a Differential scanning thermal analyzer (DSC) was used, and the temperature increase rate was 20 ℃/min.
6. And (3) testing the flame retardance:
the specimens were tested for flame retardancy according to the UL-94 standard method.
The above detailed description of the novel halogen-free copper-clad plate and the method for manufacturing the same according to the present invention is provided, and the principle and the embodiment of the present invention are illustrated herein by using specific examples, which are only used to help understand the method of the present invention and the core idea thereof, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any device or system, and implementing any combined method. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The halogen-free copper-clad plate is characterized by comprising the following raw materials in parts by weight:
2. the halogen-free copper-clad plate according to claim 1, wherein the phosphorus-containing amine bismaleimide curing agent has a structure shown in formula (I):
wherein R is selected from
The R is 1 Is selected from
The R is 2 Is selected from
/>
The epoxy resin comprises one or more of bisphenol A epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin and bisphenol F epoxy resin;
the accelerator comprises one or more of 2-methylimidazole, imidazole, 2-ethyl-4-methylimidazole and 2, 4-dimethylimidazole;
the solvent comprises one or more of DMF, cyclohexanone, acetone, butanone and propylene glycol methyl ether;
the inorganic filler comprises one or more of silicon dioxide, silicon micropowder, mica powder, magnesium hydroxide, aluminum hydroxide and magnesium hydroxide;
the phosphorus amine-containing bismaleimide curing agent comprises a phosphorus amine phenolic curing agent.
3. The halogen-free copper-clad plate according to claim 1, wherein the active group of the phosphorus-containing amine bismaleimide curing agent comprises an amine group;
the phosphorus-containing amine bismaleimide curing agent comprises a bismaleimide structure;
the raw materials also comprise glass fiber cloth;
the phosphorus-containing amine bismaleimide curing agent is a curing agent for epoxy resin;
the Tg of the cured epoxy resin prepared from the phosphorus-containing amine bismaleimide curing agent is more than 200 ℃;
the raw materials do not contain other amine curing agents;
the phosphorus-containing amine bismaleimide curing agent is a phosphorus-containing amine bismaleimide curing agent with a flame retardant effect;
the flame retardant effect is specifically a nitrogen-phosphorus synergistic flame retardant effect.
4. The halogen-free copper-clad plate according to claim 1, wherein the preparation method of the phosphorus-containing amine bismaleimide curing agent comprises the following steps:
1) Mixing a DOPO organic solution, a catalyst, isocyanate and an organic solvent, and reacting to obtain an intermediate solution;
2) Reacting the intermediate solution obtained in the step with diamine again to obtain a reaction solution;
3) And carrying out reflux reaction on the reaction liquid obtained in the step and a bismaleimide compound to obtain the phosphorus-containing amine bismaleimide curing agent.
5. The method according to claim 4, wherein the solvent of the DOPO organic solution comprises one or more of toluene, methyl isobutyl ketone, xylene, propylene glycol methyl ether, diethylene glycol dimethyl ether and cyclohexanone;
the catalyst comprises one or more of imidazole compounds, quaternary ammonium salt compounds and triphenylphosphine compounds;
the isocyanate comprises one or more of diphenylmethane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate and isophorone diisocyanate;
the organic solvent comprises one or more of toluene, methyl isobutyl ketone, xylene, propylene glycol methyl ether, diethylene glycol dimethyl ether and cyclohexanone;
the catalyst accounts for 0.05 to 0.2 weight percent of the total mass of the DOPO and the isocyanate;
the molar ratio of DOPO to isocyanate is (0.8-1.2): 1.
6. the method of claim 4, wherein the catalyst comprises tetrabutylammonium bromide;
the reaction temperature is 150-190 ℃;
the reaction time is 2-3 h;
the mixing mode is specifically that a catalyst and isocyanate are premixed to obtain a solution, and then the DOPO organic solution is dripped into the solution for mixing;
the dripping time is 1-3 h;
the dropping temperature is 150-190 ℃;
the molar ratio of DOPO to diamine is (0.8-1.2): 1;
the diamine includes one or more of phenylenediamine, 4' -diamino-3, 3' -dimethylbiphenyl, diaminodiphenylmethane, diaminodiphenylsulfone, bisphenol A type diether diamine, and 3,3' -dimethyl-5, 5' -diethyl-4, 4' -diaminodiphenylmethane.
7. The method according to claim 4, wherein the temperature of the secondary reaction is 110 to 130 ℃;
the secondary reaction time is 4-6 h;
the molar ratio of the DOPO to the bismaleimide compound is (0.8-1.2): 1;
the bismaleimide compound comprises one or more of DDM modified bismaleimide, DDS modified bismaleimide, 4' -diamino-3, 3' -dimethyl biphenyl modified bismaleimide, 3' -dimethyl-5, 5' -diethyl-4, 4' -diaminodiphenylmethane modified bismaleimide and bisphenol A type diether diamine modified bismaleimide;
the temperature of the reflux reaction is 110-140 ℃;
the time of the reflux reaction is 1 to 4 hours;
and heating to remove the solvent and/or dissolving after the reflux reaction.
8. The preparation method of the halogen-free copper-clad plate is characterized by comprising the following steps:
a) Mixing epoxy resin, a phosphorus-containing amine bismaleimide curing agent, an accelerator and a solvent, adding an inorganic filler, and continuously mixing to obtain a glue solution;
b) Soaking glass fiber cloth in the glue solution obtained in the step, and drying to obtain a prepreg;
c) And (3) laminating the prepregs obtained in the step, laminating the prepregs with copper foil, and pressing to obtain the halogen-free copper-clad plate.
9. The method of claim 8, wherein the mixing is performed at a speed of 400 to 1000 rpm;
the rotating speed of the continuous mixing is 400-1000 r/min;
the time for continuously mixing is 1-4 h;
the drying temperature is 100-250 ℃.
10. The method according to claim 8, wherein the pressure for pressing is 20 to 30kg/cm 2 ；
The pressing is gradient pressing;
the first gradient of the gradient pressing is that the temperature is increased to 220 ℃ from 85 ℃, and the time of the first gradient is 30min;
the heat preservation temperature of the second gradient of the gradient pressing is 220 ℃, and the heat preservation time of the second gradient is 120min;
the third gradient of the gradient pressing is that the temperature is reduced to 130 ℃ at 220 ℃, and the time of the third gradient is 30min.
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