CN114015330B - Halogen-free phosphorus-free flame-retardant epoxy powder composition and preparation method thereof - Google Patents
Halogen-free phosphorus-free flame-retardant epoxy powder composition and preparation method thereof Download PDFInfo
- Publication number
- CN114015330B CN114015330B CN202210007411.8A CN202210007411A CN114015330B CN 114015330 B CN114015330 B CN 114015330B CN 202210007411 A CN202210007411 A CN 202210007411A CN 114015330 B CN114015330 B CN 114015330B
- Authority
- CN
- China
- Prior art keywords
- parts
- epoxy resin
- flame retardant
- composition
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a halogen-free phosphorus-free flame-retardant epoxy powder composition, which comprises the following components in parts by weight: 20-30 parts of epoxy resin; 5-15 parts of organic silicon modified epoxy resin; 3-10 parts of multifunctional epoxy resin; 14-60 parts of toughening modified epoxy resin; 3-15 parts of a curing agent; 0.01-1 part of an accelerator; 10-20 parts of a filler; 25-45 parts of an inorganic flame retardant; 5-15 parts of a nitrogen-containing flame retardant; 5-15 parts of zinc stannate flame retardant; 1-5 parts of pigment; 0.5-2 parts of a leveling agent; 0.1 to 1.0 portion of thixotropic agent is added. The composition meets the flame retardant requirement of UL 94V-0 and halogen-free environmental protection requirement (Cl is less than or equal to 900ppm, Br is less than or equal to 900ppm, Cl + Br is less than or equal to 1500 ppm) by the synergistic cooperation of the nitrogen-containing flame retardant, the inorganic flame retardant and the zinc stannate flame retardant, and does not contain phosphorus flame retardants.
Description
Technical Field
The invention belongs to the technical field of electronic component packaging materials, and particularly relates to a halogen-free phosphorus-free flame-retardant epoxy powder composition and a preparation method thereof.
Background
Most of the existing halogen flame retardants are chlorine bromine flame retardants, which are replaced by halogen-free flame retardants in recent years because of carcinogenic dioxin generated in the flame retardant process. Most halogen-free flame retardant systems are phosphorus flame retardants, red phosphorus belongs to a better flame retardant, but in practical application, red phosphorus flame retardant materials are easy to oxidize and release harmful and highly toxic gases, and dust generated by combustion is easy to cause explosion, so that red phosphorus is forbidden in a plurality of environmental regulations; the introduction of the exposure level, toxicity effect and health risk evaluation of organic phosphorus flame retardants in water environment is that Organic Phosphorus Flame Retardants (OPFRs) gradually replace Brominated Flame Retardants (BFRs) and are widely applied worldwide. Increasing annual yields and increasing detection of OPFRs in environmental media have attracted widespread attention by both domestic and foreign scholars. OPFRs are generally semi-volatile, and easily enter the environment and accumulate in organisms, causing potential harm to the environment and human health. In view of the above technical evolution process, research and application of halogen-free and phosphorus-free flame retardant become the development direction of flame retardation in the later period.
The powder coating is a low VOC solid coating, is applied to the surface of a base material by a spraying or fluidized bed coating method, and has the characteristics of greenness, environmental protection, high efficiency and the like. The powder coating is applied to the field of insulation protection of electronic elements, and is a large field of application.
Through searching, no patent publication related to the present patent application has been found.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a halogen-free phosphorus-free flame-retardant epoxy powder composition and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a halogen-free phosphorus-free flame-retardant epoxy powder composition comprises the following components in parts by weight:
20-30 parts of epoxy resin;
5-15 parts of organic silicon modified epoxy resin;
3-10 parts of multifunctional epoxy resin;
14-60 parts of toughened modified epoxy resin;
3-15 parts of a curing agent;
0.01-1 part of an accelerator;
10-20 parts of a filler;
25-45 parts of an inorganic flame retardant;
5-15 parts of a nitrogen-containing flame retardant;
5-15 parts of zinc stannate flame retardant;
1-5 parts of a pigment;
0.5-2 parts of a leveling agent;
0.1 to 1.0 portion of thixotropic agent is added.
Further, the epoxy resin is bisphenol A type epoxy resin, and the softening point is as follows: 60-107 ℃, and the epoxy equivalent is as follows: 450-900 g/eq;
or the multifunctional epoxy resin is one or a composition of more than two of o-cresol formaldehyde epoxy resin, trifunctional epoxy resin and tetrafunctional epoxy resin;
or the curing agent is an acid anhydride curing agent and/or a carboxylic acid curing agent and/or a phenol curing agent
Or the accelerant is one or a composition of more than two of quaternary ammonium salt, quaternary phosphonium salt, imidazole and derivatives thereof;
or the filler is one or a composition of more than two of silica micropowder, talcum powder, mica powder, calcium silicate, zirconium silicate, calcium carbonate, barium sulfate and kaolin;
or the inorganic flame retardant is one or a combination of aluminum hydroxide and magnesium hydroxide;
or the nitrogen-containing flame retardant is one or a composition of melamine cyanurate and melamine;
Or the zinc stannate flame retardant is one or a combination of zinc stannate and zinc hydroxystannate;
or the pigment is one or a composition of more than two of titanium dioxide, phthalocyanine blue, iron oxide red, iron oxide yellow, organic yellow pigment, organic red pigment and carbon black;
or the flatting agent is a polybutyl acrylate flatting agent;
or the additional thixotropic agent is a gas-phase high-specific-surface-area substance.
Further, the o-cresol formaldehyde epoxy resin is N660, N670, N680, NPEN701, NPEN702, NPCN703 or NPEN 704; the trifunctional epoxy resin is Tactix 742; the tetrafunctional epoxy resin is HP4700, HP4710, NPPN431 or KDT 4400;
the acid anhydride curing agent is pyromellitic dianhydride, phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride or polysebacic dianhydride; the phenolic curing agent is a phenolic curing agent containing active phenolic hydroxyl groups, the hydroxyl equivalent weight is 200-800g/eq, and the softening point is 70-120 ℃.
The quaternary ammonium salt is one or a composition of more than two of tetraethyl ammonium bromide, tetrabutyl ammonium bromide, benzyl trimethyl ammonium bromide and benzyl trimethyl ammonium chloride;
The quaternary phosphonium salt is one or a combination of more than two of triphenyl ethyl phosphonium bromide, triphenyl butyl phosphonium bromide, triphenyl benzyl phosphonium bromide and triphenyl phosphine;
the imidazole is one or a composition of more than two of 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-cyanoethyl-2-methylimidazole and 1-cyanoethyl-2-undecylimidazole.
Further, the preparation method of the toughening modified epoxy resin comprises the following steps:
crushing bisphenol A type epoxy resin into particles, mixing the particles with the core-shell toughening agent and the hollow glass microspheres, uniformly mixing the particles by using a high-speed mixer, and then carrying out melt extrusion by using a double-screw extruder, wherein the set temperature of the extruder is 90-150 ℃, and carrying out cooling tabletting and primary crushing to obtain toughened modified epoxy resin;
wherein, bisphenol A type epoxy resin: core-shell toughener: the mass ratio of the hollow glass microspheres is 10-40: 2-10: 2-10, wherein the softening point of the bisphenol A type epoxy resin is as follows: 60-107 ℃, and the epoxy equivalent is as follows: 450 and 900 g/eq.
Furthermore, the core-shell toughening agent takes polyacrylate substances or organic silicon flexible materials as an inner core, and takes polyacrylate substances as a hard shell on the outer layer.
Further, the diameter of the hollow glass microsphere is less than 20 μm.
The preparation method of the halogen-free phosphorus-free flame-retardant epoxy powder composition comprises the following steps:
premixing the other raw materials except the thixotropic agent in a high-speed mixer with the rotation speed of 500-1500rpm for 5-15 minutes, adding the raw materials into a double-screw extruder, setting the temperature at 90-150 ℃, melting the resin under the screw shearing state, uniformly mixing the melted resin with the other raw materials, cooling the melt by a cooling press roll, grinding and crushing the melt by an ACM (Acrylonitrile butadiene styrene), performing air separation and screening to collect particles with required particle sizes, and finally adding the additional thixotropic agent to enable the powder to be fluidized and fluffy to obtain the halogen-free phosphorus-free flame-retardant epoxy powder composition.
The beneficial effects obtained by the invention are as follows:
1. the composition uses solid epoxy resin as a film forming material, uses organic silicon modified epoxy resin to improve moisture resistance and moisture resistance, uses toughening modified resin to improve cold and hot shock resistance, uses multifunctional epoxy resin to improve crosslinking density and increase reaction activity, and uses acid anhydride, carboxylic acid and phenol as curing agents to meet the curing conditions of 160-180 ℃/20-90 minutes. The nitrogen-containing flame retardant, the inorganic flame retardant and the zinc stannate flame retardant are cooperatively matched, so that the UL 94V-0 flame retardant requirement is met, meanwhile, the halogen-free environment-friendly requirement (Cl is less than or equal to 900ppm, Br is less than or equal to 900ppm, and Cl + Br is less than or equal to 1500 ppm) is met, and the phosphorus-containing flame retardant is not contained. The epoxy powder composition is mainly used for insulation protection of electronic elements such as a magnetic ring, a busbar, a rotor and a stator, PPTC (polymeric positive temperature coefficient), a piezoresistor, a ceramic capacitor, a network exclusion and the like.
2. By using the organic silicon modified epoxy resin, the halogen-free phosphorus-free flame-retardant epoxy powder composition has good moisture resistance and moisture resistance, the flexibility is increased, and the reliability of protected electronic elements is improved.
3. The halogen-free phosphorus-free flame-retardant epoxy powder composition has good thermal shock resistance by using the toughening modified epoxy resin, and the application environment tolerance of the protected electronic element is improved.
4. The epoxy powder composition can meet halogen-free requirements, does not use a phosphorus-containing flame retardant, meets the requirements of ROHS2.0 and SVCH, and belongs to a green environment-friendly product without halogen and phosphorus. Meets the flame retardant requirement of UL 94V-0.
Detailed Description
The present invention will be further described in detail with reference to examples for better understanding, but the scope of the present invention is not limited to the examples.
The raw materials used in the invention are all conventional commercial products if not specified, the method used in the invention is all conventional in the field if not specified, and the mass of each substance used in the invention is all conventional use mass.
A halogen-free phosphorus-free flame-retardant epoxy powder composition comprises the following components in parts by weight:
20-30 parts of epoxy resin;
5-15 parts of organic silicon modified epoxy resin;
3-10 parts of multifunctional epoxy resin;
14-60 parts of toughened modified epoxy resin;
3-15 parts of a curing agent;
0.01-1 part of an accelerator;
10-20 parts of a filler;
25-45 parts of an inorganic flame retardant;
5-15 parts of a nitrogen-containing flame retardant;
5-15 parts of zinc stannate flame retardant;
1-5 parts of pigment;
0.5-2 parts of a leveling agent;
0.1 to 1.0 portion of thixotropic agent is added.
Preferably, the epoxy resin is bisphenol A epoxy resin, and the softening point is as follows: 60-107 ℃, and the epoxy equivalent is as follows: 450-900 g/eq;
or the organosilicon modified epoxy resin is synthesized by the method disclosed in Chinese patent publication No. CN 105131254A.
Or the multifunctional epoxy resin is one or a composition of more than two of o-cresol formaldehyde epoxy resin, trifunctional epoxy resin and tetrafunctional epoxy resin;
Or the curing agent is an anhydride curing agent and/or a carboxylic acid curing agent and/or a phenol curing agent;
or the accelerant is one or a composition of more than two of quaternary ammonium salt, quaternary phosphonium salt, imidazole and derivatives thereof;
or the filler is one or a composition of more than two of silica micropowder, talcum powder, mica powder, calcium silicate, zirconium silicate, calcium carbonate, barium sulfate and kaolin;
or the inorganic flame retardant is one or a combination of aluminum hydroxide and magnesium hydroxide;
or the nitrogen-containing flame retardant is one or a composition of melamine cyanurate and melamine;
or the zinc stannate flame retardant is one or a combination of zinc stannate and zinc hydroxystannate;
or the pigment is one or a composition of more than two of titanium dioxide, phthalocyanine blue, iron oxide red, iron oxide yellow, organic yellow pigment, organic red pigment and carbon black;
or the flatting agent is a polybutyl acrylate flatting agent;
or the additional thixotropic agent is a gas-phase high-specific-surface-area substance.
Preferably, the o-cresol novolac epoxy resin is N660, N670, N680, NPEN701, NPEN702, NPCN703 or NPEN 704; the trifunctional epoxy resin is Tactix 742; the tetrafunctional epoxy resin is HP4700, HP4710, NPPN431 or KDT 4400;
The acid anhydride curing agent is pyromellitic dianhydride, phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride or polysebacic dianhydride; the phenolic curing agent is a phenolic curing agent containing active phenolic hydroxyl groups, the hydroxyl equivalent weight is 200-800g/eq, and the softening point is 70-120 ℃.
The quaternary ammonium salt is one or a composition of more than two of tetraethyl ammonium bromide, tetrabutyl ammonium bromide, benzyl trimethyl ammonium bromide and benzyl trimethyl ammonium chloride;
the quaternary phosphonium salt is one or a composition of more than two of triphenyl ethyl phosphonium bromide, triphenyl butyl phosphonium bromide, triphenyl benzyl phosphonium bromide and triphenyl phosphine;
the imidazole is one or a composition of more than two of 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-cyanoethyl-2-methylimidazole and 1-cyanoethyl-2-undecylimidazole.
Preferably, the preparation method of the toughening modified epoxy resin comprises the following steps:
crushing bisphenol A type epoxy resin into particles, mixing the particles with a core-shell toughening agent and hollow glass microspheres, uniformly mixing the particles with a high-speed mixer, performing melt extrusion by a double-screw extruder at the set temperature of 90-150 ℃, cooling and tabletting, and performing primary crushing to obtain toughened modified epoxy resin, wherein impact stress can be well absorbed through synergistic cooperation of flexible core-shell particles and rigid hollow microspheres;
Wherein, bisphenol A type epoxy resin: core-shell toughener: the mass ratio of the hollow glass microspheres is 10-40: 2-10: 2-10, wherein the softening point of the bisphenol A type epoxy resin is as follows: 60-107 ℃, and the epoxy equivalent is as follows: 450 and 900 g/eq.
Preferably, the core-shell toughening agent takes polyacrylate substances or organosilicon flexible materials as an inner core, and takes polyacrylate substances as a hard shell on the outer layer, so that the core-shell toughening agent has the effect of absorbing impact stress.
Preferably, the diameter of the hollow glass microsphere is less than 20 μm, and the hollow glass microsphere with certain strength has a good effect of absorbing impact stress.
The preparation method of the halogen-free phosphorus-free flame-retardant epoxy powder composition comprises the following steps:
premixing other raw materials except the thixotropic agent in a high-speed mixer with the rotation speed of 500 plus 1500rpm for 5-15 minutes, adding the raw materials into a double-screw extruder, setting the temperature at 90-150 ℃, melting the resin under the screw shearing state, uniformly mixing the melted resin with other raw materials, cooling the melt by a cooling press roller, grinding and crushing the melt by an ACM (activated carbon M), performing air separation and screening to collect particles with required particle size, and finally adding the additional thixotropic agent to enable the powder to be fluidized and fluffy, thus obtaining the halogen-free phosphorus-free flame-retardant epoxy powder composition.
Specifically, the preparation and detection are as follows:
the specific examples of the toughened and modified epoxy resin are as follows:
synthesis example 1: after the solid epoxy resin CYD-012 is crushed, the addition amount is 20 parts by mass, 5 parts by mass of polyacrylate soft-core hard-shell core-shell particles and 5 parts by mass of hollow glass microspheres (the diameter is less than 20 micrometers) are mixed in a high-speed mixer for 10-20 minutes, a double-screw extruder is set to be 120 ℃ for melt extrusion, and the mixture is cooled, tabletted and crushed to prepare the toughening modified epoxy resin 1.
Synthesis example 2: after crushing the solid epoxy resin CYD-012, mixing 40 parts by mass of the solid epoxy resin CYD-012, 10 parts by mass of polyacrylate soft-core and hard-shell core-shell particles and 10 parts by mass of hollow glass microspheres (the diameter is less than 20 micrometers) in a high-speed mixer for 10-20 minutes, setting a double-screw extruder to be 120 ℃ for melt extrusion, and crushing the mixture after cooling and tabletting to prepare the toughening modified epoxy resin 2.
Synthesis example 3: after crushing the solid epoxy resin CYD-012, mixing 40 parts by mass of the solid epoxy resin CYD-012, 10 parts by mass of the organosilicon soft core and polyacrylate hard shell core-shell particles and 10 parts by mass of the hollow glass microspheres (the diameter is less than 20 microns) in a high-speed mixer for 10-20 minutes, setting a double-screw extruder to be 120 ℃ for melt extrusion, and crushing the mixture after cooling and tabletting to prepare the toughening modified epoxy resin 3.
Synthesis example 4: after the solid epoxy resin CYD-012 is crushed, the addition amount is 40 parts by mass, 10 parts by mass of polyacrylate soft core-shell particles are mixed in a high-speed mixer for 10-20 minutes, a double-screw extruder is set to 120 ℃ for melt extrusion, and the toughened modified epoxy resin 4 can be prepared by cooling, tabletting and crushing.
Synthesis example 5: after crushing the solid epoxy resin CYD-012, the adding amount is 40 parts by mass, 10 parts by mass of hollow glass microspheres (the diameter is less than 20 microns) are mixed in a high-speed mixer for 10-20 minutes, a double-screw extruder is set to 120 ℃ for melt extrusion, and the mixture is cooled, tabletted and crushed to prepare the toughening modified epoxy resin 5.
The specific examples, comparative examples and related test results are as follows (the unit of the formula is weight parts):
comparative example 1
Epoxy resin CYD-01250 parts;
10 parts of organic silicon modified epoxy resin;
n6705 parts of multifunctional epoxy resin;
4.7 parts of curing agent pyromellitic anhydride;
0.05 part of accelerator 2-methylimidazole;
12 parts of filler silicon micropowder;
35 parts of an inorganic flame retardant;
10 parts of nitrogen-containing flame retardant;
8 parts of zinc stannate flame retardant;
1.5 parts of phthalocyanine blue;
1.5 parts of a leveling agent;
0.2 part of thixotropic agent is added.
The manufacturing method comprises the following steps: premixing other raw materials except the thixotropic agent in a high-speed mixer with the rotation speed of 500 plus 1500rpm for 5-15 minutes, adding the raw materials into a double-screw extruder, setting the temperature at 90-150 ℃, melting the resin under the screw shearing state, uniformly mixing the melted resin with other raw materials, cooling the melt by a cooling press roller, grinding and crushing the melt by an ACM (activated carbon M), performing air separation and screening to collect particles with required particle size, and finally adding the additional thixotropic agent to enable the powder to be fluidized and fluffy, thus obtaining the halogen-free phosphorus-free flame-retardant epoxy powder composition.
Comparative example 2
Epoxy resin CYD-01240 parts;
n6705 parts of multifunctional epoxy resin;
130 parts of toughened modified epoxy resin;
4.7 parts of curing agent pyromellitic anhydride;
0.05 part of accelerator 2-methylimidazole;
12 parts of filler silicon micropowder;
35 parts of an inorganic flame retardant;
10 parts of a nitrogen-containing flame retardant;
8 parts of zinc stannate flame retardant;
1.5 parts of phthalocyanine blue;
1.5 parts of a leveling agent;
0.2 part of thixotropic agent is added.
The manufacturing method refers to comparative example 1.
Comparative example 3
Epoxy resin CYD-01220 parts;
10 parts of organic silicon modified epoxy resin;
n6705 parts of multifunctional epoxy resin;
450 parts of toughened modified epoxy resin;
5.1 parts of curing agent pyromellitic anhydride;
0.05 part of accelerator 2-methylimidazole;
12 parts of filler silicon micropowder;
35 parts of an inorganic flame retardant;
10 parts of nitrogen-containing flame retardant;
8 parts of zinc stannate flame retardant;
1.5 parts of phthalocyanine blue;
1.5 parts of a leveling agent;
0.2 part of thixotropic agent is added.
The manufacturing method refers to comparative example 1.
Comparative example 4
Epoxy resin CYD-01220 parts;
10 parts of organic silicon modified epoxy resin;
N6705 parts of multifunctional epoxy resin;
550 parts of toughening modified epoxy resin;
5.1 parts of curing agent pyromellitic anhydride;
0.05 part of accelerator 2-methylimidazole;
12 parts of filler silicon micropowder;
35 parts of an inorganic flame retardant;
10 parts of a nitrogen-containing flame retardant;
8 parts of zinc stannate flame retardant;
1.5 parts of phthalocyanine blue;
1.5 parts of a leveling agent;
0.2 part of thixotropic agent is added.
The manufacturing method refers to comparative example 1.
Comparative example 5
Epoxy resin CYD-01230 parts;
10 parts of organic silicon modified epoxy resin;
n6705 parts of multifunctional epoxy resin;
130 parts of toughened modified epoxy resin;
4.7 parts of curing agent pyromellitic anhydride;
0.05 part of accelerator 2-methylimidazole;
30 parts of filler silicon micropowder;
35 parts of an inorganic flame retardant;
1.5 parts of phthalocyanine blue;
1.5 parts of a leveling agent;
0.2 part of thixotropic agent is added.
The manufacturing method refers to comparative example 1.
Comparative example 6
Epoxy resin CYD-01230 parts;
10 parts of organic silicon modified epoxy resin;
n6705 parts of multifunctional epoxy resin;
130 parts of toughening modified epoxy resin;
4.7 parts of curing agent pyromellitic anhydride;
0.05 part of accelerator 2-methylimidazole;
55 parts of filler silicon micropowder;
10 parts of nitrogen-containing flame retardant;
1.5 parts of phthalocyanine blue;
1.5 parts of a leveling agent;
0.2 part of thixotropic agent is added.
The manufacturing method refers to comparative example 1.
Comparative example 7
Epoxy resin CYD-01230 parts;
10 parts of organic silicon modified epoxy resin;
n6705 parts of multifunctional epoxy resin;
130 parts of toughened modified epoxy resin;
4.7 parts of curing agent pyromellitic anhydride;
0.05 part of accelerator 2-methylimidazole;
57 parts of filler silicon micropowder;
8 parts of zinc stannate flame retardant;
1.5 parts of phthalocyanine blue;
1.5 parts of a leveling agent;
0.2 part of thixotropic agent is added.
The manufacturing method refers to comparative example 1.
Comparative example 8
Epoxy resin CYD-01230 parts;
10 parts of organic silicon modified epoxy resin;
n6705 parts of multifunctional epoxy resin;
130 parts of toughened modified epoxy resin;
4.7 parts of curing agent pyromellitic anhydride;
0.05 part of accelerator 2-methylimidazole;
20 parts of filler silicon micropowder;
35 parts of an inorganic flame retardant;
10 parts of nitrogen-containing flame retardant;
1.5 parts of phthalocyanine blue;
1.5 parts of a leveling agent;
0.2 part of thixotropic agent is added.
The manufacturing method refers to comparative example 1.
Comparative example 9
Epoxy resin CYD-01230 parts;
10 parts of organic silicon modified epoxy resin;
n6705 parts of multifunctional epoxy resin;
130 parts of toughened modified epoxy resin;
4.7 parts of curing agent pyromellitic anhydride;
0.05 part of accelerator 2-methylimidazole;
22 parts of filler silicon micropowder;
35 parts of an inorganic flame retardant;
8 parts of zinc stannate flame retardant;
1.5 parts of phthalocyanine blue;
1.5 parts of a leveling agent;
0.2 part of thixotropic agent is added.
The manufacturing method refers to comparative example 1.
Comparative example 10
Epoxy resin CYD-01230 parts;
10 parts of organic silicon modified epoxy resin;
n6705 parts of multifunctional epoxy resin;
130 parts of toughened modified epoxy resin;
4.7 parts of curing agent pyromellitic anhydride;
0.05 part of accelerator 2-methylimidazole;
47 parts of filler silicon micropowder;
10 parts of nitrogen-containing flame retardant;
8 parts of zinc stannate flame retardant;
1.5 parts of phthalocyanine blue;
1.5 parts of a leveling agent;
0.2 part of thixotropic agent is added.
The manufacturing method refers to comparative example 1.
Example 1
A halogen-free phosphorus-free flame-retardant epoxy powder composition comprises the following components in parts by weight:
epoxy resin CYD-01230 parts;
10 parts of organic silicon modified epoxy resin;
n6705 parts of multifunctional epoxy resin;
30 parts of toughening modified epoxy resin 1 (prepared in synthesis example 1);
4.7 parts of curing agent pyromellitic anhydride;
0.05 part of accelerator 2-methylimidazole;
12 parts of filler silicon micropowder;
35 parts of an inorganic flame retardant;
10 parts of nitrogen-containing flame retardant;
8 parts of zinc stannate flame retardant;
1.5 parts of phthalocyanine blue;
1.5 parts of a leveling agent;
0.2 part of thixotropic agent is added.
The manufacturing method refers to comparative example 1.
Example 2
A halogen-free phosphorus-free flame-retardant epoxy powder composition comprises the following components in parts by weight:
epoxy resin CYD-01220 parts;
10 parts of organic silicon modified epoxy resin;
n6705 parts of multifunctional epoxy resin;
60 parts of toughened and modified epoxy resin 2 (prepared in synthetic example 2);
5.1 parts of curing agent pyromellitic anhydride;
0.05 part of accelerator 2-methylimidazole;
12 parts of filler silicon micropowder;
35 parts of an inorganic flame retardant;
10 parts of a nitrogen-containing flame retardant;
8 parts of zinc stannate flame retardant;
1.5 parts of phthalocyanine blue;
1.5 parts of a leveling agent;
0.2 part of thixotropic agent is added.
The manufacturing method refers to comparative example 1.
Example 3
A halogen-free phosphorus-free flame-retardant epoxy powder composition comprises the following components in parts by weight:
epoxy resin CYD-01220 parts;
10 parts of organic silicon modified epoxy resin;
n6705 parts of multifunctional epoxy resin;
60 parts of toughened and modified epoxy resin 3 (prepared in synthetic example 3);
5.1 parts of curing agent pyromellitic anhydride;
0.05 part of accelerator 2-methylimidazole;
12 parts of filler silicon micropowder;
35 parts of an inorganic flame retardant;
10 parts of nitrogen-containing flame retardant;
8 parts of zinc stannate flame retardant;
1.5 parts of phthalocyanine blue;
1.5 parts of a leveling agent;
0.2 part of thixotropic agent is added.
The manufacturing method refers to comparative example 1.
Test items and results:
the invention relates to a test item and a method:
in order to verify the beneficial effect of the invention, relevant item inspection is carried out:
(1) flame retardancy: UL94 vertical burn test.
(2) Resistance to temperature shock.
(3) PCT test of voltage dependent resistor
(4) Ceramic capacitor PCT experiment
Some performance index test methods in the invention are as follows:
(1) flame retardancy: according to UL94, vertical burning test.
(2) Temperature shock resistance: according to a method 5.2.9 in GB/T28859-2012 epoxy powder encapsulating material for electronic components, 10 components with the diameter of 20mm multiplied by (1-2) mm are encapsulated, the test condition is that the temperature is kept for 0.5h at-55 ℃, and then the temperature is raised to 125 ℃ and kept for 0.5h, and the above is used as a period. And observing whether the appearance of the element is cracked after certain test cycles. The occurrence of cracks was judged to be failure. The reference standard is no cracking by 5 experiments.
(3) Piezo-resistor PCT experiment: the piezoresistors 14D561 were encapsulated, with a monolayer thickness of 0.4-0.6mm, and curing conditions of 160 deg.C/20 min, 10pcs per group. Before the experiment, the voltage-dependent voltage, the nonlinear coefficient and the leakage current are tested. And (3) placing the sample in a sterilizer, cooking the sample in air at 121 ℃ for 12h, airing the sample for 4h, and testing the voltage-sensitive voltage, the nonlinear coefficient and the leakage current. Reference standard: the voltage-sensitive voltage change rate before and after the experiment is less than 10%, and the leakage current after the experiment is less than 100 muA.
(4) Ceramic capacitor PCT experiment: the encapsulated ceramic capacitors 472M were 0.4-0.6mm monolayer thick and cured at 160 deg.C/20 min, 10pcs per group. The capacity, loss, insulation resistance, AC4KV-60s withstand voltage were tested before the experiment. The sample is placed in a sterilizer, cooked in air for 12h at 121 ℃, dried for 4h, and tested for capacity, loss, insulation resistance and AC4KV-60s voltage resistance. Reference standard: after the experiment, the insulation resistance is more than 10G omega, and the AC4KV-60s has no poor withstand voltage.
Comparison between comparative example 1 and example 1 shows that when toughening-modified epoxy resin 1 is not added, the thermal shock resistance does not satisfy the 5-time no-crack criterion because both the nitrogen-containing flame retardant and the inorganic flame retardant significantly deteriorate the thermal shock resistance. Comparison of comparative example 2 and example 1 shows that when no silicone modified epoxy resin is added, the performance of both the pressure sensitive PCT test and the capacitance PCT test is poor and does not meet the basic moisture resistance requirements. Comparative examples 3, 4 and 2 compare, and show that toughening resin 4 modified by core-shell particles alone and toughening resin 5 modified by hollow glass microspheres have toughening effect, but the ability of improving the cold and heat shock resistance is strongest after the toughening modified epoxy resin 2 is cooperated. Comparative examples 5, 6 and 7 show that the flame retardant rating of UL 94V-0 cannot be satisfied by using the inorganic flame retardant, nitrogen-containing flame retardant and zinc stannate flame retardant alone. Comparative examples 8, 9 and 10 compare with example 1, and it is demonstrated that the flame retardant V-0 can be achieved only by the cooperation of the inorganic flame retardant, the nitrogen-containing flame retardant and the zinc stannate flame retardant, and the nitrogen-containing flame retardant and the zinc stannate flame retardant. The comparison of examples 1, 2 and 3 shows that the cold and heat shock resistance is obviously improved along with the increase of the use amount of the toughening modified epoxy resin, and the pressure-sensitive PCT experiment and the capacitance PCT experiment both meet the standard requirements. Although halogen flame retardant and phosphorus flame retardant are not used, the flame retardant of the invention meets the flame retardant requirement of UL 94V-0 grade by means of flame retardant synergistic cooperation among nitrogen flame retardant, inorganic flame retardant and zinc stannate flame retardant. The halogen-free phosphorus-free flame-retardant epoxy powder composition has a good application prospect in the aspect of electronic element packaging, and belongs to a novel green environment-friendly material.
Although the embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the embodiments disclosed.
Claims (4)
1. A halogen-free phosphorus-free flame-retardant epoxy powder composition is characterized in that: the composition comprises the following components in parts by weight:
20-30 parts of epoxy resin;
5-15 parts of organic silicon modified epoxy resin;
3-10 parts of multifunctional epoxy resin;
14-60 parts of toughened modified epoxy resin;
3-15 parts of a curing agent;
0.01-1 part of an accelerator;
10-20 parts of a filler;
25-45 parts of an inorganic flame retardant;
5-15 parts of a nitrogen-containing flame retardant;
5-15 parts of zinc stannate flame retardant;
1-5 parts of pigment;
0.5-2 parts of a leveling agent;
0.1-1.0 part of thixotropic agent is added;
the epoxy resin is bisphenol A type epoxy resin, and the softening point is as follows: 60-107 ℃, and the epoxy equivalent is as follows: 450-900 g/eq;
The multifunctional epoxy resin is one or a composition of more than two of o-cresol formaldehyde epoxy resin, trifunctional epoxy resin and tetrafunctional epoxy resin;
the curing agent is an anhydride curing agent and/or a carboxylic acid curing agent and/or a phenol curing agent;
the accelerator is one or a composition of more than two of quaternary ammonium salt, quaternary phosphonium salt, imidazole and derivatives thereof;
the filler is one or a composition of more than two of silicon micropowder, talcum powder, mica powder, calcium silicate, zirconium silicate, calcium carbonate, barium sulfate and kaolin;
the inorganic flame retardant is one or a composition of two of aluminum hydroxide and magnesium hydroxide;
the nitrogen-containing flame retardant is one or a composition of two of melamine cyanurate and melamine;
the zinc stannate flame retardant is one or a combination of zinc stannate and zinc hydroxystannate;
the pigment is one or a composition of more than two of titanium dioxide, phthalocyanine blue, iron oxide red, iron oxide yellow, organic yellow pigment, organic red pigment and carbon black;
the flatting agent is a polybutyl acrylate flatting agent;
the additional thixotropic agent is a high-specific surface area substance prepared by a gas phase method;
The preparation method of the toughening modified epoxy resin comprises the following steps:
crushing bisphenol A type epoxy resin into particles, mixing the particles with a core-shell toughening agent and hollow glass microspheres, uniformly mixing the particles with a high-speed mixer, performing melt extrusion by a double-screw extruder at the set temperature of 90-150 ℃, cooling, tabletting and primarily crushing to obtain toughened and modified epoxy resin;
wherein, bisphenol A type epoxy resin: core-shell toughener: the mass ratio of the hollow glass microspheres is 10-40: 2-10: 2-10, wherein the softening point of the bisphenol A type epoxy resin is as follows: 60-107 ℃, and the epoxy equivalent is as follows: 450-900 g/eq;
the core-shell toughening agent takes polyacrylate substances or organosilicon flexible materials as an inner core, and takes polyacrylate substances as a hard shell as an outer layer.
2. The halogen-free phosphorus-free flame retardant epoxy powder composition according to claim 1, wherein: the o-cresol formaldehyde epoxy resin is N660, N670, N680, NPEN701, NPEN702, NPCN703 or NPEN 704; the trifunctional epoxy resin is Tactix 742; the tetrafunctional epoxy resin is HP4700, HP4710, NPPN431 or KDT 4400;
the acid anhydride curing agent is pyromellitic dianhydride, phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride or polysebacic dianhydride; the phenolic curing agent is a phenolic curing agent containing active phenolic hydroxyl groups, the hydroxyl equivalent weight is 200-800g/eq, and the softening point is 70-120 ℃;
The quaternary ammonium salt is one or a composition of more than two of tetraethyl ammonium bromide, tetrabutyl ammonium bromide, benzyl trimethyl ammonium bromide and benzyl trimethyl ammonium chloride;
the quaternary phosphonium salt is one or a composition of more than two of triphenyl ethyl phosphonium bromide, triphenyl butyl phosphonium bromide, triphenyl benzyl phosphonium bromide and triphenyl phosphine;
the imidazole is one or a composition of more than two of 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-cyanoethyl-2-methylimidazole and 1-cyanoethyl-2-undecylimidazole.
3. The halogen-free phosphorus-free flame retardant epoxy powder composition according to claim 1, wherein: the diameter of the hollow glass microsphere is less than 20 mu m.
4. The method for preparing the halogen and phosphorus free flame retardant epoxy powder composition according to any of claims 1 to 3, wherein: the method comprises the following steps:
premixing other raw materials except the thixotropic agent in a high-speed mixer with the rotation speed of 500 plus 1500rpm for 5-15 minutes, adding the raw materials into a double-screw extruder, setting the temperature at 90-150 ℃, melting the resin under the screw shearing state, uniformly mixing the melted resin with other raw materials, cooling the melt by a cooling press roller, grinding and crushing the melt by an ACM (activated carbon M), performing air separation and screening to collect particles with required particle size, and finally adding the additional thixotropic agent to enable the powder to be fluidized and fluffy, thus obtaining the halogen-free phosphorus-free flame-retardant epoxy powder composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210007411.8A CN114015330B (en) | 2022-01-06 | 2022-01-06 | Halogen-free phosphorus-free flame-retardant epoxy powder composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210007411.8A CN114015330B (en) | 2022-01-06 | 2022-01-06 | Halogen-free phosphorus-free flame-retardant epoxy powder composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114015330A CN114015330A (en) | 2022-02-08 |
| CN114015330B true CN114015330B (en) | 2022-06-28 |
Family
ID=80069666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210007411.8A Active CN114015330B (en) | 2022-01-06 | 2022-01-06 | Halogen-free phosphorus-free flame-retardant epoxy powder composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114015330B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114889251B (en) * | 2022-04-29 | 2023-04-07 | 江苏耀鸿电子有限公司 | High-flame-retardant flexible epoxy resin copper-clad plate and preparation method thereof |
| CN115948097B (en) * | 2022-12-20 | 2023-10-03 | 天津凯华绝缘材料股份有限公司 | Moisture-heat resistant epoxy powder composition for magnetic ring and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7456235B2 (en) * | 2003-04-30 | 2008-11-25 | Henkel Corporation | Flame-retardant composition for coating powders |
| CN102372903B (en) * | 2010-08-18 | 2014-04-16 | 合正科技股份有限公司 | Halogen-free phosphorus-free thermosetting resin composition |
| CN102911502A (en) * | 2012-10-19 | 2013-02-06 | 广东生益科技股份有限公司 | Cyanate ester resin composition, prepreg manufactured by using cyanate ester resin composition, laminated material and metal-clad laminated material |
| CN103059516B (en) * | 2013-01-08 | 2015-12-23 | 天津市凯华绝缘材料有限公司 | A kind of Fast-cure epoxy powder composition |
| CN109825170B (en) * | 2019-02-22 | 2021-02-12 | 天津凯华绝缘材料股份有限公司 | High-temperature-resistant epoxy powder composition and preparation method thereof |
| CN110643280A (en) * | 2019-10-22 | 2020-01-03 | 广西南宁维一防腐科技有限公司 | High-temperature-resistant flame-retardant powder coating and preparation method thereof |
-
2022
- 2022-01-06 CN CN202210007411.8A patent/CN114015330B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114015330A (en) | 2022-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114015330B (en) | Halogen-free phosphorus-free flame-retardant epoxy powder composition and preparation method thereof | |
| CN109825170B (en) | High-temperature-resistant epoxy powder composition and preparation method thereof | |
| Wan et al. | Flame-retarded thermoplastic polyurethane elastomer: From organic materials to nanocomposites and new prospects | |
| Zhao et al. | A green, durable and effective flame-retardant coating for expandable polystyrene foams | |
| Huo et al. | Flame‐retardant performance and mechanism of epoxy thermosets modified with a novel reactive flame retardant containing phosphorus, nitrogen, and sulfur | |
| Hu et al. | A novel efficient halogen-free flame retardant system for polycarbonate | |
| CN103059516B (en) | A kind of Fast-cure epoxy powder composition | |
| Chen et al. | Flame retardant effects of organic inorganic hybrid intumescent flame retardant based on expandable graphite in silicone rubber composites | |
| Yao et al. | Flame retardant and toughening behaviors of bio‐based DOPO‐containing curing agent in epoxy thermoset | |
| Zhou et al. | Synergistic effect between solid wastes and intumescent flame retardant on flammability and smoke suppression of thermoplastic polyurethane composites | |
| Liu et al. | Effects of magnesium hydroxide and its synergistic systems on the flame retardance of polyformaldehyde | |
| Wang et al. | The encapsulation of intumescent flame retardants by poly-siloxane for thermoplastic polyolefin: Fire safety and water resistance | |
| CN101851391B (en) | Halogen-free phosphate-free silicon-free epoxy resin composition and cover layer prepared by using same | |
| Dong et al. | Fire hazard suppression of intumescent flame retardant polypropylene based on a novel Ni‐containing char‐forming agent | |
| Xu et al. | Synergistic effects of organically modified montmorillonite in combination with metal oxides on the fire safety enhancement of intumescent flame‐retarded epoxy resins | |
| CN101838440A (en) | Non-halogen, non-phosphorous and non-silicone epoxy resin compositions and flexible copper clad laminate prepared thereby | |
| Zhang et al. | A novel P‐S‐Si‐based cage‐structural monomer for flame‐retardant modification of unsaturated polyester resin | |
| CN105038238A (en) | Preparation method of organic silicon fire retardant of organic silicon rubber wastes | |
| CN110982465A (en) | Efficient halogen-free flame-retardant epoxy adhesive and preparation method thereof | |
| CN114015327B (en) | Halogen-free phosphorus-free low-temperature curing epoxy powder composition with storage stability and preparation method thereof | |
| CN102171613A (en) | Ultraviolet light absorbing ketones of 2-(2-hydroxyphenyl) benzotriazole | |
| CN113493624A (en) | Biomass flame retardant, water-based flame retardant coating, and preparation method and application thereof | |
| CN109517279B (en) | Halogen-free phosphorus synergistic flame retardant and flame-retardant polymer composite material and preparation method thereof | |
| Zhang et al. | A DOPO‐anchored benzothiadiazole derivative toward efficiently P/N/S synergistic flame retarding of epoxy thermoset | |
| EA028111B1 (en) | Nanoclays containing flame retardant chemicals for fire retardant applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |