CN103694631A - Halogen-free epoxy resin composition and cover film prepared by using halogen-free epoxy resin composition - Google Patents
Halogen-free epoxy resin composition and cover film prepared by using halogen-free epoxy resin composition Download PDFInfo
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- CN103694631A CN103694631A CN201310572972.3A CN201310572972A CN103694631A CN 103694631 A CN103694631 A CN 103694631A CN 201310572972 A CN201310572972 A CN 201310572972A CN 103694631 A CN103694631 A CN 103694631A
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Abstract
The present invention discloses a halogen-free fire retardation epoxy resin composition and a cover film prepared by using the composition. The halogen-free fire retardation epoxy resin composition comprises a halogen-free epoxy resin, a nitrile butadiene rubber, an aromatic amine curing agent, an imidazole curing accelerator, an aromatic amine antioxidant, a nitrogen-containing fire retardation agent, a phosphorus-containing fire retardation agent, a filler and an organic solvent. The cover film prepared by using the composition comprises a polyimide insulation film, a halogen-free fire retardation epoxy resin composition coating coated on the polyimide insulation film, and release paper compounded on the halogen-free fire retardation epoxy resin composition coating. The halogen-free fire retardation epoxy resin composition does not contain halogen, and has characteristics of fire retardation and good mechanical property. The cover film prepared by using the composition has characteristics of fire retardation, high peel strength, high insulation and high processability, wherein the fire retardation achieves the UL94VTM-0 grade.
Description
Technical field:
The present invention relates to a kind of halogen-free resin composition and printed circuit board technology field, relate in particular to a kind of halogen-free flame retardant epoxy resin composition and use said composition to prepare the method for mulch film.
Background technology:
At present, tackiness agent for packaged material and electronic material all needs to have flame retardant resistance, common mulch film reaches fire-retardant object by very high halogen resin or the halogen-containing flame retardant of employing content of halogen in addition, but the halogen-containing compound of this class can produce corrodibility and the very strong gas of toxicity in combustion processes.For environmental protection, need to replace with non-halogen material, this is especially when preparing mulch film, a kind of halogen-free flame retardant epoxy resin composition of innovation and creation, can either be fire-retardant, have again good mechanical property, it is very important that higher stripping strength, insulativity and processing characteristics just seem, this is also the key issue that needs solve to FCCL industry.
Summary of the invention:
The object of the present invention is to provide a kind of halogen-free flame retardant epoxy resin composition and use its mulch film of preparing, this halogen-free flame retardant epoxy resin composition has good flame retardant resistance and mechanical property.Prepared mulch film thermotolerance is strong, and stripping strength is high, and flame retardant resistance can reach UL94VTM-0 level.
For achieving the above object, halogen-free fire-retardant epoxy resin composition of the present invention includes following parts by weight of component: halogen-free epoxy resin 40-70 part, paracril 25-45 part, aromatic amine curing agent 1-15 part, imidazoles curing catalyst 0.05-1.5 part, appropriate containing nitrogen combustion inhibitor 15-20 part, phosphonium flame retardant 15-20 part, aromatic amine oxidation inhibitor 0.05-1.5 part, filler 0-25 part, organic solvent.
As technique scheme preferably, described paracril is acrylonitrile butadiene copolymer, vinyl cyanide mass percentage content is 25-40%, copolymer molecule chain end is by carboxylated copolymer rubber.
As technique scheme preferably, described aromatic amine curing agent is diaminodiphenylmethane (DDM), diaminodiphenylsulfone(DDS) (DDS), 3,3-bis-is chloro-4, the one or more combination thing in 4-diaminodiphenylmethane (MOCA).
As technique scheme preferably, described imidazoles curing catalyst is the one or more combination thing in glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole.
As technique scheme preferably, described is trimeric cyanamide or melamine phosphate containing nitrogen combustion inhibitor; Phosphonium flame retardant is polyphosphoric acid amine or Tritolyl Phosphate.
As technique scheme preferably, described aromatic amine oxidation inhibitor is compound and the derivatives thereof such as pentanoic, Ursol D;
Filler is one or more mixtures in aluminium hydroxide, zeolite, calcium carbonate; Organic solvent is one or more mixtures in acetone, pimelinketone, ethyl acetate.
Described halogen-free fire-retardant epoxy resin composition is for flexible printed-circuit board mulch film.
As technique scheme preferably, described flexible printed-circuit board is insulating film, the separate-type paper of 15～95 μ m with mulch film by thickness, the halogen-free fire-retardant epoxy resin composition formation that be coated on insulating film, thickness is 20～45 μ m.
As technique scheme preferably, described flexible printed-circuit board comprises the steps: the halogen-free epoxy resin of described amount, paracril, aromatic amine curing agent, curing catalyst, containing nitrogen combustion inhibitor, phosphonium flame retardant, oxidation inhibitor and filler, is dissolved in appropriate organic solvent by the preparation method of mulch film, re-uses coating equipment this liquid is coated on polyimide insulative film; Then will apply cated insulating film, 85～150 ℃ of heating 3～6 minutes; In the time of 75～85 ℃, itself and separate-type paper is laminating, rolling obtains the mulch film of described halogen-free fire-retardant epoxy resin composition.
Embodiment:
Embodiment mono-:
A halogen-free fire-retardant epoxy resin composition, includes following parts by weight of component: 40 parts of halogen-free epoxy resins, 25 parts of paracrils, 1 part of aromatic amine curing agent, 0.05 part of imidazoles curing catalyst, appropriate containing 15 parts of nitrogen combustion inhibitors, 15 parts of phosphonium flame retardants, 0.05 part, aromatic amine oxidation inhibitor, 2 parts of fillers, organic solvent.
Described paracril is acrylonitrile butadiene copolymer, and vinyl cyanide mass percentage content is 25%, and copolymer molecule chain end is by carboxylated copolymer rubber; Aromatic amine curing agent is diaminodiphenylmethane (DDM); Imidazoles curing catalyst is glyoxal ethyline; Containing nitrogen combustion inhibitor, it is trimeric cyanamide; Phosphonium flame retardant is polyphosphoric acid amine; Aromatic amine oxidation inhibitor is pentanoic; Filler is aluminium hydroxide; Organic solvent is acetone.
Described halogen-free fire-retardant epoxy resin composition is used for to flexible printed-circuit board mulch film.
The flexible printed-circuit board that contains halogen-free fire-retardant epoxy resin composition is insulating film, the separate-type paper of 15～95 μ m with mulch film by thickness, and the halogen-free fire-retardant epoxy resin composition that be coated on insulating film, thickness is 20～45 μ m forms.
Preparation method comprises the steps: first the halogen-free epoxy resin of described amount, paracril, diaminodiphenylmethane (DDM), glyoxal ethyline, trimeric cyanamide, polyphosphoric acid amine, pentanoic and aluminium hydroxide to be dissolved in appropriate acetone, re-uses coating equipment this liquid is applied on 20 μ m to 40 μ m polyimide insulative films; Then will apply cated insulating film, 85 ℃ of heating 3 minutes; In the time of 75 ℃, itself and separate-type paper is laminating, rolling obtains the mulch film of described halogen-free fire-retardant epoxy resin composition.
Embodiment bis-:
A halogen-free fire-retardant epoxy resin composition, includes following parts by weight of component: 55 parts of halogen-free epoxy resins, 35 parts of paracrils, 10 parts of aromatic amine curing agents, 1 part of curing catalyst, appropriate containing 18 parts of nitrogen combustion inhibitors, 18 parts of phosphonium flame retardants, 1 part, oxidation inhibitor, 12 parts of fillers, organic solvent.
Described paracril is that ' vinyl cyanide mass percentage content is 35% to acrylonitrile butadiene copolymer, and copolymer molecule chain end is by carboxylated copolymer rubber; Aromatic amine curing agent is diaminodiphenylsulfone(DDS) (DDS); Imidazoles curing catalyst is 2-ethyl-4-methylimidazole and 2-phenylimidazole; Containing nitrogen combustion inhibitor, it is melamine phosphate; Phosphonium flame retardant is polyphosphoric acid amine; Aromatic amine oxidation inhibitor is the compounds such as Ursol D; Filler is zeolite; Organic solvent is pimelinketone.
Described halogen-free fire-retardant epoxy resin composition is used for to flexible printed-circuit board mulch film.
The flexible printed-circuit board that contains halogen-free fire-retardant epoxy resin composition is insulating film, the separate-type paper of 15～95 μ m with mulch film by thickness, and the halogen-free fire-retardant epoxy resin composition that be coated on insulating film, thickness is 20～45 μ m forms.
Preparation method comprises the steps: first the compounds such as the halogen-free epoxy resin of described amount, paracril, diaminodiphenylsulfone(DDS) (DDS), 2-ethyl-4-methylimidazole and 2-phenylimidazole, melamine phosphate, polyphosphoric acid amine, Ursol D and zeolite to be dissolved in appropriate pimelinketone, re-uses coating equipment this liquid is applied on 30 μ m to 60 μ m polyimide insulative films; Then will apply cated insulating film, 120 ℃ of heating 5 minutes; In the time of 80 ℃, itself and separate-type paper is laminating, rolling obtains the mulch film of described halogen-free fire-retardant epoxy resin composition.
Embodiment tri-:
A halogen-free fire-retardant epoxy resin composition, includes following parts by weight of component: 70 parts of halogen-free epoxy resins, 45 parts of paracrils, 15 parts of aromatic amine curing agents, 1.5 parts of curing catalysts, appropriate containing 20 parts of nitrogen combustion inhibitors, 20 parts of phosphonium flame retardants, 1.5 parts, aromatic amine oxidation inhibitor, 25 parts of fillers, organic solvent.
Described paracril is acrylonitrile butadiene copolymer, and vinyl cyanide mass percentage content is 40%, and copolymer molecule chain end is by carboxylated copolymer rubber; Aromatic amine curing agent is that 3,3-bis-is chloro-4,4-diaminodiphenylmethane (MOCA); Imidazoles curing catalyst is 2-phenyl-4-methylimidazole; Containing nitrogen combustion inhibitor, it is trimeric cyanamide; Phosphonium flame retardant is Tritolyl Phosphate; Aromatic amine oxidation inhibitor is pentanoic; Filler is calcium carbonate; Organic solvent is ethyl acetate.
Described halogen-free fire-retardant epoxy resin composition is used for to flexible printed-circuit board mulch film.
The flexible printed-circuit board that contains halogen-free fire-retardant epoxy resin composition is insulating film, the separate-type paper of 15～95 μ m with mulch film by thickness, and the halogen-free fire-retardant epoxy resin composition that be coated on insulating film, thickness is 20～45 μ m forms.
Preparation method comprises the steps: first by the halogen-free epoxy resin of described amount, paracril, 3,3-bis-chloro-4,4-diaminodiphenylmethane (MOCA), 2-phenyl-4-methylimidazole, trimeric cyanamide, Tritolyl Phosphate, pentanoic and calcium carbonate are dissolved in appropriate ethyl acetate, re-use coating equipment this liquid is applied on 45m to 95 μ m polyimide insulative film; Then will apply cated insulating film, 150 ℃ of heating 6 minutes; In the time of 85 ℃, itself and separate-type paper is laminating, rolling obtains the mulch film of described halogen-free fire-retardant epoxy resin composition.
The performance of the formulation Example of 1 halogen-free epoxy resin composition that specifically sees the following form and the mulch film of preparation thereof.
Table 1
As can be seen from the above table, what the present invention made reaches at UL94VTM-0 level, 300 ℃ in resistance to immersed solder >5min in mulch film flame retardant resistance, possesses high-peeling strength and excellent thermotolerance and reliability.
The testing method of above characteristic is as follows:
(1) excessive glue amount is tested according to IPC-TM-6502.3.17.1 method.
(2) stripping strength, according to IPC-TM-6502.4.9 method, is tested the stripping strength of metal cap rock.
(3) resistance to immersed solder is tested according to IPC-TM-6502.4.13.
(4) incendivity (flame retardant resistance): measure according to UL94 vertical combustion method.
Claims (9)
1. a halogen-free fire-retardant epoxy resin composition; It is characterized in that including following parts by weight of component: halogen-free epoxy resin 40-70 part, paracril 25-45 part, aromatic amine curing agent 1-15 part, imidazoles curing catalyst 0.05-1.5 part, appropriate containing nitrogen combustion inhibitor 15-20 part, phosphonium flame retardant 15-20 part, aromatic amine oxidation inhibitor 0.05-1.5 part, filler 0-25 part, organic solvent.
2. halogen-free fire-retardant epoxy resin composition according to claim 1, is characterized in that: described paracril is acrylonitrile butadiene copolymer, and vinyl cyanide mass percentage content is 25-40%, and copolymer molecule chain end is by carboxylated copolymer rubber.
3. halogen-free fire-retardant epoxy resin composition according to claim 1, it is characterized in that: described aromatic amine curing agent is diaminodiphenylmethane (DDM), diaminodiphenylsulfone(DDS) (DDS), 3,3-bis-is chloro-4, the one or more combination thing in 4-diaminodiphenylmethane (MOCA).
4. halogen-free fire-retardant epoxy resin composition according to claim 1, is characterized in that: imidazoles curing catalyst is the one or more combination thing in glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole.
5. halogen-free fire-retardant epoxy resin composition according to claim 1, is characterized in that: described is trimeric cyanamide or melamine phosphate containing nitrogen combustion inhibitor; Phosphonium flame retardant is polyphosphoric acid amine or Tritolyl Phosphate.
6. halogen-free fire-retardant epoxy resin composition according to claim 1, is characterized in that: described aromatic amine oxidation inhibitor is compound and the derivatives thereof such as pentanoic, Ursol D; Filler is one or more mixtures in aluminium hydroxide, zeolite, calcium carbonate; Organic solvent is one or more mixtures in acetone, pimelinketone, ethyl acetate.
7. the halogen-free fire-retardant epoxy resin composition described in any one in claim 1～9 is used for to flexible printed-circuit board mulch film.
8. flexible printed-circuit board mulch film according to claim 7, it is characterized in that: described flexible printed-circuit board is insulating film, the separate-type paper of 15～95 μ m with mulch film by thickness, the halogen-free fire-retardant epoxy resin composition that be coated on insulating film, thickness is 20～45 μ m forms.
9. the preparation method of mulch film for the flexible printed-circuit board described in claim 7 or 8, it is characterized in that comprising the steps: by the halogen-free epoxy resin of described amount, paracril, aromatic amine curing agent, curing catalyst, containing nitrogen combustion inhibitor, phosphonium flame retardant, oxidation inhibitor and filler, be dissolved in appropriate organic solvent, re-use coating equipment this liquid is coated on polyimide insulative film; Then will apply cated insulating film, 85～150 ℃ of heating 3～6 minutes; In the time of 75～85 ℃, itself and separate-type paper is laminating, rolling obtains the mulch film of described halogen-free fire-retardant epoxy resin composition.
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| CN201310572972.3A CN103694631A (en) | 2013-11-14 | 2013-11-14 | Halogen-free epoxy resin composition and cover film prepared by using halogen-free epoxy resin composition |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106084663A (en) * | 2016-06-22 | 2016-11-09 | 柳州市强威锻造厂 | A kind of high impact strength epoxy resin cure formula |
| CN110845839A (en) * | 2019-08-08 | 2020-02-28 | 广东翔思新材料有限公司 | Halogen-free resin composition, covering film and preparation method |
| CN114149658A (en) * | 2021-12-31 | 2022-03-08 | 常熟生益科技有限公司 | Resin composition and low-flow-rate prepreg prepared from same |
| CN114716928A (en) * | 2022-02-09 | 2022-07-08 | 常州威斯双联科技有限公司 | Flame-retardant insulating thermosetting adhesive tape and preparation method thereof |
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| CN103074019A (en) * | 2013-01-22 | 2013-05-01 | 浙江华正新材料股份有限公司 | Halogen-free epoxy adhesive and flexible copper-clad plate prepared from same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102093670A (en) * | 2010-12-23 | 2011-06-15 | 广东生益科技股份有限公司 | Halogen-free flame retardant epoxy resin composition and copper clad plate prepared from same |
| CN102311613A (en) * | 2011-04-03 | 2012-01-11 | 广东生益科技股份有限公司 | Black halogen-free flame-retardant epoxy resin composition and adhesive film prepared from same |
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| CN103074019A (en) * | 2013-01-22 | 2013-05-01 | 浙江华正新材料股份有限公司 | Halogen-free epoxy adhesive and flexible copper-clad plate prepared from same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084663A (en) * | 2016-06-22 | 2016-11-09 | 柳州市强威锻造厂 | A kind of high impact strength epoxy resin cure formula |
| CN110845839A (en) * | 2019-08-08 | 2020-02-28 | 广东翔思新材料有限公司 | Halogen-free resin composition, covering film and preparation method |
| CN114149658A (en) * | 2021-12-31 | 2022-03-08 | 常熟生益科技有限公司 | Resin composition and low-flow-rate prepreg prepared from same |
| CN114149658B (en) * | 2021-12-31 | 2024-04-09 | 常熟生益科技有限公司 | Resin composition and low-gummosis prepreg prepared from same |
| CN114716928A (en) * | 2022-02-09 | 2022-07-08 | 常州威斯双联科技有限公司 | Flame-retardant insulating thermosetting adhesive tape and preparation method thereof |
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Application publication date: 20140402 |