CN101338174B - Environment protection type halogen-free flame-retardant hot-melt adhesive film for conducting cloth - Google Patents
Environment protection type halogen-free flame-retardant hot-melt adhesive film for conducting cloth Download PDFInfo
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- CN101338174B CN101338174B CN2008100218186A CN200810021818A CN101338174B CN 101338174 B CN101338174 B CN 101338174B CN 2008100218186 A CN2008100218186 A CN 2008100218186A CN 200810021818 A CN200810021818 A CN 200810021818A CN 101338174 B CN101338174 B CN 101338174B
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- red phosphorus
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Abstract
The invention relates to an environment protection halogen-free flame retardant polyamide hot melt glue film for electricity conducting fabrics which comprises raw materials with the following weight portions of 15-35 portions of tripentaerythritol, 5-15 portions of micro-capsulated red phosphorus, 10-35 portions of melamine cyanurate and 3-15 portions of DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide). The environment protection halogen-free flame retardant polyamide hot melt glue film for electricity conducting fabrics of the invention has the advantages of moisture absorb-free, nontoxic and no dense smoke production and is accorded with the environmental protection requirement.
Description
(1) technical field
The present invention relates to a kind of hot melt adhesive film, relate in particular to a kind of environmental-friendly halogen-free flame-retardant hot-melt adhesive film that is used for conductive fabric.
(2) background technology
Conductive fabric is widely used in electron trade.Because the singularity of electron trade, the accessory of electronic product is required to reach UL94V-0, therefore the use to conductive fabric has fire-retardant requirement.Conductive fabric itself is not fire-retardant, reaches fire-retardant requirement by the fire retardant hot-melt film adhesive in user that is combined with each other, and is because the conductive fabric thermal conductivity is good, more fire-retardant than the more difficult realization of general cloth.Used in the past fire retardant hot-melt film adhesive in user contains halogen flame, as the polybromodiphenyl ether class, and tetrabromo-bisphenol class, bromobenzene phenols and chlorine-based flame retardant etc.The patent of ZL200510094909.9 has been announced the environmental protection fire retardant hot-melt film adhesive in user that is used for conductive fabric, though its flame retardant resistance is good, but shortcoming is hydrogenchloride (HCL), hydrogen bromide (HBr) and other the poisonous organic halogen compound that generates strong toxicity when burning, secondly, halogen containing flame-retardant general and antimonous oxide and usefulness make that so the living cigarette amount of material is higher.From Switzerland scientist reported first in 1986 the Poly Brominated Diphenyl Ethers fire retardant when burning, can produce many bromos dibenzodioxin English and PBDF (the two all belongs to the listed carcinogenic substance category in international cancer center, prohibite in Europe) since, toxicity such as bromide fire retardants such as polybromodiphenyl ether has caused global common concern, the non-halogen cry of fire retardant is also more and more higher, and the halogen-free flameproof product of the few cigarette of development low toxicity, efficient green also just becomes one of important subject of flame retardant area in recent years.The fire retardant hot-melt film adhesive in user that is used for conductive fabric is required to fit behind the conductive fabric in the electron trade, can make the integral body that comprises conductive fabric realize the fire-retardant requirement of UL94V-0 level, putting before this, the flame-retardant hot-melt adhesive film thickness is got over Bao Yuehao, existing flame-retardant hot-melt adhesive film thickness causes the conductive fabric flexibility poor about 0.15mm.In addition, some is used for the fire retardant hot-melt film adhesive in user of conductive fabric, contains component soluble in water in the glued membrane, causes can occur suction after for some time and become wet phenomenon, and is unfavorable to the use of conductive fabric.
(3) summary of the invention
Content of the present invention is to overcome with above-mentioned deficiency, and a kind of environmental-friendly halogen-free flame-retardant hot-melt adhesive film that is used for conductive fabric non-hygroscopic, nontoxic, that do not produce thick smoke when burning is provided.
The object of the present invention is achieved like this: a kind of environmental-friendly halogen-free flame-retardant hot-melt adhesive film that is used for conductive fabric, and it is mainly to be made up of the raw material of following weight part:
30～60 parts of polyamide hots
15～35 parts of tripentaerythritols
5～15 parts in micro encapsulation red phosphorus
10～35 parts of melamine cyanurates
3～15 parts of DOPO (9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound).
The present invention is used for the environmental-friendly halogen-free flame-retardant hot-melt adhesive film of conductive fabric, it is characterized in that described micro encapsulation red phosphorus is that melamine resin coats micro encapsulation red phosphorus.
The present invention is used for the environmental-friendly halogen-free flame-retardant hot-melt adhesive film of conductive fabric, it is characterized in that described micro encapsulation red phosphorus is melamine resin/zinc borate double-coated micro encapsulation red phosphorus.
The present invention is used for the environmental-friendly halogen-free flame-retardant hot-melt adhesive film of conductive fabric, and polyamide hot plays the melted by heat bonding effect therein in the raw material, has higher softening temperature and good cementability; Polyamide hot itself can reach the flame-retardant standard of UL94V-0.
What the present invention was used for that the environmental-friendly halogen-free flame-retardant hot-melt adhesive film of conductive fabric mainly adopts is with cohesion
Phase fire retardant mechanism performance fire retardation is made up of charcoal source, acid source and source of the gas three parts.The charcoal source is the material that can generate porous expansion charcoal layer, and acid source is to discharge inorganic acid compound under heating condition, and source of the gas is the compound that is subjected to heat release rare gas element.During burning, charcoal source and the acid source inorganic acid compound that discharges that is heated carries out esterification, then dehydration carbonization, the water vapour that produces in the reaction process and make the charing system foaming that is in molten state by the non-flammable gases that source of the gas produces during this time, form porous expansion charcoal layer, it can play heat insulation, oxygen barrier, press down cigarette, anti-molten drop and the effect that stops combustible gas to enter, in burning in early days with burn-out.
Tripentaerythritol plays the effect in charcoal source at the flame-retardant hot-melt adhesive film system.Tripentaerythritol is a kind of tetravalent alcohol of typical neopentyl structure, has the typical chemical property of polyvalent alcohol, can carry out the various reactions that polyvalent alcohol can participate in, as nitrated, oxidation, etherificate, esterification, halo etc.Tripentaerythritol is dehydrated into charcoal with acid-respons that acid source produces as the charcoal source under high temperature action, the generation of charcoal has important effect to suppressing the matrix polymer thermal destruction and improving its flame retardant properties, carbide forms the charcoal layer bulk, that enclosed construction is arranged under the gas effect that source of the gas decomposes, this charcoal layer can stop the thermal conduction between base material and thermal source, the porous charcoal layer can stop gaseous diffusion in addition, stop external oxygen to be diffused into substrate surface simultaneously, reach fire-retardant purpose.In addition, tripentaerythritol is slightly soluble in water, with the charcoal source of tripentaerythritol as the flame-retardant hot-melt adhesive film system, can not produce because of the moisture absorption makes the wet phenomenon of fire retardant hot-melt film adhesive in user surface change, is more conducive to be used for the conductive fabric surface filming and uses.
Red phosphorus is a kind of fire retardant efficiently, and fire retardant mechanism is: decomposes, and formation has the metaphosphoric acid of extremely strong dehydration property, thereby makes the charing of incendiary polymer surfaces, and charring layer can reduce emitting of inflammable gas on the one hand, also has heat-absorbing action on the other hand.But in use, have following problem: inflammable in the transportation, easy oxidation, easy moisture absorption during use, with defective such as resin compatible difference, generally be difficult to directly use as fire retardant.
The micro encapsulation red phosphorus that adopts among the present invention is that one deck or which floor red phosphorus surface after grinding coat continuously and compact protective film forms micro encapsulation red phosphorus.It in the premium properties that has kept red phosphorus, the shortcoming when having overcome its original transportation, safe and convenient to use, because the existence of melamine resin layer reduces its water-intake rate, improve simultaneously with resin compatible.Micro encapsulation red phosphorus and common not encapsulated red phosphorus performance are compared as follows table:
| Performance index | Micro encapsulation red phosphorus | Common red phosphorus |
| Moisture uptake (%) | 1.2 | 10.5 |
| Spontaneous ignition temperature (℃) | 320—500 | 210 |
| PH value changes | 0.8 | 3.5 |
| Phosphuret-(t)ed hydrogen burst size----(ug/g) in air | <1 | 18 |
| Phosphuret-(t)ed hydrogen burst size----(ug/g) in water | <2 | 485 |
| The migration or ooze out | Nothing is oozed out | Ooze out and migrate to the surface and form greasy pass acidic substance |
| Particle diameter (red phosphorus powder) | Order carefully, 〉=320 | Order slightly,＜=150 |
| The dimensional stability of making | Good | Difference (long-time effect) |
Micro encapsulation red phosphorus is as the acid source in the flame-retardant hot-melt adhesive film system, the rapid aquation of hydrogenated products that produces when making red phosphorus in burning in the presence of the steam that the melamine cyanurate pyrolytic decomposition produces becomes phosphoric acid, the phosphoric acid condensation generates the poly-glassy coverture of metaphosphoric acid, in the presence of melamine cyanurate, promote poly-metaphosphoric acid and tripentaerythritol to carry out esterification, quicken the dehydration carbonization of tripentaerythritol, the liquid film of formation and charcoal layer separate oxygen, volatile fuel and the heat of outside and inner superpolymer base material and help the incendiary interruption.
Melamine cyanurate serves as the effect of source of the gas in the flame-retardant hot-melt adhesive film system, can be used as the catalyzer of esterification simultaneously, and accelerated reaction is carried out.Its nontoxic odorless, tasteless, decomposition temperature height (very stable below 300 ℃, more than 600 ℃ decompose), good flame retardation effect not only, and also it is little to add man-hour smog, and good with the macromolecular material consistency, no surface transport phenomenon.The NH that produces when melamine cyanurate is heated
3, N
2, the water vapor non-flammable gases makes the system foaming that is in molten state, the generation of water vapor makes red phosphorus become phosphoric acid in the rapid aquation of hydrogenated products that burning produces, the phosphoric acid condensation generates the poly-glassy coverture of metaphosphoric acid, has given full play to the fire retardation of red phosphorus.Melamine cyanurate has the characteristics of nontoxic low cigarette in combustion processes, do not have the melts drippage basically.
DOPO (9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound) is soluble in methyl alcohol, ethanol, chloroform, dimethyl formamide, dioxy chlorine ring, dissolves in benzene, water insoluble, hexane.The luxuriant and rich with fragrance class annular phosphate of phosphorus is the organic phosphates heterogeneous ring compound.Has higher thermostability, oxidation-resistance and good water tolerance.Because this fire retardant has phosphorus-to-carbon bonds, flame retardant properties is better than general phosphoric acid ester.DOPO (9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound) polyamide hot there is good plasticity, the consistency of reinforced polyamide hot melt adhesive and tripentaerythritol, micro encapsulation red phosphorus and melamine cyanurate, the flowability and the film-forming properties of raising component.
The present invention is used for the environmental-friendly halogen-free flame-retardant hot-melt adhesive film of conductive fabric, and non-hygroscopic, nontoxic, burning the time does not produce thick smoke, flame retardant properties is good, and compliance with environmental protection requirements will.It is compound in the conductive fabric surface, and film thickness can reach the fire-retardant requirement of UL94V-0 level at 0.12mm, makes the conductive fabric snappiness good, is beneficial to the use of conductive fabric.
(4) embodiment
Embodiment 1:
The red phosphorus of micro encapsulation described in the table is that melamine resin coats micro encapsulation red phosphorus.
Step 1, with each raw material in the B component press the described proportioning of above table mix stir standby;
Get the A component and add in the stirrer, Heating temperature to 150 ℃ adds B component after above-mentioned mixing is stirred again up to the A fusing, and heating keeps 150 ℃ of temperature constant, stir compound;
Step 2, step 1 gained compound is placed granulation in the tablets press, oven dry, hot melt adhesive tablet;
Step 3, step 2 gained hot melt adhesive tablet placed make the tubular glued membrane in the blowfilm shaping machine;
Step 4, use side cutter cuts both sides make the tubular glued membrane become biplate shape glued membrane, film thickness 0.12mm.
Embodiment 2:
The red phosphorus of micro encapsulation described in the table is melamine resin/zinc borate double-coated micro encapsulation red phosphorus.
Institute is in steps with embodiment 1.
Embodiment 3:
The red phosphorus of micro encapsulation described in the table is melamine resin double-coated micro encapsulation red phosphorus.
Institute is in steps with embodiment 1.
Claims (3)
1. environmental-friendly halogen-free flame-retardant hot-melt adhesive film that is used for conductive fabric, it is mainly to be made up of the raw material of following weight part:
30～60 parts of polyamide hots
15～35 parts of tripentaerythritols
5～15 parts in micro encapsulation red phosphorus
10～35 parts of melamine cyanurates
9, the 10-dihydro-9-oxy is assorted-the 10-phospho hetero phenanthrene-3～15 parts of 10-oxide compounds.
2. the environmental-friendly halogen-free flame-retardant hot-melt adhesive film that is used for conductive fabric as claimed in claim 1 is characterized in that described micro encapsulation red phosphorus is that melamine resin coats micro encapsulation red phosphorus.
3. the environmental-friendly halogen-free flame-retardant hot-melt adhesive film that is used for conductive fabric as claimed in claim 1 is characterized in that described micro encapsulation red phosphorus is melamine resin/zinc borate double-coated micro encapsulation red phosphorus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100218186A CN101338174B (en) | 2008-08-14 | 2008-08-14 | Environment protection type halogen-free flame-retardant hot-melt adhesive film for conducting cloth |
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| CN2008100218186A CN101338174B (en) | 2008-08-14 | 2008-08-14 | Environment protection type halogen-free flame-retardant hot-melt adhesive film for conducting cloth |
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| CN101338174A CN101338174A (en) | 2009-01-07 |
| CN101338174B true CN101338174B (en) | 2011-03-09 |
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| CN2008100218186A Expired - Fee Related CN101338174B (en) | 2008-08-14 | 2008-08-14 | Environment protection type halogen-free flame-retardant hot-melt adhesive film for conducting cloth |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103484053A (en) * | 2013-10-16 | 2014-01-01 | 上海天洋热熔胶有限公司 | Preparation method of hot-melt adhesive for conductive fabrics |
| CN103740320A (en) * | 2014-01-15 | 2014-04-23 | 长园电子（集团）有限公司 | Halogen-free flame retardant polyamide hot-melt adhesive and preparation method thereof |
| FR3032445A1 (en) * | 2015-02-05 | 2016-08-12 | Arkema France | DELAYED COMBUSTIBILITY POLYAMIDE COMPOSITION |
| CN105602004A (en) * | 2016-01-20 | 2016-05-25 | 天津商业大学 | Double-wall microencapsulated red phosphorus and preparation method and waterborne polyurethane flame-retardant film thereof |
| CN109627744A (en) * | 2018-12-08 | 2019-04-16 | 深圳市中创卓越科技有限公司 | A kind of flame retardant type material and its preparation process |
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| CN1632057A (en) * | 2004-11-09 | 2005-06-29 | 四川大学 | Melamine cyanuric acid red phosphorous-based microcapsule and its preparation method and use |
| CN1760297A (en) * | 2005-10-19 | 2006-04-19 | 江阴科隆化工材料有限公司 | Environmental protection fire retardant hot-melt film adhesive in user for electric clothes |
| CN1876716A (en) * | 2005-06-08 | 2006-12-13 | 德古萨公司 | Flame retarded polyamide moulding composition |
| WO2007031450A1 (en) * | 2005-09-16 | 2007-03-22 | Ciba Specialty Chemicals Holding Inc. | Polyurethane flame retardant compositions |
| WO2007042446A1 (en) * | 2005-10-12 | 2007-04-19 | Basf Se | Flameproof molding compounds |
| CN101125949A (en) * | 2007-09-15 | 2008-02-20 | 佛山市顺德区高怡新塑料有限公司 | Halogen-free flame-proof felt heat-resistance ABS/PA and its preparation method |
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2008
- 2008-08-14 CN CN2008100218186A patent/CN101338174B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1632057A (en) * | 2004-11-09 | 2005-06-29 | 四川大学 | Melamine cyanuric acid red phosphorous-based microcapsule and its preparation method and use |
| CN1876716A (en) * | 2005-06-08 | 2006-12-13 | 德古萨公司 | Flame retarded polyamide moulding composition |
| WO2007031450A1 (en) * | 2005-09-16 | 2007-03-22 | Ciba Specialty Chemicals Holding Inc. | Polyurethane flame retardant compositions |
| WO2007042446A1 (en) * | 2005-10-12 | 2007-04-19 | Basf Se | Flameproof molding compounds |
| CN1760297A (en) * | 2005-10-19 | 2006-04-19 | 江阴科隆化工材料有限公司 | Environmental protection fire retardant hot-melt film adhesive in user for electric clothes |
| CN101125949A (en) * | 2007-09-15 | 2008-02-20 | 佛山市顺德区高怡新塑料有限公司 | Halogen-free flame-proof felt heat-resistance ABS/PA and its preparation method |
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Owner name: JIANGYIN WEITAO PLASTIC NEW MATERIAL CO., LTD. Free format text: FORMER OWNER: KELONG CHEMICAL MATERIAL CO., LTD., JIANGYIN Effective date: 20141128 |
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Effective date of registration: 20141128 Address after: 214423, No. 22, Longteng Road, Zhou Village, Zhouzhuang Town, Jiangyin City, Jiangsu, Wuxi Patentee after: JIANGYIN WEITAO PLASTIC NEW MATERIAL CO., LTD. Address before: 214423 No. 6 Longteng Road, West Industrial Zone, Zhouzhuang Town, Jiangsu, Jiangyin Patentee before: Jiangyin Kelong Chemical Materials Co., Ltd. |
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