CN103950251A - Formula and preparation technology of light fiber-reinforced thermoplastic resin composite sheet material with high flame resistance - Google Patents
Formula and preparation technology of light fiber-reinforced thermoplastic resin composite sheet material with high flame resistance Download PDFInfo
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Abstract
The invention discloses a formula and a preparation technology of a light fiber-reinforced thermoplastic resin composite sheet material with high flame resistance. The sheet material is composed of, 30-50% of reinforced fiber, 30-50% of thermoplastic resin fiber, 5-15% of halogen-free fire retardant powder and 5-15% of a bonding glue solution. The preparation technology comprises: weighing reinforced fiber and thermoplastic resin fiber according to the ratio, and performing preliminary mixing; utilizing a blower fan to convey reinforced fiber and thermoplastic fiber to a cotton storage bin; and utilizing the effect of free fall to enable fiber to be mixed fully, dispersed uniformly and the like. The light fiber-reinforced thermoplastic resin composite sheet material with high flame resistance has the advantages of simple production technology, low cost, excellent flame resistance and no obvious reduction on mechanical properties, is extremely applicable to fields of automotive trims, building decoration and the like, and has great practical value.
Description
Technical field
The present invention relates to the manufacture forming field of fiber-reinforced thermoplastic resin composite, specifically, is a kind of formula and preparation technology of light fibre enhancing thermoplastic resin composite board of high flame retardant.
Background technology
Light fibre strengthens thermoplas tic resin composite due to features such as its higher intensity, thermoplasticity, recyclable, easy-formation processing, in automobile by mainly as structural member and important spare part.Along with the exploitation in market, light fibre strengthens thermoplas tic resin composite and has developed into gradually the fields such as building industry, Furniture manufacture.
Self-burning of vehicle is not rarely seen repeatly, its security makes consumer worry endlessly, and the burning that the very most of reason of building fire is dalle causes with diffusion, therefore, the application that strengthens thermoplas tic resin composite along with light fibre is more and more extensive, its anti-flammability ever more important that also seems.
Light fibre strengthens thermoplas tic resin composite fire-retardantly should be noted that following problem:
1, thermoplastic resin has combustibility, lights after-combustion speed fast, and macromolecular chain is decomposed into rapidly flammable little molecule, accelerated combustion.
2, fortifying fibre can serve as " wick " when burning, and the peripheral combustion heat is delivered to inside, causes internal resin matrix constantly to decompose, and supplies with peripheral burning.
3, light fibre strengthens thermoplastic resin composite board owing to being porous sheet material, and during burning, oxygen more easily enters sheet material inside, causes the decomposition combustion of inner sheet material.And because fortifying fibre is generally rigid material, melting after thermoplastic resin is heated, resin melt intensity after melting is very low, make in sheet material crooked fortifying fibre can break through the bonding of resin, slowly straighten, so light fibre strengthens thermoplastic resin composite board and become more fluffy, it is large that hole becomes, change is many, causes flame propagation faster.
Main employing fortifying fibre and thermoplastic resin fibre that the light fibre that dry method needling process is produced strengthens thermoplastic resin composite board mix shredding, lapping, acupuncture becomes felt, then through being hot pressed into plate, its production technology is different from traditional wet production fiber-reinforced thermoplastic resin composite board technique, so it fire-retardantly cannot extrude realization by fire retardant and resin matrix melt blending.At present relevant light fibre strengthens the fire-retardant research of thermoplastic resin composite board and mainly concentrates on fire-retardant and use fire resistance fibre two broad aspect of post processing.First aspect is that post processing is fire-retardant, and major way has spraying, blade coating fire retardant, dipping fire retardant technique, outer multiple flame-retardant layer etc.Blade coating fire retardant main technique is: fire retardant and solvent are mixed and made into fire resistant fluid, mode by spraying or blade coating spreads upon fire retardant the surface of composite board uniformly again, make the fiber-reinforced thermoplastic resin composite board with surface flame-retardant layer, adopting this technique to prepare fire resistance fibre enhancing thermoplastic resin composite board advantage is that production technology is simple, although being sheet material extexine, shortcoming has certain flame retardant effect, but sheet material is inner or easily burning, and therefore this fire-retardant mode effect is limited; Dipping fire retardant main technique for to flood intermediate products in fire resistant fluid, allow fire retardant infiltrate sheet material inside, make the fiber-reinforced thermoplastic resin composite board of overall flame, patent CN101812773A discloses a kind of composite material for automobile interior part and production method thereof, and the production method of this invention is that raw material are evenly mixed, dropping into shredding in opener processes, combing is afterwards shaped, then sends into cross lapping in lapping machine, then sends in needing machine, to carry out acupuncture and become felt; Fibrofelt immerse is processed in slurries, and it is big or small that the coiled material having infiltrated is cut into requirement after heated-air drying, puts into the mould sizing that is heating and curing, and may be molded to composite plate after the demoulding; Composite plate is again after dull and stereotyped thermoplastic is processed, being covered with one deck facial ornament carries out cold moudling through product mold and makes finished product, patent CN200610154436.1 adopts dipping and scrapes coating method and prepared automotive trim flame-proof sheet material, fire-retardant, antibacterial, ageing-resistant good, but production technology is very complicated, production cycle is long, patent CN201120323746.8 has introduced the outer fire retardant felt structure of flame-retardant layer again, although there is certain flame retardant effect, but felt core or easily burning, so flame retardant effect is limited.
Be to prepare flame-retarded light fiber-reinforced thermoplastic resin composite board after using the fiber with fire retardation to mix with fortifying fibre on the other hand, this sheet material itself is owing to having mixed fire resistance fibre, so has anti-flammability.The advantage of using fire resistance fibre is that composite board need not carry out post processing and just can reach reasonable flame retardant effect, and fire resistance fibre has fire-retardant thermoplastic resin fiber as flame retardant polypropylene fibers, Flameproof polyamide fiber etc.; Also have some special fibres as aramid fiber, polyimide fiber, melamine fiber etc., patent CN201110259155.3 discloses a kind of glass fibre/flame-retardant polypropylene fibre light composite board and preparation method thereof, the light composite board of preparation has good flame retardant type, processing and forming and excellent comprehensive mechanical property, but fire resistance fibre processing cost is higher.
Therefore, the light fibre of seeking the high flame retardant that a kind of production technology is simple, cost is low strengthens thermoplastic resin composite board, extremely important to automotive trim industry, building decoration field, has very large practical value.
Summary of the invention
The present invention is directed to the problem of above-mentioned existence, the light fibre that has proposed a kind of high flame retardant strengthens formula and the preparation technology of thermoplastic resin composite board, fortifying fibre and thermoplastic resin fibre are carried out to shredding processing, carding, spray paste stick and fire retardant, then cross lapping, product in the middle of acupuncture becomes, middle product are through the slaking of tentering baking oven, and after press hot pressing, the cooling light fibre that obtains high flame retardant of cold pressing roller strengthens thermoplastic resin composite board.
The present invention is achieved by the following technical solutions:
The light fibre that the invention discloses a kind of high flame retardant strengthens thermoplastic resin composite board, by the fortifying fibre of 30-50%, the bonding glue of halogen-free flame retardants powder, 5-15% of the thermoplastic resin fibre of 30-50%, 5-15% form.
As improving further, fortifying fibre of the present invention is the mixture of one or more fibers in bamboo fibre, flaxen fiber, glass fibre, carbon fiber, basalt fibre.
As improving further, thermoplastic resin fibre of the present invention is the mixture of one or more polymer fibers in polypropylene fibre PP, Fypro PA, polyethylene terephthalate fiber PET, modified viscose fiber.
As improving further, the former filament diameter of thermoplastic resin fibre of the present invention is at 10-30 μ m, and the short length of cutting is 20-100mm.
As improving further, halogen-free flame retardants powder of the present invention is one or more the mixture in magnesium hydroxide, aluminium hydroxide, APP and pentaerythrite, phosphorus-nitrogen containing flame retardant, red phosphorus, Firebrake ZB, expanded graphite, described halogen-free flame retardants powder order number at 50 orders between 2000 orders.Described fire retardant is halogen-free environment-friendly type flame-proof agent, meets the requirement of environment-friendly flame retardant, and inorganic particulate can strengthen the mechanical property of composite board to a certain extent.
As improving further, the part by weight of APP of the present invention and pentaerythrite is 1:2～5:1;
As improving further, bonding glue of the present invention by the adhesive of 85-90%, the synergist of the coupling agent of 1-3%, 0.5-10%, the antioxidant of 0.1-3% form; Bonding glue can bond fire retardant powder and composite fibre, prevents fire retardant powder and drops because of the hollow out of fibre web, affects formula rate.
As improving further, adhesive of the present invention is one or more the mixture in polyurethane adhesive, acrylate adhesive, vinylacetate adhesive or synthetic rubber latex; Described coupling agent is one or more the mixture in titanate coupling agent, aluminate coupling agent, boric acid ester coupler or silane coupler;
As improving further, antioxidant of the present invention is at least one in antioxidant 1010, antioxidant 1076, antioxidant 1222, irgasfos 168; Described synergist is a kind of in sodium-based montmorillonite, alkylammonium salt intercalated montmorillonite, quaternary ammonium salts imvite.
The light fibre that the invention also discloses a kind of high flame retardant strengthens the preparation method of thermoplastic resin composite board, it is characterized in that, concrete preparation process is as follows:
(1), after being weighed in proportion, fortifying fibre, thermoplastic resin fibre tentatively mix;
(2), utilize blower fan, fortifying fibre, thermoplastic resin fibre are delivered to Chu Miancang, sharp freely falling body fully mixes fiber, is uniformly dispersed;
(3), composite fibre enters and feeds cotton machine, through thorn rod feeding breast cylinder, then enters large cylinder through transferring roller, composite fibre is carried out through dialling cotton roller, acting as mat after abundant combing;
(4), on mat, spray successively bonding glue, halogen-free flame retardants powder, then by product in the middle of being wound into after the mat multilayer accumulation after spraying after pre-thorn and the dual reinforcing sizing of main thorn; In this stage, add spray appliance, do not affect whole production procedure, than blade coating, impregnating technique, do not insert and need the technical process of operation separately, production technology is simple to operation;
(5), middle product carry out slaking by tentering baking oven, tentering oven temperature 140-250 ℃, speed 1-10m/min; By the slaking of tentering baking oven, middle product can be preheated, can shorten the heat treatment time in subsequent technique, shorten the production time, enhance productivity.
(6) in the middle of, after slaking, product and glued membrane and fabric are sent into hot press together with unreeling and are carried out hot pressing, press temperature 150-260 ℃, time 1-30 second, pressure 5-20MPa; The mechanical property that hot press carries out hot-forming, prepared composite board to the middle product of slaking be better than conventional roller suppress composite board;
(7) sheet material, after hot pressing carries out cooling and shaping through cold pressing roller, and cold pressing roller temperature, not higher than 50 ℃, is made flame-retarded light fiber-reinforced thermoplastic resin composite board.
As improving further, step of the present invention (1) to (4) is to carry out under temperature is room temperature 15-25 ℃, humidity 50%-65% environment.
The light fibre of high flame retardant of the present invention strengthens thermoplastic resin composite board and has following advantage with respect to other composite boards:
1, fire resistance is good, by horizontal firing, tests A-0 rank, and vertical combustion test can be put out certainly;
2, production technology, without impact, is inserted spray processing in the middle of ordinary student production. art, does not affect production efficiency, and than techniques such as wet method, blade coatings, production technology is simple to operation;
3, mechanical property, without reduction, even increases, inorganic particulate be added in the mechanical property that has strengthened to a certain extent composite board;
4, cost is low, uses cheap fire retardant to reach good flame retardant effect, and production cost is than using the composite board of flame retardant fiber significantly to reduce;
5, use halogen-free environment-friendly flame-proof agent, the compound requirement that meets environment-friendly flame retardant.
6, bonding glue can bond fire retardant powder and composite fibre, prevents fire retardant powder and drops because of the hollow out of fibre web, affects formula rate.
7, by the slaking of tentering baking oven, middle product can be preheated, can shorten the heat treatment time in subsequent technique, shorten the production time, enhance productivity.
8, the mechanical property that hot press carries out hot-forming, prepared composite board to the middle product of slaking be better than conventional roller suppress composite board;
Eventually the above, the light fibre of high flame retardant of the present invention strengthens thermoplastic resin composite board and has advantages of that production technology is simple, cost is low, fire resistance is excellent, mechanical property reduces without obvious, be applicable to being very much applied to the fields such as automotive trim, building decoration, have very large practical value.
The specific embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail:
Embodiment 1
By the polypropylene fibre of the basalt fibre of 40kg and 40kg in bale opener charging, through just mixed, be delivered to Chu Miancang, carding machine becomes thin net, then the bonding glue of 8kg is sprayed to thin online, again 12kg aluminium hydroxide fire retardant is sprayed on to composite fibre online, bonding glue is mixed by acrylate adhesive, 0.2kg titanate coupling agent, 0.8kg sodium-based montmorillonite, the 0.2kg antioxidant 1010 of 6.8Kg, to spray the composite fibre net process lapping machine lapping of fire retardant, then made intermediate products through needing machine.Intermediate products are carried out to slaking by 190 ℃ of tentering baking ovens, speed 5m/min then enters 210 ℃ of hot press hot pressing 2s and carries out moulding, pressure 10MPa together with nonwoven with glued membrane, through 25 ℃ of cold pressing roller cooling and shapings, make flame-retarded light fiber-reinforced thermoplastic resin composite board again.
Embodiment 2
By the Fypro of the bamboo fibre of 40kg and 40kg in bale opener charging, through just mixed, be delivered to Chu Miancang, carding machine becomes thin net, then the bonding glue of 12kg is sprayed to thin online, again 8kg flame retardant of magnesium hydroxide is sprayed on to composite fibre online, bonding glue is mixed by acrylate adhesive, 0.3kg titanate coupling agent, 1kg sodium-based montmorillonite, the 0.2kg antioxidant 1010 of 10.5Kg, to spray the composite fibre net process lapping machine lapping of fire retardant, then made intermediate products through needing machine.Intermediate products are carried out to slaking by 210 ℃ of tentering baking ovens, speed 4m/min then enters 230 ℃ of hot press hot pressing 10s and carries out moulding, pressure 10MPa together with nonwoven with glued membrane, through 25 ℃ of cold pressing roller cooling and shapings, make flame-retarded light fiber-reinforced thermoplastic resin composite board again.
Embodiment 3
By the polyester fiber of the carbon fiber fiber of 40kg and 40kg in bale opener charging, through just mixed, be delivered to Chu Miancang, carding machine becomes thin net, then the bonding glue of 8kg is sprayed to thin online, again 9kg APP and 3kg pentaerythrite fire retardant are sprayed on to composite fibre online, bonding glue is mixed by acrylate adhesive, 0.2kg titanate coupling agent, 0.8kg sodium-based montmorillonite, the 0.2kg antioxidant 1010 of 6.8Kg, to spray the composite fibre net process lapping machine lapping of fire retardant, then made intermediate products through needing machine.Intermediate products are carried out to slaking by 210 ℃ of tentering baking ovens, speed 4m/min, then enter 250 ℃ of hot press hot pressing 5s with glued membrane and carry out moulding together with nonwoven, then through 25 ℃ of cold pressing roller cooling and shapings, make flame-retarded light fiber-reinforced thermoplastic resin composite board.
Embodiment 4
The polypropylene fibre of the glass fibre of 50kg and 50kg, in bale opener charging, through just mixed, is delivered to Chu Miancang, and carding machine becomes thin net, and then Jiang Bao Netcom crosses lapping machine and is paved into certain number of plies net, then makes intermediate products through needing machine.Intermediate products are carried out to slaking by 190 ℃ of tentering baking ovens, speed 5m/min then enters 210 ℃ of hot press hot pressing 2s and carries out moulding, pressure 10MPa together with nonwoven with glued membrane, through 25 ℃ of cold pressing roller cooling and shapings, make light fibre and strengthen thermoplastic resin composite board again.
According to testing standard GB8410-2006, the sheet material in embodiment has been carried out to flame retardant test, the results are shown in Table 1
Table 1
Result from table can be found out, do not add the formula 4 of any fire retardant, burn rate is at 50mm/min, and 1,2, the 3 comparative example results of having added fire retardant show that burning grade significantly improves, illustrate that flame retardant effect obviously improves, contrasted in addition mechanical property, found that fire retardant adds rear mechanical property to be had no significant effect.
What more than enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, can also have many distortion, all distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (9)
1. the light fibre of high flame retardant strengthens a thermoplastic resin composite board, it is characterized in that, by the fortifying fibre of 30-50%, the bonding glue of halogen-free flame retardants powder, 5-15% of the thermoplastic resin fibre of 30-50%, 5-15% form.
2. the light fibre of high flame retardant according to claim 1 strengthens thermoplastic resin composite board, it is characterized in that, described fortifying fibre is the mixture of one or more fibers in bamboo fibre, flaxen fiber, glass fibre, carbon fiber, basalt fibre.
3. the light fibre of high flame retardant according to claim 1 strengthens thermoplastic resin composite board, it is characterized in that, described thermoplastic resin fibre is the mixture of one or more polymer fibers in polypropylene fibre PP, Fypro PA, polyethylene terephthalate fiber PET, modified viscose fiber.
4. the light fibre of high flame retardant according to claim 3 strengthens thermoplastic resin composite board, it is characterized in that, the former filament diameter of described thermoplastic resin fibre is at 10-30 μ m, and the short length of cutting is 20-100mm.
5. the light fibre of high flame retardant according to claim 1 strengthens thermoplastic resin composite board, it is characterized in that, described halogen-free flame retardants powder is one or more the mixture in magnesium hydroxide, aluminium hydroxide, APP and pentaerythrite, phosphorus-nitrogen containing flame retardant, red phosphorus, Firebrake ZB, expanded graphite, described halogen-free flame retardants powder order number at 50 orders between 2000 orders.The light fibre of high flame retardant according to claim 5 strengthens thermoplastic resin composite board, it is characterized in that, described APP and the part by weight of pentaerythrite are 1:2～5:1.
6. the light fibre of high flame retardant according to claim 1 strengthens thermoplastic resin composite board, it is characterized in that, described bonding glue by the adhesive of 85-90%, the synergist of the coupling agent of 1-3%, 0.5-10%, the antioxidant of 0.1-3% form.
7. the light fibre of high flame retardant according to claim 6 strengthens thermoplastic resin composite board, it is characterized in that, described adhesive is one or more the mixture in polyurethane adhesive, acrylate adhesive, vinylacetate adhesive or synthetic rubber latex; Described coupling agent is one or more the mixture in titanate coupling agent, aluminate coupling agent, boric acid ester coupler or silane coupler; Described antioxidant is at least one in antioxidant 1010, antioxidant 1076, antioxidant 1222, irgasfos 168; Described synergist is a kind of in sodium-based montmorillonite, alkylammonium salt intercalated montmorillonite, quaternary ammonium salts imvite.
8. according to the light fibre of the high flame retardant described in claim 1 to 7 any one, strengthen the preparation method of thermoplastic resin composite board, it is characterized in that, concrete preparation process is as follows:
(1), after being weighed in proportion, fortifying fibre, thermoplastic resin fibre tentatively mix;
(2), utilize blower fan, fortifying fibre, thermoplastic resin fibre are delivered to Chu Miancang, sharp freely falling body fully mixes fiber, is uniformly dispersed;
(3), composite fibre enters and feeds cotton machine, through thorn rod feeding breast cylinder, then enters large cylinder through transferring roller, composite fibre is carried out through dialling cotton roller, acting as mat after abundant combing;
(4), on mat, spray successively bonding glue, halogen-free flame retardants powder, then by product in the middle of being wound into after the mat multilayer accumulation after spraying after pre-thorn and the dual reinforcing sizing of main thorn;
(5), middle product carry out slaking by tentering baking oven, tentering oven temperature 140-250 ℃, speed 1-10m/min;
(6) in the middle of, after slaking, product and glued membrane and fabric are sent into hot press together with unreeling and are carried out hot pressing, press temperature 150-260 ℃, time 1-30 second, pressure 5-20MPa;
(7) sheet material, after hot pressing carries out cooling and shaping through cold pressing roller, and cold pressing roller temperature, not higher than 50 ℃, is made flame-retarded light fiber-reinforced thermoplastic resin composite board.
9. the light fibre of described high flame retardant according to claim 8 strengthens the preparation method of thermoplastic resin composite board, it is characterized in that, described step (1) to (4) is to carry out under temperature is room temperature 15-25 ℃, humidity 50%-65% environment.
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