CN105111659B - A kind of transparent flame-retarding composite that infrared can be penetrated and preparation method thereof - Google Patents
A kind of transparent flame-retarding composite that infrared can be penetrated and preparation method thereof Download PDFInfo
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- CN105111659B CN105111659B CN201510620810.1A CN201510620810A CN105111659B CN 105111659 B CN105111659 B CN 105111659B CN 201510620810 A CN201510620810 A CN 201510620810A CN 105111659 B CN105111659 B CN 105111659B
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Abstract
The present invention relates to resin combination preparing technical field, more particularly to a kind of transparent flame-retarding composite that infrared can be penetrated and preparation method thereof, the composite includes the material component of following parts by weight：70 83 parts of MABS resins, 10 20 parts of brominated triazine, 15 parts of oligomeric aryl phosphate ester, 38 parts of toughener, 0.1 0.5 parts of laser engraving auxiliary agent, 0.2 0.5 parts of antioxidant, 0.9 2 parts of polyamide wax, 0 2.0 parts of toner.ABS composite material produced by the present invention, environmental requirement is not only conformed with, also with excellent laser engraving function, infrared penetration effect, the high grade of transparency and fire resistance and excellent injection molding performance；Gather around and have been widely used in remote control electrical appliance field, general infrared of alternative in the market penetrates makrolon material.
Description
Technical field
The present invention relates to resin combination preparing technical field, more particularly to a kind of transparent flame-retarding that infrared can penetrate is compound
Material and preparation method thereof.
Background technology
Infrared ray permeable material can allow for the infrared ray in a certain particular range of wavelengths to pass through, and will not produce absorption
And reflection.As the critical material in infrared technique, infrared ray permeable material is widely used in infrared remote controller reception, infrared ray
Inductor, glasses, night vision instrument, infrared ray etc..It is transparent that conventional red outside line permeable material is generally PC, PMMA, MABS and PS etc.
Material is made, although PC has high transparency and fire resistance, PC melting temperatures are high, hardly possible processing, not chemical-resistant reagent,
And the product internal stress of injection molding is big, easily cracking, limits its application in field of household appliances.Although and PMMA, MABS, PS
Equally there is the high grade of transparency, the advantage of easy processing, but these materials are combustible material, seriously limit these materials in electricity
The application in device field.
Each provided in golden hair patent CN103289293 and CN103289294 a kind of transparent flame-retarding ABS materials and
Transparent flame-retarding anti-static material.But both materials are required to actively to add antimony oxide and can be only achieved fire resistance, and antimony sheet
Body is non-renewable resources, is to belong to heavy metal again, is unfavorable for the protection of environment, although material prepared by patent has high transparency
Degree, but material made from the patent does not possess infrared ray and passed through and laser engraving function.
Therefore, need badly in the industry develop it is a kind of it is environmentally friendly, there is laser engraving function and the transparent flame-retarding material that infrared can penetrate
Material.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of transparent flame-retarding composite wood that infrared can be penetrated
Material and preparation method thereof, heavy metal antimony content is less than 1000ppm in obtained ABS composite material, not only conforms with environmental requirement, also
With excellent laser engraving function, infrared penetration effect, the high grade of transparency, good fire resistance and excellent injection molding
Performance；It is widely used in infrared remote controller reception, infrared inductor, glasses, night vision instrument, infrared ray etc..
The present invention is achieved through the following technical solutions.
A kind of transparent flame-retarding composite that infrared can be penetrated, include the material component of following parts by weight：
MABS resin 70-83 parts
Brominated triazine 10-20 parts
Oligomeric aryl phosphate ester 1-5 parts
Toughener 3-8 parts
Laser engraving auxiliary agent 0.1-0.5 parts
Antioxidant 0.2-0.5 parts
Polyamide wax 0.9-2 parts.
The transparency of material produced by the present invention, transparency is higher, and infrared penetration performance is better, and the bromine that the present invention selects
It is transparent for triazine, oligomeric aryl phosphate ester, toughener, laser engraving auxiliary agent, antioxidant, polyamide wax and toner etc.
Small-particulate materials, the scattering and barriering effect to light and infrared ray are strong, and the transparency of obtained material is high, infrared penetration performance
It is good.
Preferably, a kind of transparent flame-retarding composite that infrared can be penetrated, the material component of following parts by weight is included：
MABS resin 70-80 parts
Brominated triazine 12-18 parts
Oligomeric aryl phosphate ester 2-4 parts
Toughener 3-6 parts
Laser engraving auxiliary agent 0.1-0.2 parts
Antioxidant 0.2-0.4 parts
Polyamide wax 0.9-1.8 parts.
It is highly preferred that a kind of transparent flame-retarding composite that infrared can be penetrated, include the material component of following parts by weight：
MABS resin 70-83 parts
Brominated triazine 10-20 parts
Oligomeric aryl phosphate ester 1-5 parts
Toughener 3-8 parts
Laser engraving auxiliary agent 0.1-0.5 parts
Antioxidant 0.2-0.5 parts
Polyamide wax 0.9-2 parts
Toner 0.1-2.0 parts.
It is further preferred that a kind of transparent flame-retarding composite that infrared can be penetrated, include the raw material of following parts by weight
Component：
MABS resin 70-80 parts
Brominated triazine 12-18 parts
Oligomeric aryl phosphate ester 2-4 parts
Toughener 3-6 parts
Laser engraving auxiliary agent 0.1-0.2 parts
Antioxidant 0.2-0.4 parts
Polyamide wax 0.9-1.8 parts
Toner 0.5-2.0 parts.
The toner is the dyestuff of a variety of colors；Because pigment is to be woven into a manner of physical dispersion in media, dyestuff is
It is dissolved in media.It is particle shape that pigment, which exists in media, and dyestuff is molecularity.These the presence sides of toner in plastic matrix
Formula, directly affect the transparency and infrared penetration rate of material.Specifically, the toner include BLUE RRFG, G are green, 3G is orange,
5B is purple, H3G is red, 136 yellow one or more.Toner species and addition are adjusted according to client's color demand.Wherein, it is described to swash
Light carves auxiliary agent as antimony and the mixture of tin oxide, and the mass ratio of antimony and tin oxide is 1-2:8-9, its particle diameter are less than 1 μm, and antimony contains
Amount is less than 1000ppm.The particle diameter of antimony and tin oxide is respectively less than 1 μm, and the trade mark of the laser engraving auxiliary agent is YX001, manufacturer
For Yin Xi engineering plastics Co., Ltd.
The preparation method of the laser engraving auxiliary agent is：Antimony and tin oxide are weighed in proportion, then grinding refinement, cross 10000
Eye mesh screen, mixture surface are surface-treated using coupling agent, are dried and be can obtain YX001 laser engraving auxiliary agents.
Laser engraving is also known as laser carving, is to carry out local irradiation to workpiece using the laser of high-energy-density, makes Surface sheet
Material vaporization or the chemical reaction that color change occurs, so as to leave a kind of marking method of permanent marker.Antimony can with tin oxide
Effectively to propose the absorption of laser energy, heat energy is converted light energy into, material surface is easier that chemical change occurs, and plays mark and makees
With the laser engraving auxiliary agent that antimony is prepared with tin oxide is during engraving so that engraving font is apparent, and pattern effect is more preferable.
When the particle diameter of laser engraving auxiliary agent is more than 1 μm, the transparency of material can be reduced, reduces infrared penetration rate, of the invention swashs
The particle diameter of light engraving auxiliary agent is less than 1 μm, advantageously ensures that the transparency and infrared penetration rate of material, and laser engraving performance is excellent
It is different.
Wherein, the melt index of the MABS resins is 20-30g/10min, and notch impact strength is more than 15KJ/M2, thoroughly
Lightness is more than 85.The MABS resins are the products that the trade mark of LG Chemical Co., Ltd.s production is TR557.
MBS abbreviation MABS, has a high grade of transparency, the advantage of easy processing,
Its melt index is up to 20-30 g/10min, and obtained material has high fluidity, exempts from that spraying effect is good, in addition, material is strong
Degree is high, transparency is up to 85, it is ensured that obtained composite has the high grade of transparency and excellent injection molding performance, can use extensively
Received in infrared remote controller, infrared inductor, glasses, night vision instrument, infrared ray etc..
Wherein, the particle diameter of the brominated triazine is less than 5 μm, it is preferable that the particle diameter of brominated triazine is 1-5 μm.Brominated triazine
The trade mark be SR245, manufacturer is Japanese first industrial pharmaceutical company.
Brominated triazine is a kind of BACN with bromine/nitrogen synergistic effect, because adding particulate material in material,
There are scattering and iris action to light and infrared ray, particle size is more than 5 μm, and the scattering to light and infrared ray is imitated with barrier
Fruit is stronger, and transparency is poorer, and infrared penetration rate is smaller.If particle diameter is too small, easily reunites, be not easy to disperse, influence flame retardant effect.
The particle diameter of the brominated triazine of the present invention is preferably 1-5 μm, it is ensured that its scattering and barriering effect to light and infrared ray is strong, transparent
Degree is high, and infrared penetration rate is high, and is not easy to reunite, good flame retardation effect.
Wherein, the oligomeric aryl phosphate ester is the powdered substance that fusing point is more than 90 DEG C.Oligomeric aryl phosphate ester belongs to
Phosphorus flame retardant, trade mark PX-2202, manufacturer are Zhejiang Wansheng Co., Ltd..
Oligomeric aryl phosphoric acids are the powdered oligomeric aryl phosphate esters that a kind of fusing point is more than 90 DEG C；Choose dystectic low
Poly- aryl phosphate ester, it is that mixture temperature can raise, if fusing point is too low, easily cause to mix because in high-speed agitating process
Thing lumps, and influences mixed effect and blocks blanking pipe.Oligomeric aryl phosphoric acids form synergistic effect with brominated triazine, improve fire-retardant
Efficiency.Specifically, the oligomeric aryl phosphate ester includes poly aryl phosphate ester.
Wherein, the toughener is the MBS ternary polymerization with nucleocapsid structure
Thing, its particle diameter are less than 200nm.
The MBS terpolymer of the present invention is that the MBS trade mark is M711, production
Producer is Japanese Zhong Yuan.MBS resins are methyl methacrylates（M）, butadiene（B）And styrene（S）Terpolymer, it
With typical nucleocapsid structure.After the blended melting such as MBS resins and MABS resins, the compatibility of material is good, is advantageous to carry
The clear homogeneous of material is risen, and improves the impact strength of its product, while the cold resistance of product can also be improved and added
Work mobility.The particle diameter of MBS resins is only less than 200nm, and light could be by that will not produce scattering effect, improve composite wood
The transparency of material.
Wherein, the antioxidant is that primary antioxidant and auxiliary anti-oxidant are 1 by mass percentage:1 mixture, primary antioxidant
For antioxidant 1010 or antioxidant 1076, auxiliary antioxidant is irgasfos 168 or antioxidant 626.
Double (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites abbreviation antioxidant 626, not only to hydroperoxides
Capacity of decomposition is strong, containing available phosphorus amount it is high, meet the trend of antioxidant molecular weight, it is and stable improving product processing
Property, improve weatherability, assign excellent color etc. and all show excellent effect.
The present invention uses primary antioxidant and auxiliary anti-oxidant to improve material than configuring the antioxidant formed with extra fine quality
Antioxygenic property, and do not influence infrared penetration performance and the laser engraving performance of material, antioxidant effect is good, obtained compound
The processing characteristics of material is more excellent.
Wherein, the antioxidant is by BASF IRGANOX1010 and IRGANOX168 by weight 1:1 ratio mixing and
Into.
The antioxidant that BASF IRGANOX1010 and IRGANOX168 are configured to can delay or suppress the present invention and aoxidize
The progress of journey, so as to prevent the aging of the present invention and extend its service life.
Wherein, the dropping point of the polyamide wax is 35-145 DEG C, acid number 5-7mgkoh/g, saponification number 0.
The trade mark of the polyamide wax of the present invention is FA1, and manufacturer is Clariant Chimie S. A.Polyamide wax
It is a kind of thixotropy additive.It is effectively activated by solvent, and powerful network structure is formed in paint system, and its is excellent
Different thixotropic property, there is excellent resist sagging ability, anti-settling ability.Choose the polyamides of specific dropping point, acid number and saponification number
Amine wax is used in the present invention, can improve the mobility and release property of the present invention, prevent raw material from being adhered in extruder and produce fish
The defects of eye, and the high fluidity energy and transparency of composite are lifted, be advantageous to be lifted the infrared penetrability of composite
Energy.
A kind of preparation method for the transparent flame-retarding composite that infrared can be penetrated, comprises the following steps：
Step（1）, precise above-mentioned raw materials in proportion, put it into high-speed mixer and be sufficiently stirred 5-10 minutes
Compound is formed, material puddles rotating speed and turns/min for 180-220；
Step（2）, add mixture into double screw extruder, after melting, extrude, being granulated and drying, produce
Finished product；Wherein, extruder includes nine processing districts, and the processing temperature of each processing district is 180-230 DEG C, the vacuum of extruder
>=0.08MPa, the draw ratio of extruder is 25-40, and the screw speed of extruder is 300-600 revs/min.The twin-screw squeezes
Go out 65 double screw extruders production of the machine for the production of Rhea company.
Beneficial effects of the present invention are：
（1）The laser engraving auxiliary agent of the present invention is mixed by antimony and tin oxide, can effectively propose the absorption of laser energy,
Heat energy is converted light energy into, material surface is easier that chemical change occurs, and mark effect is played, during engraving so that carving
Carving body is apparent, and pattern effect is more preferable.When the particle diameter of laser engraving auxiliary agent is more than 1 μm, the transparency of material, drop can be reduced
Low infrared penetration rate, the particle diameter of laser engraving auxiliary agent of the invention are less than 1 μm, advantageously ensure that the transparency of material and infrared
Line penetrance, and laser engraving excellent performance.
（2）The particle diameter of the brominated triazine of the present invention is preferably 1-5 μm, it is ensured that its scattering and barrier to light and infrared ray
Effect is strong, and transparency is high, and infrared penetration rate is high, and is not easy to reunite, good flame retardation effect；Oligomeric aryl phosphate ester is a kind of fusing point
Powdered oligomeric aryl phosphate ester more than 90 DEG C.Dystectic oligomeric aryl phosphate ester is chosen, is because in high-speed stirred mistake
Cheng Zhong, mixture temperature can raise, if fusing point is too low, easily cause mixture to lump, and influence mixed effect and block tremie pipe
Road.Oligomeric aryl phosphoric acids form synergistic effect with brominated triazine, improve flame retarding efficiency.
The present invention is made using brominated triazine of the particle diameter less than 5 μm with oligomeric aryl phosphate ester compatibility of the fusing point more than 90 DEG C
With, be advantageous to significantly improve the fire resistance of composite, flame retardant rating is V0-V2 levels, and be advantageous to lifted infrared penetration
Rate, infrared penetration rate are up to 70-85%, improve the transparency of composite, and transparency is up to 75-83%.
（3）Antimony content is less than 1000ppm in the present invention, environmental requirement is not only conformed with, also with excellent laser engraving work(
Energy, the high grade of transparency, high IR line penetrate effect, fire resistance and excellent injection molding performance；Possess in remote control electrical appliance field
Extensive purposes, general infrared of alternative in the market penetrate makrolon material.
（4）Remote control brings many facilities as articles for use essential in the modern life to life；And remote control
Different coded pulses is produced, exports the various control waves using infrared ray as medium, the infrared letter that receiver will receive
Control apparatus after number.And in signals transmission, electric appliance casing is the principal element to signal shielding and decay, and the present invention
ABS composite material, not only the infrared penetration rate with more than 70% transparency and more than 75%, meets UL94 flame-retardancy requirements,
Apply in remote control, the remote control for not influenceing electrical equipment completely uses, and excellent laser carving effect, is set for the product of client
Meter, is provided convenience using function declaration.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Embodiment 1.
By the MABS of 70.0 parts by weight, the brominated triazine of 18.0 parts by weight, the polyamide wax of 1.8 parts by weight；4.0 parts by weight
Oligomeric aryl phosphate ester；The antioxidant of 0.2 parts by weight；The MBS of 6.0 parts by weight；The laser engraving auxiliary agent of 0.3 parts by weight；
Said components are well mixed at room temperature in super mixer, produced afterwards in double screw extruder.Processing conditions：Material mixes
Mix rotating speed is：180 revs/min；One area's temperature：180 DEG C, two area's temperature：190 DEG C, three area's temperature：200 DEG C, four area's temperature：210
DEG C, five area's temperature：220 DEG C, six area's temperature：220 DEG C, seven area's temperature：210 DEG C, eight area's temperature：210 DEG C, nine area's temperature：220
DEG C, screw speed：400 revs/min, the vacuum of extruder is 0.08MPa, and the draw ratio of extruder is 25.
Wherein, the laser engraving auxiliary agent is the mixture of antimony and tin oxide, and the mass ratio of antimony and tin oxide is 1:8；Institute
The melt index for stating MABS resins is 20g/10min, notch impact strength 15.5KJ/M2, transparency 86；The brominated triazine
Particle diameter is 4.5 μm；The fusing point of the oligomeric aryl phosphate ester is 91 DEG C；The particle diameter of the MBS is 195nm；The polyamide wax
Dropping point be 35 DEG C, acid number 5mgkoh/g, saponification number 0；The antioxidant by BASF IRGANOX1010 and
IRGANOX168 is by weight 1:1 ratio mixes.
Embodiment 2.
By the MABS of 74.1 parts by weight, the brominated triazine of 16.0 parts by weight, the polyamide wax of 1.5 parts by weight；3.0 parts by weight
Oligomeric aryl phosphate ester；The antioxidant of 0.3 parts by weight；The MBS of 5.0 parts by weight；The laser engraving auxiliary agent of 0.1 parts by weight；
Said components are well mixed at room temperature in super mixer, produced afterwards in double screw extruder.Processing conditions：Material mixes
Mix rotating speed is：190 revs/min；One area's temperature：180 DEG C, two area's temperature：185 DEG C, three area's temperature：190 DEG C, four area's temperature：200
DEG C, five area's temperature：210 DEG C, six area's temperature：220 DEG C, seven area's temperature：210 DEG C, eight area's temperature：210 DEG C, nine area's temperature：230
DEG C, screw speed：300 revs/min, the vacuum of extruder is 0.09MPa, and the draw ratio of extruder is 30.
Wherein, the laser engraving auxiliary agent is the mixture of antimony and tin oxide, and the mass ratio of antimony and tin oxide is 1:9；Institute
The melt index for stating MABS resins is 22g/10min, notch impact strength 17KJ/M2, transparency 87；The grain of the brominated triazine
Footpath is 4 μm；The oligomeric aryl phosphate ester is 92 DEG C of poly aryl phosphate esters of fusing point；The particle diameter of the MBS is 180nm；It is described
The dropping point of polyamide wax is 50 DEG C, acid number 6mgkoh/g, saponification number 0；The antioxidant is primary antioxidant and auxiliary anti-oxidant
It is 1 by mass percentage:1 mixture, primary antioxidant are antioxidant 1010, and auxiliary antioxidant is irgasfos 168.
Embodiment 3.
By the MABS of 77.3 parts by weight, the brominated triazine of 14.0 parts by weight, the polyamide wax of 1.2 parts by weight；3.0 parts by weight
Oligomeric aryl phosphate ester；The antioxidant of 0.4 parts by weight；The MBS of 4.0 parts by weight；The laser engraving auxiliary agent of 0.1 parts by weight；
Said components are well mixed at room temperature in super mixer, produced afterwards in double screw extruder.Processing conditions：Material mixes
Mix rotating speed is：200 revs/min；One area's temperature：180 DEG C, two area's temperature：200 DEG C, three area's temperature：210 DEG C, four area's temperature：210
DEG C, five area's temperature：230 DEG C, six area's temperature：220 DEG C, seven area's temperature：210 DEG C, eight area's temperature：210 DEG C, nine area's temperature：220
DEG C, screw speed：500 revs/min, the vacuum of extruder is 0.1MPa, and the draw ratio of extruder is 35.
Wherein, the laser engraving auxiliary agent is the mixture of antimony and tin oxide, and the mass ratio of antimony and tin oxide is 2:8；Institute
The melt index for stating MABS resins is 25g/10min, notch impact strength 18KJ/M2, transparency is more than 89；The brominated triazine
Particle diameter be 3 μm；The oligomeric aryl phosphate ester is the poly aryl phosphate ester that fusing point is 91 DEG C；The particle diameter of the MBS is
150nm；The dropping point of the polyamide wax is 100 DEG C, acid number 7mgkoh/g, saponification number 0；The antioxidant is primary antioxidant
It is 1 by mass percentage with auxiliary anti-oxidant:1 mixture, primary antioxidant are antioxidant 1076, and auxiliary antioxidant is antioxidant
168。
Embodiment 4.
By the MABS of 81.5 parts by weight, the brominated triazine of 12.0 parts by weight, the polyamide wax of 0.9 parts by weight；2.0 parts by weight
Oligomeric aryl phosphate ester；The antioxidant of 0.4 parts by weight；The MBS of 3.0 parts by weight；The laser engraving auxiliary agent of 0.2 parts by weight；
Said components are well mixed at room temperature in super mixer, produced afterwards in double screw extruder.Processing conditions：Material mixes
Mix rotating speed is：210 revs/min；One area's temperature：180 DEG C, two area's temperature：200 DEG C, three area's temperature：210 DEG C, four area's temperature：220
DEG C, five area's temperature：230 DEG C, six area's temperature：230 DEG C, seven area's temperature：210 DEG C, eight area's temperature：210 DEG C, nine area's temperature：230
DEG C, screw speed：600 revs/min, the vacuum of extruder is 0.09MPa, and the draw ratio of extruder is 40.
Wherein, the laser engraving auxiliary agent is the mixture of antimony and tin oxide, and the mass ratio of antimony and tin oxide is 2:9；Institute
The melt index for stating MABS resins is 28g/10min, and notch impact strength is more than 20KJ/M2, transparency is more than 89；The bromo
The particle diameter of triazine is 3 μm；The oligomeric aryl phosphate ester is the poly aryl phosphate ester that fusing point is 91 DEG C；The particle diameter of the MBS
For 120nm；The dropping point of the polyamide wax is 120 DEG C, acid number 6mgkoh/g, saponification number 0；The antioxidant is main antioxygen
Agent and auxiliary anti-oxidant are 1 by mass percentage:1 mixture, primary antioxidant are antioxidant 1010, and auxiliary antioxidant is antioxidant
626。
Embodiment 5.
By the MABS of 78.0 parts by weight, the brominated triazine of 15.0 parts by weight, the polyamide wax of 1.5 parts by weight；3.5 parts by weight
Oligomeric aryl phosphate ester；The antioxidant of 0.3 parts by weight；The MBS of 4.0 parts by weight；The laser engraving auxiliary agent of 0.2 parts by weight；1
The toner of parts by weight.Every part of toner is G is green, 5B is purple, H3G is red, 136 Huangs are mixed with equal weight ratio.
Wherein, the laser engraving auxiliary agent is the mixture of antimony and tin oxide, and the mass ratio of antimony and tin oxide is 1.5:
8.5；The melt index of the MABS resins is 30g/10min, and notch impact strength 21KJ/M2, transparency is more than 88；The bromine
Particle diameter for triazine is 2.5 μm；It is 93 DEG C that the oligomeric aryl phosphate ester, which includes fusing point,；The particle diameter of the MBS is 120nm；Institute
The dropping point for stating polyamide wax is 145 DEG C, acid number 6mgkoh/g, saponification number 0；The antioxidant is primary antioxidant and auxiliary antioxygen
Agent is 1 by mass percentage:1 mixture, primary antioxidant are antioxidant 1010, and auxiliary antioxidant is antioxidant 626.
Comparative example 1
By the MABS of 82.4 parts by weight, the brominated triazine of 12.0 parts by weight, the polyamide wax of 0 parts by weight；2.0 parts by weight
Oligomeric aryl phosphate ester；The antioxidant of 0.4 parts by weight；The MBS of 3.0 parts by weight；The laser engraving auxiliary agent of 0.2 parts by weight；In height
Said components are well mixed at room temperature in fast blender, produced afterwards in double screw extruder.Processing conditions：Material is puddled
Rotating speed is：220 revs/min；One area's temperature：180 DEG C, two area's temperature：200 DEG C, three area's temperature：210 DEG C, four area's temperature：210
DEG C, five area's temperature：220 DEG C, six area's temperature：220 DEG C, seven area's temperature：210 DEG C, eight area's temperature：210 DEG C, nine area's temperature：220
DEG C, screw speed：400 revs/min.
Comparative example 2
By the MABS of 77.0 parts by weight, the brominated triazine of 16.0 parts by weight, the polyamide wax of 0.9 parts by weight；2.0 parts by weight
Oligomeric aryl phosphate ester；The antioxidant of 0.4 parts by weight；The MBS of 3 parts by weight；The laser engraving auxiliary agent of 0.2 parts by weight；0.5
The antimony oxide of commercially available 99.8% purity of parts by weight（Space star antimony industry provides）, by said components in room in super mixer
Temperature is lower well mixed, is produced afterwards in double screw extruder.Processing conditions：Material puddles rotating speed：200 revs/min；One area's temperature
Degree：180 DEG C, two area's temperature：200 DEG C, three area's temperature：210 DEG C, four area's temperature：210 DEG C, five area's temperature：220 DEG C, six area's temperature
Degree：220 DEG C, seven area's temperature：210 DEG C, eight area's temperature：210 DEG C, nine area's temperature：220 DEG C, screw speed：300 revs/min.
Comparative example 3
By the MABS of 81.5 parts by weight, the brominated triazine of 12.0 parts by weight, particle diameter is 10 μm；The polyamide of 0.9 parts by weight
Wax；The oligomeric aryl phosphate ester of 2.0 parts by weight；The antioxidant of 0.4 parts by weight；The MBS of 3.0 parts by weight；0.2 parts by weight swash
Light carves auxiliary agent；Said components are well mixed at room temperature in super mixer, produced afterwards in double screw extruder.Add
Work condition：Material puddles rotating speed：200 revs/min；One area's temperature：180 DEG C, two area's temperature：200 DEG C, three area's temperature：210
DEG C, four area's temperature：210 DEG C, five area's temperature：220 DEG C, six area's temperature：220 DEG C, seven area's temperature：210 DEG C, eight area's temperature：210
DEG C, nine area's temperature：220 DEG C, screw speed：500 revs/min.
Comparative example 4
By the MABS of 81.7 parts by weight, the brominated triazine of 12.0 parts by weight, the polyamide wax of 0.9 parts by weight；2.0 parts by weight
Oligomeric aryl phosphate ester；The antioxidant of 0.4 parts by weight；The MBS of 3.0 parts by weight；The laser engraving auxiliary agent of 0 parts by weight；In height
Said components are well mixed at room temperature in fast blender, produced afterwards in double screw extruder.Processing conditions：Material is puddled
Rotating speed is：200 revs/min；One area's temperature：180 DEG C, two area's temperature：200 DEG C, three area's temperature：210 DEG C, four area's temperature：210
DEG C, five area's temperature：220 DEG C, six area's temperature：220 DEG C, seven area's temperature：210 DEG C, eight area's temperature：210 DEG C, nine area's temperature：220
DEG C, screw speed：400 revs/min.
The performance test standard of product is as follows in embodiment 1-5：
Proportion is tested by ASTM D792/ (GB/T1033) standard；
Notch impact strength is tested by ASTM D256/ (GB/T1843) standard；
Tensile property test is tested by ASTM D638/ (GB/T1040) standard；
Bending property test is tested by ASTM D790/ (GB/T9341) standard；
Fire resistance test is tested by UL-94/ (GB/T2408) standard；
Melt index test is tested by ASTM D1238/ (GB/T3682) standard；
The measure of the penetrance of infrared ray passes through TU- using the square injection model for preparing 50mm × 10mm × 2mm
1810PC types ultraviolet-visible-infrared spectrophotometer test；
Transparency presses ASTM D1003/ by test（GB/2410-80）Standard is tested；
Laser marking equipment selects the MYDP-50L laser marking equipments of Shanghai Lei Tian laser equipments Co., Ltd, laser wave
A length of 1064nm, mean power 50W.
Embodiment and comparative example performance comparision such as following table：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Density/g/cm3 | 1.2 | 1.18 | 1.16 | 1.15 | 1.17 |
| Melt index/g/10min | 5.5 | 6 | 6.3 | 7.1 | 6.7 |
| Tensile strength/MPa | 42.6 | 43.3 | 45.5 | 46.5 | 44.2 |
| Elongation at break/% | 8.9 | 10.3 | 9.6 | 13.3 | 11.6 |
| Bending strength/MPa | 76.5 | 78.3 | 76.4 | 79.2 | 77.3 |
| Bending modulus/MPa | 2335 | 2351 | 2286 | 2313 | 2346 |
| IZOD notch impact strengths/KJ/M2 | 8.9 | 10.2 | 11.2 | 11.4 | 9.5 |
| Fire-retardant -1.6mm | V1 | V0 | V2 | V1 | V2 |
| It is markup | It is good | It is good | It is good | It is good | It is good |
| Transparency/% | 70 | 73 | 77 | 82 | 83 |
| Infrared penetration rate/% | 75 | 77 | 80 | 85 | 82 |
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | ||
| Density/g/cm3 | 1.15 | 1.16 | 1.15 | 1.15 | |
| Melt index/g/10min | 7.1 | 6.1 | 7.2 | 7.1 | |
| Tensile strength/MPa | 45.8 | 44.7 | 46.2 | 45.8 | |
| Elongation at break/% | 13.4 | 6.5 | 7.6 | 13.4 | |
| Bending strength/MPa | 78.6 | 75.5 | 77.3 | 78.6 | |
| Bending modulus/MPa | 2336 | 2396 | 2287 | 2336 | |
| IZOD notch impact strengths/KJ/M2 | 10.9 | 9.5 | 11.3 | 10.9 | |
| Fire-retardant -1.6mm | V2 | V2 | V2 | V2 | |
| It is markup | It is good | It is good | It is good | Typically | |
| Transparency/% | 62 | 35 | 42 | 71.6 | |
| Infrared penetration rate/% | 55 | 20 | 23 | 71.1 |
As can be seen from the above table, composite produced by the present invention is markup good, and transparency is up to 70-83%, and compound
Material also has higher infrared penetration rate concurrently while with the high grade of transparency, and infrared penetration rate is 75-85%.In addition, resistance
The addition of agent is fired to mechanical property and laser engraving with laser engraving and the infrared transparent flame-retarding composite for penetrating function
Effect does not have much affect, and mainly influences its transparency and infrared penetration rate.
In addition, as can be seen from the above table, as fire retardant addition improves, flame retardant effect is to become better and better, but transparent
Degree and infrared penetration rate have dropped on the contrary.Embodiment 3 is compared with comparative example 2, even if only adding three oxidations two of 0.5 parts by weight
Antimony, transparency to material and infrared penetration rate are produced and had a strong impact on, it is opaque to directly result in material, under infrared penetration rate
Drop.And embodiment 4 is compared with comparative example 1, the addition of polyamide wax can various auxiliary agents effectively in dispensing formulations, improve material
Transparency and infrared penetration rate.And embodiment 4 is compared with comparative example 3, the particle diameter of bromide fire retardant to the transparency of material and
Infrared penetration rate can also have an impact, and particle diameter is only less than certain size, and light could be by that will not produce scattering effect
Should, influence transparency.And embodiment 4 is compared with comparative example 4, the addition of laser engraving auxiliary agent, material transparent degree and red is not influenceed
Outside line penetrance.Toner is added in embodiment 5, the transparency and infrared penetration rate to material all improve.
Embodiment described above, simply the present invention better embodiment, be not to limit the scope of the present invention, therefore
The equivalent change or modification that all construction, feature and principles according to described in scope of the present invention patent are done, all should include this hair
In bright patent claim.
Claims (8)
- A kind of 1. transparent flame-retarding composite that infrared can be penetrated, it is characterised in that：It is made up of the material component of following parts by weight：The laser engraving auxiliary agent is the mixture of antimony and tin oxide, and the mass ratio of antimony and tin oxide is 1-2:8-9, particle diameter are less than 1 μm, the particle diameter of the brominated triazine is less than 5 μm.
- A kind of 2. transparent flame-retarding composite that infrared can be penetrated according to claim 1, it is characterised in that：The MABS The melt index of resin is 20-30g/10min, and notch impact strength is more than 15KJ/M2, transparency is more than 85.
- A kind of 3. transparent flame-retarding composite that infrared can be penetrated according to claim 1, it is characterised in that：It is described oligomeric Aryl phosphate ester is the powdered substance that fusing point is more than 90 DEG C, and the oligomeric aryl phosphate ester includes poly aryl phosphate ester.
- A kind of 4. transparent flame-retarding composite that infrared can be penetrated according to claim 1, it is characterised in that：The toughness reinforcing Agent is the MBS terpolymer with nucleocapsid structure, and its particle diameter is less than 200nm.
- A kind of 5. transparent flame-retarding composite that infrared can be penetrated according to claim 1, it is characterised in that：The antioxygen Agent is that primary antioxidant and auxiliary anti-oxidant are 1 by mass percentage:1 mixture, primary antioxidant are antioxidant 1010 or antioxidant 1076, auxiliary antioxidant is irgasfos 168 or antioxidant 626.
- A kind of 6. transparent flame-retarding composite that infrared can be penetrated according to claim 1, it is characterised in that：The antioxygen Agent is by BASF IRGANOX1010 and IRGANOX168 by weight 1:1 ratio mixes.
- A kind of 7. transparent flame-retarding composite that infrared can be penetrated according to claim 1, it is characterised in that：The polyamides The dropping point of amine wax is 35-145 DEG C, acid number 5-7mgkoh/g, saponification number 0.
- A kind of 8. making side of transparent flame-retarding composite that infrared can be penetrated as described in any one in claim 1-7 Method, it is characterised in that：Comprise the following steps：Step (1), in proportion precise above-mentioned raw materials, put it into high-speed mixer be sufficiently stirred 5-10 minutes formed it is mixed Material is closed, material puddles rotating speed and turns/min for 180-220；Step (2), add mixture into double screw extruder, after melting, extrude, being granulated and drying, get product； Wherein, extruder includes nine processing districts, and the processing temperature of each processing district is 180-230 DEG C, and the vacuum of extruder >= 0.08MPa, the draw ratio of extruder is 25-40, and the screw speed of extruder is 300-600 revs/min.
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| CN106084622A (en) * | 2016-06-07 | 2016-11-09 | 天津金发新材料有限公司 | A kind of superelevation glossiness transparent flame-retarding ABS composite material and preparation method thereof |
| CN105936734A (en) * | 2016-06-07 | 2016-09-14 | 天津金发新材料有限公司 | Transparent flame-retardant antibacterial ABS material and preparation method thereof |
| CN105936731A (en) * | 2016-06-07 | 2016-09-14 | 天津金发新材料有限公司 | Low-smoke transparent flame-retardant ABS material, preparation method and application thereof |
| CN105985606A (en) * | 2016-06-07 | 2016-10-05 | 天津金发新材料有限公司 | Transparent flame-retardant ABS (acrylonitrile-butadiene-styrene) material, and preparation method and application thereof |
| CN106065154A (en) * | 2016-06-07 | 2016-11-02 | 天津金发新材料有限公司 | A kind of transparent flame-retardant antistatic ABS material and preparation method thereof |
| CN108164909A (en) * | 2017-11-30 | 2018-06-15 | 苏州启虹塑业有限公司 | A kind of saturating infra-red materials of scratch-resistant ABS and preparation method thereof |
| CN109553951A (en) * | 2018-12-05 | 2019-04-02 | 广州市聚赛龙工程塑料股份有限公司 | A kind of makrolon material and its preparation method and application of selectively masking near infrared ray |
| CN112011177B (en) * | 2019-05-30 | 2022-12-06 | 金旸（厦门）新材料科技有限公司 | PA/PMMA composite material, preparation raw material, preparation method and application thereof |
| CN111154250B (en) * | 2020-01-17 | 2022-05-17 | 王晖 | Transparent laser welding heat absorption PC plastic and preparation method thereof |
| US11879042B2 (en) | 2021-08-02 | 2024-01-23 | B/E Aerospace, Inc. | Fire resistant thermoplastic-based resin for fiber-reinforced composites |
| CN115246977B (en) * | 2022-08-31 | 2024-03-22 | 金发科技股份有限公司 | Glass fiber reinforced MBS composite material with high infrared permeability and preparation method and application thereof |
| CN116041952B (en) * | 2022-12-29 | 2024-01-23 | 金发科技股份有限公司 | Nylon composition and preparation method and application thereof |
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| CN101851350A (en) * | 2009-03-31 | 2010-10-06 | 上海金发科技发展有限公司 | Laser mark auxiliary agent for plastic and preparation method thereof |
| CN103289294A (en) * | 2013-06-20 | 2013-09-11 | 金发科技股份有限公司 | Transparent flame-retardant ABS material, and preparation method and application thereof |
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| CN101851350A (en) * | 2009-03-31 | 2010-10-06 | 上海金发科技发展有限公司 | Laser mark auxiliary agent for plastic and preparation method thereof |
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