CN105400189A - Resin composition permeable for laser beams and light-transmitting black plastic product - Google Patents
Resin composition permeable for laser beams and light-transmitting black plastic product Download PDFInfo
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- CN105400189A CN105400189A CN201510988103.8A CN201510988103A CN105400189A CN 105400189 A CN105400189 A CN 105400189A CN 201510988103 A CN201510988103 A CN 201510988103A CN 105400189 A CN105400189 A CN 105400189A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the technical field of plastic dedicated for laser welding and specifically relates to a resin composition permeable for laser beams and a light-transmitting black plastic product. The resin composition comprises the following raw materials in parts by weight: 100 parts of thermoplastic resin and light-transmitting black coloring agent, wherein the thermoplastic resin is a mixture composed of polyurethane and polyester according to a weight ratio of 1:1.2-1.8, and the light-transmitting black coloring agent is a mixture composed of an anthraquinone dye and a purple cyclic ketone dye. The light-transmitting black plastic product is prepared from the resin composition. The light-transmitting black plastic product has a large optical absorption coefficient in the visible light region (400 to 700nm), a large light transmittance coefficient in the near infrared region (800 to 1200 nm), and excellent heat resistant performance and mechanical properties.
Description
Technical field
The present invention relates to laser welding special plastic technical field, be specifically related to a kind of resin combination and light transmission black plastic products of transmissive laser beam.
Background technology
Plastics, as a kind of engineering materials, use continuous increase, because its good intensity, cost is low, material molding technology is simple, finished weight is light, physical property is excellent, can provide various engineering property, its be applied to industry manufacture and routine use widely.Plastics are as metal and the substitute of some other non-metallic material in engineering such as expensive iron and steel, aluminium, magnesium.
Plastics, can not single injection-molded at quite a few shape and baroque plastics due to the restriction of the factors such as Shooting Technique, often needs multiple adhering components to form.Therefore, in the course of processing of plastics, people thirst for a kind of quicker, effective, clean plastic working mode.
In recent years, developed the various methods of attachment of the plastic paste of industrial circle, mainly contained the welding technique such as Vibration welding, hot plate type Plastic Welding and ultrasonic welding, these existing methods also exist some restriction.Hot plate welding method by plastic component easily and heating source bond together and can atmospheric pollution be caused; Heat affected zone is large, and surface has distortion etc. affects outward appearance.And the thermal stresses of welded articles is very large, cause the very fast or cracking phenomena of the aging speed of intraware.Substantially reduce the work-ing life of product.The defects such as friction welding will apply larger mechanical force to welding assembly, can reduce welding strength, and welding product quality is unstable.The defect of ultrasonic welding workpiece not only betides bonding surface, and often occur in weldment surface, wherein surface heat destroys is more common one, surface heat destroys and finally also has influence on the intensity of goods, apparent mass and work-ing life to the destruction of material, and supersonic welding receives the restriction of body form and the size be bonded together in addition.In the assembling of electronic component, ultrasonic welding can damage some electronic components.
Therefore, laser welding comes into one's own just day by day as a kind of novel method that better can overcome these shortcomings.Laser is with excellent specific properties such as its coherency are good, energy density is high, collimation is good, and it is subject to the plurality of advantages such as heat sensitive material can to weld the special workpiece of shape.
Laser welding technology of plastics is a kind of non-contact welding technology in the ascendant.Compare with other welding process, it have noncontact, airtight, water-tight, welding speed is fast, precision is high, weld strength is high, non-trimming, without residue, friction, without Litter, pollution-free, there is no the plurality of advantages such as noise, thermal stresses are minimum, handiness good, adaptability is good, automatic precision numerical control advantage of lower cost.The laser welding technology of plastics is mainly used in the plastics (as medical equipment, electronic sensor etc.) etc. that ordinary soldering techniques is difficult to the plastics (as high-density circuit board) adapted to, complex-shaped plastic component and has stringent cleanliness to require.
The ultimate principle of plastics laser welding is: be clamped together at low pressures by two kinds of plastics, near infrared ray laser NIR(wavelength 810-1064nm) then absorbed (near infrared ray laser absorption) by another one goods through goods (near infrared ray laser-transmitting).Light energy conversion is heat energy by the goods of absorbing laser energy, melts at the contact surface of plastics, and heat is also transmitted to the surface of the goods of transmission near infrared ray laser simultaneously, forms melting area.Under the effect of clamping force, the melting area close contact of two parts.Under the internal force of material heat expansion generation and the acting in conjunction of clamping external force, melting range produces intermolecular mixing, in rapid cooling process, form weld seam.
The method that laser mainly adopts laser-transmitting to weld to the welding of thermoplastic materials.This method has certain requirement to soldered bi-material character, and in order to realize laser welding, two plastic pastes to be welded optical absorptive character at a particular wavelength should be not identical.Upper parts should transmission laser as far as possible, and base element should have high specific absorption, and in laser beam welding, absorbefacient part heats up and local melting, is transferred energy to the part of printing opacity by thermal conduction.Under the pressure of outside, two parts combine.The reflectivity of two parts should minimally, because along with the increase of volume reflection, needs more energy to produce heat needed for welding.Same reason, the specific absorption of upper parts should be minimum.Upper parts specific absorption is excessive, also just may degrade before base element starts to soften.In order to prevent thermolysis, laser ray transmitting material is lower than absorbing laser material melting point is favourable.
Also there is certain limitation in the application of laser welding, in laser-transmitting welding, use the plastics of non-staining as transparent plastics material always.The use of this kind of material limits the application in goods that material requires shades of colour in automotive industry and electrical/electronic industry.The particularly important is, the black material used in these fields generally adopts conventional laser welding operation at present not yet satisfactorily.
The principal element affecting plastics laser welding is the transmissivities of plastics to laser.Material category, wall thickness, weighting material content and dyestuff affect degree of transmission.Research shows, the transmissivity of polymkeric substance near infrared ray laser at least reaches 20-50%, adopts laser welding technology could obtain excellent welding effect.Because black plastic is approximately zero in the transmitance of visible ray and laser wave strong point, and absorb high.It is extremely low by 5% ~ 10% to the transmissivity of near infrared ray laser that such as black plastic reaches 90% ~ 95%(black plastic in the specific absorption of laser wave strong point, then laser cannot penetrate), namely can not adopt laser welding in this case.So on plastics laser welding process, two black plastics are welded together more difficult, because laser energy was just absorbed before arrival weld interface.In addition, someone advises, black pigment can through dilution and in the part of transmitting plastics or even adopt material compared with thin shape to improve transmissivity.But this kind of way can not ensure to make the satisfactory appearance of part and the handiness of detail design is restricted greatly.
On the other hand, plastics are also the important factor affecting laser welding effect on the specific absorption of near infrared ray laser.The application of absorption agent is very important technique in plastics laser welding process, and the essence of plastics laser welding is by the plastic melt to be welded in heat effect district, cools the joint that nature realizes plastic component subsequently.Plastic melt is allowed to need to make plastic component absorb enough laser energies.Plastics self can be naturally best with higher absorption rate absorbing laser energy, but generally when not adding absorption agent, plastics are not fine to the absorptivity of light wave, and assimilated efficiency is very low, and thawing efficiency is undesirable.In order to realize good welds, need in bottom plastic, to add absorption agent to strengthen assimilation effect.Thus greatly improving the thermal absorption effect of plastics, the material melts making heat effect district is faster, better effects if.
For the above-mentioned technical barrier of black plastic laser welding, be necessary resin combination and the light transmission black plastic products of researching and developing a kind of transmissive laser beam.
Summary of the invention
In order to overcome the shortcoming and defect existed in prior art, the object of the present invention is to provide a kind of resin combination of transmissive laser beam, this resin combination can be applied to laser welding and show better mouldability, solvability in thermoplastic resin, chemical-resistant, bleed-resistant and frosting and the transparency to laser beam wavelength.
Another object of the present invention is to the light transmission black plastic products that a kind of transmissive laser beam is provided, this light transmission black plastic products has larger optical absorption coefficient at visible region (400-700nm), meanwhile, near infrared region (wavelength 800-1200nm), there is larger optical transmission factor; And thermotolerance and excellent in mechanical performance.
Another object of the present invention is to the preparation method of the light transmission black plastic products providing a kind of transmissive laser beam, this preparation method's technique is simple, and convenient operation and control, steady quality, production efficiency is high, can large-scale industrial production.
Object of the present invention is achieved through the following technical solutions: a kind of resin combination of transmissive laser beam, and described resin combination comprises the raw material of following weight part:
Thermoplastic resin 100 parts
Light transmission black tinting material 0.01-15 part;
The mixture that described thermoplastic resin is made up of with weight ratio 1:1.2-1.8 urethane and polyester;
The mixture that the black tinting material of described light transmission is made up of anthraquinone dye and purple cyclic ketones dyestuff.
The present invention is by adopting urethane and polyester as the composite use of thermoplastic resin, and to control its weight ratio be 1:1.2-1.8, and have the performance by thermal softening, hardening by cooling, machine-shaping is easy, has higher mechanical and physical performance; And not react with, no matter heating and cooling repeat how many times, all can keep this performance.
The present invention is by adopting anthraquinone dye and purple cyclic ketones dyestuff as the composite use of the black tinting material of light transmission, obtained light transmission black plastic products has larger optical absorption coefficient at visible region (400-700nm), meanwhile, near infrared region (wavelength 800-1200nm), there is larger optical transmission factor.
Preferably, the mixture that is made up of with weight ratio 2-3:1 polycaprolactam and polyhexamethylene adipamide of described urethane.
The present invention is by adopting polycaprolactam and polyhexamethylene adipamide as the composite use of urethane, and to control its weight ratio be 2-3:1, there is the performance by thermal softening, hardening by cooling, machine-shaping is easy, has the excellent properties such as wear-resisting, heatproof, sealing, sound insulation, good processability, degradable.
Preferably, the mixture that is made up of with weight ratio 1:0.5-1.5 polyethylene terephthalate and polybutylene terephthalate of described polyester.
The present invention is by adopting polyethylene terephthalate and polybutylene terephthalate as the composite use of polyester, and to control its weight ratio be 1:0.5-1.5, there is good fiberizability, mechanical property, wear resistance, creep resistance, low water absorbable and electrical insulation capability; And low temperature crystallization speed is fast, processability good.
Preferably, the mixture that is made up of with weight ratio 6:2:1 the blue dyestuff of anthraquinone dye, purple dye or the yellow dye of the red of green dye and purple cyclic ketones dyestuff, orange dyestuff and anthraquinone dye or the yellow dye of purple cyclic ketones dyestuff of the black tinting material of described light transmission.Namely the black tinting material of described light transmission is by any one mixture formed with weight ratio 6:2:1 in any one in any one in the blue dyestuff of anthraquinone dye, purple dye or green dye three kinds and the red of purple cyclic ketones dyestuff, orange dyestuff two kinds and the yellow dye of anthraquinone dye or the yellow dye two kinds of purple cyclic ketones dyestuff.
The present invention is by adopting the blue dyestuff of anthraquinone dye, purple dye or the yellow dye of the red of green dye and purple cyclic ketones dyestuff, orange dyestuff and anthraquinone dye or the yellow dye of purple cyclic ketones dyestuff as the composite use of the black tinting material of light transmission, and to control its weight ratio be 6:2:1, obtained light transmission black plastic products has larger optical absorption coefficient at visible region (400-700nm), meanwhile, near infrared region (wavelength 800-1200nm), there is larger optical transmission factor.
Preferably, be 0.5-1.2 containing the transmissivity of the described resin combination of described absorbing black tinting material with the ratio of the transmissivity of described resin itself.Transmission rate ratio (T
the black resin of laser-transmission/ T
nature resin) be 0.5-1.2, refer at 1064nm and 940nm, this laser-transmission with, containing the transmission rate of black tinting material resin combination, with laser-transmission with, do not compare containing the transmission rate of the resin combination (natural resin) of described black tinting material.
Preferably, described resin combination also comprises toughener 6-10 part, impact modifying agent 4-8 part and heat-proof modifier 1-5 part.
Described toughener be with acicular wollastonite and flat glass fiber for nucleome material, have acrylic low-temperature ester emulsion to be the particle of shell at its Surface coating.
The present invention is by adopting with acicular wollastonite and flat glass fiber as material of main part, being coated with acrylic low-temperature ester emulsion is thereon shell, it can utilize acicular wollastonite to provide the support of radial direction and flat glass fiber to prevent the distortion of section bar, simultaneously coated acrylic low-temperature ester emulsion can improve the physicals of material under its consistency and low temperature, also has adduction to the enhancement of toughener.
Described impact modifier is MBS terpolymer, and wherein, the content of methyl methacrylate units is 40-60%, and the content of butadiene unit is 20-30%, and the content of styrene units is 20-30%.
The present invention is by adopting MBS terpolymer as pest-resistant properties-correcting agent, and the content controlling methyl methacrylate units is 40-60%, the content of butadiene unit is 20-30%, the content of styrene units is 20-30%, the shock resistance performance of material can be improved, the processing characteristics that can also reduce the melt viscosity of material, improve mobility, improve plastics, improves the erosion resistance of material, rigidity, flame retardant resistance, electrical insulating property, thermotolerance, molding processibility and resistance to elevated temperatures.
The mixture that described heat-proof modifier is made up of with weight ratio 1:2-3 the mixture of N-phenylmaleimide/fine terpolymer of vinylbenzene/propylene and alpha-methyl styrene/styrene/acrylonitrile terpolymer.
The present invention is by adopting N-phenylmaleimide/fine terpolymer of vinylbenzene/propylene and alpha-methyl styrene/styrene/acrylonitrile terpolymer as the composite use of heat-proof modifier, the resistance to elevated temperatures of material can be improved, the consistency of material, impact and processibility can also be improved.
Preferably, described resin combination also comprises fire retardant 0.5-1.5 part, viscosity modifier 0.5-1.5 part and lubricant 0.5-1.5 part.
The mixture that described fire retardant is made up of with weight ratio 1.1-1.5:1 brominated epoxy resin and antimonous oxide.
The present invention is by adopting brominated epoxy resin and antimonous oxide as the composite use of fire retardant, and to control its weight ratio be 1.1-1.5:1, can reach good flame retardant effect, can also improve Drawing abillity and mechanical property.
Described viscosity modifier is ethylene/alpha-olefin interpolymers.
The present invention, by adopting ethylene/alpha-olefin interpolymers as viscosity modifier, can improve the stability of material, use composite with lubricant, can make material in the course of processing, improve the mobility of material and the release property of goods.
The mixture that described lubricant is made up of with weight ratio 1:1.2-1.8 native paraffin and methylene bis stearamide.
The present invention adopts native paraffin as external lubricant, can reduce the friction of PVC melt and mould, machine barrel; Adopt methylene bis stearamide as internal lubricant, the intermolecular friction of PVC melt can be reduced; Two kinds of lubricants improve the mobility of material and the release property of goods with the weight ratio 1:1.2-1.8 material that can make used in combination in the course of processing.
Preferably, described resin combination also comprises thermo-stabilizer 1-5 part, oxidation inhibitor 0.5-1.5 part and anti UV agent 0.5-1.5 part.
The mixture that described thermo-stabilizer is made up of with mol ratio 1:1.4-1.8 barium stearate and Zinic stearas.
The barium zinc heat stabilizer be made up of barium stearate and Zinic stearas is nontoxic, transparent thermo-stabilizer, by catching the HCl that PVC thermolysis produces, prevent the catalyzed degradation effect of HCl, realize the thermally-stabilised of material, the present invention is 1.4-1.8:1 by selecting barium stearate and Zinic stearas as thermo-stabilizer and controlling its mol ratio, thermostable effect is good, and have oilness concurrently, make material in the course of processing, have good dispersiveness, consistency and processing fluidity, make material good heat stability, there is efficient weathering resistance.
The mixture that described oxidation inhibitor is made up of with weight ratio 1:1-2 antioxidant 1010 and irgasfos 168.
The present invention is by adopting antioxidant 1010 and irgasfos 168 as the composite use of oxidation inhibitor, and to control its weight ratio be 1:1-2, can delay or suppress the carrying out of material oxidation process, thus prevention material aging extend its work-ing life.
Described anti UV agent is the mixture be made up of with weight ratio 1.5-2.5:1 4-benzoyloxy-2,2,6,6-tetramethyl piperidine and Octabenzone.
The present invention is by adopting 4-benzoyloxy-2,2,6,6-tetramethyl piperidine and Octabenzone are as the composite use of anti UV agent, and to control its weight ratio be 1.5-2.5:1, energy strong absorption ultraviolet, has excellent synergistic effect, makes goods antiageing effect good.
Another object of the present invention is achieved through the following technical solutions: a kind of light transmission black plastic products of transmissive laser beam, described light transmission black plastic products adopts the resin combination of a kind of transmissive laser beam described in any one of claim 1-8 to obtain, the length of described light transmission black plastic products is 90-110mm, width is 70-90mm, and thickness is 0.5-6mm.
Another object of the present invention is achieved through the following technical solutions: a kind of preparation method of light transmission black plastic products of transmissive laser beam, comprises the steps:
(1) thermoplastic resin is dried 8-12h in 100-140 DEG C of vacuum drying oven, for subsequent use;
(2) THERMOPLASTIC RESINS of above-mentioned weight part and the black tinting material of light transmission stirred and mix 40-80min in stainless steel tumbler mixer, obtaining mixture;
(3) mixture is used injection moulding machine injection moulding, obtain the light transmission black plastic products of transmissive laser beam.
Beneficial effect of the present invention is: resin combination of the present invention can be applied to laser welding and show better mouldability, solvability in thermoplastic resin, chemical-resistant, bleed-resistant and frosting and the transparency to laser beam wavelength.
Light transmission black plastic products of the present invention has larger optical absorption coefficient at visible region (400-700nm), meanwhile, has larger optical transmission factor near infrared region (wavelength 800-1200nm); And this light transmission black plastic products has and meets aviation, boats and ships, automobile, medical science, industrial equipments, electrical equipment, electronics and the thermotolerance required by other field and mechanical property.
Preparation method's technique of the present invention is simple, and convenient operation and control, steady quality, production efficiency is high, can large-scale industrial production.
Embodiment
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment, the present invention is further illustrated, and the content that embodiment is mentioned not is limitation of the invention.
Embodiment 1
A resin combination for transmissive laser beam, described resin combination comprises the raw material of following weight part:
Thermoplastic resin 100 parts
The black tinting material of light transmission 0.01 part;
The mixture that described thermoplastic resin is made up of with weight ratio 1:1.2 urethane and polyester;
The mixture that described urethane is made up of with weight ratio 2:1 polycaprolactam and polyhexamethylene adipamide.
The mixture that described polyester is made up of with weight ratio 1:0.5 polyethylene terephthalate and polybutylene terephthalate.
The mixture that the black tinting material of described light transmission is made up of with weight ratio 6:2:1 the blue dyestuff of anthraquinone dye, purple dye or the yellow dye of the red of green dye and purple cyclic ketones dyestuff, orange dyestuff and anthraquinone dye or the yellow dye of purple cyclic ketones dyestuff.
Be 0.5 containing the transmissivity of the described resin combination of described absorbing black tinting material with the ratio of the transmissivity of described resin itself.
Described resin combination also comprises toughener 6 parts, impact modifying agent 4 parts and heat-proof modifier 1 part; Described toughener be with acicular wollastonite and flat glass fiber for nucleome material, have acrylic low-temperature ester emulsion to be the particle of shell at its Surface coating; Described impact modifier is MBS terpolymer, and wherein, the content of methyl methacrylate units is 40%, and the content of butadiene unit is 30%, and the content of styrene units is 30%; The mixture that described heat-proof modifier is made up of with weight ratio 1:2 the mixture of N-phenylmaleimide/fine terpolymer of vinylbenzene/propylene and alpha-methyl styrene/styrene/acrylonitrile terpolymer.
Described resin combination also comprises fire retardant 0.5 part, viscosity modifier 0.5 part and lubricant 0.5 part; The mixture that described fire retardant is made up of with weight ratio 1.1:1 brominated epoxy resin and antimonous oxide; Described viscosity modifier is ethylene/alpha-olefin interpolymers; The mixture that described lubricant is made up of with weight ratio 1:1.2 native paraffin and methylene bis stearamide.
Described resin combination also comprises thermo-stabilizer 1 part, 0.5 part, oxidation inhibitor and anti UV agent 0.5 part; The mixture that described thermo-stabilizer is made up of with mol ratio 1:1.4 barium stearate and Zinic stearas; The mixture that described oxidation inhibitor is made up of with weight ratio 1:1 antioxidant 1010 and irgasfos 168; Described anti UV agent is the mixture be made up of with weight ratio 1.5:1 4-benzoyloxy-2,2,6,6-tetramethyl piperidine and Octabenzone.
A kind of light transmission black plastic products of transmissive laser beam, described light transmission black plastic products adopts the resin combination of a kind of transmissive laser beam described above to obtain, the length of described light transmission black plastic products is 90mm, and width is 70mm, and thickness is 0.5mm.
A preparation method for the light transmission black plastic products of transmissive laser beam, comprises the steps:
(1) thermoplastic resin is dried 12h in 100 DEG C of vacuum drying ovens, for subsequent use;
(2) THERMOPLASTIC RESINS of above-mentioned weight part and the black tinting material of light transmission stirred and mix 40min in stainless steel tumbler mixer, obtaining mixture;
(3) mixture is used injection moulding machine injection moulding, obtain the light transmission black plastic products of transmissive laser beam.
Embodiment 2
A resin combination for transmissive laser beam, described resin combination comprises the raw material of following weight part:
Thermoplastic resin 100 parts
The black tinting material of light transmission 1 part;
The mixture that described thermoplastic resin is made up of with weight ratio 1:1.4 urethane and polyester;
The mixture that described urethane is made up of with weight ratio 2.2:1 polycaprolactam and polyhexamethylene adipamide.
The mixture that described polyester is made up of with weight ratio 1:0.8 polyethylene terephthalate and polybutylene terephthalate.
The mixture that the black tinting material of described light transmission is made up of with weight ratio 6:2:1 the blue dyestuff of anthraquinone dye, purple dye or the yellow dye of the red of green dye and purple cyclic ketones dyestuff, orange dyestuff and anthraquinone dye or the yellow dye of purple cyclic ketones dyestuff.
Be 0.7 containing the transmissivity of the described resin combination of described absorbing black tinting material with the ratio of the transmissivity of described resin itself.
Described resin combination also comprises toughener 7 parts, impact modifying agent 5 parts and heat-proof modifier 2 parts; Described toughener be with acicular wollastonite and flat glass fiber for nucleome material, have acrylic low-temperature ester emulsion to be the particle of shell at its Surface coating; Described impact modifier is MBS terpolymer, and wherein, the content of methyl methacrylate units is 45%, and the content of butadiene unit is 27.5%, and the content of styrene units is 27.5%; The mixture that described heat-proof modifier is made up of with weight ratio 1:2.2 the mixture of N-phenylmaleimide/fine terpolymer of vinylbenzene/propylene and alpha-methyl styrene/styrene/acrylonitrile terpolymer.
Described resin combination also comprises fire retardant 0.8 part, viscosity modifier 0.8 part and lubricant 0.8 part; The mixture that described fire retardant is made up of with weight ratio 1.2:1 brominated epoxy resin and antimonous oxide; Described viscosity modifier is ethylene/alpha-olefin interpolymers; The mixture that described lubricant is made up of with weight ratio 1:1.4 native paraffin and methylene bis stearamide.
Described resin combination also comprises thermo-stabilizer 2 parts, 0.8 part, oxidation inhibitor and anti UV agent 0.8 part; The mixture that described thermo-stabilizer is made up of with mol ratio 1:1.5 barium stearate and Zinic stearas; The mixture that described oxidation inhibitor is made up of with weight ratio 1:1.2 antioxidant 1010 and irgasfos 168; Described anti UV agent is the mixture be made up of with weight ratio 1.8:1 4-benzoyloxy-2,2,6,6-tetramethyl piperidine and Octabenzone.
A kind of light transmission black plastic products of transmissive laser beam, described light transmission black plastic products adopts the resin combination of a kind of transmissive laser beam described above to obtain, the length of described light transmission black plastic products is 95mm, and width is 75mm, and thickness is 1.5mm.
A preparation method for the light transmission black plastic products of transmissive laser beam, comprises the steps:
(1) thermoplastic resin is dried 11h in 110 DEG C of vacuum drying ovens, for subsequent use;
(2) THERMOPLASTIC RESINS of above-mentioned weight part and the black tinting material of light transmission stirred and mix 50min in stainless steel tumbler mixer, obtaining mixture;
(3) mixture is used injection moulding machine injection moulding, obtain the light transmission black plastic products of transmissive laser beam.
Embodiment 3
A resin combination for transmissive laser beam, described resin combination comprises the raw material of following weight part:
Thermoplastic resin 100 parts
The black tinting material of light transmission 5 parts;
The mixture that described thermoplastic resin is made up of with weight ratio 1:1.5 urethane and polyester;
The mixture that described urethane is made up of with weight ratio 2.5:1 polycaprolactam and polyhexamethylene adipamide.
The mixture that described polyester is made up of with weight ratio 1:1 polyethylene terephthalate and polybutylene terephthalate.
The mixture that the black tinting material of described light transmission is made up of with weight ratio 6:2:1 the blue dyestuff of anthraquinone dye, purple dye or the yellow dye of the red of green dye and purple cyclic ketones dyestuff, orange dyestuff and anthraquinone dye or the yellow dye of purple cyclic ketones dyestuff.
Be 0.9 containing the transmissivity of the described resin combination of described absorbing black tinting material with the ratio of the transmissivity of described resin itself.
Described resin combination also comprises toughener 8 parts, impact modifying agent 6 parts and heat-proof modifier 3 parts; Described toughener be with acicular wollastonite and flat glass fiber for nucleome material, have acrylic low-temperature ester emulsion to be the particle of shell at its Surface coating; Described impact modifier is MBS terpolymer, and wherein, the content of methyl methacrylate units is 50%, and the content of butadiene unit is 25%, and the content of styrene units is 25%; The mixture that described heat-proof modifier is made up of with weight ratio 1:2.5 the mixture of N-phenylmaleimide/fine terpolymer of vinylbenzene/propylene and alpha-methyl styrene/styrene/acrylonitrile terpolymer.
Described resin combination also comprises fire retardant 1 part, viscosity modifier 1 part and lubricant 1 part; The mixture that described fire retardant is made up of with weight ratio 1.3:1 brominated epoxy resin and antimonous oxide; Described viscosity modifier is ethylene/alpha-olefin interpolymers; The mixture that described lubricant is made up of with weight ratio 1:1.5 native paraffin and methylene bis stearamide.
Described resin combination also comprises thermo-stabilizer 3 parts, 1 part, oxidation inhibitor and anti UV agent 1 part; The mixture that described thermo-stabilizer is made up of with mol ratio 1:1.6 barium stearate and Zinic stearas; The mixture that described oxidation inhibitor is made up of with weight ratio 1:1.5 antioxidant 1010 and irgasfos 168; Described anti UV agent is the mixture be made up of with weight ratio 2:1 4-benzoyloxy-2,2,6,6-tetramethyl piperidine and Octabenzone.
A kind of light transmission black plastic products of transmissive laser beam, described light transmission black plastic products adopts the resin combination of a kind of transmissive laser beam described above to obtain, the length of described light transmission black plastic products is 100mm, and width is 80mm, and thickness is 3.5mm.
A preparation method for the light transmission black plastic products of transmissive laser beam, comprises the steps:
(1) thermoplastic resin is dried 10h in 120 DEG C of vacuum drying ovens, for subsequent use;
(2) THERMOPLASTIC RESINS of above-mentioned weight part and the black tinting material of light transmission stirred and mix 60min in stainless steel tumbler mixer, obtaining mixture;
(3) mixture is used injection moulding machine injection moulding, obtain the light transmission black plastic products of transmissive laser beam.
Embodiment 4
A resin combination for transmissive laser beam, described resin combination comprises the raw material of following weight part:
Thermoplastic resin 100 parts
The black tinting material of light transmission 10 parts;
The mixture that described thermoplastic resin is made up of with weight ratio 1:1.6 urethane and polyester;
The mixture that described urethane is made up of with weight ratio 2.8:1 polycaprolactam and polyhexamethylene adipamide.
The mixture that described polyester is made up of with weight ratio 1:1.2 polyethylene terephthalate and polybutylene terephthalate.
The mixture that the black tinting material of described light transmission is made up of with weight ratio 6:2:1 the blue dyestuff of anthraquinone dye, purple dye or the yellow dye of the red of green dye and purple cyclic ketones dyestuff, orange dyestuff and anthraquinone dye or the yellow dye of purple cyclic ketones dyestuff.
Be 1.1 containing the transmissivity of the described resin combination of described absorbing black tinting material with the ratio of the transmissivity of described resin itself.
Described resin combination also comprises toughener 9 parts, impact modifying agent 7 parts and heat-proof modifier 4 parts; Described toughener be with acicular wollastonite and flat glass fiber for nucleome material, have acrylic low-temperature ester emulsion to be the particle of shell at its Surface coating; Described impact modifier is MBS terpolymer, and wherein, the content of methyl methacrylate units is 55%, and the content of butadiene unit is 22.5%, and the content of styrene units is 22.5%; The mixture that described heat-proof modifier is made up of with weight ratio 1:2.8 the mixture of N-phenylmaleimide/fine terpolymer of vinylbenzene/propylene and alpha-methyl styrene/styrene/acrylonitrile terpolymer.
Described resin combination also comprises fire retardant 1.2 parts, viscosity modifier 1.2 parts and lubricant 1.2 parts; The mixture that described fire retardant is made up of with weight ratio 1.4:1 brominated epoxy resin and antimonous oxide; Described viscosity modifier is ethylene/alpha-olefin interpolymers; The mixture that described lubricant is made up of with weight ratio 1:1.6 native paraffin and methylene bis stearamide.
Described resin combination also comprises thermo-stabilizer 4 parts, 1.2 parts, oxidation inhibitor and anti UV agent 1.2 parts; The mixture that described thermo-stabilizer is made up of with mol ratio 1:1.6 barium stearate and Zinic stearas; The mixture that described oxidation inhibitor is made up of with weight ratio 1:1.8 antioxidant 1010 and irgasfos 168; Described anti UV agent is the mixture be made up of with weight ratio 2.2:1 4-benzoyloxy-2,2,6,6-tetramethyl piperidine and Octabenzone.
A kind of light transmission black plastic products of transmissive laser beam, described light transmission black plastic products adopts the resin combination of a kind of transmissive laser beam described above to obtain, the length of described light transmission black plastic products is 105mm, and width is 85mm, and thickness is 4.5mm.
A preparation method for the light transmission black plastic products of transmissive laser beam, comprises the steps:
(1) thermoplastic resin is dried 9h in 130 DEG C of vacuum drying ovens, for subsequent use;
(2) THERMOPLASTIC RESINS of above-mentioned weight part and the black tinting material of light transmission stirred and mix 70min in stainless steel tumbler mixer, obtaining mixture;
(3) mixture is used injection moulding machine injection moulding, obtain the light transmission black plastic products of transmissive laser beam.
Embodiment 5
A resin combination for transmissive laser beam, described resin combination comprises the raw material of following weight part:
Thermoplastic resin 100 parts
The black tinting material of light transmission 15 parts;
The mixture that described thermoplastic resin is made up of with weight ratio 1:1.8 urethane and polyester;
The mixture that described urethane is made up of with weight ratio 3:1 polycaprolactam and polyhexamethylene adipamide.
The mixture that described polyester is made up of with weight ratio 1:1.5 polyethylene terephthalate and polybutylene terephthalate.
The mixture that the black tinting material of described light transmission is made up of with weight ratio 6:2:1 the blue dyestuff of anthraquinone dye, purple dye or the yellow dye of the red of green dye and purple cyclic ketones dyestuff, orange dyestuff and anthraquinone dye or the yellow dye of purple cyclic ketones dyestuff.
Be 1.2 containing the transmissivity of the described resin combination of described absorbing black tinting material with the ratio of the transmissivity of described resin itself.
Described resin combination also comprises toughener 10 parts, impact modifying agent 8 parts and heat-proof modifier 5 parts; Described toughener be with acicular wollastonite and flat glass fiber for nucleome material, have acrylic low-temperature ester emulsion to be the particle of shell at its Surface coating; Described impact modifier is MBS terpolymer, and wherein, the content of methyl methacrylate units is 60%, and the content of butadiene unit is 20%, and the content of styrene units is 20%; The mixture that described heat-proof modifier is made up of with weight ratio 1:3 the mixture of N-phenylmaleimide/fine terpolymer of vinylbenzene/propylene and alpha-methyl styrene/styrene/acrylonitrile terpolymer.
Described resin combination also comprises fire retardant 1.5 parts, viscosity modifier 1.5 parts and lubricant 1.5 parts; The mixture that described fire retardant is made up of with weight ratio 1.5:1 brominated epoxy resin and antimonous oxide; Described viscosity modifier is ethylene/alpha-olefin interpolymers; The mixture that described lubricant is made up of with weight ratio 1:1.8 native paraffin and methylene bis stearamide.
Described resin combination also comprises thermo-stabilizer 5 parts, 1.5 parts, oxidation inhibitor and anti UV agent 1.5 parts; The mixture that described thermo-stabilizer is made up of with mol ratio 1:1.8 barium stearate and Zinic stearas; The mixture that described oxidation inhibitor is made up of with weight ratio 1:2 antioxidant 1010 and irgasfos 168; Described anti UV agent is the mixture be made up of with weight ratio 2.5:1 4-benzoyloxy-2,2,6,6-tetramethyl piperidine and Octabenzone.
A kind of light transmission black plastic products of transmissive laser beam, described light transmission black plastic products adopts the resin combination of a kind of transmissive laser beam described above to obtain, the length of described light transmission black plastic products is 110mm, and width is 90mm, and thickness is 6mm.
A preparation method for the light transmission black plastic products of transmissive laser beam, comprises the steps:
(1) thermoplastic resin is dried 8h in 140 DEG C of vacuum drying ovens, for subsequent use;
(2) THERMOPLASTIC RESINS of above-mentioned weight part and the black tinting material of light transmission stirred and mix 80min in stainless steel tumbler mixer, obtaining mixture;
(3) mixture is used injection moulding machine injection moulding, obtain the light transmission black plastic products of transmissive laser beam.
The mechanical and physical performance of the light transmission black plastic products that embodiment 1-5 obtains is as shown in table 1.
Table 1
| Test event | Standard value | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Visible region specific absorption (400-700nm) | ≥50% | 90 | 93 | 96 | 95 | 94 |
| Near infrared region specific absorption (wavelength 800-1200nm) | ≤50% | 10 | 8 | 5 | 7 | 9 |
| Tensile strength (MPa) | ≥15.0 | 22.7 | 24.8 | 26.1 | 26.5 | 23.6 |
| Flexural strength (MPa) | ≥15.0 | 47.3 | 49.2 | 52.1 | 54.9 | 45.7 |
| Elongation at break (%) | ≥150 | 296 | 301 | 308 | 319 | 298 |
| Heat-drawn wire (DEG C) | ≥50.0 | 118.6 | 121.5 | 123.7 | 125.3 | 119.4 |
| Impact embrittlement temperature (DEG C) | ≤-20 | -25 | -25 | -30 | -30 | -25 |
| Heat-stable time (min) when 200 DEG C | ≥60 | 100 | 120 | 130 | 130 | 110 |
| Hardness/Shore D | ≥50 | 80 | 83 | 85 | 86 | 81 |
| Fire-retardant | V0 | V0 | V0 | V0 | V0 | V0 |
As can be seen from Table 1, light transmission black plastic products of the present invention has larger optical absorption coefficient at visible region (400-700nm), meanwhile, has larger optical transmission factor near infrared region (wavelength 800-1200nm); And the properties of this light transmission black plastic products is all beyond national standard, resistance to elevated temperatures is excellent, and intensity is high, good flame retardation effect, and by force, processing characteristics is excellent, excellent combination property for compression performance and toughness.
Above-described embodiment is the present invention's preferably implementation, and in addition, the present invention can also realize by alternate manner, and any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise.
Claims (10)
1. a resin combination for transmissive laser beam, is characterized in that: described resin combination comprises the raw material of following weight part:
Thermoplastic resin 100 parts
Light transmission black tinting material 0.01-15 part;
The mixture that described thermoplastic resin is made up of with weight ratio 1:1.2-1.8 urethane and polyester;
The mixture that the black tinting material of described light transmission is made up of anthraquinone dye and purple cyclic ketones dyestuff.
2. the resin combination of a kind of transmissive laser beam according to claim 1, is characterized in that: the mixture that described urethane is made up of with weight ratio 2-3:1 polycaprolactam and polyhexamethylene adipamide.
3. the resin combination of a kind of transmissive laser beam according to claim 1, is characterized in that: the mixture that described polyester is made up of with weight ratio 1:0.5-1.5 polyethylene terephthalate and polybutylene terephthalate.
4. the resin combination of a kind of transmissive laser beam according to claim 1, is characterized in that: the mixture that the black tinting material of described light transmission is made up of with weight ratio 6:2:1 the blue dyestuff of anthraquinone dye, purple dye or the yellow dye of the red of green dye and purple cyclic ketones dyestuff, orange dyestuff and anthraquinone dye or the yellow dye of purple cyclic ketones dyestuff.
5. the resin combination of a kind of transmissive laser beam according to claim 1, is characterized in that: be 0.5-1.2 containing the transmissivity of the described resin combination of described absorbing black tinting material with the ratio of the transmissivity of described resin itself.
6. the resin combination of a kind of transmissive laser beam according to claim 1, is characterized in that: described resin combination also comprises toughener 6-10 part, impact modifying agent 4-8 part and heat-proof modifier 1-5 part; Described toughener be with acicular wollastonite and flat glass fiber for nucleome material, have acrylic low-temperature ester emulsion to be the particle of shell at its Surface coating; Described impact modifier is MBS terpolymer, and wherein, the content of methyl methacrylate units is 40-60%, and the content of butadiene unit is 20-30%, and the content of styrene units is 20-30%; The mixture that described heat-proof modifier is made up of with weight ratio 1:2-3 the mixture of N-phenylmaleimide/fine terpolymer of vinylbenzene/propylene and alpha-methyl styrene/styrene/acrylonitrile terpolymer.
7. the resin combination of a kind of transmissive laser beam according to claim 1, is characterized in that: described resin combination also comprises fire retardant 0.5-1.5 part, viscosity modifier 0.5-1.5 part and lubricant 0.5-1.5 part; The mixture that described fire retardant is made up of with weight ratio 1.1-1.5:1 brominated epoxy resin and antimonous oxide; Described viscosity modifier is ethylene/alpha-olefin interpolymers; The mixture that described lubricant is made up of with weight ratio 1:1.2-1.8 native paraffin and methylene bis stearamide.
8. the resin combination of a kind of transmissive laser beam according to claim 1, is characterized in that: described resin combination also comprises thermo-stabilizer 1-5 part, oxidation inhibitor 0.5-1.5 part and anti UV agent 0.5-1.5 part; The mixture that described thermo-stabilizer is made up of with mol ratio 1:1.4-1.8 barium stearate and Zinic stearas; The mixture that described oxidation inhibitor is made up of with weight ratio 1:1-2 antioxidant 1010 and irgasfos 168; Described anti UV agent is the mixture be made up of with weight ratio 1.5-2.5:1 4-benzoyloxy-2,2,6,6-tetramethyl piperidine and Octabenzone.
9. the light transmission black plastic products of a transmissive laser beam, it is characterized in that: described light transmission black plastic products adopts the resin combination of a kind of transmissive laser beam described in any one of claim 1-8 to obtain, the length of described light transmission black plastic products is 90-110mm, width is 70-90mm, and thickness is 0.5-6mm.
10. the preparation method of the light transmission black plastic products of a kind of transmissive laser beam as claimed in claim 9, is characterized in that: comprise the steps:
(1) thermoplastic resin is dried 8-12h in 100-140 DEG C of vacuum drying oven, for subsequent use;
(2) THERMOPLASTIC RESINS of above-mentioned weight part and the black tinting material of light transmission stirred and mix 40-80min in stainless steel tumbler mixer, obtaining mixture;
(3) mixture is used injection moulding machine injection moulding, obtain the light transmission black plastic products of transmissive laser beam.
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