CN105400189B - A kind of resin combination and translucency black plastic products of energy transmission laser beam - Google Patents
A kind of resin combination and translucency black plastic products of energy transmission laser beam Download PDFInfo
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- CN105400189B CN105400189B CN201510988103.8A CN201510988103A CN105400189B CN 105400189 B CN105400189 B CN 105400189B CN 201510988103 A CN201510988103 A CN 201510988103A CN 105400189 B CN105400189 B CN 105400189B
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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 present invention relates to laser welding special plastic technical fields, and in particular to a kind of resin combination and translucency black plastic products of energy transmission laser beam, the resin combination includes the raw material of following parts by weight：0.01 15 parts of 100 parts of thermoplastic resin and the black colorant of translucency；The thermoplastic resin is by polyurethane and polyester with weight ratio 1:The mixture of 1.2 1.8 compositions；The mixture that the black colorant of translucency is made of anthraquinone dye and purple cyclic ketones dyestuff.The translucency black plastic products are made by above-mentioned resin combination.The translucency black plastic products of the present invention are in visible light region（400‑700nm）With larger optical absorption coefficient, meanwhile, near infrared region（800 1200nm of wavelength）With larger light-transmission coefficient；And heat resistance and excellent in mechanical performance.
Description
Technical field
The present invention relates to laser welding special plastic technical fields, and in particular to a kind of resin combination of energy transmission laser beam
Object and translucency black plastic products.
Background technology
Plastics are as a kind of engineering material, using being continuously increased, because of its good intensity, and at low cost, machine-shaping skill
Art is simple, finished weight is light, physical characteristic is excellent, can provide various engineering properties, is applied to industry manufacture and routine use
Widely.Replacement of the plastics as the metals such as expensive steel, aluminium, magnesium and some other nonmetallic materials in engineering
Product.
Plastics due to the factors such as Shooting Technique limitation, quite a few shape and complicated plastic products cannot
Single injection-molded generally requires multiple adhering components and forms.Therefore, people thirst for one kind in the process of plastic products
Quicker, effective, clean plastic processing mode.
In recent years, the various connection methods for having developed the plastic part of industrial circle, mainly have Vibration welding,
Hot plate type plastics weld and the welding techniques such as ultrasonic bonding, and there is certain limitations for these existing methods.Hot plate welding method
Plastic part is easy to bond together with heating source and air pollution can be caused；Heat affected area is big, and surface has the influences such as deformation
Appearance.And the thermal stress of welded articles is very big, causes the aging speed of internal component quickly or cracking phenomena.It substantially reduces
The service life of product.Friction welding will apply welding assembly larger mechanical force, can reduce weld strength, welding product
The defects of unstable quality.The defect of ultrasonic bonding workpiece does not occur only at faying face, and frequently occurs in weldment
Surface, wherein surface heat damage are more typical one kind, and surface heat damage finally also influences the strong of product to the destruction of material
Degree, apparent mass and service life, in addition supersonic welding receive the limitation of the body form and size that are bonded together.
In terms of the assembly of electronic component, ultrasonic bonding can damage some electronic components.
Therefore, laser welding is just being paid more and more attention as a kind of new method that can preferably overcome these disadvantages.Laser with
The excellent specific properties such as its coherence is good, energy density is high, collimation is good, can weld the special workpiece of shape its by thermo-responsive material
Many advantages, such as material.
Laser welding technology of plastics is a kind of non-contact welding technology in the ascendant.Compared with other welding methods, it
With non-contact, airtight, water-tight, speed of welding is fast, precision is high, weld strength is high, non-trimming, without residue, without friction, nothing
Litter, it is pollution-free, without noise, thermal stress is minimum, flexibility is good, adaptability is good, automatic precision numerical control cost relatively
Low plurality of advantages.It is (such as highly dense that the laser welding technology of plastics is mainly used for the plastic products that ordinary soldering techniques are difficult to adapt to
Spend wiring board), complex-shaped plastic part and the plastic products (such as medical equipment, electronic sensor that have stringent cleanliness requirement
Deng) etc..
The basic principle of plastics laser welding is：Two kinds of plastics are clamped together at low pressures, near infrared ray swashs
Light NIR (wavelength 810-1064nm) passes through a product (transmission of near infrared ray laser) and then is absorbed by another product (close
Infrared laser absorbs).The product for absorbing laser energy converts light energy into thermal energy, is melted in the contact surface of plastics, while heat
It is also conducted to the surface of the product of transmission near infrared ray laser, forms fusion zone.Under the action of clamping force, the fusing of two parts
Area is in close contact.Under the collective effect of the internal force and clamping external force that are generated in material heat expansion, melting range generates intermolecular mixed
It closes, weld seam is formed during rapid cooling.
Laser is to the welding of thermoplastic material mainly using the method for laser transmission welding.The method is to soldered two kinds
Material character has certain requirement, in order to realize laser welding, the optical absorption of two plastic part to be welded at a particular wavelength
It can not answer identical.Upper parts should transmission laser, base element should be with high absorptivities, in laser beam welding as far as possible
In, the part of absorbability heats up and local melting, and the part of light transmission is transferred energy to by heat transfer.In external pressure
Lower two parts are combined together.The reflectivity of two parts should keep minimum, because with the increase of volume reflection, need more
Heat needed for energy production welding.The absorptivity of same reason, upper parts answers minimum.Upper parts absorptivity is excessive
Words, it is also possible to regard to degrading before base element starts softening.It thermally decomposes in order to prevent, laser ray transmitting material swashs than absorbing
Luminescent material fusing point is low to be advantageous.
There is also certain limitations for the application of laser welding, in laser transmission welding, use the plastics of non-staining always
As transparent plastics material.The use of such material limit material required in auto industry and electrical/electronic industry it is various
Application in terms of the product of color.It is of particular importance that the black material used in these fields is not yet satisfactorily universal at present
It is welded and is operated using conventional laser.
A principal element for influencing plastics laser welding is transmissivity of the plastics to laser.Material category, is filled out wall thickness
Filling object content and dyestuff influences degree of transmission.Studies have shown that polymer is at least up to 20- to the transmissivity of near infrared ray laser
50%, excellent welding effect could be obtained using laser welding technology.Since black plastic is in visible light and laser wave strong point
Transmitance be approximately zero, and absorb high.Such as black plastic reaches 90%~95% (black in the absorptivity of laser wave strong point
Plastics extremely low to the transmissivity of near infrared ray laser 5%~10%, then laser can not penetrate), in this case i.e. cannot use
Laser welding.So on plastics laser welding process, two black plastics are welded together it is more difficult, because of laser energy
It is just absorbed before reaching weld interface.In addition, it has been proposed that, black pigment, which can pass through, to be diluted and for transmiting modeling
Transmissivity in the part of material or is even improved using the material compared with thin shape.However, such way cannot be guaranteed that part is made
Satisfactory appearance and the flexibility of Element Design be restricted greatly.
On the other hand, plastics are also an important factor for influencing laser welding effect on the absorptivity of near infrared ray laser.It inhales
The application for receiving agent is very important technique in plastics laser welding process, and the essence of plastics laser welding is by heat effect area
Plastic melt to be welded realizes the engagement of plastic part with postcooling naturally.Plastic melt is allowed to need that plastic part is made to absorb enough
Laser energy.Plastics itself can be naturally best with higher absorption rate absorption laser energy, but is not generally adding absorbent
In the case of, plastics are not fine to the absorbability of light wave, and absorption efficiency is very low, and it is undesirable to melt efficiency.In order to realize good weldering
It connects, needs to add absorbent in bottom plastic to enhance assimilation effect.To greatly improve the heat absorption effect of plastics so that
The material melts in heat effect area faster, effect it is more preferable.
For the above-mentioned technical barrier of black plastic laser welding, it is necessary to research and develop a kind of resin group of energy transmission laser beam
Close object and translucency black plastic products.
Invention content
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of energy transmission lasers
The resin combination of beam, the resin combination can apply to laser welding and show better mouldability, in thermoplastic resin
Dissolubility, chemical-resistant, bleed-resistant and frosting in fat and the transparency to laser beam wavelength.
Another object of the present invention is to provide a kind of translucency black plastic products of energy transmission laser beam, the translucency
Black plastic products have larger optical absorption coefficient at visible light region (400-700nm), meanwhile, near infrared region
(wavelength 800-1200nm) has larger light-transmission coefficient；And heat resistance and excellent in mechanical performance.
Another object of the present invention is to provide a kind of preparation sides of the translucency black plastic products of energy transmission laser beam
Method, the preparation method is simple for process, convenient operation and control, stable quality, and production efficiency is high, can large-scale industrial production.
The purpose of the invention is achieved by the following technical solution：A kind of resin combination of energy transmission laser beam, the tree
Oil/fat composition includes the raw material of following parts by weight：
100 parts of thermoplastic resin
Black colorant 0.01-15 parts of translucency；
The thermoplastic resin is by polyamide and polyester with weight ratio 1:1.2-1.8 the mixture of composition；
The mixture that the black colorant of translucency is made of anthraquinone dye and purple cyclic ketones dyestuff.
The present invention is used in compounding by using polyamide and polyester as thermoplastic resin, and it is 1 to control its weight ratio:
1.2-1.8 has by thermal softening, the performance of hardening by cooling, and machine-shaping is easy, has higher mechanical and physical performance；And
No matter not chemically reactive, heat and cool down and repeat how many times, can keep this performance.
The present invention is used in compounding by using anthraquinone dye and purple cyclic ketones dyestuff as the black colorant of translucency, obtained
Photosensitiveness black plastic products have larger optical absorption coefficient at visible light region (400-700nm), meanwhile, near infrared region
Domain (wavelength 800-1200nm) has larger light-transmission coefficient.
Preferably, the polyamide is by polycaprolactam and polyhexamethylene adipamide with weight ratio 2-3:1 composition mixes
Close object.
The present invention is used in compounding by using polycaprolactam and polyhexamethylene adipamide as polyamide, and it is heavy to control its
Amount is than being 2-3:1, have by thermal softening, the performance of hardening by cooling, machine-shaping is easy, have wear-resisting, heatproof, sealing, sound insulation,
Processing performance is good, the excellent properties such as degradable.
Preferably, the polyester is by polyethylene terephthalate and polybutylene terephthalate (PBT) with weight ratio
1:The mixture of 0.5-1.5 compositions.
The present invention is compounded by using polyethylene terephthalate and polybutylene terephthalate (PBT) as polyester
It uses, and it is 1 to control its weight ratio:0.5-1.5 has good fibre forming property, mechanical property, wearability, creep resistance, low suction
Aqueous and electrical insulation capability；And low temperature crystallization speed is fast, processability is good.
Preferably, the black colorant of the translucency is blue dyestuff, purple dye or the green dye by anthraquinone dye and purple cyclic ketones
The yellow dye of the red dye of dyestuff, the yellow dye of orange dyestuff and anthraquinone dye or purple cyclic ketones dyestuff is with weight ratio 6:2:1 composition
Mixture.The i.e. described black colorant of translucency is by any one in three kinds of the blue dyestuff of anthraquinone dye, purple dye or green dye
Kind with the yellow dye of any one and anthraquinone dye in the red dye of purple cyclic ketones dyestuff, orange two kinds of dyestuff or purple cyclic ketones dyestuff
Any one in two kinds of yellow dye is with weight ratio 6:2:The mixture of 1 composition.
The present invention is by using blue dyestuff, purple dye or the green dye of anthraquinone dye and red dye, the orange of purple cyclic ketones dyestuff
The yellow dye of the yellow dye or purple cyclic ketones dyestuff of dyestuff and anthraquinone dye is used in compounding as the black colorant of translucency, and controls it
Weight ratio is 6:2:1, translucency black plastic products obtained at visible light region (400-700nm) there is larger optics to inhale
Coefficient is received, meanwhile, there is larger light-transmission coefficient near infrared region (wavelength 800-1200nm).
Preferably, the transmissivity of the resin combination containing the absorbing black colorant is saturating with the resin itself
It is 0.5-1.2 to penetrate the ratio between rate.Transmission rate ratio (TThe black resin of laser-transmission/TNatural resin) it is 0.5-1.2, it refers in 1064nm and 940nm,
The laser-transmission use, the transmission rate containing black colorant resin combination, are used, with laser-transmission without the black colorant
The transmission rate of resin combination (natural resin) is compared.
Preferably, the resin combination further includes 6-10 parts of reinforcing agent, 4-8 parts of impact modifying agent and heat-proof modifier 1-
5 parts.
The reinforcing agent is to be coated with low temperature third on its surface using acicular wollastonite and flat glass fiber as nucleome material
Olefin(e) acid ester lotion is the particle of shell.
The present invention is coated with low temperature third on it by using the material based on acicular wollastonite and flat glass fiber
Olefin(e) acid ester lotion is shell, and the support of acicular wollastonite offer radial direction and flat glass fiber can be utilized to prevent
The deformation of proximate matter, while coating acrylic low-temperature ester lotion and can improve the physical property of material under its compatibility and low temperature, it is right
The humidification of reinforcing agent also has adduction.
The impact modifying agent is methyl methacrylate-butadiene-styrene terpolymer, wherein metering system
The content of sour methyl esters unit is 40-60%, and the content of butadiene unit is 20-30%, and the content of styrene units is 20-
30%.
The present invention by using methyl methacrylate-butadiene-styrene terpolymer as pest-resistant modifying agent, and
The content for controlling methyl methacrylate units is 40-60%, and the content of butadiene unit is 20-30%, styrene units
Content is 20-30%, can improve the impact resistance performance of material, can also reduce material melt viscosity, improve mobility,
The processing performance for improving plastics improves the corrosion resistance of material, rigidity, anti-flammability, electrical insulating property, heat resistance, molding processibility
And high temperature resistance.
The heat-proof modifier is by N-phenylmaleimide/styrene/acrylonitrile terpolymer and Alpha-Methyl benzene
The mixture of ethylene/styrene/acrylonitrile terpolymer is with weight ratio 1:The mixture of 2-3 compositions.
The present invention by using N-phenylmaleimide/styrene/acrylonitrile terpolymer and α-methylstyrene/
Styrene/acrylonitrile terpolymer is used in compounding as heat-proof modifier, can improve the high temperature resistance of material, can be with
Improve compatibility, impact and the processability of material.
Preferably, the resin combination further includes 0.5-1.5 parts of fire retardant, 0.5-1.5 parts of viscosity modifier and lubrication
0.5-1.5 parts of agent.
The fire retardant is by brominated epoxy resin and antimony oxide with weight ratio 1.1-1.5:The mixture of 1 composition.
The present invention is used in compounding by using brominated epoxy resin and antimony oxide as fire retardant, and controls its weight
Than for 1.1-1.5:1, good flame retardant effect can be reached, moreover it is possible to improve the processing performance and mechanical performance of material.
The viscosity modifier is ethylene/alpha-olefin interpolymers.
The present invention, as viscosity modifier, can improve the stability of material by using ethylene/alpha-olefin interpolymers, with profit
Lubrication prescription is used in compounding, and can make material in process improves the mobility of material and the release property of product.
The lubricant is by natural paraffin wax and methylene bis stearamide with weight ratio 1：1.2-1.8 the mixing of composition
Object.
The present invention, as external lubricant, can reduce the friction of PVC melts and mold, machine barrel using natural paraffin wax；Using Asia
Methyl bis-stearamides can reduce the intermolecular friction of PVC melts as in-lubricant；Two kinds of lubricants are with weight ratio 1：1.2-
1.8 are used in mixed way and can make material in process and improve the mobility of material and the release property of product.
Preferably, the resin combination further includes 1-5 parts of heat stabilizer, 0.5-1.5 parts of antioxidant and UV resistant agent
0.5-1.5 parts.
The heat stabilizer is by barium stearate and zinc stearate with molar ratio 1：1.4-1.8 the mixture of composition.
It is nontoxic, transparent heat stabilizer by the barium zinc heat stabilizer that barium stearate and zinc stearate form, it can be by catching
The HCl that PVC thermal decompositions generate is caught, prevents the catalytic degradation of HCl from acting on, realizes that the thermostabilization of material, the present invention are hard by selecting
Resin acid barium and zinc stearate as heat stabilizer and control its molar ratio as 1.4-1.8:1, thermostable effect is good, and has both lubrication
Property, making material in process has good dispersibility, compatibility and processing fluidity, makes material good heat stability, has
There is efficient weatherability.
The antioxidant is by antioxidant 1010 and irgasfos 168 with weight ratio 1：The mixture of 1-2 compositions.
The present invention is used in compounding by using antioxidant 1010 and irgasfos 168 as antioxidant, and controls its weight ratio
It is 1：1-2 can delay or inhibit the progress of material oxidation process, to prevent the aging of material and extend its service life.
The UV resistant agent is by 4- benzoyloxys -2,2,6,6- tetramethyl piperidines and 2- hydroxyl -4- n-octyloxies
Benzophenone is with weight ratio 1.5-2.5：The mixture of 1 composition.
The present invention is by using 4- benzoyloxys -2,2,6,6- tetramethyl piperidines and 2- hydroxyl -4- n-octyloxy hexichol
Ketone is used in compounding as UV resistant agent, and it is 1.5-2.5 to control its weight ratio：1, ultraviolet light can be absorbed strongly, had excellent
Good synergistic effect so that product antiageing effect is good.
Another object of the present invention is achieved through the following technical solutions：A kind of translucency black plastic of energy transmission laser beam
Product, the translucency black plastic products are using a kind of resin of energy transmission laser beam of claim 1-8 any one of them
Composition is made, and the length of the translucency black plastic products is 90-110mm, width 70-90mm, thickness 0.5-
6mm。
Another object of the present invention is achieved through the following technical solutions：A kind of translucency black plastic of energy transmission laser beam
The preparation method of product, includes the following steps：
(1) thermoplastic resin is dried into 8-12h in 100-140 DEG C of vacuum drying oven, it is spare；
(2) theRMOPLASTIC RESINS of above-mentioned parts by weight and the black colorant of translucency are stirred in stainless steel rotary drum mixer
40-80min is mixed and mixed, mixture is obtained；
(3) by mixture injection moulding machine injection molding, the translucency black plastic products of energy transmission laser beam are obtained.
The beneficial effects of the present invention are：The resin combination of the present invention can apply to laser welding and show preferably
Mouldability, the dissolubility in thermoplastic resin, chemical-resistant, bleed-resistant and frosting and to the saturating of laser beam wavelength
Bright property.
The translucency black plastic products of the present invention have larger optical absorption system at visible light region (400-700nm)
Number, meanwhile, there is larger light-transmission coefficient near infrared region (wavelength 800-1200nm)；And the translucency black plastic products have
There are heat resistance and the mechanical property required by meeting aviation, ship, automobile, medicine, industrial equipment, electric appliance, electronics and other fields
Energy.
The preparation method of the present invention is simple for process, convenient operation and control, stable quality, and production efficiency is high, can extensive work
Industry metaplasia is produced.
Specific implementation mode
For the ease of the understanding of those skilled in the art, with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of resin combination of energy transmission laser beam, the resin combination includes the raw material of following parts by weight：
100 parts of thermoplastic resin
0.01 part of the black colorant of translucency；
The thermoplastic resin is by polyamide and polyester with weight ratio 1:The mixture of 1.2 compositions；
The polyamide is by polycaprolactam and polyhexamethylene adipamide with weight ratio 2:The mixture of 1 composition.
The polyester is by polyethylene terephthalate and polybutylene terephthalate (PBT) with weight ratio 1:0.5 group
At mixture.
The black colorant of translucency is by the red of blue dyestuff, purple dye or green dye and the purple cyclic ketones dyestuff of anthraquinone dye
The yellow dye of dyestuff, the yellow dye of orange dyestuff and anthraquinone dye or purple cyclic ketones dyestuff is with weight ratio 6:2:The mixture of 1 composition.
The transmissivity of the resin combination containing the absorbing black colorant and the transmissivity of the resin itself it
Than being 0.5.
The resin combination further includes 1 part of 6 parts of reinforcing agent, 4 parts of impact modifying agent and heat-proof modifier；The reinforcing agent
For using acicular wollastonite and flat glass fiber as nucleome material, the grain that acrylic low-temperature ester lotion is shell is coated on its surface
Son；The impact modifying agent is methyl methacrylate-butadiene-styrene terpolymer, wherein methyl methacrylate
The content of unit is 40%, and the content of butadiene unit is 30%, and the content of styrene units is 30%；The heat-proof modifier
It is by N-phenylmaleimide/styrene/acrylonitrile terpolymer and α-methylstyrene/styrene/acrylonitrile ternary
The mixture of copolymer is with weight ratio 1:The mixture of 2 compositions.
The resin combination further includes 0.5 part of 0.5 part of fire retardant, 0.5 part of viscosity modifier and lubricant；It is described fire-retardant
Agent is by brominated epoxy resin and antimony oxide with weight ratio 1.1:The mixture of 1 composition；The viscosity modifier be ethylene/
Alpha-olefin interpolymers；The lubricant is by natural paraffin wax and methylene bis stearamide with weight ratio 1：The mixing of 1.2 compositions
Object.
The resin combination further includes 0.5 part of 1 part of heat stabilizer, 0.5 part of antioxidant and UV resistant agent；The heat is steady
It is by barium stearate and zinc stearate with molar ratio 1 to determine agent：The mixture of 1.4 compositions；The antioxidant is by antioxidant 1010
With irgasfos 168 with weight ratio 1：The mixture of 1 composition；The UV resistant agent is by 4- benzoyloxys -2,26,6- tetra-
Methyl piperidine and 2-hydroxy-4-n-octoxybenzophenone are with weight ratio 1.5：The mixture of 1 composition.
A kind of translucency black plastic products of energy transmission laser beam, the translucency black plastic products use above-mentioned institute
A kind of resin combination for the energy transmission laser beam stated is made, and the length of the translucency black plastic products is 90mm, width
For 70mm, thickness 0.5mm.
A kind of preparation method of the translucency black plastic products of energy transmission laser beam, includes the following steps：
(1) thermoplastic resin is dried into 12h in 100 DEG C of vacuum drying ovens, it is spare；
(2) theRMOPLASTIC RESINS of above-mentioned parts by weight and the black colorant of translucency are stirred in stainless steel rotary drum mixer
40min is mixed and mixed, mixture is obtained；
(3) by mixture injection moulding machine injection molding, the translucency black plastic products of energy transmission laser beam are obtained.
Embodiment 2
A kind of resin combination of energy transmission laser beam, the resin combination includes the raw material of following parts by weight：
100 parts of thermoplastic resin
1 part of the black colorant of translucency；
The thermoplastic resin is by polyamide and polyester with weight ratio 1:The mixture of 1.4 compositions；
The polyamide is by polycaprolactam and polyhexamethylene adipamide with weight ratio 2.2:The mixture of 1 composition.
The polyester is by polyethylene terephthalate and polybutylene terephthalate (PBT) with weight ratio 1:0.8 group
At mixture.
The black colorant of translucency is by the red of blue dyestuff, purple dye or green dye and the purple cyclic ketones dyestuff of anthraquinone dye
The yellow dye of dyestuff, the yellow dye of orange dyestuff and anthraquinone dye or purple cyclic ketones dyestuff is with weight ratio 6:2:The mixture of 1 composition.
The transmissivity of the resin combination containing the absorbing black colorant and the transmissivity of the resin itself it
Than being 0.7.
The resin combination further includes 2 parts of 7 parts of reinforcing agent, 5 parts of impact modifying agent and heat-proof modifier；The reinforcing agent
For using acicular wollastonite and flat glass fiber as nucleome material, the grain that acrylic low-temperature ester lotion is shell is coated on its surface
Son；The impact modifying agent is methyl methacrylate-butadiene-styrene terpolymer, wherein methyl methacrylate
The content of unit is 45%, and the content of butadiene unit is 27.5%, and the content of styrene units is 27.5%；It is described heat-resisting to change
Property agent is by N-phenylmaleimide/styrene/acrylonitrile terpolymer and α-methylstyrene/styrene/acrylonitrile
The mixture of terpolymer is with weight ratio 1:The mixture of 2.2 compositions.
The resin combination further includes 0.8 part of 0.8 part of fire retardant, 0.8 part of viscosity modifier and lubricant；It is described fire-retardant
Agent is by brominated epoxy resin and antimony oxide with weight ratio 1.2:The mixture of 1 composition；The viscosity modifier be ethylene/
Alpha-olefin interpolymers；The lubricant is by natural paraffin wax and methylene bis stearamide with weight ratio 1：The mixing of 1.4 compositions
Object.
The resin combination further includes 0.8 part of 2 parts of heat stabilizer, 0.8 part of antioxidant and UV resistant agent；The heat is steady
It is by barium stearate and zinc stearate with molar ratio 1 to determine agent：The mixture of 1.5 compositions；The antioxidant is by antioxidant 1010
With irgasfos 168 with weight ratio 1：The mixture of 1.2 compositions；The UV resistant agent is by 4- benzoyloxys -2,26,6-
Tetramethyl piperidine and 2-hydroxy-4-n-octoxybenzophenone are with weight ratio 1.8：The mixture of 1 composition.
A kind of translucency black plastic products of energy transmission laser beam, the translucency black plastic products use above-mentioned institute
A kind of resin combination for the energy transmission laser beam stated is made, and the length of the translucency black plastic products is 95mm, width
For 75mm, thickness 1.5mm.
A kind of preparation method of the translucency black plastic products of energy transmission laser beam, includes the following steps：
(1) thermoplastic resin is dried into 11h in 110 DEG C of vacuum drying ovens, it is spare；
(2) theRMOPLASTIC RESINS of above-mentioned parts by weight and the black colorant of translucency are stirred in stainless steel rotary drum mixer
50min is mixed and mixed, mixture is obtained；
(3) by mixture injection moulding machine injection molding, the translucency black plastic products of energy transmission laser beam are obtained.
Embodiment 3
A kind of resin combination of energy transmission laser beam, the resin combination includes the raw material of following parts by weight：
100 parts of thermoplastic resin
5 parts of the black colorant of translucency；
The thermoplastic resin is by polyamide and polyester with weight ratio 1:The mixture of 1.5 compositions；
The polyamide is by polycaprolactam and polyhexamethylene adipamide with weight ratio 2.5:The mixture of 1 composition.
The polyester is by polyethylene terephthalate and polybutylene terephthalate (PBT) with weight ratio 1:1 composition
Mixture.
The black colorant of translucency is by the red of blue dyestuff, purple dye or green dye and the purple cyclic ketones dyestuff of anthraquinone dye
The yellow dye of dyestuff, the yellow dye of orange dyestuff and anthraquinone dye or purple cyclic ketones dyestuff is with weight ratio 6:2:The mixture of 1 composition.
The transmissivity of the resin combination containing the absorbing black colorant and the transmissivity of the resin itself it
Than being 0.9.
The resin combination further includes 3 parts of 8 parts of reinforcing agent, 6 parts of impact modifying agent and heat-proof modifier；The reinforcing agent
For using acicular wollastonite and flat glass fiber as nucleome material, the grain that acrylic low-temperature ester lotion is shell is coated on its surface
Son；The impact modifying agent is methyl methacrylate-butadiene-styrene terpolymer, wherein methyl methacrylate
The content of unit is 50%, and the content of butadiene unit is 25%, and the content of styrene units is 25%；The heat-proof modifier
It is by N-phenylmaleimide/styrene/acrylonitrile terpolymer and α-methylstyrene/styrene/acrylonitrile ternary
The mixture of copolymer is with weight ratio 1:The mixture of 2.5 compositions.
The resin combination further includes 1 part of 1 part of fire retardant, 1 part of viscosity modifier and lubricant；The fire retardant be by
Brominated epoxy resin and antimony oxide are with weight ratio 1.3:The mixture of 1 composition；The viscosity modifier is ethylene/alpha-olefin
Interpretation；The lubricant is by natural paraffin wax and methylene bis stearamide with weight ratio 1：The mixture of 1.5 compositions.
The resin combination further includes 1 part of 3 parts of heat stabilizer, 1 part of antioxidant and UV resistant agent；The heat stabilizer
It is by barium stearate and zinc stearate with molar ratio 1：The mixture of 1.6 compositions；The antioxidant is by antioxidant 1010 and to resist
Oxygen agent 168 is with weight ratio 1：The mixture of 1.5 compositions；The UV resistant agent is by 4- benzoyloxys -2,2,6,6- tetramethyls
Phenylpiperidines and 2-hydroxy-4-n-octoxybenzophenone are with weight ratio 2：The mixture of 1 composition.
A kind of translucency black plastic products of energy transmission laser beam, the translucency black plastic products use above-mentioned institute
A kind of resin combination for the energy transmission laser beam stated is made, and the length of the translucency black plastic products is 100mm, width
For 80mm, thickness 3.5mm.
A kind of preparation method of the translucency black plastic products of energy transmission laser beam, includes the following steps：
(1) thermoplastic resin is dried into 10h in 120 DEG C of vacuum drying ovens, it is spare；
(2) theRMOPLASTIC RESINS of above-mentioned parts by weight and the black colorant of translucency are stirred in stainless steel rotary drum mixer
60min is mixed and mixed, mixture is obtained；
(3) by mixture injection moulding machine injection molding, the translucency black plastic products of energy transmission laser beam are obtained.
Embodiment 4
A kind of resin combination of energy transmission laser beam, the resin combination includes the raw material of following parts by weight：
100 parts of thermoplastic resin
10 parts of the black colorant of translucency；
The thermoplastic resin is by polyamide and polyester with weight ratio 1:The mixture of 1.6 compositions；
The polyamide is by polycaprolactam and polyhexamethylene adipamide with weight ratio 2.8:The mixture of 1 composition.
The polyester is by polyethylene terephthalate and polybutylene terephthalate (PBT) with weight ratio 1:1.2 group
At mixture.
The black colorant of translucency is by the red of blue dyestuff, purple dye or green dye and the purple cyclic ketones dyestuff of anthraquinone dye
The yellow dye of dyestuff, the yellow dye of orange dyestuff and anthraquinone dye or purple cyclic ketones dyestuff is with weight ratio 6:2:The mixture of 1 composition.
The transmissivity of the resin combination containing the absorbing black colorant and the transmissivity of the resin itself it
Than being 1.1.
The resin combination further includes 4 parts of 9 parts of reinforcing agent, 7 parts of impact modifying agent and heat-proof modifier；The reinforcing agent
For using acicular wollastonite and flat glass fiber as nucleome material, the grain that acrylic low-temperature ester lotion is shell is coated on its surface
Son；The impact modifying agent is methyl methacrylate-butadiene-styrene terpolymer, wherein methyl methacrylate
The content of unit is 55%, and the content of butadiene unit is 22.5%, and the content of styrene units is 22.5%；It is described heat-resisting to change
Property agent is by N-phenylmaleimide/styrene/acrylonitrile terpolymer and α-methylstyrene/styrene/acrylonitrile
The mixture of terpolymer is with weight ratio 1:The mixture of 2.8 compositions.
The resin combination further includes 1.2 parts of 1.2 parts of fire retardant, 1.2 parts of viscosity modifier and lubricant；It is described fire-retardant
Agent is by brominated epoxy resin and antimony oxide with weight ratio 1.4:The mixture of 1 composition；The viscosity modifier be ethylene/
Alpha-olefin interpolymers；The lubricant is by natural paraffin wax and methylene bis stearamide with weight ratio 1：1.6 the mixing of composition
Object.
The resin combination further includes 1.2 parts of 4 parts of heat stabilizer, 1.2 parts of antioxidant and UV resistant agent；The heat is steady
It is by barium stearate and zinc stearate with molar ratio 1 to determine agent：The mixture of 1.6 compositions；The antioxidant is by antioxidant 1010
With irgasfos 168 with weight ratio 1：The mixture of 1.8 compositions；The UV resistant agent is by 4- benzoyloxys -2,26,6-
Tetramethyl piperidine and 2-hydroxy-4-n-octoxybenzophenone are with weight ratio 2.2：The mixture of 1 composition.
A kind of translucency black plastic products of energy transmission laser beam, the translucency black plastic products use above-mentioned institute
A kind of resin combination for the energy transmission laser beam stated is made, and the length of the translucency black plastic products is 105mm, width
For 85mm, thickness 4.5mm.
A kind of preparation method of the translucency black plastic products of energy transmission laser beam, includes the following steps：
(1) thermoplastic resin is dried into 9h in 130 DEG C of vacuum drying ovens, it is spare；
(2) theRMOPLASTIC RESINS of above-mentioned parts by weight and the black colorant of translucency are stirred in stainless steel rotary drum mixer
70min is mixed and mixed, mixture is obtained；
(3) by mixture injection moulding machine injection molding, the translucency black plastic products of energy transmission laser beam are obtained.
Embodiment 5
A kind of resin combination of energy transmission laser beam, the resin combination includes the raw material of following parts by weight：
100 parts of thermoplastic resin
15 parts of the black colorant of translucency；
The thermoplastic resin is by polyamide and polyester with weight ratio 1:The mixture of 1.8 compositions；
The polyamide is by polycaprolactam and polyhexamethylene adipamide with weight ratio 3:The mixture of 1 composition.
The polyester is by polyethylene terephthalate and polybutylene terephthalate (PBT) with weight ratio 1:1.5 group
At mixture.
The black colorant of translucency is by the red of blue dyestuff, purple dye or green dye and the purple cyclic ketones dyestuff of anthraquinone dye
The yellow dye of dyestuff, the yellow dye of orange dyestuff and anthraquinone dye or purple cyclic ketones dyestuff is with weight ratio 6:2:The mixture of 1 composition.
The transmissivity of the resin combination containing the absorbing black colorant and the transmissivity of the resin itself it
Than being 1.2.
The resin combination further includes 5 parts of 10 parts of reinforcing agent, 8 parts of impact modifying agent and heat-proof modifier；The enhancing
Agent is using acicular wollastonite and flat glass fiber as nucleome material, and it is shell to be coated with acrylic low-temperature ester lotion on its surface
Particle；The impact modifying agent is methyl methacrylate-butadiene-styrene terpolymer, wherein methyl methacrylate
The content of ester units is 60%, and the content of butadiene unit is 20%, and the content of styrene units is 20%；It is described heat resistance modified
Agent is by N-phenylmaleimide/styrene/acrylonitrile terpolymer and α-methylstyrene/styrene/acrylonitrile three
The mixture of membered copolymer is with weight ratio 1:The mixture of 3 compositions.
The resin combination further includes 1.5 parts of 1.5 parts of fire retardant, 1.5 parts of viscosity modifier and lubricant；It is described fire-retardant
Agent is by brominated epoxy resin and antimony oxide with weight ratio 1.5:The mixture of 1 composition；The viscosity modifier be ethylene/
Alpha-olefin interpolymers；The lubricant is by natural paraffin wax and methylene bis stearamide with weight ratio 1：The mixing of 1.8 compositions
Object.
The resin combination further includes 1.5 parts of 5 parts of heat stabilizer, 1.5 parts of antioxidant and UV resistant agent；The heat is steady
It is by barium stearate and zinc stearate with molar ratio 1 to determine agent：The mixture of 1.8 compositions；The antioxidant is by antioxidant 1010
With irgasfos 168 with weight ratio 1：The mixture of 2 compositions；The UV resistant agent is by 4- benzoyloxys -2,26,6- tetra-
Methyl piperidine and 2-hydroxy-4-n-octoxybenzophenone are with weight ratio 2.5：The mixture of 1 composition.
A kind of translucency black plastic products of energy transmission laser beam, the translucency black plastic products use above-mentioned institute
A kind of resin combination for the energy transmission laser beam stated is made, and the length of the translucency black plastic products is 110mm, width
For 90mm, thickness 6mm.
A kind of preparation method of the translucency black plastic products of energy transmission laser beam, includes the following steps：
(1) thermoplastic resin is dried into 8h in 140 DEG C of vacuum drying ovens, it is spare；
(2) theRMOPLASTIC RESINS of above-mentioned parts by weight and the black colorant of translucency are stirred in stainless steel rotary drum mixer
80min is mixed and mixed, mixture is obtained；
(3) by mixture injection moulding machine injection molding, the translucency black plastic products of energy transmission laser beam are obtained.
The mechanical and physical performance of translucency black plastic products made from embodiment 1-5 is as shown in table 1.
Table 1
As it can be seen from table 1 the present invention translucency black plastic products visible light region (400-700nm) have compared with
Big optical absorption coefficient, meanwhile, there is larger light-transmission coefficient near infrared region (wavelength 800-1200nm)；And the translucency
The properties of black plastic products all have exceeded national standard, and high temperature resistance is excellent, and intensity is high, good flame retardation effect, pressure
Contracting performance and toughness are strong, and processing performance is excellent, excellent combination property.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other manner,
Any obvious replacement is not departed under the premise of present inventive concept within protection scope of the present invention.
Claims (3)
1. a kind of resin combination of energy transmission laser beam, it is characterised in that：The resin combination includes following parts by weight
Raw material：
100 parts of thermoplastic resin
Black colorant 0.01-15 parts of translucency；
The thermoplastic resin is by polyamide and polyester with weight ratio 1:1.2-1.8 the mixture of composition；
The polyamide is by polycaprolactam and polyhexamethylene adipamide with weight ratio 2-3:The mixture of 1 composition；
The polyester is by polyethylene terephthalate and polybutylene terephthalate (PBT) with weight ratio 1:0.5-1.5 groups
At mixture；
The black colorant of translucency is by any one and the purple in three kinds of the blue dyestuff of anthraquinone dye, purple dye or green dye
Any one and the yellow dye of anthraquinone dye in the red dye of cyclic ketones dyestuff, orange two kinds of dyestuff or the yellow dye of purple cyclic ketones dyestuff
Any one in two kinds is with weight ratio 6:2:The mixture of 1 composition；
The resin combination further includes 1-5 parts of 6-10 parts of reinforcing agent, 4-8 parts of impact modifying agent and heat-proof modifier；The increasing
Strong agent is using acicular wollastonite and flat glass fiber as nucleome material, and it is shell to be coated with acrylic low-temperature ester lotion on its surface
Particle；The impact modifying agent is methyl methacrylate-butadiene-styrene terpolymer, wherein methacrylic acid
The content of methyl esters unit is 40-60%, and the content of butadiene unit is 20-30%, and the content of styrene units is 20-30%；
The heat-proof modifier is by N-phenylmaleimide/styrene/acrylonitrile terpolymer and α-methylstyrene/benzene
The mixture of ethylene/propene nitrile terpolymer is with weight ratio 1:The mixture of 2-3 compositions；
The resin combination further includes 0.5-1.5 parts of 0.5-1.5 parts of fire retardant, 0.5-1.5 parts of viscosity modifier and lubricant；
The fire retardant is by brominated epoxy resin and antimony oxide with weight ratio 1.1-1.5:The mixture of 1 composition；The viscosity
Modifying agent is ethylene/alpha-olefin interpolymers；The lubricant is by natural paraffin wax and methylene bis stearamide with weight ratio 1：
1.2-1.8 the mixture of composition；
The resin combination further includes 0.5-1.5 parts of 1-5 parts of heat stabilizer, 0.5-1.5 parts of antioxidant and UV resistant agent；Institute
It is by barium stearate and zinc stearate with molar ratio 1 to state heat stabilizer：1.4-1.8 the mixture of composition；The antioxidant be by
Antioxidant 1010 and irgasfos 168 are with weight ratio 1：The mixture of 1-2 compositions；The UV resistant agent is by 4- benzoxies
Base -2,2,6,6- tetramethyl piperidines and 2-hydroxy-4-n-octoxybenzophenone are with weight ratio 1.5-2.5：The mixing of 1 composition
Object.
2. a kind of translucency black plastic products of energy transmission laser beam, it is characterised in that：The translucency black plastic products
It is obtained using a kind of resin combination of energy transmission laser beam described in claim 1, the translucency black plastic products
Length is 90-110mm, width 70-90mm, thickness 0.5-6mm.
3. a kind of preparation method of the translucency black plastic products of energy transmission laser beam as claimed in claim 2, feature
It is：Include the following steps：
(1) thermoplastic resin is dried into 8-12h in 100-140 DEG C of vacuum drying oven, it is spare；
(2) theRMOPLASTIC RESINS of above-mentioned parts by weight and the black colorant of translucency are stirred simultaneously in stainless steel rotary drum mixer
40-80min is mixed, mixture is obtained；
(3) by mixture injection moulding machine injection molding, the translucency black plastic products of energy transmission laser beam are obtained.
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| EP3395875B2 (en) | 2017-04-24 | 2023-01-25 | Covestro Deutschland AG | Laser beam-permeable substrate material for sensor applications |
| CN107652653B (en) * | 2017-10-25 | 2020-05-08 | 延锋彼欧汽车外饰系统有限公司 | Modified plastic capable of being used for laser welding and preparation method thereof |
| US11747447B2 (en) | 2017-12-21 | 2023-09-05 | Covestro Deutschland Ag | Device comprising a multi-layer body and a LiDAR sensor |
| CN113167864A (en) | 2018-10-23 | 2021-07-23 | 科思创知识产权两合公司 | IR transparent sensor and camera system for a motor vehicle |
| CN109553910B (en) * | 2018-11-28 | 2021-08-20 | 宁波力达得为高分子科技有限公司 | Infrared transmission black plastic and preparation method and application thereof |
| CN110041696B (en) * | 2019-03-20 | 2021-07-16 | 金发科技股份有限公司 | Polyamide composite material and preparation method thereof |
| CN112175362A (en) * | 2020-10-13 | 2021-01-05 | 广州九圆塑业有限公司 | PET composite material and preparation method thereof |
| US20240101812A1 (en) * | 2021-01-21 | 2024-03-28 | Celanese International Corporation | Laser Weldable Polyester Composition |
| CN114987019A (en) * | 2022-06-16 | 2022-09-02 | 合诚技术股份有限公司 | Black reinforced and toughened polyamide composite material with high laser welding strength and preparation method and application thereof |
| CN116925543B (en) * | 2023-09-13 | 2024-01-02 | 东华大学 | Antistatic polyamide composition and preparation method and application thereof |
| CN116904025B (en) * | 2023-09-13 | 2024-01-02 | 东华大学 | Polyamide toughening composition, and preparation method and application thereof |
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| JPS62903A (en) * | 1985-06-05 | 1987-01-06 | Sumitomo Chem Co Ltd | Near infrared ray absorbing filter |
| JP4040459B2 (en) * | 2000-11-13 | 2008-01-30 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Colored thermoplastic resin composition for laser welding, anthraquinone colorant, and molded product comprising the same |
| WO2002057353A2 (en) * | 2000-11-13 | 2002-07-25 | E.I. Dupont De Nemours And Company | Fabricated resin products for laser we4lding and including transmitting and absorbing black colorants, and colored resin compositions therefor |
| DE60121042T3 (en) * | 2000-11-13 | 2015-03-26 | E.I. Dupont De Nemours And Co. | DYED THERMOPLASTIC RESIN COMPOSITIONS FOR LASER WELDING, SPECIAL NEUTRAL ANTHRACHINONE DYES AS COLORING AGENTS AND FORM PART THEREFROM |
| AU2002246661A1 (en) * | 2000-11-13 | 2002-08-06 | E.I. Dupont De Nemours And Company | Resin compositions for laser welding containing anthraquinone and monoazo dyes |
| EP1941988A4 (en) * | 2005-09-21 | 2009-02-25 | Orient Chemical Ind | Laser welded material |
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Effective date of registration: 20200904 Address after: 239000 Xincheng community, industrial park, mentaizi Town, Fengyang County, Chuzhou City, Anhui Province Patentee after: Fengyang fusion New Material Co., Ltd Address before: 523808 Dongguan University of Technology, Songshan University Road, 1, Guangdong, Dongguan Patentee before: DONGGUAN University OF TECHNOLOGY |