CN107163515A - Improve the solderable of laser-light transparent and use polyester composite - Google Patents
Improve the solderable of laser-light transparent and use polyester composite Download PDFInfo
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- CN107163515A CN107163515A CN201710347309.1A CN201710347309A CN107163515A CN 107163515 A CN107163515 A CN 107163515A CN 201710347309 A CN201710347309 A CN 201710347309A CN 107163515 A CN107163515 A CN 107163515A
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/324—Alkali metal phosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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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
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
Improve the solderable use polyester composite of laser-light transparent the invention discloses a kind of, wherein absorbing laser part includes thermoplastic polyester, phosphate compound or particle diameter are not more than the laser absorption composition based on the boride microparticle of 900nm thulium, wherein transmission laser part includes thermoplastic polyester, metal oxide and small molecular alcohol compound that the surface based on surface-modified titanium dioxide or zinc oxide that particle diameter is 30 400nm is modified, the inherent viscosity of thermoplastic polyester is 50 220 and content of carboxyl end group is 0 100meq/kg, the polyester composite improves the weldability of laser while improving laser-light transparent, there are good weld strength and longer product service life, application for light or colourless system provides selection.
Description
Technical field
The present invention relates to a kind of laser welding composite, more particularly to a kind of improve the solderable of laser-light transparent
With polyester composite, belong to modified high polymer composite material technical field.
Background technology
The concept of laser welding is started from the 1970s, its two pole usually using wavelength between 700-1200nm
Pipe laser or neodymium-doped yttrium-aluminum garnet synthetic crystal (Nd:YAG) laser produces substantial amounts of heat in welding position, that is, passes through transmission
Laser part, which is reached, absorbs laser part generation heat, so that element contact area melts and forms welding position.
Compared with conventional plastic welding procedure, laser welding can be applied in flexible and changeable various structures, and it is welded
Intensity is high, and the quick heating rate of temperature fall having can reduce the heat affecting to material, and butt-welding fitting does not produce external force effect
So that the stress of weldment and deformation are all very small；In addition the welding procedure of laser welding is stable, the surface of weld seam and inherent matter
Amount is all very good, its energy welding in vacuum, air or other gaseous environments, not high to the medium requirements of welding, and can
Welded through glass or other materials to beam transparent.Due to laser welding have the advantages that it is above-mentioned unique, its into
Work(is applied in the precision welding of micro part.
Most polymers are more or less transparent under laser welding wavelength, but the crystal property of polymer makes to gather
There is small crystal structure, so that the transparency of laser can be reduced, because the crystalline region ratio in resin is without fixed inside compound
Structure inside shape thermoplastic can be scattered greatly, reflection laser, so as to reduce the gross energy of laser light
With the precision of welding.Compared with other crystalline materials such as polyamide, polyester material PBT has especially low laser-light transparent
Degree, although here it is PBT material shows otherwise excellent properties (such as low water absorption, high-dimensional stability, economy
Property), but it is still rarer at present using its main cause as the material of laser welding component.On the other hand, crystalline resins sheet
Absorption of the body to laser is also not sufficient to ensure that the weldability that sufficient energy can be converted into heat energy by it and obtain high intensity
Can, thus often wherein addition carbon black or nigrosine come intercepting laser make its produce heat energy because carbon black and aniline
It is black that very high absorption not only can be shown in visible region but also in IR regions, but make in light color and water white transparency system
As laser absorbent it is impossible with above two material, therefore needs that offer is a kind of can to improve laser-light transparent badly
Can be as light and transparent system can laser welding polyester composite.
The content of the invention
In order to solve the above technical problems, improving the solderable compound with polyester of laser-light transparent the invention provides a kind of
Material, the polyester composite improves the weldability of laser while improving laser-light transparent, there is good weld strength
Longer product service life, the application for light or colourless system provides selection.
The technical scheme is that：
Improve the solderable use polyester composite of laser-light transparent this application provides a kind of, it includes absorbing laser
Part and transmission laser part.
The absorption laser part includes following each components by weight：50-100 parts of thermoplastic polyester, swashs
0.5-10 parts of light absorbs composition, the consumption of wherein laser absorption composition is preferably 0.5-8.0 parts, more preferably 0.5-6.0 parts,
More preferably 0.5-4.0 parts.Laser absorption composition is phosphate compound or laser absorption particulate.The phosphate
Class compound be phosphate, hypophosphites, hydrophosphate, pyrophosphate, metaphosphate, polymetaphosphate, tripolyphosphate and
One kind in phosphonium hydroxide hydrochlorate, be particularly preferred as calcium phosphate, calcium hypophosphite, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate,
Sodium phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium pyrophosphate, potassium metapbosphate, PTPP, phosphoric acid hydrogen two
Ammonium, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium metaphosphate, sodium tripolyphosphate, triammonium phosphate, ammonium dihydrogen phosphate, ferric phosphate, Jiao
At least one of ferric phosphate, magnesium monohydrogen phosphate, magnesium phosphate, manganese hypophosphite, ferric sodium pyrophosphate, hydroxide cupric phosphate and cupric phosphate,
It is still more preferably at least one of hydroxide cupric phosphate and cupric phosphate.The laser absorption particulate is not more than for particle diameter
The boride microparticle of 900nm thulium, preferably LaB6、CeB6、GdB6And YB6In one kind.
The transmission laser part includes following each components by weight：50-100 parts of thermoplastic polyester, table
0.01-5.0 parts of 0.01-5.0 parts of metal oxide and small molecular alcohol compound that face is modified.The metal oxygen that wherein surface is modified
Compound is at least one of surface-modified titanium dioxide and zinc oxide that particle diameter is 30-400nm, is preferably through organic
Silicone-modified dose or carry out surface-treated titanium dioxide, and this organic siloxane modified dose through Inorganic surface modifiers
Or Inorganic surface modifiers account for the 0.2~1.5% of the metal oxide gross mass of surface modification.It is above-mentioned organic siloxane modified
Agent is vinyltrimethoxy silane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- glycidyl-oxypropyls three
Methoxy silane, to styryl trimethoxy silane, 3- methacryloxypropyls triethoxysilane and 3- acryloyl-oxies
At least one of propyl trimethoxy silicane；The Inorganic surface modifiers are at least one in aluminium, aluminum oxide and zirconium oxide
Kind, and the processing mode of the Inorganic surface modifiers is cooxidation or co-precipitation.The metal oxide that this outer surface is modified
Particle diameter is average grain diameter, and absorption or reflection journey of the titanium dioxide in itself to laser can be caused when the average grain diameter is more than 400nm
Degree aggravation, it is impossible to make laser light, be especially unsuitable for applying in transmission laser part, be easily caused laser welding insecure.It is described
Small molecular alcohol compound is at least one of glycerine, ethylene glycol, butanediol, 1,3-PD and neopentyl glycol.
Above-mentioned thermoplastic polyester is aromatic binary carboxylic acid and C2-C10Binary aliphatic alcohol is prepared by condensation reaction
Gained, wherein the aromatic binary carboxylic acid is derived from terephthalic acid (TPA), biphenyl dicarboxylic acid, naphthalenedicarboxylic acid, include 1,5- naphthalenes
Dioctyl phthalate, 2,6- naphthalenedicarboxylic acids, 2,7- naphthalenedicarboxylic acids, 4,4 '-diphenylene dicarboxylic acids, double (to carboxyl phenyl) methane, sub- second
Base-bis- para Toluic Acids, 1,4- tetramethylenes double (to oxybenzoic acids), ethylenebis (to oxybenzoic acid), 1,4- tetramethylenes are double
At least one of (to oxybenzoic acid) and 1,3- trimethylenes double (to oxybenzoic acids)；The C2-C10Dihydric alcohol is 1,2- second
Glycol, 1,3- propane diols, 1,4- butanediols, 1,6-HD, 1,4- hexylene glycols, 1,4- cyclohexanediols, 1,4- hexamethylene diformazans
At least one of alcohol, neopentyl glycol, 1,10- decanediols and 1,8- ethohexadiols.The thermoplastic polyester is preferably poly- pair
It is PET (PET), PTT (PPT), polybutylene terephthalate (PBT) (PBT), poly-
Terephthalic acid (TPA) 1,4- cyclohexylenedimethylenes ester (PCT), poly- naphthalenedicarboxylic acid 1,4- butanediol esters (PBN) and poly- naphthalene diformazan
At least one of sour ethylene glycol (PEN), especially preferred thermoplastic polyester contain at least selected from following PET, PBT,
PPT one kind, or a kind of at least within and other thermoplastic polyesters mixtures.In addition the thermoplastic polyester root
According to ISO1628, ((weight ratio is 1 at 25 DEG C:1) solution that the concentration in phenol/o-dichlorohenzene mixture is 0.5wt.%
It is middle determine) inherent viscosity be 50-220, preferably 80-160；The thermoplastic polyester is surveyed according to Potential Titration Analysis method
The content of carboxyl end group obtained is 0-100meq/kg, preferably 10-50meq/kg, more preferably 15-40 meq/kg.
In addition the absorption laser part and transmission laser in the solderable use polyester composite of the improvement laser-light transparent
Part respectively further comprises other auxiliary agents in order to realize other feature purposes and add, other auxiliary agents be impact modifiers,
Plasticizer, UV light stabilizing agent, heat stabilizer, antioxidant, antistatic additive, nucleator, flow enhancing agent, lubricant and
At least one of toner.
The method have the benefit that：Herein described improvement the solderable of laser-light transparent uses polyester composite wood
The laser light part of material and absorb laser part, with white, light color is colored or transparent the characteristics of, solve conventional laser
Welding solves nothing by adding carbon black, nigrosine as that can also absorb the deficiency of visible ray while laser absorbent
Laser absorption need to be presented by adding inorganic pigment such as carbon black and/or organic pigment such as nigrosine.Wherein laser light portion
Divide the surface-modified metal oxide (i.e. surface-modified titanium dioxide and/or zinc oxide) for employing specified particle diameter
With small molecular alcohol compound, transmitance of the polyester resin to laser is considerably increased, especially high degree ensure that LASER Light Source
Weld is reached partially through, it is ensured that laser light energy be converted into heat energy from laser light, it is partially fused with laser absorption；And
The absorption for promoting luminous energy for the laser absorption composition high degree that laser part contains is absorbed, is inhaled in laser light incident to laser
When harvest point is upper, the free electron of the laser excitation laser absorption composition of the wave-length coverage produces electron resonance, so as to absorb energy
Amount, laser absorption composition described herein has the spy of the smaller absorptions of 380nm-780nm in visible wavelength range simultaneously
Point.
The solderable of improvement laser-light transparent obtained by the application preparation has higher visible ray with polyester composite
Transmitance (＞ 30%), it absorbs laser part to there is the maximum of absorption at 800-1100nm；Its laser light part is half-and-half
Conductor or YAG or carbon dioxide laser source laser equally have larger transmitance, and laser light part is same to laser transmittance
Sample is more than 30% (being tested by the method described in embodiment to thickness 2mm under 1064nm laser).By the composite system
The product of standby gained is especially suitable for by laser welding and with Long Service Life, therefore they are particularly suitable for system
Make covering, shell, addition component and sensor, such as automobile, electronic product, telecommunications, information technology, computer, family
With, motion, medical treatment or entertainment field in.
Embodiment
In order to better understand the technological means of the present invention, and it can be practiced according to the content of specification, below
In conjunction with specific embodiments, the embodiment to the present invention is described in further detail, and following examples are used to illustrate this hair
It is bright, but it is not limited to the scope of the present invention.
Raw material and corresponding model employed in following specific embodiments and comparative example are as described below：
Thermoplastic polyester：PBT (inherent viscosity is 125ml/g, end carboxyl 38meq/kg) selects BASF
Ultradur B4500；PET BG80s of the PET (inherent viscosity is 80.0ml/g, end carboxyl 25meq/kg) from Yizheng Fiber Optical plant.
Laser absorption particulate：Lanthanum hexaboride (LaB6), six boronation gadolinium (GdB6) and six yttrium boride (YB6) it is selected from Sumitomo gold
Belong to mine company.
Metal oxide：Zinc oxide selects the ZNO-00060 of the eternal Chemical Co., Ltd. of TaiWan, China；Organosiloxane
Handle TiO2The FRC5 that (200nm) is stepped from U.S.'s Hensel；Alumina treatment TiO2The Tronox of (180nm) from Ke Meiji
CR834；Metal oxide surface handles TiO2(250nm) originates in the Tipaque R930 of industry from Japanese stone.
Small molecular alcohol：1,3- propane diols is selected from oil of SPC；Neopentyl glycol is selected from South Korea LG.
Specific embodiment 1
Absorb laser part：100 parts of PBT, 2 parts of LaB6；
Transmission laser part：100 parts of PBT, 0.5 part of ZnO, 0.2 part of titanium dioxide FRC5,0.05 part of neopentyl glycol.
Specific embodiment 2
Absorb laser part：70 parts of PBT, 2 parts of GdB6, 20 parts of PET；
Transmission laser part：70 parts of PBT, 0.5 part of ZnO, 1.0 parts of titanium dioxide R930,0.05 part of 1,3- propane diols, 20
Part PET.
Specific embodiment 3
Absorb laser part：50 parts of PBT, 1 part of GdB6, 40 parts of PET；
Transmission laser part：50 parts of PBT, 1 part of ZnO, 0.05 part of titanium dioxide CR834,0.1 part of 1,3- propane diols, 40 parts
PET。
Specific embodiment 4
Absorb laser part：100 parts of PBT, 2 parts of hydroxide cupric phosphates；
Transmission laser part：100 parts of PBT, 0.5 part of ZnO, 0.2 part of titanium dioxide FRC5,0.05 part of neopentyl glycol.
Specific embodiment 5
Absorb laser part：70 parts of PBT, 2 parts of cupric phosphates, 20 parts of PET；
Transmission laser part：70 parts of PBT, 0.5 part of ZnO, 1.0 parts of titanium dioxide R930,0.05 part of 1,3- propane diols, 20
Part PET.
Specific embodiment 6
Absorb laser part：50 parts of PBT, 1 part of anhydrous sodium phosphate, 40 parts of PET；
Transmission laser part：50 parts of PBT, 1 part of ZnO, 0.05 part of titanium dioxide CR834,0.1 part of 1,3- propane diols, 40 parts
PET。
Comparative example 1
Absorb laser part：100 parts of PBT, 2 parts of LaB6；
Transmission laser part：100 parts of PBT.
Comparative example 2
Absorb laser part：70 parts of PBT, 20 parts of PET；
Transmission laser part：70 parts of PBT, 0.5 part of ZnO, 1.0 parts of titanium dioxide R930,0.05 part of 1.3- propane diols, 20
Part PET.
Comparative example 3
Absorb laser part：50 parts of PBT, 1 part of GdB6, 40 parts of PET；
Transmission laser part：50 parts of PBT, 0.05 part of titanium dioxide CR834,40 parts of PET.
Comparative example 4
Absorb laser part：100 parts of PBT, 2 parts of hydroxide cupric phosphates；
Transmission laser part：100 parts of PBT.
Comparative example 5
Absorb laser part：50 parts of PBT, 1 part of anhydrous sodium phosphate, 40 parts of PET；
Transmission laser part：50 parts of PBT, 0.05 part of titanium dioxide CR834,40 parts of PET.
The polyester composite of absorption laser part and transmission laser part in above-mentioned specific embodiment and comparative example can
Form various with the conventional forming method determined as needed by those skilled in the art through injection, extrusion, molding, foaming etc.
Plastic products.Can be by being mixed in conventional mixing apparatus such as screw extruder, batch (-type) or batch mixer in the application
Initial component, is then extruded and is prepared, and then extrudate can be cooled down and crushed after the extrusion.It can also be pre-mixed
Each component, is then individually added into remaining raw material and/or is added after equally they are mixed, mixing temperature is usually 230
To 290 DEG C.
Prepared by the various plastics can be used for laser welding, the weldering such as laser exposure time, radiant power of the laser welding
Depending on narrow bars part is according to respective practical application.In following specific embodiments and above-mentioned composite is distinguished in comparative example
Sheet material is made, used optical maser wavelength is between 150nm~15 μm, between preferably 808nm~1100nm, in following citings
Using by Nd:YAG or various meet the requirements wavelength diode laser as LASER Light Source.
Gained batten is prepared to formula in specific embodiment and comparative example and carries out following every tests, method of testing is as follows
It is described.
Weld batten tensile strength retention：Institute will be prepared using formula consumption in above-mentioned specific embodiment and comparative example
What is obtained absorbs laser part and the sheet material of transmission laser part, is put into continuous wavelength laser, uses Nd:YAG laser
Welded with 40mm/s speed, gained sheet material after welding be cut into the tensile sample of dumbbell shaped according to the standards of ISO 527,
And solder side is located at the centre position of batten span, relative humidity is that 50% and moisture content are not higher than 0.2% at 23 DEG C
Drying regime under carry out tensile strength test.Then laser part and transmission laser part will be absorbed using mass ratio as 1:1 is total to
Directly it is molded after mixed according to the standards of ISO 527 and prod is made, tested under conditions of same as described above, respectively
The prod of at least 5 identical compositions is tested, final testing result is used as using their tensile strength average.Finally record is passed through
The ratio of the tensile strength for the injection batten that the tensile strength of the welding batten of laser welding formation is formed with directly injection, note
To weld the conservation rate of batten tensile strength, unit is " % ".
Testing fatigue：Using fatigue tester to the tensile sample by above-mentioned welding batten and prod of interception is entered
Row testing fatigue, test frequency 10HZ, stress ratio R=0.1, from 80MPa load, 80 DEG C of test temperature, institute during being broken
Service life of the cycle-index Simulation material needed in the environment of high-frequency stress or vibration.
Laser light partial transparency is measured：It is (unpolarized purchased from Laseroptik GmbH SQ2 using beam splitter
Beam splitter) the Nd-YAG laser light velocity (wavelength is 1064nm, 2 watts of general power) is distinguished in power-take-off at 90 ° of angles
Reference beam and test beams for 1 watt.Reference beam impacts reference sensor, and measuring beam is distributed via positioned at light beam
Mould dividing plate after device and focus to 0.18 μm of focus diameter.Laser-light transparent degree measurement sensor is located at below focus at 80mm,
Test sheet material parallel to and its be centrally located at measurement sensor with top 2mm place, it is used injection test sheets of sizes be
100mm × 100mm × 2mm, cast gate is located in the middle of edge, and the overall measurement time is 30 seconds, and measurement result is in last 5 seconds
It is determined that, signal of the synchronous recording from reference sensor and measurement sensor.Start measuring method after insertion sample.Measurement
As a result calculated according to below equation, laser-light transparent degree LT=(signal (measurement sensor)/signal (reference sensor)) ×
100%.The test sheet material of 10 pieces of same compositions is taken, record measures the average value of result.
The test result of specific embodiment and comparative example is referring to described in following table.
The specific embodiment of table 1 and comparative example test result
The laser light part of the herein described solderable use polyester composite for improving laser-light transparent and absorption swash
Light part, with white, light color it is colored or transparent the characteristics of, solve conventional laser welding by add carbon black, nigrosine make
The deficiency of visible ray can also be absorbed while for laser absorbent, that is, is solved without by adding inorganic pigment such as carbon black
And/or laser absorption is presented in organic pigment such as nigrosine.Wherein laser light part employ specified particle diameter through surface
Modified metal oxide (i.e. surface-modified titanium dioxide and/or zinc oxide) and small molecular alcohol compound, are considerably increased
Polyester resin the transmitance of laser, especially high degree ensure that LASER Light Source from laser light partially through, it is ensured that
Laser light energy reaches weld and is converted into heat energy, with absorbing laser part fusion；And absorb the laser absorption that laser part contains
The absorption for promoting luminous energy of composition high degree, when on laser light incident to laser absorption composition, the wave-length coverage swash
The free electron that light excitation laser absorbs composition produces electron resonance, so as to absorb energy, laser absorption described herein into
The characteristics of point there is in visible wavelength range the smaller absorptions of 380nm-780nm simultaneously.
The solderable of improvement laser-light transparent obtained by the application preparation has higher visible ray with polyester composite
Transmitance (＞ 30%), it absorbs laser part to there is the maximum of absorption at 800-1100nm；Its laser light part is half-and-half
Conductor or YAG or carbon dioxide laser source laser equally have larger transmitance, and laser light part is same to laser transmittance
Sample is more than 30% (being tested by the method described in embodiment to thickness 2mm under 1064nm laser).By the composite system
The product of standby gained is especially suitable for by laser welding and with Long Service Life, therefore they are particularly suitable for system
Make covering, shell, addition component and sensor, such as automobile, electronic product, telecommunications, information technology, computer, family
With, motion, medical treatment or entertainment field in.
Described above is only the preferred embodiment of the present invention, is not intended to limit the invention, it is noted that for this
For the those of ordinary skill of technical field, without departing from the technical principles of the invention, some improvement can also be made
And modification, these improvement and modification also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of improve the solderable use polyester composite of laser-light transparent, including absorbs laser part and transmission laser portion
Point, it is characterised in that：
The absorption laser part includes following each components by weight：50-100 parts of thermoplastic polyester, laser are inhaled
0.5-10 parts of harvest point；
The transmission laser part includes following each components by weight：50-100 parts of thermoplastic polyester, surface change
0.01-5.0 parts of the metal oxide of property, 0.01-5.0 parts of small molecular alcohol compound；
Wherein described laser absorption composition is phosphate compound or laser absorption particulate, wherein the phosphate compound
For phosphate, hypophosphites, hydrophosphate, pyrophosphate, metaphosphate, polymetaphosphate, tripolyphosphate and phosphonium hydroxide
One kind in hydrochlorate, the laser absorption particulate is the boride microparticle for the thulium that particle diameter is not more than 900nm；It is described
The metal oxide that surface is modified is at least one in the surface-modified titanium dioxide and zinc oxide that particle diameter is 30-400nm
Kind；The thermoplastic polyester is aromatic binary carboxylic acid and C2-C10Binary aliphatic alcohol as obtained by prepared by condensation reaction,
The inherent viscosity of the thermoplastic polyester is 50-220, and the content of carboxyl end group of the thermoplastic polyester is 0-100meq/kg.
2. according to claim 1 improve the solderable use polyester composite of laser-light transparent, it is characterised in that：It is described
Phosphate compound is calcium phosphate, calcium hypophosphite, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, sodium phosphate, potassium phosphate, phosphorus
Sour hydrogen dipotassium, potassium dihydrogen phosphate, potassium pyrophosphate, potassium metapbosphate, PTPP, diammonium hydrogen phosphate, disodium hydrogen phosphate, phosphoric acid
Sodium dihydrogen, sodium metaphosphate, sodium tripolyphosphate, triammonium phosphate, ammonium dihydrogen phosphate, ferric phosphate, ferric pyrophosphate, magnesium monohydrogen phosphate, phosphoric acid
At least one of magnesium, manganese hypophosphite, ferric sodium pyrophosphate, hydroxide cupric phosphate and cupric phosphate.
3. according to claim 2 improve the solderable use polyester composite of laser-light transparent, it is characterised in that：It is described
Phosphate compound is at least one of hydroxide cupric phosphate and cupric phosphate, and the phosphate compound is in the absorption
Consumption in laser part is 0.5-4.0 parts.
4. according to claim 1 improve the solderable use polyester composite of laser-light transparent, it is characterised in that：It is described
Laser absorption particulate is LaB6、CeB6、GdB6And YB6In one kind, and the laser absorption particulate it is described absorption laser part in
Consumption be 0.5-4.0 parts.
5. according to claim 1 improve the solderable use polyester composite of laser-light transparent, it is characterised in that：It is described
The metal oxide that surface is modified is to carry out surface-treated two through organic siloxane modified dose or through Inorganic surface modifiers
Titanium oxide, and this organic siloxane modified dose or Inorganic surface modifiers account for the 0.2- of the metal oxide gross mass of surface modification
1.5%.
6. according to claim 5 improve the solderable use polyester composite of laser-light transparent, it is characterised in that：It is described
Organic siloxane modified dose is vinyltrimethoxy silane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- contractings
Water glycidoxypropyl trimethoxy silane, to styryl trimethoxy silane, 3- methacryloxypropyl triethoxysilicanes
At least one of alkane and 3- acryloxypropyl trimethoxy silanes；The Inorganic surface modifiers are aluminium, aluminum oxide and oxygen
Change at least one of zirconium, and the processing mode of the Inorganic surface modifiers is cooxidation or co-precipitation.
7. according to claim 1 improve the solderable use polyester composite of laser-light transparent, it is characterised in that：It is described
Small molecular alcohol compound is at least one of glycerine, ethylene glycol, butanediol, 1,3-PD and neopentyl glycol.
8. according to claim 1 improve the solderable use polyester composite of laser-light transparent, it is characterised in that：It is described
Aromatic binary carboxylic acid is 1,5- naphthalenedicarboxylic acids, 2,6- naphthalenedicarboxylic acids, 2,7- naphthalenedicarboxylic acids, 4,4 '-diphenylene dicarboxylic acids, double
(to carboxyl phenyl) methane, ethylidene-bis- para Toluic Acids, 1,4- tetramethylenes double (to oxybenzoic acid), ethylenebis are (to oxygen benzene
Formic acid), at least one of 1,4- tetramethylenes double (to oxybenzoic acids) and 1,3- trimethylenes pair (to oxybenzoic acid)；It is described
C2-C10Dihydric alcohol is 1,2- ethylene glycol, 1,3- propane diols, 1,4- butanediols, 1,6-HD, 1,4- hexylene glycols, 1,4- hexamethylenes
At least one of glycol, 1,4 cyclohexane dimethanol, neopentyl glycol, 1,10- decanediols and 1,8- ethohexadiols.
9. according to claim 8 improve the solderable use polyester composite of laser-light transparent, it is characterised in that：It is described
Thermoplastic polyester is polyethylene terephthalate, PTT and polybutylene terephthalate
At least one of ester, or polyethylene terephthalate, PTT and poly terephthalic acid fourth two
The mixture of at least one of alcohol ester and other thermoplastic polyesters, and the inherent viscosity of the thermoplastic polyester is
80-160, content of carboxyl end group is 15-40meq/kg.
10. according to claim 1 improve the solderable use polyester composite of laser-light transparent, it is characterised in that：Institute
State absorption laser part and transmission laser part respectively further comprise other auxiliary agents, other auxiliary agents be impact modifiers, plasticizer,
In UV light stabilizing agent, heat stabilizer, antioxidant, antistatic additive, nucleator, flow enhancing agent, lubricant and colouring agent
It is at least one.
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| CN112679918A (en) * | 2020-12-14 | 2021-04-20 | 江苏金发科技新材料有限公司 | Laser-weldable PBT composition and preparation method thereof |
| WO2022037660A1 (en) * | 2020-08-21 | 2022-02-24 | 东丽先端材料研究开发（中国）有限公司 | Polyester resin composition and molded article thereof |
| WO2022238213A1 (en) | 2021-05-11 | 2022-11-17 | Basf Se | Laser-inscribed and laser-welded shaped bodies and production thereof |
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| CN101043970A (en) * | 2004-10-20 | 2007-09-26 | 默克专利股份有限公司 | Laser-weldable polymers |
| CN101868495A (en) * | 2007-11-19 | 2010-10-20 | 沙伯基础创新塑料知识产权有限公司 | Laser-weldable thermoplastics, methods of manufacture, and articles thereof |
| CN104870562A (en) * | 2012-12-20 | 2015-08-26 | 沙特基础全球技术有限公司 | Thermoplastic compositions, methods of manufacture, and articles thereof |
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| CN101043970A (en) * | 2004-10-20 | 2007-09-26 | 默克专利股份有限公司 | Laser-weldable polymers |
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| CN112679918A (en) * | 2020-12-14 | 2021-04-20 | 江苏金发科技新材料有限公司 | Laser-weldable PBT composition and preparation method thereof |
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| WO2022238213A1 (en) | 2021-05-11 | 2022-11-17 | Basf Se | Laser-inscribed and laser-welded shaped bodies and production thereof |
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| CN107163515B (en) | 2019-05-21 |
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