CN107163515B - Improve the solderable of laser-light transparent and uses polyester composite - Google Patents
Improve the solderable of laser-light transparent and uses polyester composite Download PDFInfo
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- CN107163515B CN107163515B CN201710347309.1A CN201710347309A CN107163515B CN 107163515 B CN107163515 B CN 107163515B CN 201710347309 A CN201710347309 A CN 201710347309A CN 107163515 B CN107163515 B CN 107163515B
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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
Abstract
Improve the solderable with polyester composite of laser-light transparent the invention discloses a kind of, wherein absorbing laser part includes thermoplastic polyester, laser absorption ingredient based on the boride microparticle of the thulium of phosphate compound or partial size no more than 900nm, wherein transmission laser part includes thermoplastic polyester, partial size is the modified metal oxide and small molecular alcohol compound in the surface based on the surface-modified titanium dioxide or zinc oxide of 30-400nm, 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 color or colourless system provides selection.
Description
Technical field
The present invention relates to a kind of laser welding composite material more particularly to a kind of solderable use for improving laser-light transparent
Polyester composite belongs to modified high polymer composite material technical field.
Background technique
The concept of laser welding starts from the 1970s, its diode usually using wavelength between 700-1200nm
Laser or neodymium-doped yttrium-aluminum garnet synthetic crystal (Nd:YAG) laser pass through transmission laser in a large amount of heat of welding position generation
Part, which reaches, absorbs laser part generation heat, so that element contact area be made to melt and form welding position.
Compared with conventional plastic welding procedure, laser welding can be applied in flexible and changeable various structures, welding
Intensity is high, and possessed quick heating rate of temperature fall can reduce the heat affecting to material, and butt-welding fitting does not generate external force
To keep stress and the deformation of weldment all very small；Furthermore the welding procedure stabilization of laser welding, the surface of weld seam and inherent matter
It is all very good to measure, and energy welding, not high to the medium requirements of welding in vacuum, air or other gaseous environments, and can
Through glass or other material of beam transparent is welded.Since laser welding has the advantages that above-mentioned uniqueness, have become
Function 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 polymerize
There is small crystal structure, so that the transparency of laser can be reduced, this is because the crystalline region in resin is than amorphous inside object
Structure inside thermoplastic material can scatter greatly, reflection laser, thus reduce laser light gross energy and
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 materials to show otherwise excellent properties (such as low water absorption, high-dimensional stability, economy),
At present it is still rarer using its material as laser welding component the main reason for.On the other hand, crystalline resins itself are to sharp
The absorption of light is also not sufficient to ensure that sufficient energy can be converted into thermal energy and obtain high-intensitive welding performance by it, therefore past
It adds carbon black wherein toward meeting or nigrosine carrys out intercepting laser and its is made to generate thermal energy, this is because carbon black and nigrosine are both visible
Light region can show very high absorption in the region IR again, however use above two object in light color and colorless and transparent system
Matter is impossible as laser absorbent, thus it is urgent to provide one kind can improve laser-light transparent can be used as light color and thoroughly
Phaneroplasm system can laser welding polyester composite.
Summary of the invention
In order to solve the above technical problems, improving the solderable with polyester composite wood of laser-light transparent the present invention provides a kind of
Material, which improves the weldability of laser while improving laser-light transparent, have good weld strength and
Longer product service life, the application for light color or colourless system provide selection.
The technical scheme is that
Improve the solderable with polyester composite of laser-light transparent this application provides a kind of comprising absorb laser portion
Divide and transmission laser part.
The absorption laser part includes following each components by weight: 50-100 parts of thermoplastic polyester, being swashed
0.5-10 parts of light absorption ingredient, wherein the dosage of laser absorption ingredient is preferably 0.5-8.0 parts, and more preferably 0.5-6.0 parts, into
One step is preferably 0.5-4.0 parts.Laser absorption ingredient is phosphate compound or laser absorption particle.The phosphoric acid salt
Conjunction object is phosphate, hypophosphites, hydrophosphate, pyrophosphate, metaphosphate, polymetaphosphate, tripolyphosphate and hydrogen-oxygen
Change one of phosphate, is particularly preferred as calcium phosphate, calcium hypophosphite, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, phosphoric acid
Sodium, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium pyrophosphate, potassium metapbosphate, potassium tripolyphosphate, diammonium hydrogen phosphate, phosphorus
Sour disodium hydrogen, sodium dihydrogen phosphate, sodium metaphosphate, sodium tripolyphosphate, triammonium phosphate, ammonium dihydrogen phosphate, ferric phosphate, ferric pyrophosphate,
At least one of magnesium monohydrogen phosphate, magnesium phosphate, manganese hypophosphite, ferric sodium pyrophosphate, hydroxide cupric phosphate and cupric phosphate, further
Preferably at least one of hydroxide cupric phosphate and cupric phosphate.The laser absorption particle is that partial size is dilute no more than 900nm
The boride microparticle of earth metal element, preferably LaB6、CeB6、GdB6And YB6One of.
The transmission laser part includes following each components by weight: 50-100 parts of thermoplastic polyester, table
0.01-5.0 parts and 0.01-5.0 parts of small molecular alcohol compound of the metal oxide of face modification.The wherein modified metal oxidation in surface
Object is that partial size is at least one of surface-modified titanium dioxide and zinc oxide of 30-400nm, preferably through organosilicon oxygen
Alkane modifying agent carries out surface-treated titanium dioxide through Inorganic surface modifiers, and this organic siloxane modified dose or inorganic
Surface modifier accounts for the 0.2~1.5% of the modified metal oxide gross mass in surface.Above-mentioned organic siloxane modified dose is ethylene
Base trimethoxy silane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 3- glycidoxypropyl trimethoxy silicon
Alkane, to styryltrimethoxysilane, 3- methacryloxypropyl triethoxysilane and 3- acryloxypropyl front three
At least one of oxysilane；The Inorganic surface modifiers are at least one of aluminium, aluminium oxide and zirconium oxide, and the nothing
The processing mode of machine surface modifier is cooxidation or co-precipitation.The partial size of the modified metal oxide in this outer surface is average grain
Diameter will lead to titanium dioxide itself when the average grain diameter is greater than 400nm and aggravate to the absorption of laser or degree of reflection, cannot make
Laser light is especially unsuitable for applying in transmission laser part, it is insecure to easily lead to laser welding.The small molecular alcohol compound
For 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 prepares institute by condensation reaction
, wherein the aromatic binary carboxylic acid is derived from terephthalic acid (TPA), biphenyl dicarboxylic acid, naphthalenedicarboxylic acid, it include 1,5- naphthalene two
Formic acid, 2,6- naphthalenedicarboxylic acid, 2,7- naphthalenedicarboxylic acid, 4,4 '-diphenylene dicarboxylic acids, bis- (to carboxyl phenyl) methane, ethylidene-
Double para Toluic Acids, 1,4- tetramethylene bis- (to oxybenzoic acids), ethylenebis (to oxybenzoic acid), 1,4- tetramethylene are bis- (right
At least one of oxybenzoic acid) and 1,3- trimethylene bis- (to oxybenzoic acids)；The C2-C10Dihydric alcohol is 1,2- second two
Alcohol, 1,3- propylene glycol, 1,4- butanediol, 1,6-HD, 1,4- hexylene glycol, 1,4- cyclohexanediol, 1,4- hexamethylene diformazan
At least one of alcohol, neopentyl glycol, 1,10- decanediol and 1,8- ethohexadiol.The thermoplastic polyester is preferably poly- to benzene
Naphthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT) (PBT), poly- pair
Phthalic acid 1,4- cyclohexylenedimethylene ester (PCT), poly- naphthalenedicarboxylic acid 1,4- butanediol ester (PBN) and poly- naphthalenedicarboxylic acid
At least one of ethylene glycol (PEN), especially preferred thermoplastic polyester, which contains, is at least selected from following PET, PBT, PPT
One kind or at least one of and other thermoplastic polyesters mixtures.Furthermore the thermoplastic polyester according to
(concentration in (weight ratio is 1:1's at 25 DEG C) phenol/o-dichlorohenzene mixture is in the solution of 0.5wt.% to ISO1628
Measurement) inherent viscosity be 50-220, preferably 80-160；The thermoplastic polyester is measured according to Potential Titration Analysis method
Content of carboxyl end group be 0-100meq/kg, preferably 10-50meq/kg, more preferably 15-40 meq/kg.
Furthermore the solderable absorption laser part and transmission laser in polyester composite of the improvement laser-light transparent
Part respectively further comprises other auxiliary agents added to realize other function purpose, other auxiliary agents be impact modifiers,
Plasticizer, UV light stabilizing agent, heat stabilizer, antioxidant, antistatic agent, nucleating agent, flow enhancing agent, lubricant and coloring
At least one of agent.
The method have the benefit that: herein described improvement the solderable of laser-light transparent uses polyester composite
Laser light part and absorb laser part, have the characteristics that white, light color colour or it is transparent, solve conventional laser welding
The deficiency that visible light can also be absorbed while by addition carbon black, nigrosine as laser absorbent, that is, solve without logical
Addition inorganic pigment such as carbon black and/or organic pigment such as nigrosine are crossed laser absorption is presented.Wherein laser light part uses
The surface-modified metal oxide (i.e. surface-modified titanium dioxide and/or zinc oxide) and small molecule of specified particle diameter
Alcoholates considerably increases polyester resin and ensure that laser light source is saturating from laser to the transmitance of laser, especially high degree
It crosses and reaches weld partially through, it is ensured that laser light energy and be converted into thermal energy, it is partially fused with laser absorption；And absorb laser portion
The absorption for promoting luminous energy for dividing the laser absorption ingredient high degree contained, when on laser light incident to laser absorption ingredient,
The free electron of the laser excitation laser absorption ingredient of the wave-length coverage generates electron resonance, so that energy is absorbed, the application institute
The laser absorption ingredient stated while having the characteristics that the smaller absorption of 380nm-780nm in visible wavelength range.
The application prepares resulting the solderable of improvement laser-light transparent and uses polyester composite visible light with higher
Transmitance (> 30%) absorbs laser part to the maximum for having absorption at 800-1100nm；Its laser light part is half-and-half
Conductor or YAG or carbon dioxide laser source laser equally have biggish transmitance, and laser light part is same to laser transmittance
Sample is greater than 30% (being tested under 1064nm laser by method as described in the examples thickness 2mm).By the composite material system
Standby resulting product is very suitable to pass through laser welding and has Long Service Life, therefore they are particularly suitable for production
Covering, shell, addition component and sensor, for example, for automobile, electronic product, telecommunications, information technology, computer, household,
In movement, medical treatment or entertainment field.
Specific embodiment
In order to better understand the technical means of the present invention, it and can be implemented in accordance with the contents of the specification, below
In conjunction with specific embodiments, specific embodiments of the present invention will be described in further detail, and following embodiment is for illustrating this hair
It is bright, but be not intended to limit the scope of the invention.
Raw material employed in following specific embodiments and comparative example and corresponding model are as described below:
Thermoplastic polyester: PBT (inherent viscosity 125ml/g, carboxyl end group 38meq/kg) selects BASF
Ultradur B4500；The PET BG80 of PET (inherent viscosity 80.0ml/g, carboxyl end group 25meq/kg) selection Yizheng Fiber Optical plant.
Laser absorption particle: lanthanum hexaboride (LaB6), six boronation gadolinium (GdB6) and six yttrium boride (YB6) it is selected from Sumitomo gold
Belong to mine company.
Metal oxide: the ZNO-00060 of the zinc oxide selection eternal Chemical Co., Ltd. of TaiWan, China；At organosiloxane
Manage TiO2The FRC5 that (200nm) selects U.S.'s Hensel advanced in years；Alumina treatment TiO2The Tronox of (180nm) selection Ke Meiji
CR834；Metal oxide surface handles TiO2(250nm) selects the Tipaque R930 of the original industry of Japanese stone.
Small molecular alcohol: 1,3- propylene glycol 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- propylene glycol, 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- propylene glycol, 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- propylene glycol, 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- propylene glycol, 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- propylene glycol, 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
To form various modelings by the common forming method that those skilled in the art determine as needed through injection molding, extrusion, molding, foaming etc.
Material products.It can be by being mixed just in conventional mixing apparatus such as screw extruder, intermittent or batch mixing machine in the application
Beginning component, is then squeezed out and is prepared, and then by extrudate cooling and can be crushed after the extrusion.Each group can also be pre-mixed
Point, it is then individually added into remaining raw material and/or is added after equally mixing them, mixing temperature is usually 230 to 290
℃。
Various plastics preparation can be used for laser welding, the weldering such as laser irradiation time of the laser welding, radiant power
Narrow bars part is depending on respective practical application.Above-mentioned composite material is made in following specific embodiments and respectively in comparative example
At plate, used optical maser wavelength is between 150nm~15 μm, between preferably 808nm~1100nm, adopts in following citings
Use by Nd:YAG or various meet the requirements wavelength diode laser as laser light source.
Following every tests, the following institute of test method are carried out to formula preparation gained batten in specific embodiment and comparative example
It states.
Weld batten tensile strength retention: will be using formulation dosage preparation gained in above-mentioned specific embodiment and comparative example
Absorption laser part and transmission laser part plate, be put into continuous wavelength laser, using the laser of Nd:YAG with
The speed of 40mm/s is welded, and gained plate after welding is cut into the tensile sample of dumbbell shaped according to 527 standard of ISO, and
Welding surface is set to be located at the middle position of batten span, relative humidity is 50% at 23 DEG C and moisture content is not higher than 0.2%
Tensile strength test is carried out under drying regime.Then laser part and transmission laser part will be absorbed with mass ratio for 1:1 blending
It is directly molded afterwards according to 527 standard of ISO and prod is made, tested under conditions of same as described above, tested respectively
The prod of at least 5 identical compositions, using their tensile strength mean value as final testing result.It finally records through Laser Welding
The ratio for connecing the tensile strength of the tensile strength for the welding batten to be formed and the injection molding batten of directly injection molding formation, is denoted as welding sample
The conservation rate of tensile strength, unit are " % ".
Testing fatigue: the tensile sample of above-mentioned welding batten and prod is carried out to what will be intercepted using fatigue tester
Testing fatigue, test frequency 10HZ, stress ratio R=0.1 select the load of 80MPa, 80 DEG C of test temperature, required when being broken
Cycle-index Simulation material high-frequency stress or vibration in the environment of service life.
The measurement of laser light partial transparency: using beam splitter, (SQ2 purchased from Laseroptik GmbH is unpolarized
Beam splitter) the Nd-YAG laser light velocity (wavelength 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 via positioned at beam splitter
Rear mould partition and focus to 0.18 μm of focus diameter.Laser-light transparent degree measurement sensor is located at focus or less 80mm, surveys
Test piece material is parallel to and its center be located at measurement sensor with top 2mm at, used injection molding test sheet material is having a size of 100mm
× 100mm × 2mm, cast gate are located among edge, and the overall measurement time is 30 seconds, and measurement result determines in last 5 seconds,
Signal of the synchronous recording from reference sensor and measurement sensor.Start measurement method after insertion sample.The result root of measurement
It is calculated according to following formula, 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.
1 specific embodiment of table and comparative example test result
The herein described solderable laser light part with polyester composite for improving laser-light transparent and absorption swash
Light part has the characteristics that white, light color are colored or transparent, solves conventional laser welding and is made by addition carbon black, nigrosine
For the deficiency that can also absorb visible light while laser absorbent, that is, solve without by addition inorganic pigment such as carbon black and
Or laser absorption is presented in organic pigment such as nigrosine.Wherein laser light part uses the surface-modified of specified particle diameter
Metal oxide (i.e. surface-modified titanium dioxide and/or zinc oxide) and small molecular alcohol compound, considerably increase polyester
Resin ensure that laser light source from laser light partially through, it is ensured that laser the transmitance of laser, especially high degree
Luminous energy reaches weld and is converted into thermal energy, fuses with laser part is absorbed；And absorb the laser absorption ingredient that laser part contains
The absorption for promoting luminous energy of high degree, when on laser light incident to laser absorption ingredient, the laser excitation of the wave-length coverage
The free electron of laser absorption ingredient generates electron resonance, to absorb energy, laser absorption ingredient described herein is simultaneously
Has the characteristics that the smaller absorption of 380nm-780nm in visible wavelength range.
The application prepares resulting the solderable of improvement laser-light transparent and uses polyester composite visible light with higher
Transmitance (> 30%) absorbs laser part to the maximum for having absorption at 800-1100nm；Its laser light part is half-and-half
Conductor or YAG or carbon dioxide laser source laser equally have biggish transmitance, and laser light part is same to laser transmittance
Sample is greater than 30% (being tested under 1064nm laser by method as described in the examples thickness 2mm).By the composite material system
Standby resulting product is very suitable to pass through laser welding and has Long Service Life, therefore they are particularly suitable for production
Covering, shell, addition component and sensor, for example, for automobile, electronic product, telecommunications, information technology, computer, household,
In movement, medical treatment or entertainment field.
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of improve the solderable with polyester composite, including absorption laser part and transmission laser portion of laser-light transparent
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
Harvest divides 0.5-10 parts；
The transmission laser part includes following each components by weight: 50-100 parts of thermoplastic polyester, surface change
0.01-5.0 parts of metal oxide, 0.01-5.0 parts of the small molecular alcohol compound of property；
Wherein the laser absorption ingredient is phosphate compound or laser absorption particle, wherein the phosphate compound
For phosphate, hypophosphites, hydrophosphate, pyrophosphate, metaphosphate, polymetaphosphate, tripolyphosphate and phosphonium hydroxide
One of hydrochlorate, the laser absorption particle are the boride microparticle of thulium of the partial size no more than 900nm；
The modified metal oxide in the surface is the surface-modified titanium dioxide and zinc oxide that partial size is 30-400nm,
In surface-modified titanium dioxide be that surface-treated titanium dioxide is carried out through Inorganic surface modifiers, which changes
Property agent accounts for the 0.2-1.5% of surface-modified titanium dioxide gross mass；The Inorganic surface modifiers are aluminium, aluminium oxide and oxygen
Change at least one of zirconium, and the processing mode of the Inorganic surface modifiers is cooxidation or co-precipitation；
The thermoplastic polyester is aromatic binary carboxylic acid and C2-C10Binary aliphatic alcohol is as obtained by condensation reaction preparation
, 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；The small molecular alcohol compound is at least one of glycerine, ethylene glycol, butanediol, 1,3-PD and neopentyl glycol.
2. according to claim 1 improve the solderable with polyester composite of laser-light transparent, it is characterised in that: 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, potassium tripolyphosphate, 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 with polyester composite of laser-light transparent, it is characterised in that: described
Phosphate compound is at least one of hydroxide cupric phosphate and cupric phosphate, and the phosphate compound is in the absorption
Dosage in laser part is 0.5-4.0 parts.
4. according to claim 1 improve the solderable with polyester composite of laser-light transparent, it is characterised in that: described
Laser absorption particle is LaB6、CeB6、GdB6And YB6One of, and the laser absorption particle is in the absorption laser part
Dosage be 0.5-4.0 parts.
5. according to claim 1 improve the solderable with polyester composite of laser-light transparent, it is characterised in that: described
Aromatic binary carboxylic acid is 1,5- naphthalenedicarboxylic acid, 2,6- naphthalenedicarboxylic acid, 2,7- naphthalenedicarboxylic acid, 4,4 '-diphenylene dicarboxylic acids, double
(to carboxyl phenyl) methane, the bis- para Toluic Acids of ethylidene-, 1,4- tetramethylene bis- (to oxybenzoic acids), ethylenebis are (to oxygen benzene
Formic acid), at least one of 1,4- tetramethylene bis- (to oxybenzoic acids) and 1,3- trimethylene bis- (to oxybenzoic acids)；It is described
C2-C10Dihydric alcohol is 1,2- ethylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,6-HD, 1,4- hexylene glycol, 1,4- hexamethylene
At least one of glycol, 1,4 cyclohexane dimethanol, neopentyl glycol, 1,10- decanediol and 1,8- ethohexadiol.
6. according to claim 5 improve the solderable with polyester composite of laser-light transparent, it is characterised in that: described
Thermoplastic polyester is polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate
At least one of ester or polyethylene terephthalate, polypropylene terephthalate 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 15-40meq/kg.
7. according to claim 1 improve the solderable with polyester composite of laser-light transparent, it is characterised in that: described
It absorbs laser part and transmission laser part respectively further comprises other auxiliary agents, which is impact modifiers, plasticizer, purple
In outer light stabilizer, heat stabilizer, antioxidant, antistatic agent, nucleating agent, flow enhancing agent, lubricant and colorant extremely
Few one kind.
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| CN112679918B (en) * | 2020-12-14 | 2023-04-18 | 江苏金发科技新材料有限公司 | Laser-weldable PBT composition and preparation method 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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