CN107418158B - Flat fiber modified polyester composite material for welding with improved laser transparency - Google Patents
Flat fiber modified polyester composite material for welding with improved laser transparency Download PDFInfo
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- 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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- 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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- 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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- 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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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C08K2003/328—Phosphates of heavy metals
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- C08K2201/004—Additives being defined by their length
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- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a flat fiber modified polyester composite material for welding for improving laser transparency, wherein a laser absorption part comprises a laser absorption component of thermoplastic polyester resin, phosphate compounds or boride particles of rare earth metal elements with the particle size of not more than 900nm, a laser transmission part comprises surface modified metal oxide mainly comprising thermoplastic polyester resin, at least one of surface modified titanium dioxide with the particle size of 30-400nm and zinc oxide, the intrinsic viscosity of the thermoplastic polyester resin is 50-220, and the content of terminal carboxyl groups is 0-100 meq/kg.
Description
Technical Field
The invention relates to a composite material for laser welding, in particular to a flat fiber modified polyester composite material for welding, which improves the laser transparency, and belongs to the technical field of modified polymer composite materials.
Background
The concept of laser welding began in the 70's of the 20 th century and typically used diode lasers or neodymium-doped yttrium aluminum garnet synthetic crystal (Nd: YAG) lasers with wavelengths between 700-1200nm to generate a lot of heat at the weld site, i.e., heat is generated by transmitting the laser light portion to the laser light absorbing portion, thereby melting the element contact region to form the weld site.
Compared with the traditional plastic welding process, the laser welding can be applied to various flexible structures, the welding strength is high, the rapid heating and cooling rate can reduce the heat influence on materials, and no external force is generated on a welding piece, so that the stress and the deformation of the welding piece are very small; in addition, the welding process of laser welding is stable, the surface and the internal quality of a welding seam are very good, the laser welding can be carried out in vacuum, air or other gas environments, the requirement on welding media is not high, and the laser welding can be carried out through glass or other materials transparent to light beams. Since laser welding has the above-mentioned unique advantages, it has been successfully applied to precision welding of micro-miniature parts.
Most polymers are more or less transparent at the laser welding wavelength, but the crystalline nature of the polymer gives rise to a fine crystalline structure within the polymer, which reduces the transparency of the laser because the crystalline regions in the resin scatter and reflect the laser to a greater extent than the structure within the amorphous thermoplastic, thereby reducing the total energy transmitted by the laser and the accuracy of the weld. The polyester material PBT has a particularly low laser transparency compared to other crystalline materials such as polyamides, which is the main reason that although PBT materials exhibit otherwise excellent properties (such as low water absorption, high dimensional stability, economy), it is still less adopted as a material for laser welding at present. On the other hand, the crystalline resin itself does not sufficiently absorb laser light to ensure that it can convert sufficient energy into thermal energy to obtain high-strength welding performance, and therefore carbon black or nigrosine has been conventionally added thereto to intercept laser light to generate thermal energy because carbon black and nigrosine show very high absorption in both the visible region and the IR region, but it is impossible to use the above two substances as laser light absorbers in light-colored and colorless transparent systems, and therefore there is a demand for providing a laser-weldable polyester composite material that can be used as a light-colored and transparent system and can improve laser transparency.
Disclosure of Invention
In order to solve the technical problems, the invention provides a flat fiber modified polyester composite material for welding, which improves the laser transparency, has good welding strength and longer product service life, and provides a choice for the application of a light-colored or colorless system.
The technical scheme of the invention is as follows:
the application provides a flat fiber modified polyester composite material for welding, which improves the transparency of laser and comprises a laser absorption part and a laser transmission part.
The laser absorption part comprises the following components in parts by weight: 50-100 parts of thermoplastic polyester resin and 0.5-10 parts of laser absorption component, wherein the dosage of the laser absorption component is preferably 0.5-8.0 parts, more preferably 0.5-6.0 parts, and further preferably 0.5-4.0 parts. The laser absorption component is phosphate compound or laser absorption particles. Wherein the phosphate is of the classThe compound is one of phosphate, hypophosphite, hydrogen phosphate, pyrophosphate, metaphosphate, polymetaphosphate, tripolyphosphate and hydroxide phosphate, and specifically, is preferably at least one of calcium phosphate, calcium hypophosphite, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, sodium phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium pyrophosphate, potassium polymetaphosphate, potassium tripolyphosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium metaphosphate, sodium tripolyphosphate, triammonium phosphate, ammonium dihydrogen phosphate, iron phosphate, ferric pyrophosphate, magnesium hydrogen phosphate, magnesium phosphate, manganese hypophosphite, ferric sodium pyrophosphate, copper hydroxide phosphate and copper phosphate, and more preferably at least one of copper hydroxide phosphate and copper hydroxide. Wherein the laser absorbing particles are boride particles of rare earth metal with particle diameter not more than 900nm, preferably LaB6、CeB6、GdB6And YB6One kind of (1).
The transmission laser part comprises the following components in parts by weight: 50-100 parts of thermoplastic polyester resin and 0.01-5.0 parts of surface modified metal oxide. Wherein the surface-modified metal oxide is at least one of surface-modified titanium dioxide and zinc oxide with the particle size of 30-400nm, preferably titanium dioxide subjected to surface treatment by an organic siloxane modifier or an inorganic surface modifier, and the organic siloxane modifier or the inorganic surface modifier accounts for 0.2-1.5% of the total mass of the surface-modified metal oxide. The organic siloxane modifier is at least one of vinyl trimethoxy silane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyl trimethoxy silane, p-styryl trimethoxy silane, 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxy silane; the inorganic surface modifier is at least one of aluminum, aluminum oxide and zirconium oxide, and the treatment mode of the inorganic surface modifier is co-oxidation or co-precipitation. In addition, the particle size of the surface-modified metal oxide is an average particle size, and when the average particle size is larger than 400nm, the absorption or reflection degree of the titanium dioxide to the laser is increased, the titanium dioxide cannot transmit the laser, and the surface-modified metal oxide is particularly not suitable for being applied to a laser transmission part, and the laser welding is easy to be unstable.
The thermoplastic polyester resin is aromatic dicarboxylic acid and C2-C10A dihydric aliphatic alcohol produced by a condensation reaction wherein the aromatic dicarboxylic acid is derived from terephthalic acid, diphenyldicarboxylic acid, naphthalenedicarboxylic acid, and may be at least one of 1, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 4' -diphenylenedicarboxylic acid, bis (p-carboxyphenyl) methane, ethylene-bis-p-benzoic acid, 1, 4-tetramethylenebis (p-oxybenzoic acid), ethylenebis (p-oxybenzoic acid), 1, 4-tetramethylenebis (p-oxybenzoic acid), and 1, 3-trimethylenebis (p-oxybenzoic acid); said C is2-C10The dihydric alcohol is at least one of 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, neopentyl glycol, 1, 10-decanediol and 1, 8-octanediol. The thermoplastic polyester resin is preferably at least one of polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), 1, 4-cyclohexylenedimethylene terephthalate (PCT), 1, 4-butylene naphthalate (PBN) and polyethylene naphthalate (PEN), and particularly preferably the thermoplastic polyester resin contains at least one selected from the following PET, PBT, PPT, or a mixture of at least one with other thermoplastic polyester resins. The thermoplastic polyester resin furthermore has an intrinsic viscosity of 50 to 220, preferably 80 to 160, according to ISO1628 (measured in a 0.5 wt.% solution in a phenol/o-dichlorobenzene mixture in a weight ratio of 1:1 at 25 ℃); the thermoplastic polyester resin has a carboxyl end group content of 0 to 100meq/kg, preferably 10 to 50 meq/kg, more preferably 15 to 40meq/kg, as measured by a potentiometric titration analysis method.
In order to obtain a product which can meet the requirements of higher strength and temperature resistance, the flat fiber modified polyester composite material for welding with improved laser transparency can further comprise glass fibers as a reinforcing modifier, wherein the content of the glass fibers is not higher than 60% of the total weight of the flat fiber modified polyester composite material for welding with improved laser transparency, preferably 15% -50% of the total weight of the flat fiber modified polyester composite material for welding with improved laser transparency, and the glass fibers are flat glass fibers.
Compared with the common glass fiber, the flat glass fiber has a non-circular cross section, the cross section is generally elliptical, the ratio of the diameter of the long axis of the cross section perpendicular to the radial direction of the glass fiber to the diameter of the short axis perpendicular to the long axis of the cross section is not less than 2, and the ratio is preferably 2-5, and more preferably 3-4; the length of the minor axis diameter of the cross section of the flat glass fiber is not less than 3 μm, preferably 3-20 μm; and the length of the diameter of the long axis of the cross section is preferably 6 to 40 μm, and the flat glass fiber is present in the form of chopped fiber bundles having a length of 2 to 50 mm. Compared with the common glass fiber, the addition of the flat glass fiber greatly improves the welding strength and the fluidity of the polyester composite material, and the increase of the fluidity greatly reduces the requirements on processing process conditions, such as processing temperature, and can greatly reduce the adverse effects caused by high-temperature processing, such as gas generation and mold deposit formation, on some temperature-sensitive auxiliaries and the polyester resin. In addition, the welding strength is improved, the appearance of a product part can be improved, and the problems of poor appearance such as poor mold replication, scorching, gas marks, fiber floating and the like which are generally considered to be caused by gas generation in the injection molding process are solved.
In addition, the laser-absorbing part and the laser-transmitting part of the flat fiber-modified polyester composite material for welding, which improve the laser transparency, respectively comprise other additives added for achieving other functional purposes, wherein the other additives are at least one of an impact modifier, a plasticizer, an ultraviolet light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a nucleating agent, a flow enhancer, a lubricant and a coloring agent.
The application also discloses a welded product prepared from the flat fiber modified polyester composite material for welding for improving the laser transparency through laser welding.
The beneficial technical effects of the invention are as follows: the utility model provides improve laser transparency's flat fiber modified polyester composite material for welding's laser and see through part and absorption laser part, have white, the colored or clear characteristics of light color, solved traditional laser welding and can also absorb the not enough of visible light through adding carbon black, nigrosine as the laser absorbent simultaneously, solved promptly and need not to present laser absorptivity through adding inorganic pigment like carbon black and or organic pigment like nigrosine. The laser transmission part adopts the surface-modified metal oxide (namely the surface-modified titanium dioxide and/or zinc oxide) with specific particle size, so that the transmission rate of the polyester resin to laser is greatly increased, particularly, the laser light source is ensured to penetrate through the laser transmission part to the greatest extent, and the laser light can reach the welding part and be converted into heat energy to be fused with the absorption part; the laser absorption component contained in the laser absorption part promotes the absorption of light energy to a great extent, when laser is incident on the laser absorption component, the laser in the wavelength range excites free electrons of the laser absorption component to generate electron resonance, and therefore energy is absorbed.
The flat fiber modified polyester composite material for welding, which is prepared by the method and improves the laser transparency, has high visible light transmittance (more than 30 percent), and the laser absorption part of the composite material has the maximum absorption value at the position of 800-1100 nm; the laser-transparent part of the material has a relatively high transmission for semiconductor or YAG or carbon dioxide laser source laser, and the laser-transparent part has a transmission for laser of greater than 30% (measured at 1064nm laser for a thickness of 2mm by the method described in the examples). Articles made from the composite material are well suited for laser welding and have a long service life, are not limited to black, dark-coloured color-matched products, and are particularly suitable for light-coloured, masscoloured or coloured products which do not contain carbon black to absorb laser light, and are therefore particularly suitable for use in the manufacture of covers, housings, add-on components and sensors, for example in the automotive, electronic, telecommunications, information technology, computer, household equipment, sports equipment, medical devices, office supplies or entertainment fields.
Detailed Description
In order to clearly understand the technical means of the present invention and to implement the technical means according to the content of the specification, the following embodiments are further described in detail in the following with reference to the specific examples, which are used for illustrating the present invention and are not intended to limit the scope of the present invention.
The raw materials and the respective models used in the following specific examples and comparative examples are as follows:
thermoplastic polyester resin: PBT (intrinsic viscosity is 125ml/g, terminal carboxyl is 38meq/kg) adopts Ultradur B4500 of BASF; PET (intrinsic viscosity 80.0ml/g, carboxyl end groups 25meq/kg) is PET BG80 characterized by chemical fiber.
Laser absorption component:
phosphate-based compound: copper hydroxide phosphate (CAS No.:10103-48-7) is selected from Guangdong Wengjiang chemical Co., Ltd; copper phosphate (CAS No. 7798-23-4) is selected from the group consisting of Alfa Angsa (China) chemical Limited; the sodium phosphate is selected from Shanghai Michelin Biochemical technology, Inc., and is anhydrous sodium phosphate.
Laser absorbing particles: lanthanum hexaboride (LaB)6) Gadolinium hexaboride (GdB)6) And yttrium hexaboride (YB)6) Are all selected from sumitomo metal mining companies.
Metal oxide(s): the zinc oxide is ZNO-00060 of Taiwan perpetual chemical industry Co., Ltd; organosiloxane processing of TiO2(200nm) FRC5 from Hensman, USA; alumina treatment of TiO2(180nm) Tronox CR834 of Kemeiyl is selected; metal oxide surface treated TiO2(250nm) Tipaque R930 from Nippon Stone industries.
Ordinary glass fiber: the common chopped glass fiber is ECS301CL of Chongqing International composite materials Co., Ltd, and has a diameter of 10 μm.
Chopped flat glass fibers: available from Nitto Boseki, Japan under the trademark NITTOBO CSG3PA-820, 3mm long, with a cross-section having a major axis diameter length of 28 μm and a minor axis diameter length of 7 μm.
Carbon black: selected from carbon black of cabot M717.
Detailed description of the preferred embodiment 1
A laser-absorbing part: 100 parts of PBT and 2 parts of LaB6；
A laser-transmitting section: 100 parts of PBT, 0.5 part of ZnO and 0.2 part of titanium dioxide FRC 5.
Specific example 2
A laser-absorbing part: 60 parts of PBT (polybutylene terephthalate) and 2 parts of GdB620 parts of PET, 10 parts of CSG3 PA-820;
a laser-transmitting section: 60 parts of PBT, 0.5 part of ZnO, 1.0 part of titanium dioxide R930, 20 parts of PET and 10 parts of CSG3 PA-820.
Specific example 3
A laser-absorbing part: 40 parts of PBT and 1 part of GdB630 parts of PET, 10 parts of ECS301CL and 10 parts of CSG3 PA-820;
a laser-transmitting section: 40 parts of PBT, 1 part of ZnO, 0.05 part of titanium dioxide CR834, 30 parts of PET, 10 parts of ECS301CL and 10 parts of CSG3 PA-820.
Specific example 4
A laser-absorbing part: 40 parts of PBT and 1 part of GdB630 parts of PET, 20 parts of CSG3 PA-820;
a laser-transmitting section: 40 parts of PBT, 1 part of ZnO, 0.05 part of titanium dioxide CR834, 30 parts of PET and 20 parts of CSG3 PA-820.
Specific example 5
A laser-absorbing part: 100 parts of PBT and 2 parts of copper hydroxide phosphate;
a laser-transmitting section: 100 parts of PBT, 0.5 part of ZnO and 0.2 part of titanium dioxide FRC 5.
Specific example 6
A laser-absorbing part: 60 parts of PBT, 2 parts of copper phosphate, 20 parts of PET and 10 parts of CSG3 PA-820;
a laser-transmitting section: 60 parts of PBT, 0.5 part of ZnO, 1.0 part of titanium dioxide R930, 20 parts of PET and 10 parts of CSG3 PA-820.
Specific example 7
A laser-absorbing part: 40 parts of PBT, 1 part of anhydrous sodium phosphate, 30 parts of PET, 10 parts of ECS301CL and 10 parts of CSG3 PA-820;
a laser-transmitting section: 40 parts of PBT, 1 part of ZnO, 0.05 part of titanium dioxide CR834, 30 parts of PET, 10 parts of ECS301CL and 10 parts of CSG3 PA-820.
Specific example 8
A laser-absorbing part: 40 parts of PBT, 1 part of anhydrous sodium phosphate, 30 parts of PET and 20 parts of CSG3 PA-820;
a laser-transmitting section: 40 parts of PBT, 1 part of ZnO, 0.05 part of titanium dioxide CR834, 30 parts of PET and 20 parts of CSG3 PA-820.
Comparative example 1
A laser-absorbing part: 100 parts of PBT and 2 parts of LaB6；
A laser-transmitting section: 100 parts of PBT.
Comparative example 2
A laser-absorbing part: 60 parts of PBT, 20 parts of PET, 10 parts of ECS301 CL;
a laser-transmitting section: 60 parts of PBT, 0.5 part of ZnO, 1.0 part of titanium dioxide R930, 20 parts of PET and 10 parts of ECS301 CL.
Comparative example 3
A laser-absorbing part: 40 parts of PBT and 1 part of GdB630 parts of PET, 20 parts of ECS301 CL;
a laser-transmitting section: 40 parts of PBT, 0.05 part of titanium dioxide CR834, 30 parts of PET and 20 parts of ECS301 CL.
Comparative example 4
A laser-absorbing part: 40 parts of PBT and 1 part of GdB630 parts of PET, 20 parts of ECS301 CL;
a laser-transmitting section: 40 parts of PBT, 0.05 part of titanium dioxide CR834, 1% M717, 30 parts of PET, 20 parts of ECS301 CL.
Comparative example 5
A laser-absorbing part: 100 parts of PBT and 2 parts of copper hydroxide phosphate;
a laser-transmitting section: 100 parts of PBT.
Comparative example 6
A laser-absorbing part: 40 parts of PBT, 1 part of anhydrous sodium phosphate, 30 parts of PET, and 20 parts of ECS301 CL;
a laser-transmitting section: 40 parts of PBT, 0.05 part of titanium dioxide CR834, 30 parts of PET and 20 parts of ECS301 CL.
The polyester composite materials of the laser light absorbing part and the laser light transmitting part in the above-described embodiments and comparative examples may be formed into various plastic articles by injection molding, extrusion, molding, foaming, etc. according to a general molding method determined by those skilled in the art as needed. The present invention can be prepared by mixing the initial components in a conventional mixing device such as a screw extruder, a batch type or a batch type mixer, followed by extrusion, and then the extrudate can be cooled and pulverized after the extrusion. It is also possible to premix the components and then to add the remaining raw materials separately and/or after likewise mixing them, the mixing temperature generally being from 230 to 290 ℃.
The various plastic preparations can be used for laser welding, and the welding conditions of laser irradiation time, radiation power and the like of the laser welding are determined according to respective practical applications. In the following specific examples and comparative examples, the above-mentioned composite materials were produced respectively into a plate material using a laser wavelength of 150nm to 15 μm, preferably 808nm to 1100nm, and in the following examples, a laser light source of Nd: YAG or various diode lasers having desired wavelengths was used.
The following tests were carried out on the bars prepared according to the formulations of the specific examples and comparative examples, the test methods being as follows.
Tensile strength retention of welded sample bar: the laser light absorbing portion and the laser light transmitting portion of the plate materials prepared by the formulations in the above-described specific examples and comparative examples were put into a continuous wavelength laser, welded at a speed of 40mm/s using a laser of Nd: YAG, cut into dumbbell-shaped tensile specimens according to ISO 527 standard with the welded surface located at the middle of the span of the specimen, and subjected to tensile strength test in a dry state at 23 ℃ with a relative humidity of 50% and a water content of not higher than 0.2%. And then, blending the laser absorption part and the laser transmission part according to the mass ratio of 1:1, directly molding according to ISO 527 standard to prepare test bars, testing under the same conditions, respectively testing at least 5 test bars with the same composition, and taking the mean value of the tensile strength of the test bars as a final test result. And finally, recording the ratio of the tensile strength of the welding sample strip formed by laser welding to the tensile strength of the injection molding sample strip formed by direct injection molding, and recording the ratio as the retention rate of the tensile strength of the welding sample strip, wherein the unit is "%".
And (3) fatigue testing: and (3) carrying out fatigue test on the cut tensile sample of the welding sample strip and the test rod by using a fatigue tester, wherein the test frequency is 10HZ, the stress ratio R is 0.1, the load of 80MPa is selected, the test temperature is 80 ℃, and the service life of the simulation material in the environment of high-frequency stress or vibration is evaluated according to the cycle number required in the fracture process.
And (3) fluidity evaluation, namely evaluating the flowing length of the melt in a spiral mold (Helix length) by using an injection molding machine under a fixed process (the injection molding temperature is 250 ℃, the mold temperature is 80 ℃), wherein the cross section of the spiral is 1.5mm × 10 mm.
Appearance evaluation A350 mm × 100mm × 4mm square plate was molded by an injection molding process, injection-molded using a single gate located on one side in the long axis direction of the square plate, and evaluated according to the condition of fiber floating in the appearance of the square plate, and classified into five different grades of 5 (excellent), 4 (good), 3 (medium), 2 (poor), and 1 (extremely poor).
Laser transmission partial transparency measurement a reference beam and a test beam, each having a power of 1 watt, are branched off at a 90 ° angle at the speed of Nd-YAG laser light (wavelength of 1064nm, total power of 2 watts) using a beam splitter (SQ 2 unpolarized beam splitter available from laserptik GmbH), the reference beam strikes a reference sensor, the measurement beam is focused to a focal diameter of 0.18 μm via a die-diaphragm located behind the beam splitter, a laser transparency measurement sensor is located 80mm below the focal point, a test sheet is parallel to and with its center 2mm above the measurement sensor, an injection molded test sheet is used having a size of 100mm × 100mm × 2mm, a gate is located in the middle of the edge, the total measurement time is 30 seconds, and the measurement result is determined within the last 5 seconds, signals from the reference sensor and the measurement sensor are recorded simultaneously, a measurement method is started after inserting a sample, the measurement results are calculated according to the following formula, laser LT (signal (measurement sensor)/signal (sensor block × 100), 10% of the same composition is taken, and the measured results are recorded as an average value.
The test results of the specific examples and comparative examples are described in the following table.
TABLE 1 test results of specific examples and comparative examples
The flat fiber modified polyester composite material for welding has the characteristics of white color, light color or transparency, solves the defect that the traditional laser welding can absorb visible light by adding carbon black and nigrosine as laser absorbers, and solves the problem that the laser absorptivity is not realized by adding inorganic pigments such as carbon black and/or organic pigments such as nigrosine. The laser transmission part adopts the surface modified metal oxide (namely the surface modified titanium dioxide and/or zinc oxide) with specific particle size, so that the transmission rate of the polyester resin to laser is greatly increased, particularly, the laser light source is ensured to pass through the laser transmission part to the greatest extent, and the laser light energy is ensured to reach the welding part and be converted into heat energy to be fused with the laser absorption part; the laser absorption component contained in the laser absorption part promotes the absorption of light energy to the maximum extent, when laser is incident on the laser absorption component, the laser in the wavelength range excites free electrons of the laser absorption component to generate electron resonance, and therefore energy is absorbed.
The flat fiber modified polyester composite material for welding, which is prepared by the method and improves the laser transparency, has high visible light transmittance (more than 30 percent), and the laser absorption part of the composite material has the maximum absorption value at the position of 800-1100 nm; the laser-transparent part of the material has a relatively high transmission for semiconductor or YAG or carbon dioxide laser source laser, and the laser-transparent part has a transmission for laser of greater than 30% (measured at 1064nm laser for a thickness of 2mm by the method described in the examples). Articles made from the composite material are well suited for laser welding and have a long service life, so that they are particularly suitable for the production of coverings, housings, add-on components and sensors, for example in the automotive, electronics, telecommunications, information technology, computer, household equipment, sports equipment, medical devices, office supplies or entertainment sector. In addition, the flat fiber modified polyester composite material for welding, which is disclosed by the invention and has the improved laser transparency, uses flat glass fibers, so that the welding strength is greatly improved. Example 4 has significantly improved weld strength, fatigue resistance as a light colored product, and excellent appearance and fluidity due to the use of flat glass fibers, as compared to comparative example 4.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A flat fiber modified polyester composite material for welding for improving laser transparency, which comprises a laser absorption part and a laser transmission part, and is characterized in that:
the laser absorption part comprises the following components in parts by weight: 50-100 parts of thermoplastic polyester resin and 0.5-10 parts of laser absorption component;
the transmission laser part comprises the following components in parts by weight: 50-100 parts of thermoplastic polyester resin and 0.01-5.0 parts of surface modified metal oxide;
the laser absorption component is a phosphate compound or laser absorption particles, wherein the phosphate compound is one of phosphate, hypophosphite, hydrogen phosphate, pyrophosphate, metaphosphate, polymetaphosphate, tripolyphosphate and hydroxide phosphate, and the laser absorption particles are boride particles of rare earth metal elements with the particle size not more than 900 nm;
the surface modified metal oxide is surface modified titanium dioxide and zinc oxide with the particle size of 30-400nm, the surface modified titanium dioxide is titanium dioxide which is subjected to surface treatment by an organic siloxane modifier or an inorganic surface modifier, and the organic siloxane modifier or the inorganic surface modifier accounts for 0.2-1.5% of the total mass of the surface modified metal oxide, wherein the organic siloxane modifier is at least one of vinyl trimethoxy silane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyl trimethoxy silane, p-styrene trimethoxy silane, 3-methacryloxypropyl triethoxy silane and 3-acryloyloxypropyl trimethoxy silane; the inorganic surface modifier is at least one of aluminum, aluminum oxide and zirconium oxide, and the treatment mode of the inorganic surface modifier is co-oxidation or co-precipitation;
the thermoplastic polyester resin is aromatic dicarboxylic acid and C2-C10The aliphatic diol is prepared by condensation reaction, the intrinsic viscosity of the thermoplastic polyester resin is 50-220ml/g, and the terminal carboxyl group content of the thermoplastic polyester resin is 0-100 meq/kg.
2. The flat fiber-modified polyester composite for welding with improved laser transparency according to claim 1, wherein: the phosphate compound is at least one of calcium phosphate, calcium hypophosphite, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, sodium phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium pyrophosphate, potassium polymetaphosphate, potassium tripolyphosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium metaphosphate, sodium tripolyphosphate, triammonium phosphate, ammonium dihydrogen phosphate, iron phosphate, ferric pyrophosphate, magnesium hydrogen phosphate, magnesium phosphate, manganese hypophosphite, sodium iron pyrophosphate, copper hydroxide phosphate and copper phosphate, and the amount of the phosphate compound in a laser absorption part is 0.5-4.0 parts.
3. The flat fiber-modified polyester composite for welding with improved laser transparency according to claim 2, wherein: the phosphate compound is at least one of copper hydroxide phosphate and copper phosphate.
4. The flat fiber-modified polyester composite for welding with improved laser transparency according to claim 1, wherein: the laser absorbing particles are LaB6、CeB6、GdB6And YB6And the amount of the laser absorbing particles in the laser absorbing part is 0.5-4.0 parts.
5. The flat fiber-modified polyester composite for welding with improved laser transparency according to claim 1, wherein: the laser-absorbing part and the laser-transmitting part also comprise glass fibers, the content of the glass fibers accounts for 15-50% of the total weight of the flat fiber modified polyester composite material for welding for improving the laser transparency, the glass fibers are flat glass fibers, the ratio of the diameter of a long axis of a cross section of the flat glass fibers perpendicular to the radial direction of the glass fibers to the diameter of a short axis perpendicular to the diameter of the long axis of the cross section of the flat glass fibers is not less than 2, the length of the diameter of the short axis of the cross section of the glass fibers is not less than 3 mu m, and the flat glass fibers exist in the form of chopped fiber bundles and have the length of 2-.
6. The flat fiber-modified polyester composite for welding with improved laser transparency according to claim 5, wherein: the ratio of the diameter of the long axis of the cross section of the flat glass fiber perpendicular to the radial direction of the glass fiber to the diameter of the short axis perpendicular to the cross section of the flat glass fiber is 3-4, the length of the diameter of the short axis of the cross section of the glass fiber is 3-20 mu m, and the length of the diameter of the long axis of the cross section of the glass fiber is 6-40 mu m.
7. The flat fiber-modified polyester composite for welding with improved laser transparency according to claim 1, wherein: the aromatic dicarboxylic acid is 1, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 4' -diphenylenedicarboxylic acid, bis (p-carboxyphenyl) methane, ethylene-bis-p-benzoic acid, 1, 4-tetramethyleneAt least one of oxybis (p-oxybenzoic acid), ethylenebis (p-oxybenzoic acid), 1, 4-tetramethylenebis (p-oxybenzoic acid), and 1, 3-trimethylenebis (p-oxybenzoic acid), said C2-C10The dihydric alcohol is at least one of 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, neopentyl glycol, 1, 10-decanediol and 1, 8-octanediol.
8. The flat fiber-modified polyester composite for welding with improved laser transparency according to claim 1, wherein: the thermoplastic polyester resin is at least one of polyethylene terephthalate, polytrimethylene terephthalate and polybutylene terephthalate, or the thermoplastic polyester resin is a mixture of at least one of polyethylene terephthalate, polytrimethylene terephthalate and polybutylene terephthalate and other thermoplastic polyester resins; the intrinsic viscosity of the thermoplastic polyester resin is 80-160ml/g, and the content of terminal carboxyl groups is 15-40 meq/kg.
9. The flat fiber-modified polyester composite for welding with improved laser transparency according to claim 1, wherein: the laser absorbing part and the laser transmitting part respectively comprise other additives, and the other additives are at least one of impact modifier, plasticizer, ultraviolet light stabilizer, heat stabilizer, antioxidant, antistatic agent, nucleating agent, flow enhancer, lubricant and colorant.
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