CN116333463A - Polybutylene terephthalate modified material and preparation method and application thereof - Google Patents
Polybutylene terephthalate modified material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 68
- 229920001707 polybutylene terephthalate Polymers 0.000 title claims abstract description 60
- -1 Polybutylene terephthalate Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000004927 clay Substances 0.000 claims abstract description 61
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 32
- 239000006229 carbon black Substances 0.000 claims abstract description 21
- 239000003365 glass fiber Substances 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001748 polybutylene Polymers 0.000 claims description 8
- 239000004113 Sepiolite Substances 0.000 claims description 7
- 229910052624 sepiolite Inorganic materials 0.000 claims description 7
- 235000019355 sepiolite Nutrition 0.000 claims description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- RRJHFUHAKCSNRY-UHFFFAOYSA-L [Cu+2].[O-]P([O-])=O Chemical compound [Cu+2].[O-]P([O-])=O RRJHFUHAKCSNRY-UHFFFAOYSA-L 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- 239000004599 antimicrobial Substances 0.000 claims 1
- 229910052901 montmorillonite Inorganic materials 0.000 claims 1
- 238000010330 laser marking Methods 0.000 abstract description 37
- 238000000034 method Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000009977 dual effect Effects 0.000 abstract description 3
- 229920006351 engineering plastic Polymers 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 238000005187 foaming Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 229910052622 kaolinite Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XCPFSALHURPPJE-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 XCPFSALHURPPJE-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
-
- 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
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of modification of high molecular engineering plastics, and particularly discloses a polybutylene terephthalate modified material, a preparation method and application thereof. The polybutylene terephthalate modified material comprises the following components in parts by weight: 40 to 85 parts of PBT resin, 20 to 50 parts of glass fiber, 0.1 to 1 part of carbon black, 0.3 to 2 parts of laser auxiliary agent and 0.5 to 5 parts of clay. The polybutylene terephthalate modified material can achieve the dual effects of high definition of laser marking black marking white marking and high marking writing fastness, and the modified material has the advantages of simple realization method, low cost and high laser marking efficiency; wherein, clay component is added to sinter at high temperature, so as to stabilize and strengthen microbubbles for marking writing, thereby improving laser marking fastness. The polybutylene terephthalate modified material prepared by the invention can be applied to other deep color materials with white characters printed by deep ground color, and has wide application range.
Description
Technical Field
The invention relates to the technical field of modification of high molecular engineering plastics, in particular to a polybutylene terephthalate modified material, a preparation method and application thereof.
Background
Along with the improvement of environmental protection requirements and the improvement of production efficiency, the traditional printing modes such as mimeograph, silk screen printing and the like are being further replaced by laser marking. The laser marking technology has the advantages of high efficiency, low cost, small pollution, wide application range and the like. The laser marking is mainly applied to light-ground color marking of dark color writing and dark-ground color marking of white writing, and is also applied to color marking in recent years. The mature laser marking is mainly used for marking black writing with light ground color and white writing with deep ground color, the former is called white blackening for short, and the latter is called black whitening for short. The white blacking mechanism is that the surface of the material absorbs laser energy and is degraded and carbonized, so that black writing is developed. For black and white, the material is heated and decomposed to generate gas, micro-foaming is generated on the surface of the material, and a visual white handwriting effect is achieved on diffuse reflection of light.
For the black-and-white technology, patent CN103467956a discloses a polycarbonate compound capable of laser marking and a preparation method thereof, wherein a laser marking auxiliary agent with a silicon-oxygen bond and a benzene ring is added to realize a laser marking effect. Patent CN112266500B provides a laser marking powder, which is PAN-based carbon fiber powder with oxazole groups, and can be applied to PC resin to reduce the photo-thermal conversion efficiency, absorb light energy of partial wave bands, reflect blue light and obtain a clearer black and white effect.
At present, the laser marking technology related to black and white marking is less, the main concern of the prior art is to solve the problem of whether the mark can be marked, and individual patents mention to improve the definition of the mark, but no effective technology is disclosed to discuss the problem of improving the mark writing fastness. The marking effect of black and white is derived from micro-foaming on the surface of the material, the micro-foaming has weak strength, and the micro-foaming is easy to fall off when being scraped by external force, so that the marking effect is obviously reduced. In practical application, the clear mark and the durable mark are indispensable. Therefore, it is necessary to develop a material that can be identified clearly and with high fastness.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a polybutylene terephthalate modified material, a preparation method and application thereof. The polybutylene terephthalate modified material solves the technical problems of marking definition and marking fastness of laser marking black and white.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a polybutylene terephthalate modified material, which comprises the following components in parts by weight:
40 to 85 parts of PBT resin, 20 to 50 parts of glass fiber, 0.1 to 1 part of carbon black, 0.3 to 2 parts of laser auxiliary agent and 0.5 to 5 parts of clay.
According to the invention, glass fiber, carbon black, laser auxiliary agent and clay are added into the PBT resin, so that the prepared polybutylene terephthalate modified material is suitable for laser marking black and white marking, and has higher laser marking definition and marking fastness.
The laser auxiliary agent added can homogenize the light absorption of the polybutylene terephthalate modified material, so that the boundary of the mark writing is clearer. The addition of a proper amount of carbon black can promote the laser absorption capacity of the polybutylene terephthalate modified material and can improve the foaming degree of the polybutylene terephthalate modified material. The laser auxiliary agent and the carbon black are compounded, so that the clarity of laser marking can be better improved.
In addition, clay is added in the preparation process of the polybutylene terephthalate modified material, when laser marking is performed, the position burned by the laser beam is instantaneously heated, clay components are sintered at high temperature, and microbubbles for marking handwriting are stabilized and enhanced, so that the laser marking fastness is improved.
As a preferred embodiment of the polybutylene terephthalate-modified material of the invention, the carbon black is 0.2 to 0.6 part by weight, and the clay is 1 to 3 parts by weight.
The invention optimizes the weight parts of the carbon black and the clay, the prepared polybutylene terephthalate modified material has higher laser marking definition on the white character of the black matrix, obviously improves the marking fastness, is durable and realizes double effects. The prepared polybutylene terephthalate modified material is applied to other deep color materials with white characters of deep ground color, and has wide application range.
As a preferred embodiment of the polybutylene terephthalate-modified material according to the present invention, the clay is at least one of kaolin Dan Lei clay, sepiolite clay, montmorillonite clay, and bentonite clay, and preferably the clay is sepiolite clay. The above clay is preferred because it has high temperature sintering characteristics while not reacting with the modified material components to cause excessive deterioration in performance.
When the clay is at least one of kaolinite clay, sepiolite clay, montmorillonite clay and bentonite clay, microbubbles for marking handwriting can be better stabilized and enhanced, so that the laser marking fastness is improved, and the product is durable.
As a preferred embodiment of the polybutylene terephthalate modified material of the invention, the specific surface area of the clay is more than or equal to 90m 2 Preferably, the clay has a specific surface area of > 100m 2 And/g. Specific surface area test method of clay refers to GB/T19587-2004 "determination of specific surface area of solid substance by gas adsorption BET method".
When the specific surface area of clay is more than 100m 2 And in the process of/g, the clay component is sintered at high temperature, so that microbubbles for marking handwriting can be well stabilized and enhanced, and the laser marking fastness is improved. The specific surface area of the clay may be 110, 120, 150, 160, 180, etc., and the specific surface area of the clay selected in the present invention is not limited thereto.
Preferably, the specific surface area of the clay is 210-230 m 2 /g。
When the specific surface area of clay is 210-230 m 2 And in the process of/g, the effect of stabilizing and enhancing the microbubbles of the mark writing is better, so that the effect of improving the laser marking fastness is also better. When the specific surface area is too large, clay dispersion is difficult, so that the performance of the modified material is obviously deteriorated, and meanwhile, extrusion feeding is not smooth.
Preferably, the carbon black is an inorganic carbon black used as a pigment.
As a preferred embodiment of the polybutylene terephthalate-modified material according to the invention, the glass fibers are alkali-free glass fibers, and the glass fibers have an average diameter of 7 to 13. Mu.m.
The alkali-free glass fiber with the diameter can improve the mechanical property of the prepared polybutylene terephthalate modified material, and has higher tensile strength.
As a preferred embodiment of the polybutylene terephthalate modified material, the laser auxiliary agent comprises a basic copper phosphonate laser auxiliary agent, or a laser auxiliary agent of a mixture of titanium oxide and pigment, or a tin-antimony compound laser auxiliary agent. Preferably, the laser auxiliary agent is at least one of Iriotec 8800 series laser auxiliary agent, iriotec8200 series laser auxiliary agent and FABULASE series laser auxiliary agent.
The laser auxiliary agent of the type can be added to homogenize the light absorption of the polybutylene terephthalate modified material, so that the boundary of the identification mark is clearer; the laser auxiliary agent and the carbon black can be compounded to better improve the definition degree of laser marking.
As a preferred embodiment of the polybutylene terephthalate modified material, the polybutylene terephthalate modified material further comprises 0-2 parts of processing aid, wherein the processing aid is at least one of antioxidant, lubricant, weather-resistant aid, coupling agent, antibacterial agent, anti-dripping agent, transesterification inhibitor and colorant. Preferably, the processing aids are antioxidants and lubricants.
The second object of the present invention is to provide a method for preparing the polybutylene terephthalate modified material, comprising the following steps:
adding the PBT resin, the glass fiber, the carbon black, the laser auxiliary agent, the clay and the processing auxiliary agent into an extruder according to the proportion, carrying out melt extrusion at 180-260 ℃, cooling and granulating to obtain the polybutylene terephthalate modified material.
The third object of the invention is to provide the application of the polybutylene terephthalate modified material in products such as automobiles, e.g. controller shells and sensor shells, electronic appliances, e.g. miniature circuit breakers and connectors.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a polybutylene terephthalate modified material, a preparation method and application thereof, wherein the polybutylene terephthalate modified material can realize the dual effects of high definition of black and white marks of laser marking and high fastness of marks, and the polybutylene terephthalate modified material has the advantages of simple realization method, low cost and high laser marking efficiency; wherein, clay component is added to sinter at high temperature, so as to stabilize and strengthen microbubbles for marking writing, thereby improving laser marking fastness. The polybutylene terephthalate modified material prepared by the invention can be applied to other deep color materials with white characters printed by deep ground color, and has wide application range.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
In the following examples and comparative examples, the experimental methods used were conventional methods unless otherwise specified, and the materials, reagents and the like used, unless otherwise specified, were all commercially available.
The sources of the raw materials used in the following examples and comparative examples are as follows:
PBT resin, the model is PBT GX121, the relative density is 1.31, the intrinsic viscosity is 1.00dl/g, and the PBT resin is purchased from China petrochemical company asset management and management company, instrument division; the PBT resin intrinsic viscosity test method is based on GB/T14190-2017;
glass fiber, alkali-free chopped, with average diameter of 11 μm, model ECS11-4.5-534A, purchased from China boulder Co., ltd;
carbon black, model M717, inorganic carbon black, purchased from cabot corporation;
clay 1, model Clay 80T, is sepiolite Clay with specific surface area 210m 2 And/g, purchased from Shanghai Zhuang Jing chemical Co., ltd;
clay 2, model Clay 20, is sepiolite Clay with specific surface area of 230m 2 And/g, purchased from Shanghai Zhuang Jing chemical Co., ltd;
clay 3, model CMP-1, is kaolinite clay with specific surface area of 255m 2 /g, purchased from chinese kaolin limited;
clay 4, model kaolin, is kaolinite clay with specific surface area of 90m 2 According to the formula of the powder with the granularity of/g and 600 meshes, the main component of the product is Al 2 O 3 /SiO 2 =45/52, cas No. 1332-58-7, purchased in the mineral processing plant of the hundreds of benefits in the county of life;
clay 5, model bentonite, is organobentonite clay with specific surface area of 195m 2 Per g,1000 mesh, the main component of the product is Al 2 O 3 /SiO 2 =57/19, cas number 1302-78-9, purchased from astrochemical company, inc;
laser auxiliary agent 1, model FABULASE 330, basic copper phosphonates, purchased from bourdon sea company;
laser auxiliary 2, model Iriotec 8850, the main body is a mixture of titanium oxide and pigment, purchased from merck company;
antioxidant, pentaerythritol tetrakis [ beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, commercially available;
lubricants, pentaerythritol fatty acid esters, commercially available.
In the following examples and comparative examples, the PBT resin, glass fiber, antioxidant and lubricant were the same in parallel experiments.
The components (in parts by weight) of the polybutylene terephthalate-modified materials of examples 1 to 16 and comparative examples 1 to 4 are shown in Table 1.
The preparation method of the polybutylene terephthalate modified material comprises the following steps:
adding PBT resin, carbon black, a laser auxiliary agent, clay and a processing auxiliary agent into a premixing machine according to a proportion, mixing for 1-2min to obtain a premix, adding the premix into a main feeding port of a double-screw extruder, adding glass fibers into a side feeding port of a fifth zone of the double-screw extruder, wherein the temperature of a first zone of the double-screw extruder is 30-200 ℃, the temperature of a second zone of the double-screw extruder is 220-260 ℃, the temperature of a third zone of the double-screw extruder is 210-250 ℃, the temperature of a fourth zone of the double-screw extruder is 200-240 ℃, the temperature of a fifth zone of the double-screw extruder is 180-240 ℃, the temperature of a sixth zone of the double-screw extruder is 180-240 ℃, the temperature of a seventh zone of the double-screw extruder is 180-240 ℃, the temperature of a ninth zone of the double-screw extruder is 180-240 ℃, the main machine rotating speed of the double-screw extruder is 300-500 rpm, and cooling, granulating and drying after extrusion, obtaining the polybutylene terephthalate modified material. The process conditions of the preparation method are the same in each parallel experiment.
TABLE 1
The mechanical properties of the polybutylene terephthalate modified materials of the examples 1-16 and the comparative examples 1-4 of the invention are specifically tested by the following method:
1) Tensile strength: the test is carried out with reference to standard ISO 527-2-2012, the sample size is 150 x 10 x 4mm, the stretching speed is 10mm/min;
2) Contrast ratio: and (3) carrying out laser marking on the middle part of the color plate with the size of 80 x 55 x 2mm by using a laser carving machine with an infrared light source, marking a circle with the size of not less than 30mm in diameter, testing the hue of the laser marking position before and after marking under a D65 light source, and marking the color difference value as contrast. The higher the contrast, the higher the perceived clarity of the logo by human vision.
3) Fastness: at the color plate middle part of size 80 x 55 x 2mm, carry out laser marking using the radium carving machine of infrared light source, the sign figure is the two-dimensional code, scrape the two-dimensional code 3 times through reciprocal wearing and tearing mode, reciprocal wearing and tearing scratch speed is 200mm/s, load 20N, friction medium is with the #400 mu abrasive paper of selection with GB/T9258-2000, judge fastness good and bad with the definition and the microbubble condition that the two-dimensional code is scraped 3 times after being scraped, wherein, after the two-dimensional code was scraped:
preferably: the area of the shedding part of the microbubbles accounts for less than 30 percent of the total area of the microbubbles;
good: the area of the bubble shedding part accounts for 30-60% of the total area of the microbubbles;
difference; the area of the bubble falling part accounts for more than 60 percent of the total area of the microbubbles;
table 2 test results for examples and comparative examples
| Group of | Tensile Strength | Contrast ratio | Fastness to light |
| Example 1 | 138 | 27.66 | Excellent (excellent) |
| Example 2 | 145 | 26.02 | Excellent (excellent) |
| Example 3 | 135 | 17.40 | Excellent (excellent) |
| Example 4 | 141 | 19.25 | Excellent (excellent) |
| Example 5 | 140 | 25.74 | Excellent (excellent) |
| Example 6 | 136 | 24.16 | Excellent (excellent) |
| Example 7 | 138 | 29.75 | Excellent (excellent) |
| Example 8 | 135 | 29.76 | Excellent (excellent) |
| Example 9 | 130 | 27.78 | Excellent (excellent) |
| Example 10 | 137 | 29.2 | Excellent (excellent) |
| Example 11 | 142 | 29.35 | Good grade (good) |
| Example 12 | 121 | 30.3 | Excellent (excellent) |
| Example 13 | 140 | 29.52 | Excellent (excellent) |
| Example 14 | 136 | 29.82 | Excellent (excellent) |
| Example 15 | 137 | 27.78 | Good grade (good) |
| Example 16 | 131 | 27.92 | Good grade (good) |
| Comparative example 1 | 138 | 27.66 | Difference of difference |
| Comparative example 2 | 145 | 5.11 | Good grade (good) |
| Comparative example 3 | 139 | 6.62 | Good grade (good) |
| Comparative example 4 | 136 | 5.32 | Excellent (excellent) |
As can be seen from the results in Table 2, the polybutylene terephthalate modified materials prepared in examples 1-16 of the invention can achieve the dual effects of improving the marking definition and the marking fastness of laser marking black and white, and the modified materials have better mechanical properties and better comprehensive properties. In the embodiment of the invention, the tensile strength reaches more than 121MPa, the contrast reaches 17.4, and the mark fastness grade is more than good.
Examples 7 and 11-14 the weight parts of clay are adjusted, and the polybutylene terephthalate modified material prepared in examples 7 and 13-14 can achieve better effect of improving the marking fastness of laser marking black and white than example 11. Example 12 has a lower tensile strength due to a higher proportion of clay. Compared with comparative example 1, examples 7, 11-14 are prepared by adding clay in the preparation process of polybutylene terephthalate modified material, when laser marking auxiliary agent is added, the position burned by laser beam is instantly heated, clay component is sintered at high temperature, and the micro-bubble for marking writing is stabilized and enhanced, thereby improving laser marking fastness.
Compared with the comparative example 2, the carbon black with the weight fraction of 0.1-1 part is added to promote the laser absorption capacity of the polybutylene terephthalate modified material, improve the foaming degree of the polybutylene terephthalate modified material and further improve the marking definition of laser marking black and white. The contrast ratio of examples 5-7 is better than that of examples 3-4, and the clarity of the mark is better.
In comparison with comparative examples 3 and 4, in example 7, good marking definition of laser marking black and white could not be obtained when the amount of the laser auxiliary agent is too small, the amount of the carbon black is excessive, or when the amount of the carbon black is too small, the amount of the laser auxiliary agent is excessive.
Examples 7 to 9 and examples 15 and 16 were compared with each other when the specific surface area of the clay was less than 200m 2 At/g, the marking fastness of the prepared polybutylene terephthalate modified material is reduced.
According to the invention, glass fiber, carbon black, laser auxiliary agent and clay are added into the PBT resin, so that the prepared polybutylene terephthalate modified material is suitable for laser marking black and white marking, and has higher laser marking definition and marking fastness.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The polybutylene terephthalate modified material is characterized by comprising the following components in parts by weight:
40 to 85 parts of PBT resin, 20 to 50 parts of glass fiber, 0.1 to 1 part of carbon black, 0.3 to 2 parts of laser auxiliary agent and 0.5 to 5 parts of clay.
2. The polybutylene terephthalate modified material as claimed in claim 1, characterized in that the carbon black is 0.2 to 0.6 parts by weight and the clay is 1 to 3 parts by weight.
3. The polybutylene terephthalate-modified material according to claim 1 or 2, wherein the clay is at least one of kaolin Dan Lei clay, sepiolite-based clay, montmorillonite-based clay, bentonite clay, preferably the clay is sepiolite-based clay.
4. The polybutylene terephthalate-modified material as claimed in claim 3, wherein the specific surface area of the clay is not less than 90m 2 Preferably, the clay has a specific surface area of > 100m 2 /g。
5. The polybutylene terephthalate modified material as claimed in claim 4, wherein the specific surface area of the clay is 210 to 230m 2 /g。
6. The polybutylene terephthalate modified material as claimed in claim 1, wherein the glass fiber is alkali-free glass fiber having an average diameter of 7 to 13 μm.
7. The polybutylene terephthalate-modified material as claimed in claim 1, wherein the laser auxiliary agent comprises a basic copper phosphonate-based laser auxiliary agent, or a laser auxiliary agent of a mixture of titanium oxide and pigment, or a laser auxiliary agent of a tin-antimony compound.
8. The polybutylene terephthalate modified material of claim 1, further comprising 0-2 parts of a processing aid, wherein the processing aid is at least one of an antioxidant, a lubricant, a weather-resistant aid, a coupling agent, an antimicrobial agent, an anti-drip agent, a transesterification inhibitor, and a colorant.
9. The method for producing a polybutylene terephthalate-modified material as claimed in any one of claims 1 to 8, comprising the steps of:
adding the PBT resin, the glass fiber, the carbon black, the laser auxiliary agent, the clay and the processing auxiliary agent into an extruder according to the proportion, carrying out melt extrusion at 180-260 ℃, cooling and granulating to obtain the polybutylene terephthalate modified material.
10. Use of the polybutylene terephthalate modified material as claimed in any one of claims 1-8 in automobiles and electronic and electric products.
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