CN110791062A - Gray or black flame-retardant PBT (polybutylene terephthalate) material capable of being marked by laser - Google Patents
Gray or black flame-retardant PBT (polybutylene terephthalate) material capable of being marked by laser Download PDFInfo
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- CN110791062A CN110791062A CN201911104224.6A CN201911104224A CN110791062A CN 110791062 A CN110791062 A CN 110791062A CN 201911104224 A CN201911104224 A CN 201911104224A CN 110791062 A CN110791062 A CN 110791062A
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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
- C08K3/2279—Oxides; Hydroxides of metals of antimony
- C08K2003/2282—Antimonates
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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
- C08K2003/387—Borates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention relates to a grey or black flame-retardant PBT material capable of being marked by laser, which comprises the following raw materials: PBT resin, glass fiber, a brominated flame retardant, a laser auxiliary agent, a foaming agent, sodium antimonate, a toughening agent, carbon black and a processing aid. The material can generate permanent white marks with high contrast and high definition under the action of laser, is convenient for quickly marking irregular workpieces, is favorable for industrial automatic production, and saves a large amount of manpower and material resources.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a gray or black flame-retardant PBT material capable of being marked by laser.
Background
At present, the PBT brominated flame-retardant system on the market mainly uses Sb2O3As flame retardant synergist, but Sb2O3After laser energy is absorbed, the carbonization of the matrix is promoted, so that the whiteness of the mark is reduced, and the contrast is poor. Sodium antimonate and Sb2O3Compared with the prior art, the coloring power is weaker, the use of carbon black is reduced, the influence of the brownian motion of the carbon black is reduced, and the mark whiteness is improved. Meanwhile, a certain amount of laser auxiliary agent and foaming agent are added, the laser auxiliary agent converts laser into heat energy to generate local high temperature, and the foaming agent promotes bubble formation in the matrix, so that light rays are subjected to color reversal, refraction and scattering to form a bright white mark.
Chinese patent application with publication number CN104231566A and application number CN 201410422697 discloses a flame-retardant reinforced polybutylene terephthalate material capable of being marked by laser and a preparation method thereof, and the material is Sb2O3And the flame retardant synergist is marked in gray under a black background, and has poor contrast with the background.
The laser marking has the advantages that:
1. the laser mark has great freedom degree on the shape, the size and the processing environment of a processing part, and is convenient for realizing automatic processing;
2. the laser mark has no contact with the part, no cutting force and local heating, and maintains the mechanical property and the size of the original workpiece;
3. the laser marking machine has high precision, lines can reach millimeter to micron magnitude, and micro font carving can be realized.
4. Through a computer automatic system, various characters, symbols and patterns can be designed by software, and modern automatic production is realized;
5. compared with the traditional printing technology, the printing technology has no pollution source, and is a clean and pollution-free high-environment-protection processing technology.
Because of the advantages of laser marking, it is a difficult problem to develop a material that can make laser marking produce high-contrast and high-definition permanent white marks.
Disclosure of Invention
Technical problem to be solved
In order to solve the above problems of the prior art, the present invention provides a flame retardant PBT material which can be marked by laser and can generate permanent white marks with high contrast and high definition under the action of laser.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a grey or black flame-retardant PBT material capable of being marked by laser comprises the following raw materials in percentage by weight:
PBT resin: 52 to 72 percent
Glass fiber: 10 to 30 percent
Brominated flame retardants: 8 to 15 percent
Laser auxiliary agent: 0.1 to 0.5 percent
Foaming agent: 0.5 to 1 percent
Sodium antimonate: 3 to 7 percent
A toughening agent: 2 to 5 percent
Carbon black: 0.01 to 0.3 percent
Processing aid: 0.5 to 1 percent.
Further, the PBT resin is pure resin or a mixture of pure resin and PET, such as vinpocetine PBT1100, Tunhe PBT6080, and the like.
Further, the glass fiber is one of the following: alkali-free glass fiber, medium-alkali glass fiber and high-alkali glass fiber, wherein the diameter of the glass fiber is 7-15 microns, such as boulder glass fiber 534A, Chongqing glass fiber 303K and the like.
The bromine flame retardant is one or more of brominated styrenes, brominated epoxies and brominated polycarbons, such as Kaimei 2025K, CXB-2000H.
Further, the laser adjuvant can convert laser with wavelength of 1.064 micron into heat energy, such as Merck Iriotec 8835.
Further, the blowing agent is capable of generating gas at high temperatures to form bubbles in the matrix, such as hydrated zinc borate (2ZnO 3B)2O3·3.5H2O), and the like.
Further, the toughening agent is an ethylene-butyl acrylate-glycidyl methacrylate copolymer, an ethylene methyl acrylate copolymer, or an ethylene-vinyl acetate copolymer, such as dupont PTW.
(III) advantageous effects
The invention has the beneficial effects that: book (I)The material can generate a permanent white mark with high contrast and high definition under the action of laser, so that irregular workpieces can be conveniently and quickly marked, industrial automatic production is facilitated, and a large amount of manpower and material resources are saved; the laser assistant can quickly convert laser energy into heat energy, and the local energy is instantly increased to decompose the matrix into gas (CO)2,CO,H2O, etc.), bubbles are rapidly formed, thereby achieving rapid marking; the foaming agent releases gas under the condition of heating, bubbles are formed in the matrix, and the marking contrast is increased.
Drawings
FIG. 1 is a diagram showing the effect of laser marking according to an embodiment 1 of the present invention;
FIG. 2 is a diagram illustrating the effect of laser marking according to an embodiment 2 of the present invention;
FIG. 3 is a diagram of laser marking effects according to an embodiment 3 of the present invention;
fig. 4 is a diagram illustrating laser marking effects according to an embodiment 4 of the present invention.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The grey or black flame-retardant PBT material capable of being marked by laser comprises the following raw materials in percentage by weight:
PBT resin: 52 to 72 percent
Glass fiber: 10 to 30 percent
Brominated flame retardants: 8 to 15 percent
Laser auxiliary agent: 0.1 to 0.5 percent
Foaming agent: 0.5 to 1 percent
Sodium antimonate: 3 to 7 percent
A toughening agent: 2 to 5 percent
Carbon black: 0.01 to 0.3 percent
Processing aid: 0.5 to 1 percent.
Further, the PBT resin is pure resin or a mixture of pure resin and PET, such as vinpocetine PBT1100, Tunhe PBT6080, and the like.
Further, the glass fiber is one of the following: alkali-free glass fiber, medium-alkali glass fiber and high-alkali glass fiber, wherein the diameter of the glass fiber is 7-15 microns, such as boulder glass fiber 534A, Chongqing glass fiber 303K and the like.
The bromine flame retardant is one or more of brominated styrenes, brominated epoxies and brominated polycarbons, such as Kaimei 2025K, CXB-2000H.
Further, the laser adjuvant can convert laser with wavelength of 1.064 micron into heat energy, such as Merck Iriotec 8835.
Further, the blowing agent is capable of generating gas at high temperatures to form bubbles in the matrix, such as hydrated zinc borate (2ZnO 3B)2O3·3.5H2O), and the like.
Further, the toughening agent is an ethylene-butyl acrylate-glycidyl methacrylate copolymer, an ethylene methyl acrylate copolymer, or an ethylene-vinyl acetate copolymer, such as dupont PTW.
The laser auxiliary agent in the embodiment can quickly convert laser energy into heat energy, and local energy is instantly increased, so that the matrix is decomposed into gas (CO)2,CO,H2O, etc.), bubbles are rapidly formed, thereby achieving rapid labeling, and the chemical reaction is as follows:
the blowing agent in this embodiment releases gas when heated to form bubbles in the matrix and increase the contrast of the mark, for example, hydrated zinc borate, and releases water of crystallization when heated, and the chemical reaction is as follows:
Sb2O3absorbing laser energy, promoting polymer carbonization, generating amorphous carbon substances, reducing mark whiteness, and substituting Sb with sodium antimonate2O3The charring of the polymer can be reduced, the whiteness of the mark is improved, and the permanent white mark is realized.
The following examples are presented for different weight percentages of the component materials.
Table 1 examples 1-4 component ratios (experiments were carried out according to the following ratios, the resin dosage was large, weighing was inconvenient after accurate decimal point, the resin could be fine-tuned so that the percentage addition equals to one hundred percent, and no effect on the labeling was observed):
uniformly mixing PBT resin, a flame retardant and processing aids (an antioxidant and a lubricant) according to the proportion shown in the table 1, adding the mixture into a double-screw extruder feeder, and adding glass fibers from a side feeder after the resin is molten in order to keep the length of the glass fibers; after passing through a double-screw extruder, carrying out water cooling, granulation, drying and sample preparation on the material; the temperature of the double-screw extruder from the blanking section to the head is set as follows: 200 deg.C, 230 deg.C, 250 deg.C, 255 deg.C.
Table 2 examples 1-4 marking effect
As can be seen from Table 2, as shown in FIGS. 1-4, the flame retardant grades of examples 1-4 all reach V0, and the flame retardant synergist utilizes sodium antimonate to replace Sb2O3Then, a permanent white mark with high contrast and high definition can be produced under the action of laser.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
1. A grey or black flame-retardant PBT material capable of being marked by laser is characterized by comprising the following raw materials in percentage by weight:
PBT resin: 52 to 72 percent
Glass fiber: 10 to 30 percent
Brominated flame retardants: 8 to 15 percent
Laser auxiliary agent: 0.1 to 0.5 percent
Foaming agent: 0.5 to 1 percent
Sodium antimonate: 3 to 7 percent
A toughening agent: 2 to 5 percent
Carbon black: 0.01 to 0.3 percent
Processing aid: 0.5 to 1 percent.
2. The laser-markable gray or black flame retardant PBT material of claim 1, wherein the PBT resin is a pure resin or a mixture of a pure resin and PET.
3. The laser-markable grey or black flame retardant PBT material of claim 1, wherein the glass fiber is one of: alkali-free glass fiber, medium-alkali glass fiber and high-alkali glass fiber, wherein the diameter of the glass fiber is 7-15 microns.
4. The laser-markable gray or black flame retardant PBT material of claim 1, wherein said brominated flame retardant is one or more of brominated styrenes, brominated epoxies, and brominated polycarbons.
5. The laser-markable gray or black flame retardant PBT material of claim 1, wherein the laser assistant can convert laser light with a wavelength of 1.064 microns into heat energy.
6. The laser-markable gray or black flame retardant PBT material of claim 1, wherein the blowing agent is capable of generating a gas at elevated temperatures to form bubbles in the matrix.
7. The laser-markable gray or black flame retardant PBT material of claim 1, wherein the toughening agent is an ethylene-butyl acrylate-glycidyl methacrylate copolymer, an ethylene methyl acrylate copolymer, or an ethylene-vinyl acetate copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911104224.6A CN110791062A (en) | 2019-11-09 | 2019-11-09 | Gray or black flame-retardant PBT (polybutylene terephthalate) material capable of being marked by laser |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911104224.6A CN110791062A (en) | 2019-11-09 | 2019-11-09 | Gray or black flame-retardant PBT (polybutylene terephthalate) material capable of being marked by laser |
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| CN110791062A true CN110791062A (en) | 2020-02-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201911104224.6A Pending CN110791062A (en) | 2019-11-09 | 2019-11-09 | Gray or black flame-retardant PBT (polybutylene terephthalate) material capable of being marked by laser |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106566068A (en) * | 2016-10-19 | 2017-04-19 | 玫瑰塑胶(昆山)有限公司 | Composition capable of laser color marking and preparation method thereof |
| CN109880308A (en) * | 2019-01-21 | 2019-06-14 | 宁波华腾首研新材料有限公司 | A kind of bromine/stibium flame retardancy enhancing PBT composite and preparation method thereof |
| CN110028765A (en) * | 2019-03-25 | 2019-07-19 | 广东顺德顺炎新材料股份有限公司 | A kind of high-glowing-filament-temperature flame-retardancy enhancing laser print wrongly written or mispronounced character PBT plastic and preparation method thereof |
-
2019
- 2019-11-09 CN CN201911104224.6A patent/CN110791062A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106566068A (en) * | 2016-10-19 | 2017-04-19 | 玫瑰塑胶(昆山)有限公司 | Composition capable of laser color marking and preparation method thereof |
| CN109880308A (en) * | 2019-01-21 | 2019-06-14 | 宁波华腾首研新材料有限公司 | A kind of bromine/stibium flame retardancy enhancing PBT composite and preparation method thereof |
| CN110028765A (en) * | 2019-03-25 | 2019-07-19 | 广东顺德顺炎新材料股份有限公司 | A kind of high-glowing-filament-temperature flame-retardancy enhancing laser print wrongly written or mispronounced character PBT plastic and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 金国珍主编: "《工程塑料》", 31 January 2001 * |
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Application publication date: 20200214 |