CN113897057A - Polyamide composite material and preparation method and application thereof - Google Patents
Polyamide composite material and preparation method and application thereof Download PDFInfo
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- CN113897057A CN113897057A CN202111164092.3A CN202111164092A CN113897057A CN 113897057 A CN113897057 A CN 113897057A CN 202111164092 A CN202111164092 A CN 202111164092A CN 113897057 A CN113897057 A CN 113897057A
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
- B23K26/362—Laser etching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
- B23K26/40—Removing material taking account of the properties of the material involved
- B23K26/402—Removing material taking account of the properties of the material involved involving non-metallic material, e.g. isolators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/30—Organic material
- B23K2103/42—Plastics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
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Abstract
The invention relates to the technical field of engineering plastics, and discloses a polyamide composite material which comprises the following components: 65-96 parts of short-carbon-chain aliphatic polyamide resin, 10-50 parts of glass fiber and 0.02-0.15 part of laser marking agent; wherein, the laser marking agent is inorganic compound containing metal elements of antimony, tin, iron, copper, neodymium, bismuth and titanium and mixture thereof. According to the invention, by selecting the short-carbon-chain aliphatic polyamide resin, on the basis of the short-carbon-chain aliphatic polyamide resin, the specific metal element is added, and meanwhile, the content of the metal element in the composite material is controlled, so that on one hand, the light absorption energy of the short-carbon-chain aliphatic polyamide resin can be promoted, and meanwhile, clear white characters can be carved on bright-colored products, so that the environment-friendly problem caused by the silk-screen printing process adopted by the bright-colored products is solved, the marking efficiency is greatly improved, meanwhile, the cost performance of the material is very high, and the enterprise cost can be greatly reduced.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a polyamide composite material and a preparation method and application thereof.
Background
The polyamide is commonly called nylon, is a general name of a high polymer containing amide groups in a macromolecular main chain repeating unit, has excellent mechanical property, wear resistance and heat resistance, simultaneously has certain flame retardant property, is easy to process and form, is engineering plastic which is most widely applied at present, and has main varieties of nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 46, nylon 1010 and the like.
The halogen-free flame-retardant nylon has good thermal stability and is widely applied to the field of electronics and electricity. In order to mark use conditions in the electronic and electrical industry, products often need laser marking or silk-screen printing. With the development of environmental protection and technology, laser marking is superior to silk-screen printing in the aspects of environmental protection, marking effect, cost control, marking stability and the like, so that laser marking is a marking development trend of the future market. At present, the laser marking technology for engraving white fonts on black products or engraving black fonts on light-colored products is mature, but the technology for engraving white fonts on bright-colored products is relatively backward, and meanwhile, the contrast of engraving light-colored fonts on bright-colored products is more obvious than that of engraving black fonts, so that the technical requirement for engraving white fonts on light-colored products in the market is more urgent.
In view of the above problems, no better solution is available at present. Traditional bright-colored flame retardant nylon products still often use silk screen printing as the main, but the printing ink that uses in the silk screen printing technology often needs more solvent, is not conform to the environmental protection requirement, and the silk screen printing technology needs several processes simultaneously, leads to production efficiency low. Many electronic products desire to select bright colors for better identification and color development, and this problem limits product designs of downstream customers to some extent.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide a polyamide composite material, which can be used for engraving clear white characters on a product with bright color, not only solves the environmental protection problem caused by adopting a silk-screen printing process for the product with bright color, but also greatly improves the marking efficiency, has very high cost performance of the material, and can greatly reduce the enterprise cost.
The second purpose of the invention is to provide a preparation method of the polyamide composite material, which has simple preparation process and can be popularized in a large range.
The invention also provides a method for applying the polyamide composite material to laser marking of electronic products, and can be applied to laser marking in the fields of automobile parts, household appliances, industrial mechanical equipment and the like.
One of the purposes of the invention is realized by adopting the following technical scheme:
a polyamide composite material comprises the following components in parts by weight:
65-96 parts of short-carbon-chain aliphatic polyamide resin, 10-50 parts of glass fiber and 0.02-0.15 part of laser marking agent; the laser marking agent is an inorganic compound containing metal elements and a mixture thereof, and the metal elements are one or more than two of antimony, tin, iron, copper, neodymium, bismuth and titanium.
The laser marking technology is not necessarily applicable to all polyamide materials, nor is it necessarily applicable to all formulation systems, and generally needs to be further improved to obtain marking effects with clear outlines and obvious contrast with ground colors under laser irradiation. According to the invention, by selecting the short-carbon-chain aliphatic polyamide resin, on the basis of the short-carbon-chain aliphatic polyamide resin, the specific metal element is added, and meanwhile, the content of the metal element in the composite material is controlled, so that on one hand, the light absorption energy of the short-carbon-chain aliphatic polyamide resin can be promoted, and meanwhile, clear white characters can be carved on bright-colored products, so that the environment-friendly problem caused by the silk-screen printing process adopted by the bright-colored products is solved, the marking efficiency is greatly improved, meanwhile, the cost performance of the material is very high, and the enterprise cost can be greatly reduced. Meanwhile, the addition of the glass fiber can improve various properties of the material, such as tensile strength, impact strength and the like, and can reduce the shrinkage rate of the material.
The short-carbon-chain aliphatic polyamide resin is one or more of a polyamide resin obtained by polycondensation of a diamine and a dicarboxylic acid, a polyamide resin obtained by ring-opening polymerization of a lactam, a polyamide resin obtained by self-condensation of an aminocarboxylic acid, and a polyamide copolymer obtained by copolymerization of two or more of the units or monomers constituting the polyamide resin.
Preferably, the short carbon chain aliphatic polyamide resin is one or two of nylon 66 and nylon 6. In one embodiment, the short carbon chain aliphatic polyamide resin is composed of nylon 66 and nylon 6 in a mass ratio of 58: 10. Nylon 66 is formed by condensing ethanediol ethanediamine ethanedioic acid, nylon 6 is formed by condensing caprolactam, the hydrogen bond between adjacent molecules of nylon 66 is combined more firmly, the melting point is higher than that of nylon 6 by about 40 ℃, the heat resistance is good, but the elasticity of nylon 6 is larger than that of nylon 66, the impact resistance and the dissolution resistance are good, and the combination of the nylon 66 and the nylon 6 can effectively improve the performance of the material and is beneficial to laser marking.
Further, the total content of the metal elements is controlled to be 20ppm to 100 ppm. The total content of metal elements in the material is lower than 20ppm, which causes poor light absorption performance of the material and makes the material not suitable for laser marking; the total content of the metal elements in the material is higher than 100ppm, which can cause the material to have larger light absorption performance, so that the clear white characters can not be carved on the product with bright color, and only the black characters can be carved.
Furthermore, the mass ratio of the short carbon chain aliphatic polyamide resin to the laser marking agent is 68 (0.02-0.15).
Further, the composition also comprises the following components in parts by weight: 1-2 parts of processing aid.
Further, the processing aid is one or two of an antioxidant and a lubricant. The addition of the antioxidant can avoid the decomposition of the polyamide resin in the extrusion process, and the addition of the lubricant can reduce the friction between the material and the screw, so that the material is smoothly extruded.
The second purpose of the invention is realized by adopting the following technical scheme:
a preparation method of a polyamide composite material comprises the following preparation steps:
s1: preparing each component of the polyamide composite material;
s2: putting the components into a mixer for mixing until the components are uniform to obtain a premix;
s3: and putting the premix into a double-screw extruder for melt mixing, and extruding and granulating to obtain the polyamide composite material.
Further, in step S1, the process parameters of the twin-screw extruder are: the length-diameter ratio of the screw is (40-48): 1, the temperature of the screw barrel is 220-270 ℃, and the rotation speed of the screw is 200-450 rpm.
The third purpose of the invention is realized by adopting the following technical scheme:
an application of polyamide composite material in laser marking of electronic products.
Compared with the prior art, the invention has the beneficial effects that:
according to the polyamide composite material, the short-carbon-chain aliphatic polyamide resin is selected, the specific metal element is added on the basis of the short-carbon-chain aliphatic polyamide resin, and the content of the metal element in the composite material is controlled, so that on one hand, the light absorption energy of the short-carbon-chain aliphatic polyamide resin can be promoted, and meanwhile, clear white characters can be carved on bright-colored products, so that the environmental protection problem caused by the silk-screen printing process adopted by the bright-colored products is solved, the marking efficiency is greatly improved, the cost performance of the material is very high, and the enterprise cost can be greatly reduced. Meanwhile, the addition of the glass fiber can improve various properties of the material, such as tensile strength, impact strength and the like, and can reduce the shrinkage rate of the material.
The preparation method of the polyamide composite material has the characteristics of simple preparation process and suitability for large-scale production.
The polyamide composite material can be applied to laser marking of electronic products, and can also be applied to laser marking in the fields of automobile parts, household appliances, industrial mechanical equipment and the like.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
The following are specific examples of the present invention, and raw materials, equipments and the like used in the following examples can be obtained by purchasing them unless otherwise specified.
In the following examples:
nylon 66, melting point 265 ℃, PA66 EP-158, purchased from zhejiang huafeng group;
nylon 6, melting point 225 deg.C, PA6 HY-2500A, available from Jiangsu Haiyang chemical fibers, Inc.;
antimony trioxide, S-05N, purchased from antimony Limited liability company, Chandney;
n, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine (IRGANOX 1098), purchased from basf;
stearyl stearate, LOXIOL G32, purchased from german corning.
Examples 1 to 7 and comparative examples 1 to 2
The contents of the components of the polyamide composite materials of examples 1 to 7 and comparative examples 1 to 2 are shown in table 1 below:
TABLE 1
In the above embodiments, each material is not limited to the above-mentioned components, and each material may also be composed of other single components or multiple components described in the present invention, and the component content of each material is not limited to the above-mentioned content, and the component content of each material may also be a combination of other component contents described in the present invention, and will not be described again here.
The above composition is prepared by the following preparation method except for special indication:
a preparation method of a polyamide composite material comprises the following preparation steps:
s1: preparing each component of the polyamide composite material;
s2: putting the components into a mixer for mixing until the components are uniform to obtain a premix;
s3: and putting the premix into a double-screw extruder for melt mixing, and extruding and granulating to obtain the composite material, wherein the length-diameter ratio of a screw is 45:1, the temperature of a screw cylinder is 250 ℃, and the rotating speed of the screw is 300 rpm.
Performance testing
The polyamide composite materials prepared in the above examples and comparative examples were subjected to a performance test.
The laser marking device is marked on the polyamide composite material by using a fiber laser marking machine FX-220 of Shanghai Ficksu tool Co., Ltd, wherein the power is 20W-50W, the laser wavelength is 1064 nm.
The test results are shown in table 2 below.
TABLE 2
From the above table, it can be known that clear white characters can be carved on the product with bright color by proper content of metal elements.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. The polyamide composite material is characterized by comprising the following components in parts by weight:
65-96 parts of short-carbon-chain aliphatic polyamide resin, 10-50 parts of glass fiber and 0.02-0.15 part of laser marking agent; the laser marking agent is an inorganic compound containing metal elements and a mixture thereof, and the metal elements are one or more than two of antimony, tin, iron, copper, neodymium, bismuth and titanium.
2. The polyamide composite material according to claim 1, wherein the short-carbon-chain aliphatic polyamide resin is one or more of a polyamide resin obtained by polycondensation of a diamine and a dicarboxylic acid, a polyamide resin obtained by ring-opening polymerization of a lactam, a polyamide resin obtained by self-condensation of an aminocarboxylic acid, and a polyamide copolymer obtained by copolymerization of two or more of the units or monomers constituting the polyamide resin.
3. The polyamide composite material according to claim 1, wherein the short carbon chain aliphatic polyamide resin is one or both of nylon 66 and nylon 6.
4. Polyamide composite material according to claim 1, characterized in that the total content of the metallic elements is controlled between 20ppm and 100 ppm.
5. The polyamide composite material as claimed in claim 1, wherein the mass ratio of the short carbon chain aliphatic polyamide resin to the laser marking agent is 68 (0.02-0.15).
6. The polyamide composite material according to claim 1, further comprising the following components in parts by weight: 1-2 parts of processing aid.
7. The polyamide composite material according to claim 6, wherein the processing aid is one or both of an antioxidant and a lubricant.
8. The preparation method of the polyamide composite material is characterized by comprising the following preparation steps:
s1: disposing the components of the polyamide composite of any one of claims 1-7;
s2: putting the components into a mixer for mixing until the components are uniform to obtain a premix;
s3: and putting the premix into a double-screw extruder for melt mixing, and extruding and granulating to obtain the polyamide composite material.
9. The method for preparing a polyamide composite material as claimed in claim 8, wherein in step S1, the process parameters of the twin-screw extruder are: the length-diameter ratio of the screw is (40-48): 1, the temperature of the screw barrel is 220-270 ℃, and the rotation speed of the screw is 200-450 rpm.
10. Use of a polyamide composite material according to any one of claims 1 to 7 for laser marking of electronic products, automotive parts, household appliances, industrial mechanical devices.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111164092.3A CN113897057A (en) | 2021-09-30 | 2021-09-30 | Polyamide composite material and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111164092.3A CN113897057A (en) | 2021-09-30 | 2021-09-30 | Polyamide composite material and preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN113897057A true CN113897057A (en) | 2022-01-07 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007098939A (en) * | 2005-08-18 | 2007-04-19 | Mitsubishi Engineering Plastics Corp | Polyamide resin composition for laser marking and laser-marked polyamide resin molding |
| CN106414607A (en) * | 2014-05-20 | 2017-02-15 | 帝斯曼知识产权资产管理有限公司 | Laser-markable polyamide composition |
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2021
- 2021-09-30 CN CN202111164092.3A patent/CN113897057A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007098939A (en) * | 2005-08-18 | 2007-04-19 | Mitsubishi Engineering Plastics Corp | Polyamide resin composition for laser marking and laser-marked polyamide resin molding |
| CN106414607A (en) * | 2014-05-20 | 2017-02-15 | 帝斯曼知识产权资产管理有限公司 | Laser-markable polyamide composition |
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