CN110229507A - One kind can laser labelling halogen-free flame-retardant polyamide composition and preparation method thereof - Google Patents
One kind can laser labelling halogen-free flame-retardant polyamide composition and preparation method thereof Download PDFInfo
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- CN110229507A CN110229507A CN201910573387.2A CN201910573387A CN110229507A CN 110229507 A CN110229507 A CN 110229507A CN 201910573387 A CN201910573387 A CN 201910573387A CN 110229507 A CN110229507 A CN 110229507A
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- halogen
- laser
- free flame
- retardant polyamide
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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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention discloses one kind can laser labelling halogen-free flame-retardant polyamide composition and preparation method thereof, including 47.4~78.8wt% of polyamide, 10~20wt% of halogen-free flame retardants, 10~30wt% of mineral filler, self-control 1~3wt% of laser additive, 0.1~0.4wt% of 0.1~0.3wt% of dispersing agent and antioxidant；Wherein, laser additive is made by oneself to be in mass ratio 10~10.4:2.5~7.2:1.4~1.5:1 mixture by titanium dioxide, mica powder, nanometer tin-antimony oxide and copper chromite, it is processed and is prepared by screw extruder melt blending, gained daiamid composition meets infrared laser and the clear dark signs of ultraviolet laser simultaneously, and keeps preferable mechanically and electrically performance.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to one kind can the combination of laser labelling halogen-free flame-retardant polyamide
Object and preparation method thereof.
Background technique
In low-voltage electrical field, laser labelling mode is because it is just fast the features such as efficient, environmental protection and label be not easy to wear
Speed replaces the modes such as traditional ink printing, silk-screen.The equipment of laser marking can be divided into two kinds according to its optical maser wavelength, be respectively
The ultraviolet laser machine and wavelength of wavelength 355nm is the infrared laser machine of 1060nm.Laser absorption of the different materials to different wave length
Effect is different, and polyamide material is because its true qualities characteristic can not effectively absorb infrared laser and ultraviolet laser.So not
It cannot achieve in the case where adding other laser auxiliary agents and marked under infrared or ultraviolet laser.It at present on the market can laser labelling
Polyamide material can only realize under single ultraviolet laser mark under mark or infrared laser, for there are many model laser
The enterprise of marking machine needs to select in the process of production and processing marking machine use according to the characteristic of material, brings for scheduling of production all
It is mostly inconvenient.Therefore, it is necessary to develop a kind of can carry out the dark polyamide material of light color label under ultraviolet and infrared laser.
In the laser labelling performance for improving polyamide material, conventional way is to absorb laser into polyamide to help
Agent such as antimony trioxide, mica, aluminium oxide etc., as Chinese patent application CN109337359A is disclosed comprising antimony trioxide, mica
The composition of class laser auxiliary agent, CN102492291A joined magnesium hydroxide, tin oxide on the basis of adding antimony to improve polyamides
The shortcomings that laser labelling performance of amine, above scheme is that laser labelling may be only available for single ultraviolet laser label.
C107033586A disclose a kind of heat conductive flame-retarding can laser labelling daiamid composition, pass through and a large amount of magnesium hydroxide, three be added
Antimony oxide, titanium dioxide make it have infrared laser mark performance, but do not propose its mark effect under ultraviolet laser, and are added
The deterioration of the high amount of inorganic filler mechanical property of materials is serious, while being not easy quantization production.
Summary of the invention
It is an object of the invention to overcome existing daiamid composition can not meet simultaneously infrared laser and it is ultraviolet swash
The difficulty of clear marking is carried out under light.There is provided one kind can laser labelling halogen-free flame-retardant polyamide composition, the composition is infrared
Clearly dark signs can be achieved under laser and ultraviolet laser, while keeping preferable mechanical, electric property and anti-flammability
Energy.
Above-mentioned purpose of the invention is achieved through the following technical solutions:
It is of the invention can laser labelling halogen-free flame-retardant polyamide composition, including following components:
Wherein, combination (a) to the sum of component (f) accounts for the 100wt% of the daiamid composition altogether.
The polyamide is the polycaprolactam that viscosity is 2.4~2.9, the polycaprolactam of preferred viscosities 2.6~2.9
Amine.
The halogen-free flame retardants be melamine cyanurate (MCA), pentaerythritol bis (dihydrogen phosphate) melamine salt (MPP),
One or more of composition in alkyl hypophosphites and metal phosphinate salt.
The melamine cyanurate (MCA) is melamine and cyanuric acid polymerizate, is divided according to the production process
For wet process and two kinds of dry method, preferred wet production.
The pentaerythritol bis (dihydrogen phosphate) melamine salt (MPP) preferably decomposition temperature is more preferably to decompose temperature greater than 365 DEG C
Degree is greater than 375 DEG C.
Composition in the alkyl hypophosphites and metal phosphinate salt is pure or mixed metal phosphinic acids
Salt, the preferably OP1400 of the more preferable Clariant of OP1314, OP1400 of Clariant.
The mineral filler is one or more of talcum powder or glass fibre；Wherein: talcum powder is britesorb
Class mineral talc talc is obtained by crushing, with laminated structure.The preferred SiO of talcum powder2Content is greater than 55%, more
It is preferred that SiO2Content is greater than 60%.The glass fibre is the glass fibre with round or profiled cross-section, the abnormity
Glass fibre its cross section in cross section can have various shapes, including cocoon shape, rectangle, ellipse, rectangle and polygon etc., institute
The circular arc interface glass fiber single filament diameter stated is 5~20 μm, and preferably 7~17 μm, more preferable 9~13 μm, the abnormity is horizontal
The glass fibre section ratio in section is 2~5, and its section minor axis is 3~13 μm, major diameter is 10~50 μm, preferred cross-sections ratio
It is 4.
Further, the self-control laser additive is titanium dioxide, mica powder, nanometer tin-antimony oxide and copper chromite
It is in mass ratio 10~10.4:2.5~7.2:1.4~1.5:1 mixture.
Further, be divided by crystal form can rutile-type and anatase titanium dioxide, preferably the two of rutile-type for the titanium dioxide
Titanium oxide.
Further, the mica powder is a kind of silicate of layer structure, and structure is clipped by two layers of oxygen-octahedron
The compound silica layer that one layer of alumina octahedral is constituted, can be divided into phlogopite powder and sericite in powder, preferably thin,tough silk cloud according to component difference
Female powder.
Further, the nanometer tin-antimony oxide is antimony-doped tin oxide, wherein SnO2: Sb2O3Molar ratio is 95:5
~90:10, partial size are 3~30nm, preferably SnO2: Sb2O3Molar ratio is 90:10, and more preferable partial size is 3~10nm.
The copper chromite is a kind of inorganic pigment, 0.3~1.5 μm of partial size, 0.3~1 μm of preferable particle size, and molecule knot
Structure is
The dispersing agent is a kind of ethylene-acrylic acid copolymer zinc salt ionomer, and preferably Huo Liweier (Honeywell) is raw
285A, 295A of production, more preferable 295A
The antioxidant is phosphite ester antioxidant or amine antioxidants, these phosphite esters or amine antioxidants are real
Example includes but is not limited to:
(a) bis- (2,4-DTBP) pentaerythritol diphosphites CAS#:26741-53-7, molecular weight 604.7,
Molecular structure is
(b) three [2.4- di-tert-butyl-phenyl] phosphite esters, CAS#:31570-04-4, molecular weight 647, molecular structure are
(c) N, N'- be bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, CAS#:23128-74-7
Molecular weight 636.96, molecular structure are as follows:
The daiamid composition is the blend of melting preparation, carries out blending processing using double screw extruder.Add
The step of work is will first to make laser additive by oneself to mix 2~5min in high speed mixer with dispersing agent.Batch mixer speed is preferred
2000 revs/min of >, 4000 revs/min of more preferable revolving speed.Then once all add in owner's spout (first segment spout)
Enter or be gradually added in a batch mode auxiliary agent after polyamide substrate slice and mixing, mine is added in section side spout in an extruder
Object filler, all combinations obtain composition after squeezing out tie rod, pelletizing, drying after extruder screw is sufficiently mixed.
Laser marking technology (light color label is dark) of plastics its principle are as follows: carbon black occurs for resin surface under laser action
Dark writing is formed, but different resins are different to infrared, ultraviolet two kinds of wavelength lasers assimilation effect, it at present can laser labelling polyamides
Amine scheme can only realize single laser mark function.It is of the invention can laser labelling halogen-free flame-retardant polyamide composition, it is significant
Advantage is only to need to add low scaled laser auxiliary agent to be just able to use ultraviolet and infrared laser marking machine progress dark signs, institute
Need that power is low, mark speed is fast.It is set using 3w ultraviolet laser marking machine and 10w infrared optical fiber machine in 5% power, speed
Clearly dark signs can be achieved under the conditions of 5000mm/s.And the daiamid composition is with extraordinary anti-flammability and electrically
Performance, according to different product demand, flame retardant rating can meet 0.75mmV0 or 0.75mmV2, and CIT can satisfy 600V.
Specific embodiment
By following embodiment, the present invention will be further described.It should be appreciated that following embodiment is for illustration purposes only,
And it is not used to the present invention into limitation.
Following material is used in embodiment and comparative example:
PA6 refers to PA6 2701BR, derives from Tianjin Hai Jing, has 2.7 viscosity.
GF-1 refers to short glass fiber OCV 983-10P, derives from OWENS CORNING (Owens Coring
Vetrotex), circular arc interface, 10 μm of filament diameter (producer's nominal value).
GF-2 refers to short glass fiber CSG 3PA-820, derives from day east and spins, and odd-shaped cross section, section ratio is 4, section
28 μm of major diameter, 7 μm of section minor axis (producer's nominal value).
MCA is melamine and cyanurateMC-25 is derived from BASF (BASF), and effective content >=
99.5wt%.
OP1400 is alkyl hypophosphites composition, is derived from Klein (Clariant).
MPP is pentaerythritol bis (dihydrogen phosphate) melamine salt200-70 derives from BASF, degradation temperature >=375 DEG C.
AO-1 refers to bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites626, it is all to derive from sub- Supreme Being
Special (Addivant).
AO-2 refers to N, N'- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine
1098, it derives from BASF (BASF).
Titanium dioxide is rutile titanium dioxide RL-69, derives from Mei Lilian, TiO2>=99.5wt%.
Mica powder is sericite in powder KAl2, derives from Shijiazhuang Xing Hai high-tech, and mesh number is 2500 mesh.
Nanometer tin-antimony oxide is antimony-doped tin oxide, derives from the macro military new material in Guangzhou, tin oxide: antimony oxide molar ratio
For 90:10,3~10nm of partial size.
Copper chromite is that analysis is pure, derives from macro first chemical industry, and partial size is 0.6 μm.
Dispersing agent is ethylene-acrylic acid copolymer zinc salt ionomer Aclyn 295A, is obtained from Huo Liweier (Honeywell).
Autogamy laser additive 1 refers to titanium dioxide/mica powder/nano antimony tin oxide/copper chromite mixture, ratio
Example is that 52:36:7:5 is configured by Jin Lun company.
Autogamy laser additive 2 refers to titanium dioxide/mica powder/nano antimony tin oxide/copper chromite mixture, ratio
Example is that 10:5:3:2 is configured by Jin Lun company.
Method
Preparation method
Remaining each component is weighed according to the composition that it is as shown in the table of table 1, first by autogamy laser additive and dispersing agent in high speed
2~5min is mixed in batch mixer.2000~4000 revs/min of batch mixer speed.It is put into the main spout of double screw extruder
Glass fibre or talcum powder are added from extruder side spout by forced feed machine for polyamide and additive, processing
Temperature setting is 200~255 DEG C, and screw speed is set as 250~350rpm, and second from the bottom section in mouth mold take out to melt
Vacuum, vacuum degree control are 50~70cm-Hg.Composition after shearing and mixing from extrusion, draw tie rod carry out it is cooling,
Metal is packed after screening out, dry and being homogenized.The moisture content of material need to be ensured lower than 0.2wt% when packaging.
Sample molded and adjusting
Sample molded and adjusting are carried out by method as defined in ISO6396-2, mold 255~275 DEG C of melt temperature, mold temperature
80 DEG C of degree.It is sealed in aluminium foil bag after test piece molding, deposits in 23 ± 2 DEG C of environment and adjust 16 hours or more, and ensure to try
Piece moisture content is less than 0.2%.
Measuring mechanical property
Tensile property is carried out by method as defined in ISO 527-2, and sample is 1A type, and 170mm × 10mm × 4mm is stretched strong
Degree and breaking strain rate of extension 5mm/min.
Bending property is tested according to 178 prescriptive procedure of ISO, and specimen size is 80mm × 10mm × 4mm.
Impact strength is tested according to 179 prescriptive procedure of ISO, and specimen size is that 80mm × 10mm × 4mm notch type is A
Model.
Flame retardant property test is tested according to 94 prescriptive procedure of UL, and specimen size is 125mm × 13mm × 0.75mm.
The test of creepage trace index is tested according to 4202 prescriptive procedure of GB/T, and specimen size is 60mm × 60mm × 3mm.
Laser marking effect testing method: using infrared optical fiber marking machine and ultraviolet laser marking machine simultaneously to every group of sample
Laser marking test is carried out, visual comparison marks clarity and scores.Specimen size 80mm × 55mm × 2.5mm.
Test is respectively as follows: using equipment and parameter
Ultraviolet laser machine: Zhejiang Glan fort GLB-2W3W, power setting 5%, mark speed 5000mm/s.
Infrared optical fiber machine: Zhejiang Glan fort GLB-H10w power setting 5%, mark speed 5000mm/s.
Embodiment and comparative example
Table 1 enumerates the composition of embodiment 1 to 4 and comparative example 1 to 3.
Embodiment 1, embodiment 2, comparative example 1 and comparative example 2 have provided different filling systems and laser compositions of additives
Performance in laser marking performance, these embodiments and comparative example display be added autogamy laser additive 1 composition after
Clear marking can be achieved under infrared and ultraviolet laser marking machine, talcum powder is used to be better than as laser labelling effect when filling
Glass, while mechanical performance is deteriorated compared with the comparative example for being not added with laser additive without obvious.It is not added with the comparison of laser additive
Example then cannot achieve clear marking under infrared and ultraviolet laser.
Embodiment 3, embodiment 4 and comparative example 3 have provided under fiberglass reinforced different flame retardant system in laser marking performance
On performance.These embodiments and comparative example show that laser compositions of additives 2, which is added, may be implemented under ultraviolet and infrared laser
Clear marking, while flame retardant property, electric property have no obvious deterioration compared with the comparative example 3 for being not added with laser additive.Embodiment 3
It is shown with embodiment 4, flame retardant rating 0.75mmV-0 can be achieved as fire retardant in MPP, OP1400, but uses OP1400's
Composition has better mechanical performance.Embodiment 4 and embodiment 5 display addition autogamy laser additive 2 circular arc interface
There is extraordinary laser labelling effect through gathering in odd-shaped cross section glass fibre filling system, while using the combination of odd-shaped cross section glass
Object has better mechanical performance.
Table 1
Remarks :+indicate that mark effect is general；++ indicate that mark effect is good；+++ indicate that mark effect is very good；Expression is beaten
It is poor to mark effect, cannot identify.
Claims (10)
1. one kind can laser labelling halogen-free flame-retardant polyamide composition, which is characterized in that including following components:
Wherein, combination (a) to the sum of component (f) accounts for the 100wt% of the daiamid composition；
The viscosity of the polyamide is 2.4~2.9；
The self-control laser additive is to be in mass ratio by titanium dioxide, mica powder, nanometer tin-antimony oxide and copper chromite
10~10.4:2.5~7.2:1.4~1.5:1 composition mixture.
2. as described in claim 1 can laser labelling halogen-free flame-retardant polyamide composition, which is characterized in that
The titanium dioxide be rutile titanium dioxide and/or anatase titanium dioxide, and/or
The mica powder be phlogopite powder and/or sericite in powder, and/or
The nanometer tin-antimony oxide is by SnO2: Sb2O39~19:1 of molar ratio composition antimony-doped tin oxide, partial size be 3~
30nm, and/or
The partial size of the copper chromite is 0.3~1.5 μm.
3. as claimed in claim 1 or 2 can laser labelling halogen-free flame-retardant polyamide composition, which is characterized in that
The titanium dioxide is rutile titanium dioxide, and/or
The mica powder is sericite in powder, and/or
The nanometer tin-antimony oxide is by SnO2: Sb2O3The antimony-doped tin oxide of molar ratio 9:1 composition, partial size are 3~10nm,
And/or
The partial size of the copper chromite is 0.3~1.0 μm.
4. as described in claims 1 or 2 or 3 can laser labelling halogen-free flame-retardant polyamide composition, which is characterized in that it is described poly-
Amide is the polycaprolactam that viscosity is 2.6~2.9.
5. as described in claim 1 can laser labelling halogen-free flame-retardant polyamide composition, which is characterized in that the halogen-free flameproof
Agent is one in melamine cyanurate, pentaerythritol bis (dihydrogen phosphate) melamine salt, alkyl hypophosphites and metal phosphinate salt
Kind or two or more compositions.
6. as claimed in claim 5 can laser labelling halogen-free flame-retardant polyamide composition, which is characterized in that the alkyl time phosphorus
Hydrochlorate is diethyl hypo-aluminum orthophosphate.
7. as described in claim 1 can laser labelling halogen-free flame-retardant polyamide composition, which is characterized in that the mineral filler
For SiO2One of talcum powder of the content greater than 55%, circular cross-section glass fibre or anisotropic section glass fiber.
8. as claimed in claim 7 can laser labelling halogen-free flame-retardant polyamide composition, which is characterized in that the round boundary
Surface glass fiber filament diameter is 5~20 μm, or
The cross section of the profiled cross-section glass fibre includes a kind of in cocoon shape, rectangle, ellipse, rectangle or polygon
Or it is two or more, and section ratio is 2~5, section minor axis is 3~13 μm, major diameter is 10~50 μm.
9. as described in claim 1 can laser labelling halogen-free flame-retardant polyamide composition, which is characterized in that the mineral are filled out
Material is SiO2Content is greater than 60% talcum powder, and/or
The circular arc interface glass fiber single filament diameter is 7~17 μm, or
The section ratio of the profiled cross-section glass fibre is 4.
10. it is according to any one of claims 1 to 9 can laser labelling halogen-free flame-retardant polyamide composition preparation method, it is special
Sign is, is processed and is made by screw extruder melt blending, step are as follows: will first make laser additive and dispersing agent by oneself in speed
In the high speed mixer that 2000 revs/min of > mix 2~5min, then squeeze out owner's spout once all be added or with point
The mode criticized is gradually added polyamide substrate slice and auxiliary agent, and mineral filler, processing temperature is added in section side spout in an extruder
Degree is 200~255 DEG C, and screw speed is 250~350rpm, and second from the bottom section in mouth mold vacuumize to melt, vacuum
Degree control is 50~70cm~Hg, and mixed material squeezes out tie rod after extruder screw is sufficiently mixed, pelletizing, is dried to obtain.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910573387.2A CN110229507A (en) | 2019-06-28 | 2019-06-28 | One kind can laser labelling halogen-free flame-retardant polyamide composition and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112940492A (en) * | 2021-03-30 | 2021-06-11 | 江苏江山红化纤有限责任公司 | Flame-retardant polyamide composite material and preparation method thereof |
| CN117447836A (en) * | 2023-12-21 | 2024-01-26 | 广东永鑫华新型材料有限公司 | Laser marking composite nylon material and preparation method thereof |
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| CN112940492A (en) * | 2021-03-30 | 2021-06-11 | 江苏江山红化纤有限责任公司 | Flame-retardant polyamide composite material and preparation method thereof |
| CN117447836A (en) * | 2023-12-21 | 2024-01-26 | 广东永鑫华新型材料有限公司 | Laser marking composite nylon material and preparation method thereof |
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