CN104448531B - A kind of laser carving master batch for light color mark and its preparation method and application - Google Patents
A kind of laser carving master batch for light color mark and its preparation method and application Download PDFInfo
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- CN104448531B CN104448531B CN201410837554.7A CN201410837554A CN104448531B CN 104448531 B CN104448531 B CN 104448531B CN 201410837554 A CN201410837554 A CN 201410837554A CN 104448531 B CN104448531 B CN 104448531B
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Abstract
The invention belongs to functional agglomerate preparing technical field, disclose a kind of laser carving master batch for light color mark and its preparation method and application.This master batch includes the component of following parts by weight: vector resin 95～66 parts；Light absorbs toner 0.01～0.5 part；Luminous reflectance powder 0.01～0.5 part；Foaming agent 0.7～6 parts；White carbon black 0.05～1.5 parts；Whiting filler 5～20 parts；Processing modified oily 0.01～4 part.The laser carving master batch of the present invention can be selected according to the matrix resin of application due to the vector resin in master batch, its compatibility in matrix resin is uniformly dispersed well, a small amount of interpolation can have engraving and foaming effect under laser action concurrently, go in different matrix resins, labelling uniform in effect, clear and resin contrast are high, and the mechanical performance that maintains primary resin material is unaffected, can be applicable to, in laser marking modified plastics field, be widely used in various general-purpose plastics and engineering plastics.
Description
Technical field
The invention belongs to functional agglomerate preparing technical field, female particularly to a kind of laser carving for light color mark
Grain and its preparation method and application.
Background technology
Laser marking technology is development in recent years a kind of industry labeling method rapidly, with traditional indicia means
Comparing, laser marking has clear advantage: (1) signature velocity is fast, and writing is clear, permanent；(2) non-
Contact is processed, and pollutes little, without abrasion；(3) easy to operate, antiforge function is strong；(4) high-speed automated
Running, production cost is low.At present, in label print industry, laser marking has occupied more than 90%
Market.Along with the development of modified plastics technology, laser marking technology is increasingly being applied to modified plastics row
Industry.Frosting application laser realizes mark mainly four kinds of different mechanism: (1) variable color, laser irradiates
Under, material surface generation carbonization；(2) engraving, uses when removing material by the way of fusing and gasification；
(3) foaming, material surface is melted by laser, produces bubble, and light reflects on micro-bubble, makes labelling
Color is visible；(4) ablation, material surface coating is removed by laser, thus is formed bigger with primer
Contrast.Wherein, dark material surface realizes light color mark main use engraving and foam process.At present,
Realizing light color labelling for a certain specific dark material surface, basic skills is all to add mark auxiliary agent, logical
A kind of technique crossed in engraving, foaming realizes.But, some have the mark auxiliary agent of excellent mark effect
Often composition is more complicated, and preparation technology is loaded down with trivial details, which limits its industrial volume production.Additionally, want to obtain
Comparatively ideal mark effect, needs to add the mark agent of high number.So, on the one hand product cost is caused
Rise, it addition, mark agent is the most all powder body material, be difficult to dispersed in polymeric matrix,
Substantial amounts of interpolation will cause matrix material mark effect unshapeliness and affects the mechanical performance of material.
At present, in published mark patent, as disclosed in Chinese patent application CN 102741360 A
A kind of core, shell blend play white auxiliary agent as black, although mark is respond well, but preparation technology is numerous
Trivial, it is unfavorable for industrialized production.
Summary of the invention
In order to overcome the powder body mark auxiliary agent of above-mentioned prior art in resin matrix bad dispersibility, easily affect
Resin mechanical performance, and the shortcoming such as mark mechanism is single, effect is limited is with not enough, the primary and foremost purpose of the present invention
It is to provide a kind of laser carving master batch for light color mark.This master batch can be directly appended in modified plastics carry out
Production and preparation, for combining engraving and two kinds of mark techniques of foaming in low cost integrally, high-efficiency marking laser carving
Master batch.
Another object of the present invention is to provide the preparation method of a kind of above-mentioned laser carving master batch for light color mark.
Still a further object of the present invention is to provide the above-mentioned laser carving master batch for light color mark modified at laser marking
Application in plastic applications.
The purpose of the present invention is realized by following proposal:
A kind of laser carving master batch for light color mark, including the component of following parts by weight:
Described vector resin arbitrarily can be selected according to the modified plastics of master batch subsequent applications, as by this
Bright master batch is applied in PS, then can be selected for PS or preferable with PS compatibility resin as this master batch system
Standby vector resin, therefore, can arbitrarily select resin generally in the art, such as logical polystyrene, poly-second
Alkene, polypropylene, ethylene-vinyl acetate, polymethyl methacrylate, SAN,
Polyurethane Thermoplastic Elastomer.
It can be any pigment absorption commonly used in the art that light used absorbs toner, in order to the most real
The existing present invention, described light absorb toner be preferably yellow class pigment or dyestuff, blue class pigment or dyestuff,
At least one in green class pigment or dyestuff；It is highly preferred that described yellow class pigment or dyestuff include idol
At least one in nitrogen Huang, benzidine yellow and quinophthalone Huang；Described blue class pigment or dyestuff include phthalocyanine
At least one in indigo plant and anthraquinone blue；Described green class pigment or dyestuff include phthalocyanine green, fluorescence green and anthracene
At least one during quinone is green.
Described light emission powder refers to the pearl essence having transmitting effect to light, can be that this area is arbitrarily conventional
Pearl essence.In order to the present invention is better achieved, described light emission powder be preferably pearly-lustre silver and pearly-lustre white in
At least one.
In order to the present invention is better achieved, described foaming agent is preferably sodium bicarbonate, melamine cyanurate
At least one in salt, ammonium polyphosphate and melamine pyrophosphate.
In order to the present invention is better achieved, described white carbon black is preferably in coloring white carbon black and conductive black at least
A kind of；It is highly preferred that the particle diameter of described white carbon black is 10～100nm, BDP oil factor is 40～300cc/100
g。
In order to the present invention is better achieved, described Whiting filler is preferably zinc sulfide, barium sulfate, titanium dioxide
At least one in titanium, Pulvis Talci, Kaolin, calcium carbonate, zinc stearate and calcium stearate.
In order to the present invention is better achieved, described processing modified oil is preferably in naphthenic oil and silicone oil at least
A kind of.
In order to the present invention is better achieved further, female in the laser carving for light color mark not affecting the present invention
On the premise of the grain impact of performance, can further include at least one in following additive: fire retardant, anti-quiet
The auxiliary agents commonly used in the art such as electricity agent, heat stabilizer, coloring agent, lubricant.
Present invention also offers the preparation method of a kind of above-mentioned laser carving master batch for light color mark, including following
Concrete steps:
(1) by vector resin and processing modified oil premix, premix material is obtained；
(2) light absorbs toner, luminous reflectance powder, foaming agent, white carbon black, Whiting filler and step (1) obtain
The premix material mix homogeneously arrived, through double screw extruder extruding pelletization, obtains the laser carving for light color mark female
Grain.
In above-mentioned preparation method, the consumption of each component is:
In above-mentioned preparation method, the feeding rotating speed of described double screw extruder is preferably 100～350rpm,
Screw zones temperature is preferably 80～230 DEG C, and screw speed is preferably 150～400rpm.
The laser carving master batch for light color mark of the present invention can be directly appended to beat for laser in matrix resin
Mark, and owing to the vector resin in master batch can be selected according to the matrix resin of application, it is at matrix resin
The middle compatibility is uniformly dispersed well, and does not affect the original mechanical performance of resin, and a small amount of interpolation can make at laser
Make matrix resin realize engraving and foaming under with simultaneously, there is good laser marking effect, therefore can apply
In laser marking modified plastics field, be widely used in PS, ABS, ASA, SAN, PMMA,
The engineering plastics such as general-purpose plastics and PA, PC, PPE, PBT, POM such as PP, PE.
The present invention, relative to prior art, has such advantages as and beneficial effect:
(1) the laser carving master batch preparation technology for light color mark of the present invention is simple, without complicated process journey
Sequence, easily realizes industrialization and produces；
(2) present invention carries out compounding obtained master batch by the different component that selection comprises specific function and exists
Have engraving and foaming effect under laser action concurrently, go in different matrix resins；
(3) addition in the laser carving master batch application process of light color mark of the present invention is few, direct and tree
Fat is blended and just can realize laser labelling, and labelling uniform in effect, clear and resin contrast are high.
Accompanying drawing explanation
Fig. 1 is the ABS resin mark design sketch obtained by comparative example 1.
Fig. 2 is the ABS resin mark design sketch obtained by embodiment 1.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but the embodiment party of the present invention
Formula is not limited to this.
Embodiment 1: for the preparation of the laser carving master batch of light color mark
A kind of laser carving master batch for light color mark, including the component of following parts by weight: EVA 90 parts；
Phthalocyanine blue 0.1 part；Pearly-lustre silvery white 0.05 part；Sodium bicarbonate 1 part；White carbon black 0.05 part；3 parts of barium sulfate；
Calcium stearate 2 parts；Naphthenic oil 0.2 part.
(1) 20g naphthenic oil and 9Kg EVA resin are joined high-speed stirred batch mixer mixing 2min
Obtain resin premixed thing；
(2) by 10g phthalocyanine blue toner, 5g pearly-lustre white lead, 100g sodium bicarbonate, 5g white carbon black, 300
G barium sulfate, 200g calcium stearate is added sequentially to resin premixed thing, by mixture at high-speed stirred batch mixing
Machine mixing 5min；
(3) joining in double screw extruder by said mixture material, regulation feeding rotating speed is 200rpm,
The each section of extruder temperature of double screw extruder temperature from charge door to head is respectively set to 80 DEG C,
140 DEG C, 180 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, screw speed is preferably 250rpm.
Mixture, through double screw extruder fusion plastification, extrusion, tie rod pelletizing, obtains having light identification function
Laser carving master batch.
Embodiment 2: for the preparation of the laser carving master batch of light color mark
A kind of laser carving master batch for light color mark, including the component of following parts by weight: PE 88 parts；Anthracene
Green 0.05 part of quinone；White 0.06 part of pearly-lustre；Ammonium polyphosphate 2 parts；White carbon black 0.5 part；2.5 parts of zinc sulfide；
Zinc stearate 3 parts；Naphthenic oil 0.2 part.
(1) 20g naphthenic oil and 8.8Kg PE resin are joined high-speed stirred batch mixer mixing 2min
Obtain resin premixed thing；
(2) by 5g phthalocyanine blue toner, 6g pearly-lustre white lead, 200g ammonium polyphosphate, 50g white carbon black,
250g zinc sulfide, 300g zinc stearate is added sequentially to resin premixed thing, is mixed in high-speed stirred by mixture
Material machine mixing 5min；
(3) joining in double screw extruder by said mixture material, regulation feeding rotating speed is 300rpm,
The each section of extruder temperature of double screw extruder temperature from charge door to head is respectively set to 80 DEG C,
140 DEG C, 180 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, screw speed is preferably 400rpm.
Mixture, through double screw extruder fusion plastification, extrusion, tie rod pelletizing, obtains having light identification function
Laser carving master batch.
Embodiment 3: for the preparation of the laser carving master batch of light color mark
A kind of laser carving master batch for light color mark, including the component of following parts by weight: AS 80 parts；Connection
Aniline yellow 0.5 part；Pearly-lustre silvery white 0.5 part；Melamine cyanurate 1 part；White carbon black 1 part；Titanium dioxide
Titanium 5 parts；Naphthenic oil 0.4 part.
(1) 40g naphthenic oil and 8Kg AS resin are joined high-speed stirred batch mixer mixing 2min to obtain
To resin premixed thing；
(2) by 50g benzidine yellow toner, 5g pearly-lustre silvery white powder, 100g melamine cyanurate,
100g white carbon black, 500g titanium dioxide is added sequentially to resin premixed thing, by mixture at high-speed stirred batch mixing
Machine mixing 5min；
(3) joining in double screw extruder by said mixture material, regulation feeding rotating speed is 200rpm,
The each section of extruder temperature of double screw extruder temperature from charge door to head is respectively set to 80 DEG C,
140 DEG C, 180 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, screw speed is preferably 250rpm.
Mixture, through double screw extruder fusion plastification, extrusion, tie rod pelletizing, obtains having light identification function
Laser carving master batch.
Embodiment 4: for the preparation of the laser carving master batch of light color mark
A kind of laser carving master batch for light color mark, including the component of following parts by weight: PMMA 66 parts；
Anthraquinone blue 0.01 part；Pearly-lustre silvery white 0.02 part；Sodium bicarbonate 1 part；Melamine pyrophosphate 2 parts；
White carbon black 0.08 part；Pulvis Talci 5 parts；Calcium carbonate 2 parts；Zinc stearate 2 parts；Naphthenic oil 0.2 part.
(1) PMMA resin dried to 20g naphthenic oil and 6.6Kg is joined high-speed stirred batch mixing
Machine mixing 2min obtains resin premixed thing；
(2) by 1g anthraquinone blue toner, 2g pearly-lustre silvery white powder, 100g sodium bicarbonate, 200g melamine
Amine pyrophosphate, 8g white carbon black, 500g Pulvis Talci, 200g calcium carbonate, 200g calcium stearate is sequentially added into
To resin premixed thing, by mixture at high-speed stirred batch mixer mixing 5min；
(3) joining in double screw extruder by said mixture material, regulation feeding rotating speed is 180rpm,
The each section of extruder temperature of double screw extruder temperature from charge door to head is respectively set to 80 DEG C,
140 DEG C, 200 DEG C, 220 DEG C, 220 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, screw speed is preferably 200rpm.
Mixture, through double screw extruder fusion plastification, extrusion, tie rod pelletizing, obtains having light identification function
Laser carving master batch.
Embodiment 5: for the preparation of the laser carving master batch of light color mark
A kind of laser carving master batch for light color mark, including the component of following parts by weight: TPU 95 parts；
Fluorescence green 0.3 part；White 0.1 part of pearly-lustre；Melamine cyanurate 2 parts；Ammonium polyphosphate 1 part；Charcoal
Black 0.2 part；3 parts of barium sulfate；1 part of zinc sulfide；Zinc stearate 2 parts；Naphthenic oil 0.2 part.
(1) 20g naphthenic oil and 9.5Kg EVA resin are joined high-speed stirred batch mixer mixing 2min
Obtain resin premixed thing；
(2) by 30g fluorescence green powder, 10g pearly-lustre white lead, 200g melamine cyanurate, 100g
Ammonium polyphosphate, 20g white carbon black, 300g barium sulfate, 100g zinc sulfide, 200g zinc stearate adds successively
Enter to resin premixed thing, by mixture at high-speed stirred batch mixer mixing 5min；
(3) joining in double screw extruder by said mixture material, regulation feeding rotating speed is 200rpm,
The each section of extruder temperature of double screw extruder temperature from charge door to head is respectively set to 80 DEG C,
140 DEG C, 180 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, screw speed is preferably 300rpm.
Mixture, through double screw extruder fusion plastification, extrusion, tie rod pelletizing, obtains having light identification function
Laser carving master batch.
Embodiment 6: for the application of the laser carving master batch of light color mark
It is applied to implementing the 1～5 laser carving master batches prepared in modified plastics, and sets two comparative examples,
Concrete formula (by weight) as shown in table 1 below:
Table 1 laser carving master batch application formula
What in table 1 formula system, raw material was all selected is commercially available common resins and auxiliary agent.PP is extra large in using
The copolymerization PP EP 300M of shell, ABS resin is toray MABS 920, and PMMA selects Taiwan
Strange beautiful PMMA CM-207, the PBT PBT 1100-211M, PC selected from Changchun, Taiwan uses Korea S
The PC 1300-10NP of LG, primary antioxidant is THANOX 1010, and auxiliary antioxidant is THANOX
168, commercially available mark agent is respectively Merck 8208 and 8825.
Embodiment application and the preparation technology of comparative example:
(1) by resin dry for standby in advance (ABS, PMMA resin at 80 DEG C predrying 4 hours,
PBT, PC resin at 120 DEG C predrying 4 hours), the resin after dried and the present invention are implemented
Laser carving master batch that example prepares, primary antioxidant, auxiliary antioxidant add high-speed stirred batch mixer mix homogeneously
Or enter in double screw extruder separately through metering feeding device；
(2) sending in double screw extruder by said mixture material, regulation feeding rotating speed is 300rpm,
The each section of extruder temperature of double screw extruder temperature from charge door to head is respectively preferably district's temperature
80 DEG C, (PP, ABS, PMMA are 180 DEG C to two district's temperature；PBT, PC are 235 DEG C), three district's temperature
(PP, ABS, PMMA are 200 DEG C to degree；PBT, PC are 245 DEG C), four district's temperature (PP, ABS,
PMMA is 200 DEG C；PBT, PC are 255 DEG C), (PP, ABS, PMMA are 210 DEG C to five district's temperature；
PBT, PC are 255 DEG C), (PP, ABS, PMMA are 210 DEG C to six district's temperature；PBT, PC are
255 DEG C), (PP, ABS, PMMA are 200 DEG C to seven district's temperature；PBT, PC are 255 DEG C), 8th district
(PP, ABS, PMMA are 200 DEG C to temperature；PBT, PC are 255 DEG C), nine district's temperature (PP, ABS,
PMMA is 200 DEG C；PBT, PC are 255 DEG C), (PP, ABS, PMMA are 200 DEG C to head temperature；
PBT, PC are 255 DEG C), screw speed is preferably 350rpm, the draw ratio of double screw extruder be 40～
50, under the conveying and shear action of double screw extruder, abundant fusion plastification, mediate mixing, through head
Extrusion, tie rod, cooling, pelletizing, it is dried, finally packs, i.e. obtain having the group at light color identification function
Polymer beads.
The above-mentioned compositions with light identification function prepared is carried out performance test, testing result
As shown in table 2 and Fig. 1, Fig. 2, testing standard is as follows:
Hot strength is tested according to ISO 527-2 standard, and bending strength is carried out according to ISO 178 standard
Test, Izod notched impact strength is tested according to ISO 180/1A standard.
Laser marking equipment selects the YAG-50 model laser of laser Science and Technology Co., Ltd. of Shenzhen big nation
Marking arrangement, optical maser wavelength is 1064nm, and laser power is 50W.
Scanning electron microscope is used the foaming degree of laser printing labelling to be estimated, uses color difference meter to mark mark
Whiteness is estimated by the △ L-value change knowing district, and by foaming, grade is ascending is designated as A, B, C respectively,
Tetra-grades of D, whiteness effect is respectively labeled as 1,2,3,4 by differing from.
Table 2 has the composition properties index of light identification function
From table 2 and Fig. 1, Fig. 2, the laser carving master batch for light color mark of the present invention its in matrix tree
In fat, the compatibility is uniformly dispersed well, and a small amount of interpolation can make matrix resin realize engraving and send out under laser action
Bubble, labelling uniform in effect, clear and resin contrast are high, and maintain the mechanicalness of primary resin material
Can unaffected, therefore can be applicable in laser marking modified plastics field, be widely used in PS, ABS,
General-purpose plastics and PA, PC, PPE, PBT, the POM etc. such as ASA, SAN, PMMA, PP, PE
Engineering plastics, and there is good laser marking effect.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-mentioned reality
Execute the restriction of example, the change made under other any spirit without departing from the present invention and principle, modification,
Substitute, combine, simplify, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. the laser carving master batch for light color mark, it is characterised in that include the component of following parts by weight:
Laser carving master batch for light color mark the most according to claim 1, it is characterised in that: described
Light to absorb toner be in yellow class pigment or dyestuff, blue class pigment or dyestuff, green class pigment or dyestuff
At least one；Described luminous reflectance powder refers to the pearl essence having transmitting effect to light.
Laser carving master batch for light color mark the most according to claim 2, it is characterised in that: described
Yellow class pigment or dyestuff include at least one in azophosphine, benzidine yellow and quinophthalone Huang；Described
Blue class pigment or dyestuff include at least one in phthalocyanine blue and anthraquinone blue；Described green class pigment or dye
Material includes at least one in phthalocyanine green, fluorescence green and anthraquinone green；
Described luminous reflectance powder be pearly-lustre silver and pearly-lustre white at least one.
Laser carving master batch for light color mark the most according to claim 1, it is characterised in that: described
Foaming agent be in sodium bicarbonate, melamine cyanurate, ammonium polyphosphate and melamine pyrophosphate
At least one.
Laser carving master batch for light color mark the most according to claim 1, it is characterised in that: described
Whiting filler be zinc sulfide, barium sulfate, titanium dioxide, Pulvis Talci, Kaolin, calcium carbonate, stearic acid
At least one in zinc and calcium stearate.
Laser carving master batch for light color mark the most according to claim 1, it is characterised in that: described
White carbon black be coloring white carbon black and conductive black at least one；Described processing modified oil is naphthenic oil and silicon
At least one in oil.
Laser carving master batch for light color mark the most according to claim 1, it is characterised in that: also wrap
Containing at least one in following additive: fire retardant, antistatic additive, heat stabilizer, coloring agent, lubricant.
8. the preparation according to the laser carving master batch for light color mark described in any one of claim 1～7
Method, it is characterised in that include step in detail below:
(1) by vector resin and processing modified oil premix, premix material is obtained；
(2) light absorbs toner, luminous reflectance powder, foaming agent, white carbon black, Whiting filler and step (1) obtain
The premix material mix homogeneously arrived, through double screw extruder extruding pelletization, obtains the laser carving for light color mark female
Grain.
The preparation method of the laser carving master batch for light color mark the most according to claim 8, its feature
Be: the feeding rotating speed of described double screw extruder is 100～350rpm, screw zones temperature be 80～
230 DEG C, screw speed is 150～400rpm.
10. beat at laser according to the laser carving master batch for light color mark described in any one of claim 1～7
Application in mark modified plastics field.
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