CN104448531A - Laser etching master batch for light color identification, preparation method thereof and application - Google Patents

Laser etching master batch for light color identification, preparation method thereof and application Download PDF

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Publication number
CN104448531A
CN104448531A CN201410837554.7A CN201410837554A CN104448531A CN 104448531 A CN104448531 A CN 104448531A CN 201410837554 A CN201410837554 A CN 201410837554A CN 104448531 A CN104448531 A CN 104448531A
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master batch
light color
radium carving
color mark
resin
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CN104448531B (en
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李斌
王亮
官焕祥
魏金刚
李卫领
程庆
王林
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Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
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Abstract

The invention belongs to the technical field of functional master batch preparation, and discloses a laser etching master batch for light color identification, a preparation method thereof and application. The master batch comprises, by weight, 65-66 parts of carrier resin, 0.01-0.5 part of light absorption color powder, 0.01-0.5 part of light reflection powder, 0.7-6 parts of foaming agents, 0.05-1.5 parts of carbon black, 5-20 parts of whitening fillers and 0.01-4 parts of processed modified oil. As the carrier resin in the laser etching master batch can be selected according to applied matrix resin, the carrier resin is fine in compatibility and uniform in dispersion in the matrix resin and can function in carving and foaming under the action of laser when less carrier resin is added, the carrier resin is applicable to different matrix resin, marking effects are uniform and clear, resin contrast ratio is high, the mechanical performance of original resin materials cannot be affected, and the laser etching master batch can be applied to the field of laser marking modified plastics and is widely applicable to various universal plastics and engineering plastics.

Description

A kind of radium carving master batch for light color mark and its preparation method and application
Technical field
The invention belongs to functional agglomerate preparing technical field, particularly a kind of radium carving master batch for light color mark and its preparation method and application.
Background technology
Laser marking technology is development in recent years a kind of industrial marking method rapidly, and compared with traditional indicia means, laser marking has obvious advantage: (1) marking speed is fast, and writing is clear, permanent; (2) noncontact procession, pollutes little, without wearing and tearing; (3) easy to operate, antiforge function is strong; (4) high-speed automated operation, production cost is low.At present, in label print industry, laser marking has occupied the market of more than 90%.Along with the development of modified plastics technology, laser marking technology is applied to modified plastic industry more and more.Frosting application laser realization mark mainly contains four kinds of different mechanism: (1) variable color, under laser radiation, and material surface generation carbonization; (2) carve, use when removing material by the mode melted and gasify; (3) foam, material surface melts by laser, and produce bubble, light reflects on micro-bubble, makes marker color visible; (4) ablation, material surface coating is removed by laser, thus forms larger contrast gradient with primer.Wherein, dark material surface realizes light color mark and mainly uses engraving and foam process.At present, realize light color mark for a certain specific dark material surface, basic skills is all add mark auxiliary agent, is realized by a kind of technique in engraving, foaming.But some have the mark auxiliary agent of excellent mark effect, and often composition is more complicated, and preparation technology is loaded down with trivial details, which limits its industrial volume production.In addition, want to obtain comparatively ideal mark effect, need the mark agent adding high number.Like this, cause the rising of product cost on the one hand, in addition, mark agent is all generally powder body material, is difficult to dispersed in polymeric matrix, and a large amount of interpolations will cause body material mark effect unshapeliness and the mechanical property affecting material.
At present, in published mark patent, as disclosed a kind of core in Chinese patent application CN 102741360 A, shell blend plays white auxiliary agent as black, although mark is respond well, preparation technology is loaded down with trivial details, is unfavorable for suitability for industrialized production.
Summary of the invention
In order to overcome above-mentioned prior art powder mark auxiliary agent in resin matrix bad dispersibility, easily affect resin mechanical property, and the shortcomings such as mark mechanism is single, limited efficiency are with not enough, primary and foremost purpose of the present invention is to provide a kind of radium carving master batch for light color mark.This master batch directly can add in modified plastics and carry out production and preparation, for combining two kinds of mark techniques of carving and foam in low cost, the high-efficiency marking radium carving master batch of one.
Another object of the present invention is the preparation method providing a kind of above-mentioned radium carving master batch for light color mark.
Still a further object of the present invention is to provide the above-mentioned application of radium carving master batch in laser marking modified plastics field for light color mark.
Object of the present invention is realized by following proposal:
For a radium carving master batch for light color mark, comprise the component of following parts by weight:
Described vector resin can be selected arbitrarily according to the modified plastics of master batch subsequent applications, as master batch of the present invention is applied in PS, the vector resin then can selected PS or prepare as this master batch with the good resin of PS consistency, therefore, the resin that can this area selected arbitrarily general, as logical polystyrene, polyethylene, polypropylene, ethylene-vinyl acetate, polymethylmethacrylate, styrene-acrylonitrile copolymer, Polyurethane Thermoplastic Elastomer.
Photoabsorption toner used can be the conventional any pigment absorption in this area, in order to realize the present invention better, described photoabsorption toner is preferably at least one in yellow class pigment or dyestuff, blue class pigment or dyestuff, green class pigment or dyestuff; More preferably, described yellow class pigment or dyestuff comprise at least one in azophosphine, diarylide yellow and quinophthalone Huang; Described blue class pigment or dyestuff comprise at least one in phthalocyanine blue and anthraquinone blue; Described green class pigment or dyestuff comprise at least one in phthalocyanine green, fluorescence green and anthraquinone green.
Described light emission powder refers to pearlescence light being had to transmitting effect, can be the pearlescence that this area is commonly used arbitrarily.In order to realize the present invention better, described light emission powder be preferably pearly-lustre silver and pearly-lustre in vain at least one.
In order to realize the present invention better, described whipping agent is preferably at least one in sodium bicarbonate, melamine cyanurate, ammonium polyphosphate and melamine pyrophosphate.
In order to realize the present invention better, described carbon black is preferably at least one in painted carbon black and graphitized carbon black; More preferably, the particle diameter of described carbon black is 10 ~ 100nm, BDP oil-absorption(number) is 40 ~ 300cc/100g.
In order to realize the present invention better, described Whiting filler is preferably at least one in zinc sulphide, barium sulfate, titanium dioxide, talcum powder, kaolin, calcium carbonate, Zinic stearas and calcium stearate.
In order to realize the present invention better, described processing modified oil is preferably at least one in naphthenic oil and silicone oil.
In order to realize the present invention better further, under the prerequisite not affecting the radium carving master batch impact of performance for light color mark of the present invention, at least one in following additive can be comprised further: the auxiliary agent that this areas such as fire retardant, static inhibitor, thermo-stabilizer, tinting material, lubricant are conventional.
Present invention also offers a kind of preparation method of the above-mentioned radium carving master batch for light color mark, comprise following concrete steps:
(1) by vector resin and processing modified oily premix, Preblend is obtained;
(2) Preblend that photoabsorption toner, luminous reflectance powder, whipping agent, carbon black, Whiting filler obtain with step (1) is mixed, through twin screw extruder extruding pelletization, obtain the radium carving master batch for light color mark.
In above-mentioned preparation method, the consumption of each component is:
In above-mentioned preparation method, the feeding rotating speed of described twin screw extruder is preferably 100 ~ 350rpm, and screw zones temperature is preferably 80 ~ 230 DEG C, and screw speed is preferably 150 ~ 400rpm.
Radium carving master batch for light color mark of the present invention can directly add in matrix resin for laser marking, and due to the vector resin in master batch can according to application matrix resin select, its consistency in matrix resin is uniformly dispersed well, and do not affect the original mechanical property of resin, a small amount of interpolation can make matrix resin realize engraving and foaming under lasing simultaneously, there is good laser marking effect, therefore can be applicable in laser marking modified plastics field, be widely used in PS, ABS, ASA, SAN, PMMA, PP, the general-purpose plastics such as PE and PA, PC, PPE, PBT, the engineering plastics such as POM.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) the radium carving master batch preparation technology for light color mark of the present invention is simple, without complicated handling procedure, easily realizes industrialization and produces;
(2) the present invention has engraving and foaming effect concurrently by selecting the different components comprising specific function to carry out composite obtained master batch under lasing, goes in different matrix resins;
(3) of the present invention few for addition in the radium carving master batch application process of light color mark, directly and resin alloy just can realize laser labelling, mark uniform in effect, clear, and the contrast gradient of resin high.
Accompanying drawing explanation
The ABS resin mark design sketch that Fig. 1 obtains for comparative example 1.
The ABS resin mark design sketch that Fig. 2 obtains for embodiment 1.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1: for the preparation of the radium carving master batch of light color mark
For a radium carving master batch for light color mark, comprise 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; Carbon black 0.05 part; 3 parts, barium sulfate; Calcium stearate 2 parts; Naphthenic oil 0.2 part.
(1) 20g naphthenic oil and 9Kg EVA resin are joined high-speed stirring mixer mixing 2min and obtain resin premixed thing;
(2) by 10g phthalocyanine blue toner, 5g pearly-lustre white powder, 100g sodium bicarbonate, 5g carbon black, 300g barium sulfate, 200g calcium stearate joins resin premixed thing successively, by mixture at high-speed stirring mixer mixing 5min;
(3) said mixture material is joined in twin screw extruder, feeding rotating speed is regulated to be 200rpm, the temperature of each section of extruder temperature from charging opening to head of twin screw extruder is set to 80 DEG C, 140 DEG C, 180 DEG C respectively, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, screw speed is preferably 250rpm.Mixture through twin screw extruder fusion plastification, extrude, tie rod pelletizing, obtain having the radium carving master batch of light identification function.
Embodiment 2: for the preparation of the radium carving master batch of light color mark
For a radium carving master batch for light color mark, comprise the component of following parts by weight: PE 88 parts; Anthraquinone green 0.05 part; White 0.06 part of pearly-lustre; Ammonium polyphosphate 2 parts; Carbon black 0.5 part; 2.5 parts, zinc sulphide; Zinic stearas 3 parts; Naphthenic oil 0.2 part.
(1) 20g naphthenic oil and 8.8Kg PE resin are joined high-speed stirring mixer mixing 2min and obtain resin premixed thing;
(2) by 5g phthalocyanine blue toner, 6g pearly-lustre white powder, 200g ammonium polyphosphate, 50g carbon black, 250g zinc sulphide, 300g Zinic stearas joins resin premixed thing successively, by mixture at high-speed stirring mixer mixing 5min;
(3) said mixture material is joined in twin screw extruder, feeding rotating speed is regulated to be 300rpm, the temperature of each section of extruder temperature from charging opening to head of twin screw extruder is set to 80 DEG C, 140 DEG C, 180 DEG C respectively, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, screw speed is preferably 400rpm.Mixture through twin screw extruder fusion plastification, extrude, tie rod pelletizing, obtain having the radium carving master batch of light identification function.
Embodiment 3: for the preparation of the radium carving master batch of light color mark
For a radium carving master batch for light color mark, comprise the component of following parts by weight: AS 80 parts; Diarylide yellow 0.5 part; Pearly-lustre silvery white 0.5 part; Melamine cyanurate 1 part; Carbon black 1 part; Titanium dioxide 5 parts; Naphthenic oil 0.4 part.
(1) 40g naphthenic oil and 8Kg AS resin are joined high-speed stirring mixer mixing 2min and obtain resin premixed thing;
(2) by 50g diarylide yellow toner, 5g pearly-lustre silvery white powder, 100g melamine cyanurate, 100g carbon black, 500g titanium dioxide joins resin premixed thing successively, by mixture at high-speed stirring mixer mixing 5min;
(3) said mixture material is joined in twin screw extruder, feeding rotating speed is regulated to be 200rpm, the temperature of each section of extruder temperature from charging opening to head of twin screw extruder is set to 80 DEG C, 140 DEG C, 180 DEG C respectively, 210 DEG C, 220 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, screw speed is preferably 250rpm.Mixture through twin screw extruder fusion plastification, extrude, tie rod pelletizing, obtain having the radium carving master batch of light identification function.
Embodiment 4: for the preparation of the radium carving master batch of light color mark
For a radium carving master batch for light color mark, comprise 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; Carbon black 0.08 part; Talcum powder 5 parts; 2 parts, calcium carbonate; Zinic stearas 2 parts; Naphthenic oil 0.2 part.
(1) 20g naphthenic oil and the dried PMMA resin of 6.6Kg are joined high-speed stirring mixer mixing 2min and obtain resin premixed thing;
(2) by 1g anthraquinone blue toner, 2g pearly-lustre silvery white powder, 100g sodium bicarbonate, 200g melamine pyrophosphate, 8g carbon black, 500g talcum powder, 200g calcium carbonate, 200g calcium stearate joins resin premixed thing successively, by mixture at high-speed stirring mixer mixing 5min;
(3) said mixture material is joined in twin screw extruder, feeding rotating speed is regulated to be 180rpm, the temperature of each section of extruder temperature from charging opening to head of twin screw extruder is set to 80 DEG C, 140 DEG C, 200 DEG C respectively, 220 DEG C, 220 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, screw speed is preferably 200rpm.Mixture through twin screw extruder fusion plastification, extrude, tie rod pelletizing, obtain having the radium carving master batch of light identification function.
Embodiment 5: for the preparation of the radium carving master batch of light color mark
For a radium carving master batch for light color mark, comprise 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; Carbon black 0.2 part; 3 parts, barium sulfate; 1 part, zinc sulphide; Zinic stearas 2 parts; Naphthenic oil 0.2 part.
(1) 20g naphthenic oil and 9.5Kg EVA resin are joined high-speed stirring mixer mixing 2min and obtain resin premixed thing;
(2) by 30g fluorescence green powder, 10g pearly-lustre white powder, 200g melamine cyanurate, 100g ammonium polyphosphate, 20g carbon black, 300g barium sulfate, 100g zinc sulphide, 200g Zinic stearas joins resin premixed thing successively, by mixture at high-speed stirring mixer mixing 5min;
(3) said mixture material is joined in twin screw extruder, feeding rotating speed is regulated to be 200rpm, the temperature of each section of extruder temperature from charging opening to head of twin screw extruder is set to 80 DEG C, 140 DEG C, 180 DEG C respectively, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, screw speed is preferably 300rpm.Mixture through twin screw extruder fusion plastification, extrude, tie rod pelletizing, obtain having the radium carving master batch of light identification function.
Embodiment 6: for the application of the radium carving master batch of light color mark
Radium carving master batch enforcement 1 ~ 5 prepared is applied in modified plastics, and establishes two comparative examples, concrete formula (by weight) as shown in table 1 below:
Table 1 radium carving master batch application formula
What in table 1 formula system, starting material were all selected is commercially available common resins and auxiliary agent.PP adopts the copolymerization PP EP 300M of CSPC, ABS resin is toray MABS 920, PMMA selects the strange beautiful PMMA CM-207 in Taiwan, PBT is selected from the PBT 1100-211M in Changchun, Taiwan, PC adopts the PC 1300-10NP of Korea S LG, primary antioxidant is THANOX 1010, and auxiliary antioxidant is THANOX168, and commercially available mark agent is respectively Merck 8208 and 8825.
The preparation technology of embodiment application and comparative example:
(1) by resin dry for standby (ABS, PMMA resin at 80 DEG C predrying 4 hours in advance, PBT, PC resin at 120 DEG C predrying 4 hours), the radium resin after drying treatment and the embodiment of the present invention prepared carves master batch, primary antioxidant, auxiliary antioxidant add high-speed stirring mixer and mix or enter in twin screw extruder separately through metering feeding device;
(2) said mixture material is sent in twin screw extruder, regulate feeding rotating speed to be 300rpm, each section of extruder temperature of twin screw extruder from charging opening to head temperature is preferably district's temperature 80 DEG C respectively, (PP, ABS, PMMA are 180 DEG C to two district's temperature; PBT, PC are 235 DEG C), (PP, ABS, PMMA are 200 DEG C to three district's temperature; PBT, PC are 245 DEG C), (PP, ABS, PMMA are 200 DEG C to four district's temperature; 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), (PP, ABS, PMMA are 200 DEG C to eight district's temperature; PBT, PC are 255 DEG C), (PP, ABS, PMMA are 200 DEG C to nine district's temperature; 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 length-to-diameter ratio of twin screw extruder is 40 ~ 50, under the conveying and shearing action of twin screw extruder, abundant fusion plastification, mediate mixing, extrude through head, tie rod, cooling, pelletizing, drying, finally pack, namely obtain that there is the composition grain at light identification function.
Carry out performance test to the above-mentioned composition with light identification function prepared, detected result as shown in table 2 and Fig. 1, Fig. 2, testing standard is as follows:
Tensile strength is tested according to ISO 527-2 standard, and flexural strength is tested according to ISO 178 standard, and Izod notched impact strength is tested according to ISO 180/1A standard.
Laser marking equipment selects the YAG-50 model laser marking equipment of laser Science and Technology Co., Ltd. of Shenzhen big nation, and optical maser wavelength is 1064nm, and laser power is 50W.
The foaming degree adopting scanning electron microscope to mark Laser Printing is assessed, adopt the △ L value change of color difference meter to mark tag slot to assess whiteness, and by foaming, grade is ascending is designated as A, B respectively, C, D tetra-grades, whiteness effect is labeled as 1 respectively by differing from, 2,3,4.
Table 2 has the composition properties index of light identification function
By table 2 and Fig. 1, Fig. 2 is known, its consistency in matrix resin of radium carving master batch for light color mark of the present invention is uniformly dispersed well, a small amount of interpolation can make matrix resin realize engraving and foaming under lasing, mark uniform in effect, clear, high with the contrast gradient of resin, and the mechanical property maintaining unmodified resin material is unaffected, therefore can be applicable in laser marking modified plastics field, be widely used in PS, ABS, ASA, SAN, PMMA, PP, the general-purpose plastics such as PE and PA, PC, PPE, PBT, the engineering plastics such as POM, and there is good laser marking effect.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (10)

1., for a radium carving master batch for light color mark, it is characterized in that the component comprising following parts by weight:
2. the radium carving master batch for light color mark according to claim 1, is characterized in that: described photoabsorption toner is at least one in yellow class pigment or dyestuff, blue class pigment or dyestuff, green class pigment or dyestuff; Described light emission powder refers to pearlescence light being had to transmitting effect.
3. the radium carving master batch for light color mark according to claim 2, is characterized in that: described yellow class pigment or dyestuff comprise at least one in azophosphine, diarylide yellow and quinophthalone Huang; Described blue class pigment or dyestuff comprise at least one in phthalocyanine blue and anthraquinone blue; Described green class pigment or dyestuff comprise at least one in phthalocyanine green, fluorescence green and anthraquinone green;
Described light emission powder be pearly-lustre silver and pearly-lustre in vain at least one.
4. the radium carving master batch for light color mark according to claim 1, is characterized in that: described whipping agent is at least one in sodium bicarbonate, melamine cyanurate, ammonium polyphosphate and melamine pyrophosphate.
5. the radium carving master batch for light color mark according to claim 1, is characterized in that: described Whiting filler is at least one in zinc sulphide, barium sulfate, titanium dioxide, talcum powder, kaolin, calcium carbonate, Zinic stearas and calcium stearate.
6. the radium carving master batch for light color mark according to claim 1, is characterized in that: described carbon black is at least one in painted carbon black and graphitized carbon black; Described processing modified oil is at least one in naphthenic oil and silicone oil.
7. the radium carving master batch for light color mark according to claim 1, is characterized in that: also comprise at least one in following additive: fire retardant, static inhibitor, thermo-stabilizer, tinting material, lubricant.
8. a preparation method for the radium carving master batch for light color mark according to any one of claim 1 ~ 7, is characterized in that comprising following concrete steps:
(1) by vector resin and processing modified oily premix, Preblend is obtained;
(2) Preblend that photoabsorption toner, luminous reflectance powder, whipping agent, carbon black, Whiting filler obtain with step (1) is mixed, through twin screw extruder extruding pelletization, obtain the radium carving master batch for light color mark.
9. the preparation method of the radium carving master batch for light color mark according to claim 8, is characterized in that: the feeding rotating speed of described twin screw extruder is 100 ~ 350rpm, and screw zones temperature is 80 ~ 230 DEG C, and screw speed is 150 ~ 400rpm.
10. the application of radium carving master batch in laser marking modified plastics field for light color mark according to any one of claim 1 ~ 7.
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