CN109608770A - A kind of black matrix blue laser labelling polymer composition and preparation method - Google Patents

A kind of black matrix blue laser labelling polymer composition and preparation method Download PDF

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Publication number
CN109608770A
CN109608770A CN201910066086.0A CN201910066086A CN109608770A CN 109608770 A CN109608770 A CN 109608770A CN 201910066086 A CN201910066086 A CN 201910066086A CN 109608770 A CN109608770 A CN 109608770A
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blue
polymer composition
black matrix
basf
phthalocyanine
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Inventor
东为富
袁皓
李婷
马丕明
汪洋
张洪吉
陈明清
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Jiangnan University
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Jiangnan University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0893Zinc
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2265Oxides; Hydroxides of metals of iron
    • C08K2003/2275Ferroso-ferric oxide (Fe3O4)

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The present invention provides a kind of black matrix blue laser labelling polymer composition and preparation methods, belong to polymeric material field.Polymer composition components include: by high molecular polymer be 100 parts by weight in terms of, the content of contained blue colorant is 0.1~10 parts by weight;Atrament content is 0.1~20 parts by weight.Component including the high molecular polymer, blue colorant, atrament is pressed the component proportion melt blending by this method.The present invention marks blue markings in the surface laser of dark material by addition blue colorant.

Description

A kind of black matrix blue laser labelling polymer composition and preparation method
Technical field
The present invention relates to a kind of black matrix blue laser labelling polymer composition and preparation methods, belong to macromolecule Material Field, and in particular to can be with the polymer composition and preparation method of laser color label.
Background technique
With the development of the times, laser marking technology oneself had become a kind of effective label processing method, in each row Each industry has obtained more and more extensive utilization.The superiority of laser marking Technology application is increasingly clearly presented in face of people, It can get various texts, symbol and pattern etc., and character boundary can be from millimeter to micron dimension, this has the anti-fake of product Special meaning.
Laser marking technology at present at home and abroad just gradually paid attention to by people by industrial application, various novel mark systems System emerges one after another, it is replacing traditional labeling method with its unique advantage.Some developed countries are by the skill in the world Technological standards of the art as industrial processes, China also pay much attention to this technology, which is classified as " eight or five fire by State Scientific and Technological Commission Torch plan " is developed and is promoted.It has caused the attention of domestic more and more manufacturers now, will can replace passing The marking process of system injects new vitality to production.Therefore, laser marking has huge development potentiality and wide city Field prospect.
The character and pattern of laser index carving, the selective problems of the color shown also gradually by the attention of user, and As most important index in several technical indicators that must pay close attention in various manufacturers' market competition of production laser marking machine it One.Currently, progress colour-coded is relatively difficult on plastic substrate, how to obtain colour-coded and be applied to beautifying and decorating It is the challenge in future work.Therefore, laser color Mark technology is the technology of an innovation, will be had in following market Be widely applied.106566068 A of patent CN can be swashed using laser marking powder, warming substance, polymer's mixing treatment for one kind The composition of honorable color marker, but its not light color or white base, need to add specific laser marking powder can laser labelling face Color.107353604 A of patent CN also need to add laser marking powder on the basis of black masterbatch and can mark.The application is in one kind On the basis of atrament, without adding additional laser marking powder, it is only necessary to after colorant, atrament are blended with polymer, Laser labelling can be formed, it is simple and convenient, it is low in cost.
Summary of the invention
To solve the problem in the prior art, the present invention provides a kind of polymerizations of black matrix blue laser labelling Compositions and preparation method.The composition can form blue markings in substrate surface with laser, so that marking and background There is higher contrast.
Technical solution of the present invention is as follows:
A kind of black matrix blue laser labelling polymer composition, the polymer composition include a kind of blue-colored Agent, a kind of atrament and high molecular polymer.
By high molecular polymer be 100 parts by weight in terms of, the content of contained blue colorant is 0.1~10 parts by weight, preferably 1 ~5 parts by weight;Atrament content is 0.1~20 parts by weight, preferably 1~10 parts by weight.
The finished product is laser marked au bleu.
The high molecular polymer is polyethylene, polypropylene, polyisobutene, polystyrene, polyvinyl chloride, polymethyl One or more of sour methyl esters, polycarbonate, polyamide, polyester, polyphenylene oxide, polyurethane, nylon66 fiber, Acrylonitrile Butadiene-Styrene copolymer Mixing.
The blue colorant is the pigments or dyes with phthalocyanine frame, anthraquinone skeleton.
Further, the blue colorant is PB15 α-phthalocyanine blue b/BX, PB15:1 α-phthalocyanine blue NCNC, PB15:2 α- Phthalocyanine blue NCNF, PB15:3 β-phthalocyanine blue, PB15:4 β-phthalocyanine blue, PB15:6 ε-phthalocyanine blue, PB60 indanthrene blue, ultramarine, Cobalt blue, barba hispanica, the sea K6850 regent indigo plant (BASF), the sea FR7079 regent indigo plant (BASF), K6902 indigo plant (BASF), Basf- Heliogen Blue L 6990F、Basf-Heliogen Blue L 6989F、Basf-Heliogen Blue L 6700F、 Basf-Heliogen Blue L 7101F, Basf-Heliogen Blue L 7072D, DIC-5412SD phthalocyanine blue, Clariant-Hostaperm Blue 01 or Ciba-Cromophtal Blue A3R.
The atrament is that carbon black, melanin, black iron oxide, titanium be black, the mixing of one or more of zinc powder.
Auxiliary agent is added in the polymer composition according to actual needs, the auxiliary agent is lubricant or antioxidant.
The laser for carrying out laser labelling to polymer composition of the invention can be CO2Laser (wavelength 10600nm), Nd:YAG laser (wavelength 1064nm and 532nm), pulsed UV laser (excimer laser) etc..
A kind of preparation method of black matrix blue laser labelling polymer composition specifically will include the high score Sub- polymer, blue colorant and atrament are prepared by component proportion melt blending.
In the preparation process of Inventive polymers composition, material melts blending temperature is that usual polymer material adds Blending temperature used in work, can be depending on polymer melting temperature.
Various mixings used in the prior art can be used in the blending equipment of material mixing in the preparation process in accordance with the present invention Equipment, such as blender, kneader.
Used melt blending equipment is the general blending equipment in Plastics Processing Industry in the preparation process in accordance with the present invention, It can be double screw extruder, single screw extrusion machine, open mill or mixer etc..
A kind of laser labeling method of black matrix blue laser labelling polymer composition, detailed process are as follows: will be high Molecularly Imprinted Polymer, blue colorant and atrament are uniformly mixed in a high speed mixer;By mixture in double screw extruder Middle melting extrusion, cooling and dicing;By gained pellet in 90 DEG C of dry 12h, it is injection moulded at 180~240 DEG C, prepares as required Standard batten simultaneously carries out laser labelling.
To the characterization of label can by visual observation font tags lines it is whether smooth, clear, whether wide area surface smooth To determine.
Beneficial effects of the present invention: preparation method simple and reliable process of the present invention can be applied to nearly all On the polymeric articles for needing to be marked in industrial department.For example, it is desired on article indicate the date of manufacture, validity date, Bar code, house mark, series number etc..
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.
Embodiment 1:
For acrylic resin: by 100 parts by weight of acrylic resin, 0.1 parts by weight of carbon black, blue colorantThe sea K6850 Regent indigo plant (BASF)It is uniform that 0.1 parts by weight are placed in stirrer for mixing, then adds mixture into double screw extruder and carries out Melt blending, extruding pelletization, extrusion temperature are 160~220 DEG C, screw speed 300rpm.By the material grain of extrusion in 90 DEG C of baking ovens Then middle dry 12h is injected into standard batten under conditions of 160~220 DEG C again, carry out laser marking test.
Embodiment 2:
For polyvinyl resin: by 100 parts by weight of polyvinyl resin, 2 parts by weight of melanin, blue colorantK6902 is blue (BASF)It is uniform that 1 parts by weight are placed in stirrer for mixing, then adds mixture into and carries out melt blending in double screw extruder, Extruding pelletization, extrusion temperature are 160~220 DEG C, screw speed 300rpm.The material grain of extrusion is dried into 12h in 90 DEG C of baking ovens, Then standard batten is injected under conditions of 160~220 DEG C again, carries out laser marking test.
Embodiment 3:
For polystyrene resin: by 100 parts by weight of polystyrene resin, 10 parts by weight of black iron oxide, blue-colored AgentDIC-5412SD phthalocyanine blueIt is uniform that 5 parts by weight are placed in stirrer for mixing, then adds mixture into double screw extruder Melt blending, extruding pelletization are carried out, extrusion temperature is 160~220 DEG C, screw speed 300rpm.By the material grain of extrusion at 90 DEG C Then dry 12h in baking oven is injected into standard batten under conditions of 160~220 DEG C again, carries out laser marking test.
Embodiment 4:
For ABS resin: by 100 parts by weight of ABS resin, black 20 parts by weight of titanium, blue colorantBasf-Heliogen Blue L 6700FIt is uniform that 10 parts by weight are placed in stirrer for mixing, then adds mixture into double screw extruder and carries out Melt blending, extruding pelletization, extrusion temperature are 160~220 DEG C, screw speed 300rpm.By the material grain of extrusion in 90 DEG C of baking ovens Then middle dry 12h is injected into standard batten under conditions of 160~220 DEG C again, carry out laser marking test.
Embodiment 5:
For polycarbonate resin: by 100 parts by weight of polycarbonate resin, 12 parts by weight of zinc powder, blue colorantCiba- Cromophtal Blue A3RIt is uniform that 8 parts by weight are placed in stirrer for mixing, then adds mixture into double screw extruder Middle carry out melt blending, extruding pelletization, extrusion temperature are 160~220 DEG C, screw speed 300rpm.By the material grain of extrusion 90 Then dry 12h in DEG C baking oven is injected into standard batten under conditions of 160~220 DEG C again, carries out laser marking test.
Comparative example 1~2:
Other than blue colorant is not added, remaining condition is identical as previous embodiment.
Comparative example 3:
For polyvinyl resin: 100 parts by weight of polyvinyl resin, blue colorant K6902 is blue (BASF).3 parts by weight It is uniform to be placed in stirrer for mixing, then adds mixture into and carries out melt blending in double screw extruder, extruding pelletization squeezes out Temperature is 160~220 DEG C, screw speed 300rpm.By the material grain of extrusion in 90 DEG C of baking ovens dry 12h, then again 160~ It is injected into standard batten under conditions of 220 DEG C, carries out laser marking test.
Specific formula is shown in Table 1, and wherein each component content is in parts by weight.Laser labelling effect is as shown in table 1.
Table 1
It is not added with blue colorant in comparative example 1,2, after mark, marker color is white or canescence;In comparative example 3, Be not added with atrament, the matrix color be it is transparent or white, be unable to laser labelling.In embodiment 1-5, while black is added Substance and blue colorant, laser labelling excellent effect.

Claims (10)

1. a kind of black matrix blue laser labelling polymer composition, which is characterized in that the polymer composition includes one Kind blue colorant, a kind of atrament and high molecular polymer;
By high molecular polymer be 100 parts by weight in terms of, the content of contained blue colorant is 0.1~10 parts by weight;Atrament Content is 0.1~20 parts by weight;
The atrament is that carbon black, melanin, black iron oxide, titanium be black, the mixing of one or more of zinc powder.
2. a kind of black matrix blue laser labelling polymer composition according to claim 1, which is characterized in that blue The content of chromatic colorant agent is 1~5 parts by weight, and atrament content is 1~10 parts by weight.
3. a kind of black matrix blue laser labelling polymer composition according to claim 1 or 2, feature exist In the high molecular polymer is polyethylene, polypropylene, polyisobutene, polystyrene, polyvinyl chloride, poly-methyl methacrylate The mixing of one or more of ester, polycarbonate, polyamide, polyester, polyphenylene oxide, polyurethane, nylon66 fiber, Acrylonitrile Butadiene-Styrene copolymer; The blue colorant is the pigments or dyes with phthalocyanine frame, anthraquinone skeleton.
4. a kind of black matrix blue laser labelling polymer composition according to claim 1 or 2, feature exist In, the blue colorant be PB15 α-phthalocyanine blue b/BX, PB15:1 α-phthalocyanine blue NCNC, PB15:2 α-phthalocyanine blue NCNF, PB15:3 β-phthalocyanine blue, PB15:4 β-phthalocyanine blue, PB15:6 ε-phthalocyanine blue, PB60 indanthrene blue, ultramarine, cobalt blue, barba hispanica, The sea K6850 regent is blue, the sea FR7079 regent is blue, K6902 is blue, Basf-Heliogen Blue L 6990F, Basf-Heliogen Blue L 6989F、Basf-Heliogen Blue L 6700F、Basf-Heliogen Blue L 7101F、Basf- Heliogen Blue L7072D, DIC-5412SD phthalocyanine blue, Clariant-Hostaperm Blue 01 or Ciba- Cromophtal Blue A3R。
5. a kind of black matrix blue laser labelling polymer composition according to claim 3, which is characterized in that institute Stating blue colorant is PB15 α-phthalocyanine blue b/BX, PB15:1 α-phthalocyanine blue NCNC, PB15:2 α-phthalocyanine blue NCNF, PB15:3 β- Phthalocyanine blue, PB15:4 β-phthalocyanine blue, PB15:6 ε-phthalocyanine blue, PB60 indanthrene blue, ultramarine, cobalt blue, barba hispanica, K6850 Hai Li The brilliant blue, sea FR7079 regent indigo plant, K6902 indigo plant, Basf-Heliogen Blue L 6990F, Basf-Heliogen Blue L 6989F、Basf-Heliogen Blue L6700F、Basf-Heliogen Blue L 7101F、Basf-Heliogen Blue L 7072D, DIC-5412SD phthalocyanine blue, Clariant-Hostaperm Blue 01 or Ciba-Cromophtal Blue A3R。
6. according to claim 1, a kind of black matrix blue laser labelling polymer composition, feature described in 2 or 5 It is, add auxiliary agent in the polymer composition according to actual needs, the auxiliary agent is lubricant or antioxidant.
7. a kind of black matrix blue laser labelling polymer composition according to claim 3, which is characterized in that institute Auxiliary agent is added in the polymer composition stated according to actual needs, the auxiliary agent is lubricant or antioxidant.
8. a kind of black matrix blue laser labelling polymer composition according to claim 4, which is characterized in that institute Auxiliary agent is added in the polymer composition stated according to actual needs, the auxiliary agent is lubricant or antioxidant.
9. a kind of preparation method of black matrix blue laser labelling polymer composition, which is characterized in that specifically will packet It is prepared containing the high molecular polymer, blue colorant and atrament by component proportion melt blending.
10. a kind of laser labeling method of black matrix blue laser labelling polymer composition, which is characterized in that specific mistake Journey are as follows: be uniformly mixed high molecular polymer, blue colorant and atrament in a high speed mixer;By mixture in double spiral shells Melting extrusion in bar extruder, cooling and dicing;By gained pellet in 90 DEG C of dry 12h, it is injection moulded, presses at 180~240 DEG C It is required that preparation standard batten and carrying out laser labelling.
CN201910066086.0A 2019-01-24 2019-01-24 A kind of black matrix blue laser labelling polymer composition and preparation method Pending CN109608770A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112143107A (en) * 2020-09-30 2020-12-29 江苏金发科技新材料有限公司 Dark laser-markable master batch and preparation method thereof
CN112375347A (en) * 2020-11-12 2021-02-19 江苏金发科技新材料有限公司 Black PBT composition capable of laser marking blue fonts and preparation thereof
CN112521729A (en) * 2020-11-12 2021-03-19 上海金发科技发展有限公司 High-fluidity black flame-retardant reinforced polyethylene glycol terephthalate composition and preparation method thereof
WO2021068275A1 (en) * 2019-10-08 2021-04-15 江南大学 Dark-colored system photopolymerized composition
CN114456535A (en) * 2022-01-26 2022-05-10 天津金发新材料有限公司 Black ABS material marked by blue laser and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW314534B (en) * 1993-09-01 1997-09-01 Hoechst Ag
CN1910238A (en) * 2004-01-16 2007-02-07 大科能树脂有限公司 Colored colorant for multicolor laser marking, composition for multicolor laser marking, molded article containing the composition, molded article with multicolor mark, and laser marking method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW314534B (en) * 1993-09-01 1997-09-01 Hoechst Ag
CN1910238A (en) * 2004-01-16 2007-02-07 大科能树脂有限公司 Colored colorant for multicolor laser marking, composition for multicolor laser marking, molded article containing the composition, molded article with multicolor mark, and laser marking method
CN101497287A (en) * 2004-01-16 2009-08-05 大科能树脂有限公司 Molded article with multicolor mark and laser marking method

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021068275A1 (en) * 2019-10-08 2021-04-15 江南大学 Dark-colored system photopolymerized composition
CN112143107A (en) * 2020-09-30 2020-12-29 江苏金发科技新材料有限公司 Dark laser-markable master batch and preparation method thereof
CN112375347A (en) * 2020-11-12 2021-02-19 江苏金发科技新材料有限公司 Black PBT composition capable of laser marking blue fonts and preparation thereof
CN112521729A (en) * 2020-11-12 2021-03-19 上海金发科技发展有限公司 High-fluidity black flame-retardant reinforced polyethylene glycol terephthalate composition and preparation method thereof
CN112521729B (en) * 2020-11-12 2023-04-18 上海金发科技发展有限公司 High-fluidity black flame-retardant reinforced polyethylene glycol terephthalate composition and preparation method thereof
CN114456535A (en) * 2022-01-26 2022-05-10 天津金发新材料有限公司 Black ABS material marked by blue laser and preparation method and application thereof
CN114456535B (en) * 2022-01-26 2023-06-06 天津金发新材料有限公司 Blue laser marked black ABS material and preparation method and application thereof

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Application publication date: 20190412