CN106317565B - A kind of composition additive for laser labelling - Google Patents
A kind of composition additive for laser labelling Download PDFInfo
- Publication number
- CN106317565B CN106317565B CN201610704782.6A CN201610704782A CN106317565B CN 106317565 B CN106317565 B CN 106317565B CN 201610704782 A CN201610704782 A CN 201610704782A CN 106317565 B CN106317565 B CN 106317565B
- Authority
- CN
- China
- Prior art keywords
- methyl benzenesulfonic
- composition
- benzenesulfonic acid
- laser
- homologue
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
The invention discloses a kind of composition additives for laser labelling, belong to technical field of laser processing.By iron, nickel, cobalt, lead, tin, one or several kinds of mixtures and its precursor composition of the reaction product (or salt) of the p-methyl benzenesulfonic acid (or its homologue) of antimony or bismuth, wherein metal ion is with the molar ratio of its corresponding oxide and p-methyl benzenesulfonic acid root (or its homologue): 1:2-6.The present invention develops a kind of microgranular laser marking additives composition for being used for low color polymers according to MOLECULE DESIGN thinking, the particulate composition energy absorbing wavelength is that 1.06 microns of laser radiation energy makes the particle and the polymer foil being wrapped in outside it all decompose reaction, the dark product generated is decomposed under positive coopertive effect, low color polymers are formed with dark label, the image in 2 D code of the label reaches machine-scannable identification grade.
Description
Technical field
The invention belongs to technical field of laser processing, especially according to new mechanism, the laser mark obtained based on MOLECULE DESIGN
Remember compositions of additives.
Background technique
Laser marking technology has the characteristics that high speed, efficient, energy-saving and environmental protection, has obtained in the industrial production extensively
Application, plastics (polymer) product manufacture field have its unique advantage.Especially laser labelling product is produced than printing
The strong points such as product have long service life, anti-scratch is drawn.The Nd:YAG pulse laser for emitting 1.06 mum wavelengths is commonly used for light polymerization
The marking device of object.Most polymer (P) are very high for 1.06 μm of light wave transmitance for wavelength, thus cannot directly answer
With laser technology mark.It to be added in the polymer thus laser marking additives (A).It, can be with to improve laser labelling efficiency
Synergist (I) is added in A.Such as: it is Sb that US4816374, which discloses A,2O3, dosage is the 2%-6% of P, and CN1152911 is draped over one's shoulders
Reveal after the I of 0.3%-3% pearlescent pigment is added, Sb2O3Dosage be 0.5%-5%；US7169471, A are BiOCl, and I is more
Kind organic matter；CN102597081, A are Bi2O3；I is bismuth citrate；US7187396, A are ATO, and I is PETG；Etc..In technique
On, A, I and P are mixed through blending technology machine-shaping, therefore they belong to the synergisting method of physical modification.
Document: Beijing University of Technology Yang Wei's in 2010 is entitled: " research of plastic surface laser marking and discoloration technique "
Master's thesis, the report such as US6693657, US8877332 A the mechanism of action be: when laser beam is irradiated to the P added with A,
Microgranular A absorbs laser radiation energy and luminous energy is converted to thermal energy, heat itself and is wrapped in the polymer thin on its surface
The tiny area of layer, is allowed to temperature and sharply increases, and causes the polymer foil that pyrolysis, reaction product carbon and carbonization occurs
Object forms dark label in low color polymers；It is above-mentioned since most laser marking additives particles are in the inside of P
Document has all been reported carburizing reagent and has been occurred in the inside of polymer.According to this mechanism, between laser marking additives particle and P
Effect should be carried out between their contact interface.Contribution to label colour generation is thermal decomposition product (carbon and the carbon by P
Compound) it makes.
Summary of the invention
The present invention in order to overcome the above-mentioned deficiencies of the prior art,
A kind of composition additive for laser labelling, by iron, nickel, cobalt, lead, tin, antimony or bismuth p-methyl benzenesulfonic acid (or
Its homologue) reaction product (or salt) one or several kinds of mixtures and its precursor composition, wherein metal ion is right with its
The oxide answered is (with molecular formula MO, M2O3Or MO2Indicate) and p-methyl benzenesulfonic acid root (or its homologue) molar ratio: 1:2-6；
Wherein M is iron, nickel, cobalt, lead, tin, antimony or bismuth.
A kind of preparation method of above-mentioned composition additive for laser labelling carries out: metal oxygen as steps described below
Compound (or hydration of its oxide) and p-methyl benzenesulfonic acid (including its homologue) are evaporated after heating reaction in aqueous solution, then
110 DEG C of -140 DEG C of drying 30min, cooling are milled down to D50 between 10-50um.
Advantages of the present invention: the laser action that this technology is 1.06 μm in wavelength using the composition additive of laser labelling
Raw intramolecular chemical reaction is issued, thus not only energy utilization is abundant, rapid reaction；And the composition of laser labelling adds
The dark product for adding agent to react can be with the thermal decomposition product of the polymer foil for being wrapped in additive particulate surface in positive coorperativity
Under effect, so that the color ratio for forming label does not have intramolecule to react Shi Gengshen；Therefore addition small amount (refers to contained in A
The amount of metal) the two-dimension code pattern that is obtained through mark of polymer of the A by chemical modification can reach machine
It can scanning recognition grade.
Specific embodiment
It is contemplated that:
If the compound that the laser emission for making the interparticle of A contain 1.06 μm of absorbable wavelength is decomposed, due to changing
Reaction inside adduct molecule does not need mass transfer and diabatic process, thus can greatly improve the efficiency of reaction；If set again
Meter makes the intramolecular dark product thermally decomposed to yield and the polymer foil generation heat point for being wrapped in additive particulate surface
The dark product (carbon and carbide) that solution reaction obtains is in positive coopertive effect, so that it may obtain more dark label.Based in this way
Thinking, the invention proposes a kind of microgranular laser marking additives compositions for being used for low color polymers.This programme it is micro-
Contain p-methyl benzenesulfonic acid (including its homologue) root in granular composition, while also containing metals such as iron, nickel, cobalt, lead, tin, antimony, bismuths
Ion；Since p-methyl benzenesulfonic acid (including its homologue) is a strong acid, it can be easy to and above-mentioned metal or semimetal oxygen
Compound reaction generates p-methyl benzenesulfonic acid (including its homologue) salt；(O/ (C+H)) and (atomic ratio) of (O/C) are small in molecular structure
To being enough that it is made to keep local reaction area to be in strong reducing property environment in high temperature thermal response.Under laser irradiation, local is anti-
Answer area to be under strong reducing property environment, reaction obtains following product: 1. element sulphur will be reduced simultaneously and metallic atom generates dark color
Sulfide；(2) small (O/C) (atomic ratio) makes to generate residual carbon in pyrolysis.In this way, thermal decomposition product-the carbon and A of P
Thermal decomposition product-dark color sulfide, carbide and carbon residue, under positive coopertive effect so that formed label color ratio do not have
Intramolecule reacts Shi Gengshen；Therefore add what the polymer of the less amount of A by chemical modification was obtained through mark
Two-dimension code pattern can reach machine-scannable identification grade.
Obviously, the mechanism of this particulate composition is the optical and thermal point inside the compound molecule inside additive particulate
Solution reaction and additive particulate inside pyrolysis carries out simultaneously, make along with the fever by additive particulate wrap in
The pyrolysis of polymer outside it；Obviously it is not influenced by the kind and structure in wrapping in the polymer outside it, thus
It can be suitably used for the mixture of any kind polymer or polymer, such as thermoplastic resin, thermosetting resin and elastomer.?
In the case that polymer is thermosetting resin, it is also suitable their precursor polymer and combinations thereof.This intramolecule simultaneously
Reaction do not need heat transfer and mass transport process, therefore than need by heat transfer and mass transfer additive have reaction more rapidly, energy
Amount utilizes more efficient feature.
The increase with bombardment with laser beams energy is also known that from above-mentioned mechanism, the temperature of additive particulate will be higher,
Decomposition reaction will be fiercer, and the color of label can be deeper；Operating distance degree of the particle to the thin layer for the P being wrapped in outside it simultaneously
It will increase, the area of obtained spot also will be enlarged by, so as to reduce resolution ratio or the clarity of label.
Foundation of the invention:
1 as described in above-mentioned document, and laser marking additives particle is in by the state of polymer wrapped, therefore in laser
The extremely short moment of impulse action can be laser marking additives particulate composition and the polymer thin for being wrapped in its surface
The tiny area of layer regards an isolated system as, it gets along well, and there are mass transfers and diabatic process for atmosphere.
In the molecular structure of the p-methyl benzenesulfonic acid such as 2 iron, nickel, cobalt, lead, tin, antimony, bismuth (including its homologue) salt (O/C+H)
(atomic ratio) of (O/C), which is small enough to, makes it establish strong reducing property environment in local reaction region in high temperature thermal response；
In such a case, their thermal decomposition product has: (1) element sulphur will be reduced and generate coloured sulfide with metallic atom；
(2) small (O/C) (atomic ratio) makes pyrolysis not only establish strong reducing property environment, but also generates carbide and residual carbon.
The presence of 3 residual carbons also confirm above-mentioned 1 and 2 in turn described in mechanism.
The coloured sulfide of the thermal decomposition product-of 4 above-mentioned p-methyl benzenesulfonic acid (including its homologue) salt, carbon (including carbonization
Object) and polymer heated reaction product carbon (including carbide), under positive coopertive effect so that formed label color ratio
The carbon only thermally decomposed to yield by polymer it is darker.
The present invention is to realize above-mentioned technical purpose by following technological means.
P-methyl benzenesulfonic acid (including its homologue): benzene sulfonic acid, toluenesulfonic acid, acid dimethyl and detergent alkylate sulphur
Acid is all very strong acid；They can directly and basic anhydride reaction generates salt.Have to react by Acid-Base in the market and close
At copper p-toluenesulfonate, the benzene sulfonates supply of commodities such as p-methyl benzenesulfonic acid iron and dodecyl benzene sulfonic acid iron；Document has report
The method for leading copper dodecylbenzenesulphate.They are all to be concentrated, tied after directly being reacted in aqueous solution by corresponding Acid-Base
Crystalline substance is dried to obtain.Because p-methyl benzenesulfonic acid (including its homologue) is strong acid, even if above compound do not have commodity, do not have
Reported in literature should not also have technical difficulty using acid-base reaction preparation above compound.Antimony oxide is iron, nickel,
Cobalt, antimony, bismuth, lead, most weak one of the oxides such as tin neutral and alkali, it is also one that in Acid-Base and salt-forming reaction activity is worst；
Therefore, by that by taking the reaction product of p-methyl benzenesulfonic acid and antimony oxide as an example, can demonstrate again that above-mentioned oxide can be with
P-methyl benzenesulfonic acid (including its homologue) carries out salt-forming reaction.Through the XRD analysis to p-methyl benzenesulfonic acid and antimony oxide product,
When p-methyl benzenesulfonic acid relative usage increases, the strength reduction of the spectral line of antimony oxide is so that disappear (seeing attached list 1), in spectrogram
One group of spectral line that cannot belong to antimony oxide is seen, although there is no the spectral line of p-methyl benzenesulfonic acid antimonic salt for control on document
Compare, but according to the kind that feeds intake, feed ratio and reaction principle, it is only possible to be antimony oxide and p-methyl benzenesulfonic acid reaction life
At salt；The above-mentioned spectral line for not belonging to antimony oxide is only possible to be the reaction for belonging to p-methyl benzenesulfonic acid and antimony oxide
The spectral line of product.
The preparation of laser marking additives particle:
P-methyl benzenesulfonic acid (including its homologue) is strong acid, can be with oxide (or hydrate of its oxide) water-soluble
It is evaporated after being reacted in liquid, then in 110 DEG C of -140 DEG C of drying 30min, cooling is milled down to D50 between 10-50um.
The preparation and performance measurement of mark sample:
It is blended, is granulated with conventional method, the polymer containing laser marking additives particulate composition is made in tabletting
Test piece.
The model KDD-50 institute laser marking machine mark produced with Suzhou Kai Tai laser Science and Technology Ltd..The work of mark
Skill condition: electric current: 9-13A；Scanning speed: 500-2000mm/min.
Color difference is measured with the color difference meter of the model 7000A of X. Rite Inc., the U.S..According to the CIE Lab colour space, from survey
The Δ L that must be marked, Δ a and Δ b, are calculated Δ E.According to reported in literature, when total color difference Δ E > 4 of label, the label
It is distinguished.
The label obtained under the conditions of to different marks Δ E statistics and and 15 × 15mm text are as follows:
The possibility that the image in 2 D code of " cczu.edu.cn " is known in machine scans has following rule:
1 requires certain color difference in machine scans identification image in 2 D code；
The 2 available higher color difference of mark electric current improved；
The 3 mark electric currents (power) improved as previously described may make the clarity decline for forming the unit of image, influence machine
The possibility of device scanning recognition；
As previously mentioned, the mechanism of action of physical modification is: being reacted between the interface of A, I and P, the biography of this reaction
Matter and the resistance of heat transfer are all relatively large, and are made based on the contribution of colour generation with the thermal decomposition product of P to label.
It is the embodiment of this technology below.
Embodiment 1
By Sb2O3: p-methyl benzenesulfonic acid=1:2 (molar ratio) obtains composition in (110 DEG C) reactions.Polymer P E.Mark is swept
Retouch speed: 500mm/s.The color of the polymer of particulate composition after processing: white is added.
Test result
Embodiment 2
By Sb2O3: 125 DEG C of reactions of p-methyl benzenesulfonic acid=1:4 (molar ratio) obtain composition.Polymer P E.Mark scanning speed
Degree: 500mm/s.It is still white that the color of the polymer of particulate composition after processing, which is added,.
Test result
Comparative example data
Comparative example 1, embodiment 2 and comparative example data can be confirmed with the modified Sb of p-methyl benzenesulfonic acid2O3Identical
Sb2O3The Δ E of label can be significantly increased under content；P-methyl benzenesulfonic acid radical content height is than inefficient fruit especially in additive
It is more significant.Embodiment 3
By Bi2O3: 110 DEG C of reactions of p-methyl benzenesulfonic acid=1:2 (molar ratio) obtain composition.Polymer P E.Mark scanning speed
Degree: 500mm/s.The color of the polymer of composition after processing: white is added.
Test result
| Composition levels/% | Bi2O3Content % | Mark electric current/A suitable for machine scans identification image in 2 D code |
| 0.4 | 0.23 | 11-13 |
Embodiment 4
By Bi2O3: 110 DEG C of reactions of p-methyl benzenesulfonic acid=1:2 (molar ratio) obtain composition.Polymer TPU.Composition contains
Amount: 0.4/%；Bi2O3Content: 0.23%.
The color of the polymer of composition after processing: white is added.
Test result
Embodiment 5
By Bi2O3: p-methyl benzenesulfonic acid=1:4 (molar ratio) obtains composition in 110 DEG C of reactions.Polymer TPU.Composition
Content: 0.4/%；Bi2O3Content: 0.17%.Mark scanning speed: 500mm/s.The polymer of composition is added after processing
Color: white.
Test result
| Mark scanning speed mm/min | Mark electric current/A suitable for machine scans identification image in 2 D code |
| 500 | 9-13 |
| 1000 | 10-13 |
Embodiment 6
By Bi2O3: p-methyl benzenesulfonic acid=1:6 (molar ratio) obtains composition in 110 DEG C of reactions.Polymer P E.Mark scanning
Speed: 500mm/s.The color of the polymer of composition after processing: white is added.
Test result
| Composition levels/% | Bi2O3Content % | Mark electric current/A suitable for machine scans identification image in 2 D code |
| 0.4 | 0.13 | 13 |
Embodiment 7
By Fe2O3: p-methyl benzenesulfonic acid=1:4 (molar ratio) obtains composition in 140 DEG C of reactions.Composition levels:
0.4/%；Fe2O3Content: 0.083%.Polymer P E.It is in light brown red that the color of the polymer of composition after processing, which is added,.
Test result
| Mark scanning speed mm/min | Mark electric current/A suitable for machine scans identification image in 2 D code |
| 500 | 11-13 |
| 1000 | 13 |
The XRD spectral line that 1 p-methyl benzenesulfonic acid of subordinate list and antimony oxide react to obtain composition compares
RI indicates that RI is most strong with 1 in table, and weakens according to the increasing of number.
Claims (2)
1. a kind of preparation method of the composition additive for laser labelling, it is characterised in that the composition additive by
One or several kinds of mixtures and its precursor composition of the reaction product of the p-methyl benzenesulfonic acid of iron, nickel, cobalt, lead, tin, antimony or bismuth,
Wherein metal ion is with the molar ratio of its corresponding metal oxide and p-methyl benzenesulfonic acid root: 1:2-6；The preparation method according to
Following step carries out: metal oxide and p-methyl benzenesulfonic acid are heated after reacting in aqueous solution and are evaporated, then at 110 DEG C -140 DEG C
30min is dried, cooling is milled down to D50 between 10-50um；
The metal oxide is with molecular formula MO, M2O3Or MO2It indicates；Wherein M is iron, nickel, cobalt, lead, tin, antimony or bismuth.
2. a kind of preparation method of composition additive for laser labelling according to claim 1, it is characterised in that
The p-methyl benzenesulfonic acid is replaced by its homologue, p-methyl benzenesulfonic acid homologue are as follows: benzene sulfonic acid, toluenesulfonic acid, dimethyl benzene sulphur
Acid or dodecyl benzene sulfonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610704782.6A CN106317565B (en) | 2016-08-22 | 2016-08-22 | A kind of composition additive for laser labelling |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610704782.6A CN106317565B (en) | 2016-08-22 | 2016-08-22 | A kind of composition additive for laser labelling |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106317565A CN106317565A (en) | 2017-01-11 |
| CN106317565B true CN106317565B (en) | 2019-07-26 |
Family
ID=57741421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610704782.6A Expired - Fee Related CN106317565B (en) | 2016-08-22 | 2016-08-22 | A kind of composition additive for laser labelling |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106317565B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107057301B (en) * | 2017-05-13 | 2019-04-19 | 广东圆融新材料有限公司 | A kind of fire-retardant reinforced PBT composite material and preparation method thereof of excellent laser printing effect |
| CN110590611B (en) * | 2019-09-11 | 2021-11-02 | 常州大学 | Laser marking additive and preparation method and application thereof |
| CN113621150A (en) * | 2021-08-20 | 2021-11-09 | 江苏澳盛复合材料科技有限公司 | Carbon fiber reinforced polycarbonate composite material and molded product prepared from same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101039997A (en) * | 2004-10-15 | 2007-09-19 | 化学制造布敦海姆两合公司 | Pigment for laser-writable plastic materials and use thereof |
| CN101987922A (en) * | 2009-08-04 | 2011-03-23 | 三星Total株式会社 | Resin composition for a white laser marking |
| CN102356131A (en) * | 2009-03-18 | 2012-02-15 | 默克专利股份有限公司 | Pigment for laser marking |
-
2016
- 2016-08-22 CN CN201610704782.6A patent/CN106317565B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101039997A (en) * | 2004-10-15 | 2007-09-19 | 化学制造布敦海姆两合公司 | Pigment for laser-writable plastic materials and use thereof |
| CN102356131A (en) * | 2009-03-18 | 2012-02-15 | 默克专利股份有限公司 | Pigment for laser marking |
| CN101987922A (en) * | 2009-08-04 | 2011-03-23 | 三星Total株式会社 | Resin composition for a white laser marking |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106317565A (en) | 2017-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106317565B (en) | A kind of composition additive for laser labelling | |
| JP4827920B2 (en) | Laser imaging method using malonate or aldonate | |
| CN109963702B (en) | Additives for laser-markable and laser-weldable polymer materials | |
| CN107849290B (en) | Laser markable polymers and coatings | |
| CN107075260B (en) | Laser-markable and laser-weldable polymer material | |
| JP5209968B2 (en) | Pigments for laser writable plastic materials and their use | |
| RU2666872C1 (en) | Doped copper (ii) hydroxide-phosphate, method for producing same and use thereof | |
| US20050269304A1 (en) | Laser coding | |
| CN107345029A (en) | Laser carving master batch, can laser marking be high flows high brilliant black polypropene composition and preparation method thereof | |
| KR102501334B1 (en) | Antimony-Free Compositions for Laser Marking Thermoplastic Compounds | |
| CN107107640B (en) | Laser-markable and laser-weldable polymer material | |
| CN107057301B (en) | A kind of fire-retardant reinforced PBT composite material and preparation method thereof of excellent laser printing effect | |
| CN111718557B (en) | Polymer/modified organic montmorillonite laser marking material and preparation method and antibacterial application thereof | |
| Pering et al. | Investigation of solution-based synthesis of non-toxic perovskite materials using Mg, Ca, Mn, Fe, Cu, and Zn as the B-site cation for photovoltaic applications | |
| CN107662948A (en) | A kind of preparation method of tungstic trioxide nano-slice | |
| CN101230190B (en) | Laser markable polyamide composition and preparation method thereof | |
| JP2005075674A (en) | Laser-markable compound oxide | |
| KR100618083B1 (en) | Invisible-Light Absorption Material and Ink and Manufacturing Method of the same | |
| CN115595145A (en) | Preparation method and application of nitrogen-zinc doped carbon dot-hydrotalcite nanocomposite | |
| CN112119128B (en) | Laser additives and their use in polymeric materials | |
| Ning et al. | Preparation and Application of Sb2o3@ Sno2 Core-Shell Functional Materials for Laser Labeling | |
| JPH0647646B2 (en) | Epoxy resin composition for laser printing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190726 Termination date: 20210822 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |