CN110590611A - Laser marking additive and preparation method and application thereof - Google Patents
Laser marking additive and preparation method and application thereof Download PDFInfo
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- CN110590611A CN110590611A CN201910857277.9A CN201910857277A CN110590611A CN 110590611 A CN110590611 A CN 110590611A CN 201910857277 A CN201910857277 A CN 201910857277A CN 110590611 A CN110590611 A CN 110590611A
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- laser marking
- additive
- compound
- marking additive
- sulfonic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/04—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing only one sulfo group
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Abstract
The invention discloses a laser marking additive and a preparation method thereof, wherein a product obtained by the reaction of sulfonic acid and an M compound (the M compound is an oxide containing antimony or bismuth or a hydrate of the oxide containing antimony or bismuth) is washed by water to remove freepost-HA compound; the preparation method comprises the following steps of according to the feeding molar ratio of M to sulfonic acid: 1: 0.05-2.00, heating in water solution for reaction, dispersing with water, filtering, washing filter cake for many times to remove free HA, drying to obtain compound, grinding compound to grain size D501-9 μm to obtain the laser marking additive. The additive can be used for light-color or dark-color polymers, and can display dark-color marks in the former or light-color marks in the latter under the irradiation of laser with the wavelength of 1.06 mu m; the two-dimensional code image of the mark reaches the machine scannable identification level.
Description
Technical Field
The invention belongs to the technical field of laser marking, and particularly relates to a laser marking additive, and a preparation method and application thereof.
Background
The laser marking technology has the characteristics of high speed, high efficiency, energy conservation, environmental protection and the like, is widely applied to industrial production, and has unique advantages in the field of processing of plastic (polymer) products. In particular, the laser marking product has the advantages of longer service life, scratch resistance and the like compared with a printing product. A Nd: YAG pulse laser emitting a wavelength of 1.06 μm is a commonly used marking device. Most of the polymers have high transmittance for light having a wavelength of 1.06. mu.m, and thus cannot be directly marked by laser. For this purpose, laser marking additives are added to the polymer. To improve laser marking efficiency, a synergist may be added to the laser marking additive. The techniques disclosed in US4816374, CN1152911, CN102597081 and the like are all physical modification and synergy methods for processing and shaping after mixing laser marking additives and synergists. CN106317565A discloses a synergistic method of chemical modification. The above laser marking additives have only the function of "blacking out" i.e. showing a dark mark on a light-colored polymer. Another class of laser marking additives that only have the function of "black and white" (i.e., to show a light marking on a polymer with a dark color) is disclosed in US5445923, 5866644, 61274575, etc. (using laser wavelengths of 1.06 μm or 10600 μm). No laser marking additive with the dual functions of 'white blacking' and 'black whiteing' is reported in the literature.
Although the CN106317565A patent technology has synergistic effect of chemical modification, the disadvantage is that the additive of the composition contains p-toluenesulfonic acid as precursor, so the following disadvantages exist: (1) the p-toluenesulfonic acid is in a molten state under the reaction condition and becomes a binder of other reaction products in the cooling solidification process, so that the p-toluenesulfonic acid forms hard blocks adhered to the wall of the reactor, and the subsequent processing (namely, the reaction products are taken out of the reactor and ground) is difficult; (2) the presence of p-toluene sulfonic acid in the composition additives may affect the stability of certain polymers and corrosion of post processing equipment.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a laser marking additive and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a laser marking additive comprises the following steps: dispersing, filtering and washing a product obtained by the sulfonic acid reaction of the M compound in water in sequence until the pH value of a washing solution is more than or equal to 5, drying and cooling the washed product at 105-140 ℃ to obtain a compound, and grinding the prepared compound to D50Obtaining the laser marking additive within 1-9 mu m;
the molar ratio of the M compound to the sulfonic acid is 1.00: 0.05-2.00; the M compound is an oxide containing antimony or bismuth, or a hydrate of the oxide containing antimony or bismuth; the sulfonic acid is a compound containing sulfo and phenyl, and the sulfo is directly connected with the phenyl. Further, the sulfonic acid is p-toluenesulfonic acid or a homologue thereof.
A laser marking additive is prepared by the preparation method of the laser marking additive.
Use of an additive for laser marking in a thermoplastic or thermoset polymer material by:
the additive for laser marking is directly mixed into a thermoplastic or thermosetting polymer material, preferably, the mass percentage of the additive for laser marking in the thermoplastic or thermosetting polymer material is 0.05-1%; or, the additive for laser marking is processed into master batches, and then the master batches are mixed into thermoplastic polymer granules for injection molding, wherein the mass percentage of the additive for laser marking in the master batches is preferably 5-25%.
The application method of the additive for laser marking in the coating comprises the following steps: the additive for laser marking is uniformly mixed into liquid paint, and the liquid paint is brushed or sprayed to form a coating, wherein the thickness of the coating is 10-70 mu m.
Compared with the prior art, the preparation method of the laser marking additive comprises the following treatment processes of washing and the like, wherein the product is washed by water to remove free sulfonic acid (the definition of the free sulfonic acid is that unreacted sulfonic acid contained in the reaction product and sulfonic acid generated by hydrolysis of partial reaction product in the washing process) to obtain a compound (the definition of the compound is that the compound is fed according to a certain proportion, the free sulfonic acid is removed from the product obtained after the reaction through washing, and the mixture is dried).
The two-dimensional code icon printed after the prepared laser marking additive is applied to thermoplastic or thermosetting polymer can reach the machine scannable recognition level; the prepared laser marking additive has the following advantages: (1) the prepared powder product is convenient for subsequent processing; (2) the product does not contain free sulfonic acid, and the stability of some polymers cannot be influenced; (3) the post-processing equipment cannot be corroded; (4) less than the technique disclosed in CN 106317565A; (5) the image has higher definition; (6) under the irradiation of 1.06 μm laser, the product has the dual functions of 'black and white beating' under the condition of changing the compatibility condition (the compatibility condition is defined as the compatibility of the additive, different polymers and the auxiliary agents).
The basis of the invention is as follows:
1. experiments have shown that the water washing process removes free sulphonic acid and gives a loose powdered compound which is nearly neutral, stable in water, convenient for subsequent processing and grinding.
2. Experiments prove that when the doping amount of the additive is reduced to 0.05 percent (mass) of the polymer, a clear marking image can be obtained, and the two-dimensional code image reaches the machine scannable identification level.
3. Although the components, molecular formulas and structures of the additives cannot be provided at present, and the mechanism of the additives with double functions of ' black striking and ' black striking ' cannot be provided, experiments prove that the additives are really efficient additives with double functions, so the related theories and mechanisms are the problems to be paid attention to and solved by theoretical workers in the future.
P-toluenesulfonic acid (HA), including homologs thereof: benzene sulfonic acid, methyl benzene sulfonic acid, dimethyl benzene sulfonic acid and dodecyl benzene sulfonic acid are all very strong acids; they are all reactive with the oxide of M and are therefore all obtainable by the process for the preparation of the additives described above.
As mentioned above, unlike the technology disclosed in CN106317565A, the key measure is to add a process of washing with water to remove the free sulfonic acid in the reaction product in the process of preparing the compound, so that the product becomes a nearly neutral, powdery product stable in water; therefore, the laser marking additive of the present invention has the aforementioned advantages (1) to (6).
Detailed Description
The invention is described in more detail below with reference to the following examples:
the charge ratio (molar ratio) for preparing the compound is as follows: m: HA 1.00: 1.00 for example:
weigh 30.0 mmoles of Bi2O3In a 100ml round bottom flask, the round bottom flask was placed in an oil bath and 60.0 mmole HA and 20ml water were added. After uniform mixing, heating the oil bath to 115 ℃, quickly changing the color of a reactant from yellow at the beginning to white, then heating to 120 ℃ to react for 2.5 hours, then thickening the reactant from white paste to a basically non-flowing state, cooling, heating with 30ml of water to disperse the reactant, transferring the dispersed material into a Buchner funnel for filtering, and then transferring the reactant into the Buchner funnel with 20ml of water for suction filtration; the filtrate was tested at pH 1.0 (precision pH paper range 0.5-5). The filter cake was dispersed by beating with 30ml of water, and the above-mentioned filtration, transfer, and suction filtration were repeated 2 times. The final filtrate had a pH of 5.0, and the resulting filter cake was dried at 120 ℃ and cooled to give a powdery compound; grinding the compound gave a white additive. The HA content in the filtrate and wash liquor during the above water washing was about 5 millimoles, from which Bi: HA ≈ 1: 0.91 in the white compound was calculated.
The similar process is used for preparing the raw materials with the following charge ratio (molar ratio): when M: HA is 1.00: 2.00(120.0 mmole) of the compound, the HA content in the filtrate and wash liquor during the water wash is about 10.5 mmole, from which Bi: HA is calculated to be 1: 1.84 in the white compound.
This technique was compared with the method disclosed in CN106317565A, albeit in the preparation of M of the additive2O3In part the same as the molar ratio of HA, but the water washing process of the present technology caused the compound to differ from the composition additive disclosed in CN106317565A, the M: HA (molar ratio) in the compound was slightly greater than the feed molar ratio after the compound of the present technology was washed with water to remove free HA from the product. For example, in the above example, the molar ratio of M to HA is increased from 1.00: 1.00 to nearly 1: 0.91. The XRD data demonstrate that: the compound obtained by the water washing process and the additive of the composition obtained by the non-water washing process disclosed in CN106317565A are materials with different compositions (see attached 1). Batch feed ratio in comparative attachment 1: the additive and additive of the composition prepared at Bi: HA of 1.00: 2.00 also had different XRD, which proved that they were substances of different compositions.
The XRD of the additive prepared in the Bi: HA ratio of 1.00: 0.038-0.050 is given in the accessory 1. And (3) displaying data: except that Bi: HA is 1.00: 0.038, the compound and Bi2O3Similarly, the XRD of the compound differs from that of Bi at a Bi: HA ratio of 1.00: 0.047 and a Bi: HA ratio of 1.00: 0.0502O3。
From the literature available, it is only possible to determine the presence of M in the reaction product2O3And HA, but no reference XRD standard spectrum data was found, the formula of the additive and its structure could not be determined, and thus was characterized by the molar ratio of the feeds.
Raw materials for preparing the additive:
bismuth oxide: micron-sized, industrial-grade, content 99.9%.
Antimony oxide: micron-level, industrial-level, and the content is 99.0-99.5%.
P-toluenesulfonic acid (monohydrate), technical grade: the content is 93-99%.
The additives prepared by the above process are shown in Table 1.
TABLE 1 feed ratio for the preparation of additives
The use mode of the additive is as follows:
use of the additive micropowder: the additive micro powder is directly mixed with thermoplastic polymer granules according to a conventional method and processed by a conventional injection molding process, and the dosage of the additive is 0.1 to 1 percent (mass) of the thermoplastic polymer.
Preparing additive masterbatch: mixing the raw materials by using auxiliary agents such as a carrier, color master batches, an antioxidant, a dispersing agent and the like according to a conventional master batch formula, and processing the mixture into granular master batches by a conventional double-screw extrusion process. The mixing amount of the additive in the master batch is 5 to 25 percent (mass) of the master batch. PE and TPU are listed in Table 2.
TABLE 2 additive content in masterbatch and polymers suitable for use
Preparation of the additive-containing coating:
the additive is suitable for coatings which are film-forming substances such as phenolic compounds, alkyd compounds, amino compounds, nitro compounds, epoxy compounds, chlorinated rubbers, acrylic compounds, polyurethane compounds, vinyl resins and the like.
The additive can be used for single-component coating or double-component cross-linked film-forming coating, and the dosage of the additive is 0.05-1% of the solid content of the coating. The film thickness is 10 to 70 μm.
For example: two-component coating of acrylic resin: the amount of acrylic resin (60% solids, curing agent in 30% resin) and diluent (ethyl acetate: xylene 1: 1 (volume ratio)) was about 1/3 for the acrylate two-component coating. ② aqueous polyurethane coating: 16g of dark green waterborne polyurethane coating (manufactured by Shaoguan Deke beautifying chemical Co., Ltd., brand number W6637), 2g of curing agent (model number W7135) and 2g of water.
The coating formulation is not limited to the above examples and may be other conventional formulations, formulated by conventional techniques.
Preparing a standard sample and measuring the performance:
blending, granulating, tabletting, spraying and brushing by a conventional method to prepare a test piece of the polymer containing the particulate additive.
The mark is marked by a laser marking machine manufactured by Suzhou Kaitai laser technology Co., Ltd, with the model of KDD-50. Marking process conditions are as follows: current: 12A; scanning speed: 450 mm/min.
Two-dimensional code images of marks obtained under different marking conditions: markable (in OK), not markable (in x); machine scanning and recognition: recognizable (in OK) and unrecognizable (in x).
The following are examples of the present technique, see Table 3, for examples 1-18, powdered additives for direct use in light colored polymer injection molding processes.
TABLE 3
Except that the black mark was not recognized by machine scanning when the additive was added in an amount of 0.05% in examples 1 and 10, the black mark was recognized by machine scanning when the additive was added in an amount of 0.10% or more.
Examples 19-26 masterbatches with additive loadings of 5% to 25% by mass were used in light-coloured polymer injection moulding processes, see table 4.
TABLE 4
The black marks are machine scan identifiable.
Examples 27-41 acrylic two-component coatings, a natural (unpigmented) coating, were applied to an epoxy board as shown in Table 5.
Except for the additive of example 27-example 37, the addition amount of which is 0.05-1.0%, and the film thickness of which is 10-70 μm, the black mark can be identified by machine scanning.
Examples 42-53 waterborne polyurethane coatings, dark green coatings were applied to polyurethane plaques, see Table 6.
TABLE 6
When the doping amount of the additive is more than or equal to 0.10%, the film thickness is 10-50 μm, and the near-white marks can be scanned and identified by a machine.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the spirit of the present invention, and these are all within the scope of the present invention.
Accessory 1
XRD of additives prepared by different feeding molar ratios
XRD of additive prepared without and with water washing
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.
Claims (6)
1. A preparation method of a laser marking additive is characterized by comprising the following steps: the method comprises the following steps: dispersing, filtering and washing a product obtained by the sulfonic acid reaction of the M compound in water in sequence until the pH value of a washing solution is more than or equal to 5, drying and cooling the washed product at 105-140 ℃ to obtain a compound, and grinding the prepared compound to D50Obtaining the laser marking additive within 1-9 mu m;
the molar ratio of the M compound to the sulfonic acid is 1.00: 0.05-2.00; the M compound is an oxide containing antimony or bismuth, or a hydrate of the oxide containing antimony or bismuth; the sulfonic acid is a compound containing sulfo and phenyl, and the sulfo is directly connected with the phenyl.
2. The method of preparing a laser marking additive according to claim 1, wherein: the sulfonic acid is p-toluenesulfonic acid or a homologue thereof.
3. A laser marking additive characterized by: is prepared by the method for preparing the laser marking additive as described in claim 1 or 2.
4. The application of the laser marking additive in thermoplastic or thermosetting polymer materials comprises the following steps:
mixing the laser marking additive of claim 3 directly into a thermoplastic or thermoset polymer material; alternatively, the laser marking additive of claim 3 is processed into a masterbatch, and the masterbatch is then mixed into thermoplastic polymer pellets for injection molding.
5. Use of a laser marking additive according to claim 4 in thermoplastic or thermoset polymer materials, wherein: the mass percentage of the laser marking additive in the thermoplastic or thermosetting polymer material is 0.05-1%; the mass percentage of the laser marking additive mixed in the master batch is 5-25%.
6. The application method of the additive for laser marking in the coating is as follows: the laser marking additive according to claim 3 is uniformly mixed into a liquid coating, and a coating is formed by brushing or spraying, wherein the thickness of the coating is 10-70 μm.
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| CN105330898A (en) * | 2015-12-08 | 2016-02-17 | 四川大学 | Laser marker additive and preparation method and application thereof |
| CN105916812A (en) * | 2014-01-16 | 2016-08-31 | 默克专利股份有限公司 | Pigments based on bismuth compounds |
| CN106317565A (en) * | 2016-08-22 | 2017-01-11 | 常州大学 | Composition additive for laser marker |
| EP3281974A1 (en) * | 2016-08-11 | 2018-02-14 | Innocabs B.V. | Laser marking additive |
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2019
- 2019-09-11 CN CN201910857277.9A patent/CN110590611B/en active Active
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|---|---|---|---|---|
| CN1403514A (en) * | 2002-09-06 | 2003-03-19 | 上海工程技术大学 | Laser-absorbing nano oxide paint |
| CN102597081A (en) * | 2009-10-29 | 2012-07-18 | 帝斯曼知识产权资产管理有限公司 | Laser-marking additive |
| CN105916812A (en) * | 2014-01-16 | 2016-08-31 | 默克专利股份有限公司 | Pigments based on bismuth compounds |
| CN105330898A (en) * | 2015-12-08 | 2016-02-17 | 四川大学 | Laser marker additive and preparation method and application thereof |
| EP3281974A1 (en) * | 2016-08-11 | 2018-02-14 | Innocabs B.V. | Laser marking additive |
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