CN115772362B - Laser ablation composition for flexographic printing plate and preparation method thereof - Google Patents
Laser ablation composition for flexographic printing plate and preparation method thereof Download PDFInfo
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- CN115772362B CN115772362B CN202211642878.6A CN202211642878A CN115772362B CN 115772362 B CN115772362 B CN 115772362B CN 202211642878 A CN202211642878 A CN 202211642878A CN 115772362 B CN115772362 B CN 115772362B
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- 238000003756 stirring Methods 0.000 claims description 31
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Landscapes
- Materials For Photolithography (AREA)
Abstract
The invention relates to a laser ablation composition for a flexible printing plate and a preparation method thereof, belonging to the technical field of flexible printing plates, and comprising the following raw materials in percentage by mass: 15-20% of modified carbon black, 15-20% of polymer binder and the balance of solvent; the preparation method comprises the following steps: the modified carbon black, the polymer binder and the solvent are weighed according to the formula proportion and uniformly mixed, the self-made modified carbon black is added into the laser ablation composition prepared by the invention, the compatibility with a matrix is good, agglomeration and deposition are not easy to occur, the generation of pits is reduced, the end part of the hyperbranched polymer is grafted with the sensitizer, the introduction of the sensitizer can improve the photosensitivity of the laser ablation composition, the introduction of laser dye is not needed, the energy required by ablation is reduced, and the generation of edge burrs of an ablation pattern is reduced.
Description
Technical Field
The invention belongs to the technical field of flexographic printing plates, and particularly relates to a laser ablation composition for a flexographic printing plate and a preparation method thereof.
Background
Flexography is printing by using a flexography plate and using an anilox roller to transfer ink, and is one of relief printing processes, and is called flexography for short.
The flexographic printing plate was manufactured as follows: (1) Irradiating ultraviolet rays on the back surface of the photosensitive resin composition layer on the substrate, and exposing to light, thereby providing a uniform cured layer; (2) Removing a part of the laser ablation layer by peeling off the cover film on the laser ablation layer, exposing the laser ablation layer, and irradiating laser to draw a pattern, thereby manufacturing an image mask; (3) Irradiating the photosensitive resin composition layer with ultraviolet relief exposure from the image mask to photo-cure the portion from which the laser ablation layer was removed; (4) The non-exposed portions (i.e., the portions not photo-cured) of the photosensitive resin composition layer were removed to form a relief image as a desired image, thereby obtaining a flexographic printing plate.
Where some ash is generated during laser ablation, which may be collected by a closed exhaust system, sent to an incinerator or disposed of as waste. The only work-up procedure required is a water wash and a short drying process to remove residual ash. Therefore, the laser direct imaging plate making technology process simultaneously solves the problem of wastewater discharge.
The technology has the obvious advantages of environmental protection, can perform accurate tone correction, can obtain the best dark tone area without influencing a highlight area, improves the printing plate quality and the printing quality, and obviously increases the market share of flexographic printing.
However, the laser ablation composition for the existing flexographic printing plate has low light sensitivity, high energy required for ablation, the obtained ablation pattern generates more edge burrs, the printing quality is reduced, and the radiation absorbing compound (dye, carbon black and graphite) in the laser ablation composition is unevenly dispersed, so that the surface of the laser ablation layer obtained by coating has pits, and when laser engraving is carried out in the presence of the pits, the photosensitive resin composition contacted with the pits is exposed, so that an image which is not needed is easily formed, and the subsequent printing effect is influenced.
Disclosure of Invention
The invention provides a laser ablation composition for a flexible printing plate and a preparation method thereof, which solve the technical problems that the existing laser ablation composition is low in light sensitivity and uneven in dispersion of internal radiation absorbing compounds (dye, carbon black and graphite).
The aim of the invention can be achieved by the following technical scheme:
a laser ablation composition for flexographic printing plates comprising the following raw materials in mass percent: 15-20% of modified carbon black, 15-20% of polymer binder and the balance of solvent;
the laser ablation composition for flexographic printing plates is made by the steps of:
weighing modified carbon black, a polymer binder and a solvent according to the formula proportion, and adding the mixture into a mixer to mix for 3-5 hours to obtain the laser ablation composition for the flexographic printing plate.
Further, the polymer binder is one of a polyamide resin, a polyolefin resin, an acrylic resin, a polyacetal resin, a polybutadiene resin, and a polycarbonate resin, and preferably is a polyamide resin.
Further, the modified carbon black is prepared by the following steps:
step a, adding triethylenetetramine into a flask, adding a methanol solution of butyl acrylate, stirring at normal temperature under the protection of nitrogen for reacting for 5-6 hours, then distilling under reduced pressure to remove methanol, heating to 140 ℃, and continuing stirring for reacting for 4-5 hours to obtain amino-terminated hyperbranched polyamide;
wherein, the mole ratio of triethylenetetramine to butyl acrylate is 1:1, the ratio of butyl acrylate to methanol in the methanol solution of butyl acrylate is 0.1mol:130-150mL, triethylenetetramine and butyl acrylate are used as raw materials, and amino-terminated hyperbranched polyamide is obtained through polycondensation reaction;
step b, adding acidified carbon black, EDC and HOBt into a flask, stirring and reacting for 2 hours, dropwise adding DMF solution of amino-terminated hyperbranched polyester, stirring and reacting at room temperature for 24 hours after the dropwise adding is finished, filtering after the reaction is finished, washing a filter cake with deionized water, and drying at 110 ℃ in a drying oven to constant weight to obtain an intermediate product;
wherein, the mass ratio of the acidified carbon black to the EDC to the HOBt to the amino-terminated hyperbranched polyester is 5:0.56:0.44:10.5-12.5, the dosage ratio of the amino-terminated hyperbranched polyester to DMF in the DMF solution of the amino-terminated hyperbranched polyester is 1g:20-25mL of the catalyst is used in EDC [ 1-ethyl- (3-dimethylaminopropyl) carbodiimide]And HOBt (1-hydroxybenzotriazole) to enable-COOH on the surface of the acidified carbon black and-NH of amino-terminated hyperbranched polyester 2 Amidation reaction to obtain intermediate product;
step c, adding an intermediate product, triethylamine and acetone into a flask, stirring for 3-5min, controlling the reaction temperature to be 0-5 ℃ and the rotating speed to be 300r/min, dropwise adding an acetone solution of 2-diazonium-1-naphthol-5-sulfonyl chloride while stirring, heating to 50 ℃ after the dropwise adding is finished, stirring for 4-5h, filtering after the reaction is finished, washing for multiple times with deionized water, and drying to obtain modified carbon black;
wherein the mass ratio of the intermediate product to the triethylamine to the 2-diazonium-1-naphthol-5-sulfonyl chloride is 6.8-7.5:2.63:5.9, under the action of triethylamine, enabling the intermediate product and 2-diazonium-1-naphthol-5-sulfonyl chloride to undergo nucleophilic substitution reaction to obtain the modified carbon black.
The modified carbon black is obtained by performing synergistic treatment on the surface of the carbon black, firstly introducing more active carboxyl groups, then grafting hyperbranched polymer, and finally using a photosensitizer to end cap, and the modified carbon black is added into a laser ablation composition, and has the following characteristics: the modified carbon black has high dispersibility because the hyperbranched polymer is grafted on the surface, has larger steric hindrance, is not easy to tangle molecular chains, has good compatibility with a matrix, can improve the repulsive interaction between carbon black and reduce agglomeration and deposition; secondly, the photosensitivity of the laser ablation composition is improved, on one hand, the hyperbranched polymer grafted on the surface of the modified carbon black improves the dispersity of the laser dye through the steric hindrance effect and the electrostatic repulsion effect, so that the flatness of a laser ablation layer is improved, and the generation of pits is reduced, and on the other hand, the end part of the hyperbranched polymer is grafted with a sensitizer, so that the photosensitivity of the laser ablation composition can be improved, the dosage of the laser dye is reduced, the energy required by ablation is reduced, and the generation of edge burrs of an ablation pattern is further reduced.
The acidified carbon black is prepared by the following steps:
placing carbon black in a flask, connecting a tail gas treatment device, dropwise adding concentrated nitric acid under stirring, heating to reflux reaction for 3h after the dropwise adding is finished, pouring out acid liquor on the upper layer after the reaction is finished, filtering, washing with deionized water until the washing liquid is neutral, and drying at 110 ℃ until the weight is constant to obtain acidified carbon black, wherein the dosage ratio of the carbon black to the concentrated nitric acid is 1g:10mL, the mass fraction of the concentrated nitric acid is 65%, the granularity of the carbon black is 50-300nm, and a large amount of active carboxyl groups are generated on the surface of the carbon black by oxidizing the carbon black with the concentrated nitric acid.
Further, the solvent is one of methanol, ethanol, N-propanol, isopropanol, N-butanol, cyclohexanol, hexanediol, ethyl acetate, acetone, propylene glycol monomethyl ether acetate, N-dimethylformamide, N-dimethylacetamide, toluene, cyclohexane and dioxane.
The invention has the beneficial effects that:
in order to solve the technical problems that the ablation pattern of the existing flexible printing plate generates more edge burrs and is easy to form an image which is not needed, the invention provides the laser ablation composition for the flexible printing plate, which is characterized in that the self-made modified carbon black is added, and the overall performance of the ablation composition can be effectively improved, compared with the existing composition, the invention has the following reasons:
the modified carbon black is nano-scale carbon black subjected to chemical grafting of photosensitive agent end-capped hyperbranched polyamide, the modified carbon black is added into a composition, the compatibility with a matrix is good, aggregation and deposition are not easy, and due to the steric hindrance effect and electrostatic repulsion effect of the hyperbranched polymer grafted on the surface of the modified carbon black, the dispersibility of laser dye in the matrix can be improved, the smoothness of a laser ablation layer is further improved, the generation of pits is reduced, the photosensitive agent is grafted at the end part of the hyperbranched polymer, the photosensitivity of the laser ablation composition can be improved due to the introduction of the photosensitive agent, the introduction of the laser dye is not needed, the energy required by ablation is reduced, and the generation of edge burrs of an ablation pattern is reduced.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A modified carbon black made by the steps of:
step a, adding 0.1mol of triethylenetetramine into a flask, adding 130mL of butyl acrylate methanol solution containing 0.1mol of butyl acrylate, stirring at normal temperature under the protection of nitrogen for reacting for 5 hours, then distilling under reduced pressure to remove methanol, heating to 140 ℃, and continuing stirring for reacting for 4 hours to obtain amino-terminated hyperbranched polyamide;
step b, adding 5g of acidified carbon black, 0.56g of EDC and 0.44g of HOBt into a flask, stirring and reacting for 2h, dropwise adding an amino-terminated hyperbranched polyester DMF solution containing 10.5g of amino-terminated hyperbranched polyester, stirring and reacting for 24h at room temperature after the dropwise adding is finished, filtering after the reaction is finished, washing a filter cake with deionized water, and drying the filter cake to constant weight at 110 ℃ in a drying oven to obtain an intermediate product, wherein the dosage ratio of the amino-terminated hyperbranched polyester to DMF in the amino-terminated hyperbranched polyester DMF solution is 1g:20mL;
and c, adding 6.8g of intermediate product, 2.63g of triethylamine and 80mL of acetone into a flask, stirring for 3min, controlling the reaction temperature to be 0 ℃, controlling the rotating speed to be 300r/min, dropwise adding 50mL of 2-diazonium-1-naphthol-5-sulfonyl chloride acetone solution containing 5.9g of 2-diazonium-1-naphthol-5-sulfonyl chloride while stirring, heating to 50 ℃ after the dropwise adding is finished, stirring for 4h, filtering after the reaction is finished, washing for multiple times by deionized water, and drying to obtain the modified carbon black.
The acidified carbon black is prepared by the following steps:
placing 5g of carbon black into a flask, connecting a tail gas treatment device, dropwise adding 50mL of concentrated nitric acid under stirring, heating to reflux reaction for 3h after the dropwise adding is finished, pouring out acid liquor on the upper layer after the reaction is finished, filtering, washing with deionized water until the washing liquid is neutral, and drying at 110 ℃ until the weight is constant to obtain acidified carbon black, wherein the mass fraction of the concentrated nitric acid is 65%, and the granularity of the carbon black is 50-300nm.
Example 2
A modified carbon black made by the steps of:
step a, adding 0.1mol of triethylenetetramine into a flask, adding 150mL of butyl acrylate methanol solution containing 0.1mol of butyl acrylate, stirring at normal temperature under the protection of nitrogen for reaction for 6 hours, then distilling under reduced pressure to remove methanol, heating to 140 ℃, and continuing stirring for reaction for 5 hours to obtain amino-terminated hyperbranched polyamide;
step b, adding 5g of acidified carbon black, 0.56g of EDC and 0.44g of HOBt into a flask, stirring and reacting for 2h, dropwise adding an amino-terminated hyperbranched polyester DMF solution containing 12.5g of amino-terminated hyperbranched polyester, stirring and reacting for 24h at room temperature after the dropwise adding is finished, filtering after the reaction is finished, washing a filter cake with deionized water, and drying the filter cake to constant weight at 110 ℃ in a drying oven to obtain an intermediate product, wherein the dosage ratio of the amino-terminated hyperbranched polyester to DMF in the amino-terminated hyperbranched polyester DMF solution is 1g:25mL;
step c, adding 7.5g of intermediate product, 2.63g of triethylamine and 100mL of acetone into a flask, stirring for 5min, controlling the reaction temperature to be 5 ℃, controlling the rotating speed to be 300r/min, dropwise adding 50mL of 2-diazonium-1-naphthol-5-sulfonyl chloride acetone solution containing 5.9g of 2-diazonium-1-naphthol-5-sulfonyl chloride while stirring, heating to 50 ℃ after the dropwise adding is finished, stirring and reacting for 5h, filtering after the reaction is finished, washing for multiple times by deionized water, and drying to obtain the modified carbon black.
The acidified carbon black is prepared by the following steps:
placing 5g of carbon black into a flask, connecting a tail gas treatment device, dropwise adding 50mL of concentrated nitric acid under stirring, heating to reflux reaction for 3h after the dropwise adding is finished, pouring out acid liquor on the upper layer after the reaction is finished, filtering, washing with deionized water until the washing liquid is neutral, and drying at 110 ℃ until the weight is constant to obtain acidified carbon black, wherein the mass fraction of the concentrated nitric acid is 65%, and the granularity of the carbon black is 50-300nm.
Comparative example 1
This comparative example is the acidified carbon black of example 1.
Comparative example 2
This comparative example is the intermediate product obtained in step b of example 2.
Example 3
A laser ablation composition for flexographic printing plates comprising the following raw materials in mass percent: 15% of modified carbon black of example 1, 15% of polyamide resin (Macromelt 6900 polyamide resin, henkle company) and the balance of n-butanol;
the laser ablation composition for flexographic printing plates is made by the steps of:
weighing modified carbon black, a polymer binder and n-butanol according to the formula proportion, and adding the mixture into a mixer to mix for 3 hours to obtain the laser ablation composition for the flexographic printing plate.
Example 4
A laser ablation composition for flexographic printing plates comprising the following raw materials in mass percent: 18% of modified carbon black of example 2, 18% of polyamide resin (Macromelt 6900 polyamide resin, henkle company) and the balance of isopropanol;
the laser ablation composition for flexographic printing plates is made by the steps of:
weighing modified carbon black, a polymer binder and isopropanol according to the formula proportion, and adding the mixture into a mixer to mix for 4 hours to obtain the laser ablation composition for the flexographic printing plate.
Example 5
A laser ablation composition for flexographic printing plates comprising the following raw materials in mass percent: 20% of modified carbon black of example 2, 20% of polyamide resin (Macromelt 6900 polyamide resin, henkle company) and the balance of n-propanol;
the laser ablation composition for flexographic printing plates is made by the steps of:
the modified carbon black, the polymer binder and the n-propanol are weighed according to the formula proportion and added into a mixer to be mixed for 5 hours, so as to obtain the laser ablation composition for the flexographic printing plate.
Comparative example 3
In comparison with example 3, the modified carbon black of example 3 was replaced with the material of comparative example 1, and the remaining raw materials and the production process were the same as in example 3.
Comparative example 4
In comparison with example 3, the modified carbon black of example 3 was replaced with the material of comparative example 2, and the remaining raw materials and the production process were the same as in example 3.
The laser ablation compositions obtained in examples 3 to 5 and comparative examples 3 to 4 were applied to a PET film having a thickness of 100. Mu.m, dried at 90℃for 2 minutes to obtain a laminate of a laser ablation layer having a film thickness of 2.6. Mu.m and a cover film, placed on a photometry table, subjected to microscopic examination, and the number of pits having a length of 20 μm or more were counted in the laser ablation layer, averaged, and the thickness of the film was calculated (number/m 2 ) Is a value of (2);
afterwards, the optical density of each set of the laser ablation layer to be tested and the laminate of the cover film before ablation was tested using a CDI SPAPK4835 platemaking machine (manufactured by ESKO corporation);
using a CDI SPAPK4835 plate-making machine (manufactured by ESKO Co.) at 2540ppi, the imaging speed was set to 0ptics10.0, the laser ablation layers in examples and comparative examples were ablated, and the exposure density of the ablated image was observed with Densitometer DENS (TECHKON GmbH, germany), and the smaller the exposure density, the higher the sensitivity of the laser ablation layer, the smaller the energy required, and the better the printing effect;
sensitivity evaluation criteria:
good (the edge of the ablated net point is clean and sharp without burrs, and the white exposure density of the ablated pattern is less than or equal to 0.1);
delta represents good (the edge of the ablated net point is cleaner and sharper, the burr is less, and the white exposure density of the ablated pattern is 0.1-0.2);
x represents difference (the edge of the ablated net point is cleaner and sharper, the burr is less, and the white exposure density of the ablated pattern is more than or equal to 0.2);
after the laminate ablation of each set of the laser ablation layer and the cover film to be tested was tested using a CDI SPAPK4835 platemaking machine (manufactured by ESKO corporation), the optical density at 50% of the dots;
the test results are shown in table 1:
TABLE 1
| Project | Example 3 | Example 4 | Example 5 | Comparative example 3 | Comparative example 4 |
| Pit (m/m) 2 ) | 3 | 2 | 1 | 6 | 4 |
| Optical density before ablation | 3.9 | 4.0 | 4.2 | 3.6 | 3.7 |
| Sensitivity of sensitivity | ○ | ○ | ○ | × | △ |
| 50% dot optical density | 0.30 | 0.31 | 0.32 | 0.36 | 0.34 |
As can be seen from Table 1, the laser ablatable compositions prepared in examples 3-5 had better sensitivity and the ablated layer formed was smooth and uniform, with less dishing, and the flexographic printing plates formed were of high quality as compared to comparative examples 3-4.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (9)
1. A laser ablation composition for flexographic printing plates comprising the following raw materials in mass percent: 15-20% of modified carbon black, 15-20% of polymer binder and the balance of solvent;
the modified carbon black is prepared by the following steps:
mixing acidified carbon black, EDC and HOBt, stirring and reacting for 2 hours, dropwise adding DMF solution of amino-terminated hyperbranched polyester, and stirring and reacting at room temperature for 24 hours after the dropwise adding is finished to obtain an intermediate product;
mixing the intermediate product, triethylamine and acetone, controlling the reaction temperature to be 0-5 ℃, dropwise adding an acetone solution of 2-diazonium-1-naphthol-5-sulfonyl chloride while stirring, heating to 50 ℃ after the dropwise adding is finished, and stirring for reacting for 4-5 hours to obtain modified carbon black;
the amino-terminated hyperbranched polyester is prepared by the following steps:
adding triethylenetetramine into a flask, adding a methanol solution of butyl acrylate, stirring at normal temperature under the protection of nitrogen for reacting for 5-6 hours, then distilling under reduced pressure to remove methanol, heating to 140 ℃, and continuing stirring for reacting for 4-5 hours to obtain the amino-terminated hyperbranched polyamide.
2. The laser ablation composition for flexographic printing plates according to claim 1, wherein the mass ratio of acidified carbon black, EDC, HOBt and amino terminated hyperbranched polyester is 5:0.56:0.44:10.5-12.5, the dosage ratio of the amino-terminated hyperbranched polyester to DMF in the DMF solution of the amino-terminated hyperbranched polyester is 1g:20-25mL.
3. A laser ablation composition for flexographic printing plates according to claim 1, characterized in that the mass ratio of intermediate product, triethylamine and 2-diazonium-1-naphthol-5-sulfonyl chloride is 6.8-7.5:2.63:5.9.
4. a laser ablation composition for flexographic printing plates according to claim 1, characterized in that the molar ratio of triethylenetetramine to butyl acrylate is 1:1, the dosage ratio of butyl acrylate to methanol in the methanol solution of butyl acrylate is 0.1mol:130-150mL.
5. A laser ablation composition for flexographic printing plates according to claim 1 wherein the acidified carbon black is made by the steps of:
and (3) placing the carbon black in a flask, dropwise adding concentrated nitric acid under stirring, heating to reflux for 3h after the dropwise adding, pouring out the acid liquor on the upper layer after the reaction is finished, filtering, washing and drying to obtain the acidified carbon black.
6. A laser ablation composition for flexographic printing plates according to claim 5 wherein the ratio of carbon black to concentrated nitric acid is 1g:10mL, 65% of concentrated nitric acid by mass and 50-300nm of carbon black particle size.
7. A method of preparing a laser ablation composition for flexographic printing plates according to claim 1, comprising the steps of:
weighing modified carbon black, a polymer binder and a solvent according to the formula proportion, and adding the mixture into a mixer to mix for 3-5 hours to obtain the laser ablation composition for the flexographic printing plate.
8. The method for producing a laser ablation composition for flexographic printing plates according to claim 7, wherein the polymer binder is one of a polyamide-based resin, a polyolefin-based resin, an acrylic resin, a polyacetal-based resin, a polybutadiene-based resin and a polycarbonate-based resin.
9. The method according to claim 7, wherein the solvent is one of methanol, ethanol, N-propanol, isopropanol, N-butanol, cyclohexanol, hexylene glycol, ethyl acetate, acetone, propylene glycol monomethyl ether acetate, N-dimethylformamide, N-dimethylacetamide, toluene, cyclohexane, and dioxane.
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