CN114790568B - Electrolyte for CTP plate base production - Google Patents
Electrolyte for CTP plate base production Download PDFInfo
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- CN114790568B CN114790568B CN202210572130.7A CN202210572130A CN114790568B CN 114790568 B CN114790568 B CN 114790568B CN 202210572130 A CN202210572130 A CN 202210572130A CN 114790568 B CN114790568 B CN 114790568B
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- acid
- electrolyte
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- branched polyol
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/04—Etching of light metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N3/00—Preparing for use and conserving printing surfaces
- B41N3/03—Chemical or electrical pretreatment
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention relates to an electrolyte for CTP plate base production, which belongs to the technical field of printing and comprises the following raw materials: corrosion components, surfactants and water; the corrosion components are hydrochloric acid, sulfuric acid, citric acid and phosphoric acid according to the mass ratio of 10-15:1-3:1.5-4.5:0.5-1.5. The invention adopts hydrochloric acid, sulfuric acid, citric acid and phosphoric acid as corrosion components, and can realize that the mixed acid contains inorganic acid and inorganic acid, and can achieve effective electrolysis of CTP plate base and coordinate and control the distribution uniformity of formed small pits by utilizing scientific compatibility among the mixed acids, and the surfactant is amphiphilic, so that the stability of the mixed acid solution is improved, cations are contained, the electrolysis efficiency is improved, and the mixed acid contains imidazole rings, plays a corrosion inhibition role, and plays a role in macroscopically regulating and controlling the uniformity of the size of the formed small pits.
Description
Technical Field
The invention belongs to the technical field of printing, and particularly relates to an electrolyte for CTP plate base production.
Background
The CTP plate consists of a plate base and a photosensitive layer. Wherein the substrate is commercial pure aluminum of A1050, H18. Plate-based processing generally includes the following processes: deoiling, electrolysis, ash removal, oxidation, hole sealing and the like. Wherein electrolysis has a crucial impact on the performance of CTP plates. The electrolysis is a process of generating sand, the forms of the generated sand are different from each other due to different electrolysis processes, and the quality of the forms of the sand directly influences the sensitivity, the printing resistance, the plate density and the ink balance of CTP plates in the printing process.
Existing aluminum substrate electrolysis processes typically employ electrochemical corrosion (i.e., electrochemical plating). The electrochemical plate grinding is to immerse the aluminum plate in dilute acid solution, and to apply AC to the aluminum to generate Al-Al in the positive half cycle 3+ Negative half cycle H + H2 is repeated alternately so that a number of small pits, called grains, are formed on the aluminum surface. The shape and uniformity of these "pits" is particularly important to the performance of CTP plates. The "pits" are uneven, and the thickness of the photosensitive layer coated on the pits is not uniform. At the same time, the depth of the pit is also important: too deep, the coating is too thick and requires high laser energy to easily produce bottom ash; too shallow, the photosensitive layer coated thereon is not firmly adsorbed and the print resistance is not achieved. The formation of these "pits" is affected by the electrolyte and the electrolytic process.
The new process for electrolysis of CTP plate base disclosed in Chinese patent CN101872125A is characterized in that alkaline washing and water washing are added in the electrolysis process, a single HCl solution is used as electrolyte, the use requirement of CTP plate base is met, the concentration of HCl in the electrolyte is 1.4-2.0%, and the alkaline washing process is as follows: naOH solution with concentration of 0.5-1.5 percent, alkali washing time of 10-60s, alkali washing temperature of 20-30 ℃, and water washing process comprising the following steps: the water washing flow is more than 100L/min, the flow speed is more than 3m/s, the water washing time is 10-60s, the electrolysis process is cheap and easy to control stably, but in the electrolysis process, a single HCl solution is adopted as electrolyte, the formed sand is not uniform in distribution, large pits are formed, meanwhile, a platform without plate grinding is also formed, the development quality of the follow-up CTP plate is affected, and the problems of low resolution, low sensitivity and the like exist.
Thus, the present invention provides an electrolyte for CTP plate-based production.
Disclosure of Invention
The invention aims to provide an electrolyte for CTP plate base production, which is used for solving the problem that the 'pits' formed by corrosion of the aluminum substrate by the existing CTP plate base electrolysis process are unevenly distributed.
The aim of the invention can be achieved by the following technical scheme:
an electrolyte for CTP plate base production, which comprises the following raw materials: corrosion components, surfactants and water.
Further, the corrosion components are hydrochloric acid, sulfuric acid, citric acid and phosphoric acid according to the mass ratio of 10-15:1-3:1.5-4.5:0.5-1.5.
Further, the concentration of HCl in the electrolyte is 5-20g/L.
Further, the addition mass of the surfactant is 1.5-3.5% of the water mass.
Further, the surfactant comprises the following steps:
a1, filling p-hydroxybenzoic acid and diethylenetriamine into a reaction container, heating until reactants are completely melted, heating to 140-150 ℃ under the action of condensed water, starting a vacuum pump when gas is discharged, sucking out the reaction gas, continuously stirring and reacting for 2-4h, heating to 200-210 ℃ when no gas is discharged, reacting for 2-3h, cooling to room temperature under vacuum, washing with water for several times, and drying to obtain an imidazole derivative, wherein the dosage ratio of the p-hydroxybenzoic acid to the diethylenetriamine is 1mol:1.5-1.8mol;
in the reaction, the imidazole ring is obtained by utilizing the cyclization reaction of carboxyl and diethylenetriamine, and the molecular structure of the obtained imidazole derivative is shown as follows;
a2, adding pentaerythritol glycidyl ether and DMAC when the imidazole derivative is heated and completely melted, heating to 50-60 ℃ under the action of condensed water, stirring and reacting for 4-7 hours, stopping the reaction, performing reduced pressure rotary evaporation, washing with methanol, and drying to obtain branched polyol, wherein the mass ratio of the imidazole derivative to the pentaerythritol glycidyl ether is 72-75:36;
in the above reaction, the amino group in the imidazole derivative and the epoxy group in the pentaerythritol glycidyl ether are utilized to react to form branched polyol (hydroxyl group obtained from ring-opening reaction and hydroxyl group in the imidazole derivative) with pentaerythritol ether as a core and imidazole derivative as a shell;
a3, uniformly mixing branched polyol and DMAC, regulating the pH to 10-11 by using a sodium hydroxide aqueous solution, heating to 50-60 ℃ under the action of condensed water, slowly dropwise adding a 75wt% glycidyl trimethyl ammonium chloride aqueous solution under stirring, continuously stirring for reacting for 2-4 hours after adding, stopping the reaction, performing reduced pressure rotary evaporation, washing by methanol, and drying to obtain ionized branched polyol, wherein the mass ratio of the branched polyol to the glycidyl trimethyl ammonium chloride is 108:60-65;
in the reaction, hydroxyl in the branched polyol and epoxy in the glycidyl trimethyl ammonium chloride are utilized to react, and cations are introduced into the branched polyol to obtain ionized branched polyol, so that the water solubility of the ionized polyol is improved;
and A4, uniformly mixing ionized branched polyol and glacial acetic acid, regulating the pH to 10-11 by using an ethanol solution of sodium hydroxide, heating to 75-85 ℃ under the action of condensed water, slowly dropwise adding bromohexadecane under stirring, continuously stirring for 2-4 hours after adding, stopping the reaction, performing reduced pressure rotary evaporation, washing by using methanol, and drying to obtain the surfactant, wherein the mass ratio of the ionized branched polyol to the bromohexadecane is 8:1-2.
In the above reaction, the hydroxyl group in the ionized polyol and bromine in the bromohexadecane are utilized to react, hexadecyl is introduced into the ionized polyol to obtain a surfactant, and the surfactant is endowed with amphipathy, wherein cations, hydroxyl groups and ether groups are hydrophilic, and hexadecane chains are oleophilic.
The invention has the beneficial effects that:
in order to solve the problem that the distribution of 'pits' formed by etching an aluminum substrate by using electrolyte of single hydrochloric acid is uneven, the invention adopts hydrochloric acid, sulfuric acid, citric acid and phosphoric acid as etching components, and can know that the mixed acid contains inorganic acid and inorganic acid, and can achieve effective electrolysis of CTP (computer to plate) base (namely aluminum plate) by utilizing scientific compatibility among the mixed acid, and can coordinate and control the distribution uniformity of the 'pits' formed, and simultaneously, in order to reduce the interfacial tension of the electrolyte and the aluminum plate, the invention introduces self-made surfactant which is amphiphilic, not only improves the stability of the mixed acid solution, but also contains cations, improves the electrolysis efficiency, the imidazole ring is easy to form a complex with aluminum ions formed by electrolysis of an aluminum substrate, and then is matched with pi-pi bond accumulation, so that imidazole derivative structures in surfactant molecules are easy to accumulate on the surface of the aluminum plate, long alkyl chains and cation chains in the surfactant are directed to water to form protection on the aluminum plate, corrosion inhibition is realized, the mechanism is particularly prominent in larger pits, because the contact area of the larger pits is large, aluminum-containing ion concentration is high, the surfactant is easier to enter the pits, the imidazole derivative structures in the molecules are easier to form a protection surface with the larger pits, corrosion inhibition is realized, the size of the pits formed by corrosion is regulated and controlled macroscopically, and uniform corrosion pits are promoted to be obtained;
in summary, the electrolyte for CTP plate production provided by the invention has good electrolytic efficiency in the process of preparing the aluminum substrate, and the size and distribution of the pits on the surface of the electrolytic aluminum substrate are regulated, so that the obtained pits on the surface of the aluminum substrate are uniform in size and uniform in distribution.
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
Preparation of a surfactant:
a1, filling 1mol of p-hydroxybenzoic acid and 1.5mol of diethylenetriamine into a reaction container, heating until reactants are completely melted, heating to 140 ℃ under the action of condensed water, starting a vacuum pump when gas is discharged, sucking out reaction gas, continuously stirring and reacting for 4 hours, heating to 200 ℃ when no gas is discharged, reacting for 3 hours, cooling to room temperature under vacuum, washing with water for several times, and drying to obtain imidazole derivatives;
a2, when 72g of imidazole derivative is heated and completely melted, 36g of pentaerythritol glycidyl ether and 100mL of DMAC are added, and the mixture is heated to 50 ℃ under the action of condensed water, stirred and reacted for 7 hours, the reaction is stopped, the mixture is subjected to rotary evaporation under reduced pressure, washed by methanol and dried, and branched polyol is obtained;
a3, uniformly mixing 108g of branched polyol and 100mL of DMAC, regulating the pH to 10-11 by using a 30wt% sodium hydroxide aqueous solution, heating to 50 ℃ under the action of condensed water, slowly dropwise adding a 60g of glycidyl trimethyl ammonium chloride aqueous solution (75 wt%) under stirring, continuing stirring and reacting for 4 hours after adding, stopping the reaction, performing reduced pressure rotary evaporation, washing by methanol, and drying to obtain the ionized branched polyol;
and A4, uniformly mixing 80g of ionized branched polyol and 100mL of glacial acetic acid, regulating the pH to 10-11 by using an ethanol solution of 30wt% of sodium hydroxide, heating to 75 ℃ under the action of condensed water, slowly dropwise adding 10g of bromohexadecane under stirring, continuing stirring and reacting for 4 hours after adding, stopping the reaction, decompressing and steaming, washing by methanol, and drying to obtain the surfactant.
Example 2
Preparation of a surfactant:
a1, filling 1mol of p-hydroxybenzoic acid and 1.8mol of diethylenetriamine into a reaction container, heating until reactants are completely melted, heating to 150 ℃ under the action of condensed water, starting a vacuum pump when gas is discharged, sucking out reaction gas, continuously stirring and reacting for 2 hours, heating to 210 ℃ when no gas is discharged, reacting for 2 hours, cooling to room temperature under vacuum, washing with water for several times, and drying to obtain imidazole derivatives;
a2, when 75g of imidazole derivative is heated and completely melted, 36g of pentaerythritol glycidyl ether and 100mL of DMAC are added, the mixture is heated to 60 ℃ under the action of condensed water, and the mixture is stirred and reacted for 4 hours, the reaction is stopped, the mixture is subjected to rotary evaporation under reduced pressure, washed by methanol and dried to obtain branched polyol;
a3, uniformly mixing 108g of branched polyol and 100mL of DMAC, regulating the pH to 10-11 by using a 30wt% sodium hydroxide aqueous solution, heating to 60 ℃ under the action of condensed water, slowly dropwise adding a 65g of glycidyl trimethyl ammonium chloride aqueous solution (75 wt%) under stirring, continuing stirring and reacting for 4 hours after adding, stopping the reaction, performing reduced pressure rotary evaporation, washing by methanol, and drying to obtain the ionized branched polyol;
and A4, uniformly mixing 80g of ionized branched polyol and 100mL of glacial acetic acid, regulating the pH to 10-11 by using an ethanol solution of 30wt% of sodium hydroxide, heating to 85 ℃ under the action of condensed water, slowly dropwise adding 20g of bromohexadecane under stirring, continuing stirring and reacting for 2 hours after adding, stopping the reaction, decompressing and steaming, washing by methanol, and drying to obtain the surfactant.
Example 3
An electrolyte for CTP plate base production, which comprises the following raw materials: a corrosion component, the surfactant prepared in example 1, and water; the addition mass of the surfactant is 1.5% of the water mass;
wherein the corrosion components comprise hydrochloric acid, sulfuric acid, citric acid and phosphoric acid according to the mass ratio of 10:1:1.5:0.5; the concentration of HCl in the electrolyte is 5g/L.
Example 4
An electrolyte for CTP plate base production, which comprises the following raw materials: a corrosion component, the surfactant prepared in example 2, and water; the addition mass of the surfactant is 2% of the water mass;
wherein the corrosion components are hydrochloric acid, sulfuric acid, citric acid and phosphoric acid according to the mass ratio of 12:2:3:1; the concentration of HCl in the electrolyte is 10g/L.
Example 5
An electrolyte for CTP plate base production, which comprises the following raw materials: a corrosion component, the surfactant prepared in example 1, and water; the addition mass of the surfactant is 3.5% of the water mass;
wherein the corrosion components are hydrochloric acid, sulfuric acid, citric acid and phosphoric acid according to the mass ratio of 15:3:4.5:1.5; the concentration of HCl in the electrolyte is 20g/L.
Comparative example 1
An electrolyte for CTP plate base production, which comprises the following raw materials: a corrosion component, the surfactant prepared in example 1, and water; surfactants the resulting ionized branched polyol prepared in step A3 of example 1; the addition mass of the surfactant is 1.5% of the water mass;
wherein the corrosion components comprise hydrochloric acid, sulfuric acid, citric acid and phosphoric acid according to the mass ratio of 10:1:1.5:0.5; the concentration of HCl in the electrolyte is 5g/L.
Comparative example 2
An electrolyte for CTP plate base production, which comprises the following raw materials: corrosion components, surfactants (sodium lauryl sulfate) and water; the addition mass of the surfactant is 2% of the water mass;
wherein the corrosion components are hydrochloric acid, sulfuric acid, citric acid and phosphoric acid according to the mass ratio of 12:2:3:1; the concentration of HCl in the electrolyte is 10g/L.
Comparative example 3
An electrolyte for CTP plate base production, which comprises the following raw materials: corrosion components and water;
wherein the corrosion components are hydrochloric acid, sulfuric acid, citric acid and phosphoric acid according to the mass ratio of 15:3:4.5:1.5; the concentration of HCl in the electrolyte is 20g/L.
Example 6
The electrolytes obtained in examples 3 to 5 and comparative examples 1 to 3 were subjected to the following tests:
the selected aluminum substrate is AA1050 aluminum, which is soaked in NaOH solution of 20g/L at 65deg.C for 20 seconds, then washed rapidly with running water, and ground in the electrolyte obtained in examples 3-5 and comparative examples 1-2, the electrolyte temperature is kept at 30deg.C, and the current density is 50A/dm 2 Electrolysis time is 20s;
SEM of 500 times and 2000 times of 10 different points is carried out on the grain form (uniform, no big pit and no platform) of the aluminum surface obtained after plate grinding, so that the grade of the plate grinding effect obtained under each plate grinding condition is obtained, wherein '1' (best) represents uniform and fine, no platform and no big pit, and '10' (worst) represents that big pits with the size of more than 30 mu m or a large number of platforms or no grains are formed at all; the evaluation results of the morphology of the aluminum surface after electrolysis of the electrolytes obtained in examples 3 to 5 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1
| Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Grade | 1 | 1 | 1 | 2-3 | 2-3 | 5 |
From the data in Table 1, it can be seen that the electrolytes provided in examples 3 to 5 have a good electrolytic effect on aluminum substrates.
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 (6)
1. An electrolyte for CTP plate base production, characterized in that: the preparation method comprises the following raw materials: corrosion components, surfactants and water;
the corrosion components are hydrochloric acid, sulfuric acid, citric acid and phosphoric acid according to the mass ratio of 10-15:1-3:1.5-4.5:0.5-1.5;
the surfactant comprises the following steps:
uniformly mixing branched polyol and DMAC, regulating the pH of the solution to 10-11, heating to 50-60 ℃ under the action of condensed water, slowly dropwise adding 75wt% of aqueous solution of glycidyl trimethyl ammonium chloride under stirring, continuing stirring for reaction for 2-4h after adding, and performing aftertreatment to obtain ionized branched polyol;
uniformly mixing ionized branched polyol and glacial acetic acid, regulating the pH of the solution to 10-11, heating to 75-85 ℃ under the action of condensed water, slowly dropwise adding bromohexadecane under stirring, continuously stirring for 2-4 hours after adding, stopping the reaction, performing reduced pressure rotary evaporation, washing with methanol, and drying to obtain the surfactant;
the branched polyol comprises the steps of:
a1, filling p-hydroxybenzoic acid and diethylenetriamine into a reaction container, heating until reactants are completely melted, heating to 140-150 ℃ under the action of condensed water, starting a vacuum pump when gas is discharged, sucking out reaction gas, continuously stirring and reacting for 2-4h, heating to 200-210 ℃ when no gas is discharged, reacting for 2-3h, cooling to room temperature under vacuum, washing with water for several times, and drying to obtain imidazole derivatives;
a2, when the imidazole derivative is heated and completely melted, pentaerythritol glycidyl ether and DMAC are added, the mixture is heated to 50-60 ℃ under the action of condensed water, and the mixture is stirred for 4-7 hours to stop the reaction, and the mixture is decompressed, steamed by rotating, washed by methanol and dried to obtain the branched polyol.
2. The electrolyte for CTP plate-based production according to claim 1, wherein: the mass ratio of the ionized branched polyol to the bromohexadecane is 8:1-2.
3. The electrolyte for CTP plate-based production according to claim 1, wherein: the concentration of HCl in the electrolyte is 5-20g/L.
4. The electrolyte for CTP plate-based production according to claim 1, wherein: the mass ratio of the branched polyol to the glycidyl trimethyl ammonium chloride is 108:60-65.
5. The electrolyte for CTP plate-based production according to claim 1, wherein: in the step A1, the dosage ratio of the parahydroxybenzoic acid to the diethylenetriamine is 1mol:1.5-1.8mol.
6. The electrolyte for CTP plate-based production according to claim 1, wherein: in the step A2, the mass ratio of the imidazole derivative to the pentaerythritol glycidyl ether is 36:72-75.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3755116A (en) * | 1971-04-17 | 1973-08-28 | Sumitomo Light Metal Ind | Process for the production of aluminum base offset printing plates |
| JP2000127639A (en) * | 1998-10-29 | 2000-05-09 | Fuji Photo Film Co Ltd | Manufacture of lithographic printing block aluminum substrate |
| CN101210340A (en) * | 2006-12-30 | 2008-07-02 | 比亚迪股份有限公司 | Electrochemical etching liquid and etching method |
| CN101872125A (en) * | 2009-09-28 | 2010-10-27 | 上海强邦印刷器材有限公司 | Novel electrolysis process of CTP base |
| CN113403672A (en) * | 2021-06-09 | 2021-09-17 | 安徽强邦新材料股份有限公司 | Electrolyte for heat-sensitive positive image CTP plate and preparation method thereof |
-
2022
- 2022-05-24 CN CN202210572130.7A patent/CN114790568B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3755116A (en) * | 1971-04-17 | 1973-08-28 | Sumitomo Light Metal Ind | Process for the production of aluminum base offset printing plates |
| JP2000127639A (en) * | 1998-10-29 | 2000-05-09 | Fuji Photo Film Co Ltd | Manufacture of lithographic printing block aluminum substrate |
| CN101210340A (en) * | 2006-12-30 | 2008-07-02 | 比亚迪股份有限公司 | Electrochemical etching liquid and etching method |
| CN101872125A (en) * | 2009-09-28 | 2010-10-27 | 上海强邦印刷器材有限公司 | Novel electrolysis process of CTP base |
| CN113403672A (en) * | 2021-06-09 | 2021-09-17 | 安徽强邦新材料股份有限公司 | Electrolyte for heat-sensitive positive image CTP plate and preparation method thereof |
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