Preparation method of modified phenolic resin for PS plate photoresist

Abstract

The invention discloses a preparation method of modified phenolic resin for PS plate photo-sensitive resist, relates to the technical field of high polymer materials, and aims to solve the problem of unstable reaction of thermosetting linear phenolic resin, oxalic acid catalyst is added in three times, nodes of the oxalic acid catalyst added in three times and reaction time in different temperature intervals are strictly controlled, and the service life of the modified phenolic resin is prolonged. Comprising the following steps: S1, feeding: according to a process ratio, sequentially pumping m-cresol and p-cresol and a formaldehyde aqueous solution into a reaction kettle by adopting a vacuum weight reduction method, and meanwhile, adding an oxalic acid catalyst for bottoming for the first time; heat conduction oil is injected into an interlayer of the reaction kettle, heating is started, when the temperature is 50-70 DEG C, 70-80 DEG C and 80-100 DEG C, the reaction time of each section is controlled within 160 min, when the temperature is increased to 100 DEG C, the oxalic acid catalyst is supplemented for the second time, and after an interval of 1 h, the oxalic acid catalyst is supplemented for the third time.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a method for preparing a modified phenolic resin for PS plate photosensitive adhesive. Background Art

[0002] In the printing industry, PS plate photosensitive adhesive plays a vital role in printing quality, and modified phenolic resin is the key film-forming resin of PS plate photosensitive adhesive. Its performance is directly related to the final quality and effect of printing. As the printing industry continues to develop towards high precision and high quality, more stringent requirements are placed on the quality stability of modified phenolic resin.

[0003] However, the production difficulties of modified phenolic resins are prominent, and the core lies in the poor stability of the production process. From the perspective of raw materials, the supply of cresol and formaldehyde is complex, and the purity, impurities and chemical activity of different batches vary greatly. When the impurities exceed the standard, the polycondensation reaction is disturbed, the speed is abnormal, and side reactions occur frequently, affecting the quality and efficiency of the synthesis. In terms of the environment, the temperature of the production environment fluctuates due to seasons, day and night, and equipment thermal effects. Heating causes the polycondensation reaction to overspeed and become difficult to control, and the molecular structure and performance of the product are damaged; cooling causes the reaction to be delayed, the production cycle to be long, and the cost to be high.

[0004] The combination of raw materials and environmental factors makes the reaction rate unstable, resulting in unstable viscosity and melting point of the resin, poor quality consistency and reliability, and difficult to meet the needs of high-end printing. When it is subsequently processed into photosensitive adhesive and prepared into printing plates, it is also prone to molding defects, reduced resolution and print durability, and other degradation phenomena, which seriously hinder the large-scale industrial production and industry expansion of modified phenolic resins. Effective solutions are urgently needed to improve production stability and product quality. Summary of the invention

[0005] In order to solve the above problems, that is, to solve the problems raised by the above background technology, the present invention proposes a method for preparing a modified phenolic resin for PS plate photosensitive adhesive, which includes adding an oxalic acid catalyst three times, strictly controlling the nodes of adding the oxalic acid catalyst in batches and the reaction time in different temperature ranges, and includes the following steps: S1, feeding: according to the process ratio, vacuum weight loss method is used to sequentially draw m-paracresol and formaldehyde aqueous solution into the reactor, and at the same time, oxalic acid catalyst is added for the first time to prime; S2, heating polycondensation reaction: heat transfer oil is injected into the interlayer of the reactor to start heating, and when the temperature is between 50-70°C , 70-80℃ and 80-100℃, the reaction time of each section is controlled within 160min. When the temperature rises to 100℃, oxalic acid catalyst is added for the second time. After an interval of 1h, oxalic acid catalyst is added for the third time. The liquid temperature in the kettle is kept at 100℃ for 3h; S3, dehydration: heating dehydration; S4, dephenolization: start the vacuum pump for dephenolization; S5, central control: observe the dephenolization process in the sight glass, and the excess phenol fraction that does not participate in the reaction will not be removed until it stops. Sampling is sent to the laboratory for central control to detect the viscosity and melting point. After passing the test, the material is discharged to obtain a thermosetting linear phenolic resin.

[0006] The present invention is further configured as follows: the chemical reaction formula of the thermosetting linear phenolic resin is as follows:

[0007] The present invention is further configured as follows: the weight ratio of the oxalic acid catalyst used three times is 1:1.2:1.2.

[0008] The present invention is further configured as follows: in S3, the dehydration temperature range is 220±10° C., and the reaction time range is 6-8 h.

[0009] The present invention is further configured as follows: in S4, the dephenolization temperature range is 160±10° C., and the reaction time range is 2-3 h.

[0010] The present invention is further configured as follows: in S5, the viscosity of the thermosetting linear phenolic resin is in the range of 8.18-8.30 mm 2 / s, melting point range is 120-126℃.

[0011] The present invention is further configured as follows: the raw materials are composed of the following components by weight: 62.5%-63.5% of m-para-cresol, 35.5%-37.5% of formaldehyde aqueous solution and 0.3%-0.5% of oxalic acid catalyst.

[0012] The present invention is further configured as follows: the concentration range of the formaldehyde aqueous solution is 36.5%-37.5%.

[0013] The beneficial technical effects of the present invention are as follows: the modified phenolic resin of the present invention has a stable reaction, and the viscosity of the obtained product is 8.18-8.30 mm 2 / s, the melting point is 120-126℃. In the synthesis stage, the oxalic acid catalyst is added three times, and the nodes of adding the oxalic acid catalyst in batches and the reaction time in different temperature ranges are strictly controlled to ensure a smooth reaction in the production process. The reaction time is easier to control. The insulation time is set to 3h and the insulation temperature is set to 100℃, which can maximize the guarantee of phenolic full reaction. The product obtained is heavy, with less by-products, high yield and extremely high stability. The PS plate photosensitive glue made of modified phenolic resin has a fast photosensitivity, high resolution and increased printing durability. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 The process flow chart of the present invention is shown. DETAILED DESCRIPTION

[0015] Please refer to the attached Figure 1 Those skilled in the art should understand that these embodiments are only used to explain the technical principles of the present invention and are not intended to limit the protection scope of the present invention.

[0016] The test index requirements of the embodiments and comparative examples of the present invention are: viscosity 8.18-8.30mm 2 / s, melting point 120-126℃, the PS plate photosensitive adhesive made of modified phenolic resin within this viscosity and melting point range has fast photosensitivity, high resolution and increased printing durability, which is within the ideal product indicator range. Example

[0017] Batch number: 2023-174.

[0018] S1. Feeding: According to the process ratio, 600 kg of m-p-cresol and 350 kg of 36.5% formaldehyde aqueous solution are pumped into the reactor in sequence by vacuum weight loss method, and 1.15 kg of oxalic acid catalyst is added for the first time from the manhole as a base; S2, heating polycondensation reaction: inject heat transfer oil into the reactor interlayer to start heating, and monitor the reaction time of the temperature in the reactor in real time: 9:00 The temperature of the liquid in the kettle is 50°C; 10:20 The temperature of the liquid in the kettle is 60°C; 11: The temperature of the liquid in the 40 kettle is 70°C; 14:20 The temperature of the liquid in the kettle is 80°C; At 17:00, the temperature of the liquid in the kettle reached 100°C. At this time, 1.38 kg of oxalic acid catalyst was added from the manhole for the second time. After an interval of 1 hour; At 18:00, 1.38 kg of oxalic acid catalyst was added from the manhole for the third time, and the liquid temperature in the kettle was refluxed and kept warm for 3 hours at 100°C; S3, 21:00 dehydration: heating to 210℃, dehydration for 8h, removing 220kg of acidic phenolic process wastewater; S4, dephenolization at 5:00 the next day: start the vacuum pump for dephenolization, cool down to 160℃, and dephenolize for 2h; S5, 8:30 Central Control: Observe the dephenolization process in the sight glass, and the excess phenol fraction that does not participate in the reaction will not be removed. At 9:30, take samples and send them to the laboratory for central control to test the product viscosity and melting point indicators: viscosity 8.21mm 2 / s, melting point 121℃, detection indexes meet the standards, material was discharged, cooled, crushed, packaged and stored at 11:00 to obtain thermosetting linear phenolic resin, product weight 560kg, yield 93.3%, and kettle residue 170kg. Example

[0019] Batch number: 2024-136.

[0020] S1. Feeding: According to the process ratio, 600 kg of m-p-cresol and 350 kg of 36.5% formaldehyde aqueous solution are pumped into the reactor in sequence by vacuum weight loss method, and 1.15 kg of oxalic acid catalyst is added for the first time from the manhole as a base; S2, heating polycondensation reaction: inject heat transfer oil into the reactor interlayer to start heating, and monitor the reaction time of the temperature in the reactor in real time: 9:20 The temperature of the liquid in the kettle is 50°C; 10: The temperature of the liquid in the 40 kettle is 60°C; 12:00 The temperature of the liquid in the kettle is 70°C; 14: The temperature of the liquid in the 40 kettle is 80°C; 17:20 The temperature of the liquid in the kettle reached 100°C. At this time, 1.38 kg of oxalic acid catalyst was added from the manhole for the second time. After an interval of 1 hour; At 18:20, 1.38 kg of oxalic acid catalyst was added from the manhole for the third time, and the liquid in the kettle was refluxed and kept warm for 3 hours at a temperature of 100°C; S3, 21:20 Dehydration: Heat to 210℃, dehydrate for 8h, remove 219kg of acidic phenolic process wastewater; S4, 5:20 the next day, dephenolization: start the vacuum pump to dephenolize, cool down to 160℃, dephenolize for 2h; S5, 8:50 Central Control: Observe the dephenolization process in the sight glass, and the excess phenol fraction that does not participate in the reaction will not be removed. At 9:50, take samples and send them to the laboratory for central control to test the product viscosity and melting point indicators: viscosity 8.25mm 2 / s, melting point 123℃, detection indexes meet the standards, material discharge, cooling, crushing, packaging and storage at 11:20, thermosetting linear phenolic resin was obtained, product weight 562kg, yield 93.7%, and kettle residue 169kg. Example

[0021] Batch number: 2024-180.

[0022] S1. Feeding: According to the process ratio, 600 kg of m-p-cresol and 350 kg of 36.5% formaldehyde aqueous solution are pumped into the reactor in sequence by vacuum weight loss method, and 1.15 kg of oxalic acid catalyst is added for the first time from the manhole as a base; S2, heating polycondensation reaction: inject heat transfer oil into the reactor interlayer to start heating, and monitor the reaction time of the temperature in the reactor in real time: 8:20 The temperature of the liquid in the kettle is 50°C; 9: The temperature of the liquid in the 40 kettle is 60°C; 11:00 The temperature of the liquid in the kettle is 70°C; 13: The temperature of the liquid in the 40 kettle is 80°C; 16:20 The temperature of the liquid in the kettle reached 100°C. At this time, 1.38 kg of oxalic acid catalyst was added from the manhole for the second time. After an interval of 1 hour; 17:20 1.38 kg of oxalic acid catalyst was added from the manhole for the third time, and the liquid temperature in the kettle was refluxed at 100°C for 3 hours; S3, 20:20 dehydration: heat to 210℃, dehydrate for 8h, remove 221kg of acidic phenolic process wastewater; S4, dephenolization at 4:20 the next day: start the vacuum pump for dephenolization, cool down to 160℃, and dephenolize for 2h; S5, 7:50 Central Control: Observe the dephenolization process in the sight glass, and the excess phenol fraction that does not participate in the reaction will not be removed. At 8:50, take a sample and send it to the laboratory for central control to test the product viscosity and melting point index: viscosity 8.20mm 2 / s, melting point 120℃, detection indexes meet the standards, material discharge, cooling, crushing, packaging and storage at 10:20, to obtain thermosetting linear phenolic resin, product weight 558kg, yield 93%, kettle residue 171kg.

[0023] Reaction conditions: catalyst was added all at once, insulation time was 3 h, insulation temperature was 100 °C.

[0024] S1. Feeding: According to the process ratio, 600 kg of m-p-cresol and 350 kg of 36.5% formaldehyde aqueous solution were pumped into the reactor in sequence by vacuum weight loss method, and 3.91 kg of oxalic acid catalyst was added from the manhole at one time; S2, heating polycondensation reaction: inject heat transfer oil into the reactor interlayer to start heating, and monitor the reaction time of the temperature in the reactor in real time: 9:00 The temperature of the liquid in the kettle is 50°C; 10:10 The temperature of the liquid in the kettle is 60°C; 11:10 The temperature of the liquid in the kettle is 70°C; 13:20 The temperature of the liquid in the kettle is 80°C; 16:00 The temperature of the liquid in the kettle reaches 100°C and is kept at reflux for 3 hours; S3, 19:00 Dehydration: The temperature was raised to 210℃. During the dehydration process, the power was greater than 15KW. Stirring was stopped. As the temperature gradually increased, the coagulated liquid gradually melted. Stirring was started again. The dehydration was continued for 8 hours. 226kg of acidic phenol-containing process wastewater was removed. S4, dephenolization at 3:00 the next day: start the vacuum pump for dephenolization, cool down to 160℃, and dephenolize for 2h; S5, 8:30 Central Control: Observe the dephenolization process in the sight glass, and the excess phenol fraction that does not participate in the reaction will not be removed. At 9:30, take samples and send them to the laboratory for central control to test the product viscosity and melting point indicators: viscosity 8.52mm 2 / s, melting point 128℃, detection index does not meet the standard, marked as unqualified product, product weight 544kg, yield 90.7%, kettle residue 180kg.

[0025] Reaction conditions: the catalyst was added in two portions, the insulation time was 3 hours, and the insulation temperature was 100°C.

[0026] S1. Feeding: According to the process ratio, 600 kg of m-p-cresol and 350 kg of 36.5% formaldehyde aqueous solution are pumped into the reactor in sequence by vacuum weight loss method, and 1.15 kg of oxalic acid catalyst is added for the first time from the manhole as a base; S2, heating polycondensation reaction: inject heat transfer oil into the reactor interlayer to start heating, and monitor the reaction time of the temperature in the reactor in real time: 9:20 The temperature of the liquid in the kettle is 50°C; 10: The temperature of the liquid in the 40 kettle is 60°C; 12:00 The temperature of the liquid in the kettle is 70°C; 14:40 The temperature of the liquid in the kettle is 80°C; 17:20 The temperature of the liquid in the kettle reached 100°C. At this time, 2.76 kg of oxalic acid catalyst was added from the manhole for the second time. The reaction was intense and the liquid level in the kettle rose to the sight glass. The liquid in the kettle was refluxed and kept warm for 3 hours at a temperature of 100°C. S3, 20:20 dehydration: heat to 210℃, dehydrate for 10h, remove 224kg of acidic phenolic process wastewater; S4, 6:20 the next day, dephenolization: start the vacuum pump to dephenolize, cool down to 160℃, dephenolize for 3h; S5, 9:20 Central Control: Observe the dephenolization process in the sight glass, and the excess phenol fraction that does not participate in the reaction will not be removed. At 10:20, take samples and send them to the laboratory for central control to test the product viscosity and melting point indicators: viscosity 7.92mm 2 / s, melting point 119℃, detection indexes meet the standards, material discharge, cooling, crushing, packaging and storage at 11:20, thermosetting linear phenolic resin was obtained, product weight 551kg, yield 91.8%, and kettle residue 175kg.

[0027] Reaction conditions: the catalyst was added in three times, the insulation time was 2 hours, and the insulation temperature was 90°C.

[0028] S1. Feeding: According to the process ratio, 600 kg of m-p-cresol and 350 kg of 36.5% formaldehyde aqueous solution are pumped into the reactor in sequence by vacuum weight loss method, and 1.15 kg of oxalic acid catalyst is added for the first time from the manhole as a base; S2, heating polycondensation reaction: inject heat transfer oil into the reactor interlayer to start heating, and monitor the reaction time of the temperature in the reactor in real time: 8:20 The temperature of the liquid in the kettle is 50°C; 9: The temperature of the liquid in the 40 kettle is 60°C; 11:00 The temperature of the liquid in the kettle is 70°C; 13: The temperature of the liquid in the 40 kettle is 80°C; 15:20 The temperature of the liquid in the kettle reached 90°C. At this time, 1.38 kg of oxalic acid catalyst was added from the manhole for the second time. After an interval of 1 hour; At 16:20, 1.38 kg of oxalic acid catalyst was added from the manhole for the third time, and the liquid in the kettle was refluxed and kept warm for 2 hours at 90°C; S3, 18:20 Dehydration: Heating to 210℃, dehydration for 9.5h, removing 220kg of acidic phenolic process wastewater; S4, dephenolization at 3:50 the next day: start the vacuum pump to dephenolize, cool down to 160℃, and dephenolize for 3h; S5, 6:50 Central control: Observe the dephenolization process in the sight glass, and the excess phenol fraction that does not participate in the reaction will not be removed. Take samples and send them to the laboratory for central control to test the product viscosity and melting point indicators: viscosity 7.68mm 2 / s, melting point 108℃, detection index does not meet the standard, marked as unqualified product, product weight 520kg, yield 86.7%, kettle residue 210kg.

[0029]

[0030] Comparative Example 1: Oxalic acid catalyst was added at one time. During the production process, the reaction was intense at 50-80°C. It was extremely difficult to control the reaction time of each stage. The temperature of the material in the kettle rose sharply. During the dehydration process, the material had a high viscosity and the stirring operation had to be stopped. The viscosity was detected to be 8.52 mm. 2 / s, the melting point is 128℃, the indicators deviate greatly from the ideal range, the stability of oxalic acid catalyst is poor after one-time investment, the production process is difficult to control, the indicators deviate greatly, there are many by-products, and the yield is low.

[0031] Comparative Example 2: The oxalic acid catalyst was added twice. After the second addition of the catalyst, the reaction in the kettle was intense, and the liquid level in the kettle rose to the sight glass, which was very dangerous and difficult to control. The subsequent dehydration and dephenolization stages were difficult to control, and the viscosity was detected to be 7.92 mm. 2 / s, the melting point is 119℃, the index is low and still cannot meet the ideal index requirements, and there are more by-products and the yield is low.

[0032] Comparative Example 3: The oxalic acid catalyst was added three times, the holding time was shortened to 2 hours, and the holding temperature was set to 90°C. Due to the poor holding time and temperature, the aqueous solution of m-p-cresol and formaldehyde could not fully react, and the detected viscosity was 7.68 mm. 2 / s, with a melting point of 108°C, it is still an unqualified product, with more by-products and a low yield.

[0033] It can be seen that the oxalic acid catalyst in Examples 1-3 is added three times, and the nodes of the oxalic acid catalyst being added in batches and the reaction time in different temperature ranges are strictly controlled, so that the production process can be guaranteed to have a smooth reaction, and the reaction time is easier to control. The insulation time is set to 3h and the insulation temperature is set to 100°C, which can maximize the guarantee of full reaction of phenolic formaldehyde, and the obtained product has a large weight, few by-products, high yield, and extremely high stability, providing a highly stable resin raw material for PS plate photosensitive adhesive.

[0034] Product inspection equipment and manufacturer model

[0035] Since the tested values ​​such as viscosity, melting point and weight are all obtained by manual transcription from reading instruments and equipment, it is impossible to issue an electronic version of the relevant test certificate report.

[0036] Although the present invention has been described with reference to preferred embodiments, various modifications may be made thereto and parts thereof may be replaced by equivalents without departing from the scope of the present invention. In particular, the various technical features mentioned in the various embodiments may be combined in any manner as long as there is no structural conflict. The present invention is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims.

[0037] In the description of the present invention, the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer" and the like indicating directions or positional relationships are based on the directions or positional relationships shown in the drawings, which are only for the convenience of description, and do not indicate or imply that the device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present invention. In addition, the terms "first", "second", and "third" are used for descriptive purposes only, and cannot be understood as indicating or implying relative importance.

[0038] In addition, it should be noted that in the description of the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For those skilled in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0039] The term "comprise" or any other similar term is intended to cover a non-exclusive inclusion, such that a process, article, or apparatus / device that includes a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, article, or apparatus / device.

[0040] So far, the technical solutions of the present invention have been described in conjunction with the preferred embodiments shown in the accompanying drawings. However, it is easy for those skilled in the art to understand that the protection scope of the present invention is obviously not limited to these specific embodiments. Without departing from the principle of the present invention, those skilled in the art can make equivalent changes or substitutions to the relevant technical features, and the technical solutions after these changes or substitutions will fall within the protection scope of the present invention.

Claims

1. A method for preparing a modified phenolic resin for PS plate photosensitive adhesive, characterized in that: The oxalic acid catalyst is added in three times, and the nodes of adding the oxalic acid catalyst in batches and the reaction time in different temperature ranges are strictly controlled, including the following steps: S1. Feeding: according to the process ratio, m-p-cresol and formaldehyde aqueous solution are pumped into the reactor in sequence by vacuum weight loss method, and oxalic acid catalyst is added for the first time as a base; S2, heating polycondensation reaction: heat transfer oil is injected into the reactor interlayer to start heating. When the temperature is at 50-70°C, 70-80°C and 80-100°C, each reaction time is controlled within 160min. When the temperature rises to 100°C, oxalic acid catalyst is added for the second time. After an interval of 1h, oxalic acid catalyst is added for the third time. The liquid temperature in the reactor is refluxed and kept warm for 3h at 100°C. S3, dehydration: heating and dehydration; S4, dephenolization: start the vacuum pump to dephenolize; S5. Central control: During the dephenolization process, observe the sight glass to see if the excess phenol fraction that does not participate in the reaction is no longer removed. Take a sample and send it to the laboratory for central control to test the viscosity and melting point. After passing the test, release the material to obtain a thermosetting linear phenolic resin.

2. The method for preparing a modified phenolic resin for PS plate photosensitive adhesive according to claim 1, characterized in that: The chemical reaction formula of the thermosetting linear phenolic resin is as follows: 。 3. The method for preparing a modified phenolic resin for PS plate photosensitive adhesive according to claim 1, characterized in that: The weight ratio of the oxalic acid catalyst used three times is 1:1.2:1.

2.

4. The method for preparing a modified phenolic resin for PS plate photosensitive adhesive according to claim 1, characterized in that: In S3, the dehydration temperature range is 220±10° C., and the reaction time range is 6-8 h.

5. The method for preparing a modified phenolic resin for PS plate photosensitive adhesive according to claim 1, characterized in that: In the step S4, the dephenolization temperature range is 160±10° C., and the reaction time range is 2-3 h.

6. The method for preparing a modified phenolic resin for PS plate photosensitive adhesive according to claim 1, characterized in that: In S5, the viscosity of the thermosetting linear phenolic resin is in the range of 8.18-8.30 mm 2 / s, melting point range is 120-126℃.

7. A modified phenolic resin for PS plate photosensitive adhesive according to claim 1, characterized in that: The raw materials are composed of the following components by weight: 62.5%-63.5% of m-cresol, 35.5%-37.5% of formaldehyde aqueous solution and 0.3%-0.5% of oxalic acid catalyst.

8. The modified phenolic resin for PS plate photosensitive adhesive according to claim 7, characterized in that: The concentration range of the formaldehyde aqueous solution is 36.5%-37.5%.

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