Alkali-soluble alicyclic co-polyether resin, and preparation method and application thereof

Abstract

The application belongs to the technical field of high polymer materials, and particularly relates to an alkali-soluble alicyclic copolyether resin as well as a preparation method and application thereof. The alkali-soluble alicyclic copolyether resin is prepared by using 3,4-epoxycyclohexylmethyl acrylate and tetrahydrofuran to prepare an alicyclic copolyether intermediate, and then performing ultraviolet light click reaction on the alicyclic copolyether intermediate and 3-mercaptopropionic acid to prepare the alkali-soluble alicyclic copolyether. The alkali-soluble alicyclic copolyether resin prepared by ring-opening polymerization not only retains the cyclic structure of 3,4-epoxycyclohexylmethyl acrylate itself, improves the rigidity of the resin, but also has a tetrahydrofuran flexible segment. The application adopts ultraviolet light click reaction to endow the resin with alkali development activity. The preparation process does not require high temperature and high pressure, the process is simple, the reaction condition is mild, is suitable for large-scale production, and has high practical application value.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer materials, and particularly relates to an alkali-soluble alicyclic copolyether resin as well as a preparation method and application thereof. BACKGROUND

[0002] With the continuous development of optoelectronic technology, display technology and electronic manufacturing industry, photosensitive resin is increasingly applied in the fields of optical display, electronic components, flexible display and integrated circuit manufacturing. As a key material in the processes of photoetching, image transfer and protective coating, photosensitive resin is required to have good flexibility, thermal stability and UV curing performance. However, the existing photosensitive resin often has trade-offs between these properties, and it is difficult to fully meet the high performance requirements. Although the existing resin can meet the demand of a certain performance, it often compromises in other aspects, especially in the balance between thermal stability, flexibility and light curing performance, and there is still a technical bottleneck.

[0003] Although alicyclic epoxy monomers have excellent thermal stability and light curing performance, which can improve the curing effect and heat resistance of traditional resins, how to improve the comprehensive performance of the resin on this basis, especially to maintain good mechanical properties (such as the balance between flexibility and rigidity), is still a technical problem. Especially in modern electronic manufacturing, the requirements for the flexibility and thermal stability of the resin are getting higher and higher, and how to break through the limitations of existing materials and develop a resin that has excellent curing performance and maintains high mechanical properties has become the focus of current research.

[0004] Polyether resin as an ideal resin material has been widely used in many fields due to its low viscosity, good flexibility and low cost. However, the thermal stability and light curing performance of traditional polyether resin often cannot meet higher application requirements. Therefore, developing polyether resin with improved molecular structure can meet multiple performance requirements and expand its application potential in modern electronic industry. SUMMARY

[0005] The present application aims to provide an alkali-soluble alicyclic copolyether resin as well as a preparation method and application thereof, so as to solve at least one of the above technical problems.

[0006] According to one aspect of the present application, an alkali-soluble alicyclic copolyether resin is provided, and its structural formula is as follows:

[0007] ,

[0008] wherein a, b and c respectively represent mass fraction, and satisfy a+b+c=1, 0.23≤a≤0.27, 0.365≤b≤0.385, 0.365≤c≤0.385.

[0009] According to another aspect of the present application, a method for preparing the above-mentioned alkali-soluble alicyclic copolyether resin is provided, comprising the following steps:

[0010] S1, uniformly mixing a solvent, a polyol, tetrahydrofuran and a catalyst, then adding dropwise 3,4-epoxycyclohexyl methacrylate at 0-5℃, then increasing the temperature to 15-25℃, reacting for 4-6h, adding water to terminate the reaction, and then removing the solvent to obtain an alicyclic copolyether intermediate;

[0011] S2, uniformly mixing the alicyclic copolyether intermediate prepared in S1, 3-mercaptopropionic acid, an organic solvent and a photoinitiator, then reacting under ultraviolet light for 10-30min, and then removing the solvent to obtain an alkali-soluble alicyclic copolyether.

[0012] The method for preparing the alkali-soluble alicyclic copolyether resin provided by the present application first uses 3,4-epoxycyclohexyl methacrylate and tetrahydrofuran to prepare an alicyclic copolyether intermediate, and then performs ultraviolet light click reaction on the alicyclic copolyether intermediate and 3-mercaptopropionic acid to prepare the alkali-soluble alicyclic copolyether. Specifically, the catalyst boron trifluoride etherate generates a proton by reacting with a polyol initiator, initiates the ring-opening cationic polymerization of tetrahydrofuran and the epoxy group of 3,4-epoxycyclohexyl methacrylate, and generates the alicyclic copolyether intermediate; then, 3-mercaptopropionic acid and the photoinitiator generate mercapto radicals under the action of ultraviolet light, attack the unsaturated carbon-carbon double bond in the alicyclic copolyether intermediate to perform grafting, and obtain a mercapto-alkene product, i.e. the alkali-soluble alicyclic copolyether.

[0013] In some embodiments, the structure of the alicyclic copolyether intermediate in step S1 is as follows:

[0014] ,

[0015] wherein a and b represent mass fractions, and satisfy a+b=1, 0.24≤a≤0.26, and 0.74≤b≤0.76.

[0016] In some embodiments, the molar ratio of 3,4-epoxycyclohexyl methacrylate to tetrahydrofuran in step S1 is (2-5):1.

[0017] In some embodiments, the solvent in step S1 is one or more of acetone, dichloromethane, butanone, and toluene, and the amount of the solvent is 1-3 times the total mass of 3,4-epoxycyclohexyl methacrylate and tetrahydrofuran.

[0018] In some embodiments, the catalyst in step S1 is boron trifluoride etherate, and the amount of the catalyst is 0.5-3 wt% of the total mass of 3,4-epoxycyclohexyl methacrylate and tetrahydrofuran.

[0019] In some embodiments, the polyol in step S1 is one or more of ethylene glycol, propylene glycol, butylene glycol, glycerol, trimethylolpropane and trimethylolethane, and the amount is 0.5-2 wt% of the total mass of 3,4-epoxycyclohexyl methacrylate and tetrahydrofuran.

[0020] In some embodiments, the molar ratio of the double bond in the alicyclic copolyether intermediate in step S2 to the thiol group of 3-mercaptopropionic acid is 1:(0.4-0.6).

[0021] In some embodiments, the organic solvent in step S2 is at least one of acetone, dichloromethane, butanone, toluene, and the amount is 1-3 times of the total mass of the alicyclic copolyether intermediate and 3-mercaptopropionic acid. Preferably, the organic solvent in step S2 is dichloromethane.

[0022] In some embodiments, the photoinitiator in step S2 can be any cleavage type free radical photoinitiator, such as any one or several of photoinitiator BDK (main component benzoin diethyl ether), photoinitiator 651 (main component dimethyl benzil ketal), photoinitiator 184 (main component 1-hydroxy-cyclohexyl phenyl ketone), TPO (main component 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide), and the amount is 0.5-2 wt% of the total mass of the alicyclic copolyether intermediate and 3-mercaptopropionic acid.

[0023] In some embodiments, the irradiation power of the ultraviolet light in step S2 is 300-500 W, and the wavelength is 260-400 nm. Preferably, the irradiation power of the ultraviolet light is 350-450 W, and the wavelength is 365 nm.

[0024] According to another aspect of the present application, the above-mentioned alkali-soluble alicyclic copolyether resin is provided for use in the preparation of a photosensitive dry film. Specifically, the alkali-soluble alicyclic copolyether resin of the present application is mixed with a reactive diluent, a photoinitiator, and a pigment to prepare a photosensitive dry film, which can obtain an image with good comprehensive performance and high resolution, and has good application prospects in the fields of optical display, electronic manufacturing, flat and flexible display device UV packaging and coating protection, etc.

[0025] Compared with the prior art, the present application has the following advantages:

[0026] (1) The alkali-soluble alicyclic copolyether resin prepared by ring-opening polymerization in the present application not only retains the cyclic structure of 3,4-epoxycyclohexyl methacrylate itself, improving the rigidity of the resin, but also has a flexible segment of tetrahydrofuran, and the present application uses ultraviolet light click reaction to endow the resin with alkali development activity. The preparation process does not require high temperature and high pressure, and the process is simple and the reaction conditions are mild.

[0027] (2) The alkali-soluble alicyclic copolyether resin of the present invention has a moderate molecular weight, with a number average molecular weight of about 1900 g / mol, which effectively improves the development resolution, and has good flexibility and moderate acidity, which meets the application requirements of photosensitive resins.

[0028] (3) The process flow of the present invention is simple, suitable for large-scale production, and has high practical application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 Schematic diagram of the synthesis route of the alkali-soluble alicyclic copolyether resin of the present invention.

[0030] Figure 2 This is the infrared spectrum of Example 1 of the present invention. DETAILED DESCRIPTION

[0031] The present invention will be further described in detail below with reference to the accompanying drawings, but the embodiments of the present invention are not limited thereto. The raw materials and reagents involved in the following examples can be obtained from commercial channels. Figure 1 .

[0032] Example 1

[0033] The preparation method of the alkali-soluble alicyclic copolyether resin of this embodiment comprises the following steps:

[0034] (1) Add 0.62g 1,4-butanediol, 0.31g boron trifluoride etherate, 7.21g tetrahydrofuran, 123.76g dichloromethane to a 500mL three-necked flask, stir, cool, and when the temperature is around 0℃, begin to dropwise add 54.67g 3,4-epoxycyclohexyl methacrylate. After the addition is complete, raise the temperature to 20℃, continue the reaction for 5 hours, and then add 20mL pure water to the system to terminate the reaction. Add 100mL of dichloromethane, stir, separate the liquids, and rotary evaporate the solvent to obtain the alicyclic copolyether intermediate. Figure 2 As shown in the infrared spectrum, the original 3,4-epoxycyclohexyl methacrylate has a 904 cm -1 The peak of the epoxy group disappears after the reaction, and the peak at 1725 cm-1 of 3,4-epoxycyclohexyl methacrylate -1 The C=O characteristic peak at 1635cm-1 and the C=C characteristic peak at 1635cm-1 indicate that the intermediate has been successfully synthesized.

[0035] (2) Add 55.07 g of alicyclic copolyether intermediate, 12.74 g of 3-mercaptopropionic acid, 0.71 g of photoinitiator BDK and 141.98 g of dichloromethane to a 500 mL three-necked flask, and react under 300 W, 365 nm ultraviolet light for 20 min. Then, remove the dichloromethane by rotary evaporation to obtain an alkali-soluble alicyclic copolyether. The infrared spectrum shows that at 3492 cm-1 The characteristic stretching vibration absorption peak of hydroxyl group appears at left and right, and the double bond peak at 1635 cm -1 The thiol propionic acid is successfully grafted into the C=C of the intermediate. It can be known from the spectrum that the functional group of the product designed in the application appears.

[0036] Example 2

[0037] The preparation method of the alkali-soluble alicyclic copolyether resin in the embodiment comprises the following steps:

[0038] (1) 0.62g of 1,4-butanediol, 0.62g of boron trifluoride etherate, 7.21g of tetrahydrofuran, and 123.76g of dichloromethane were added into a 500mL three-necked flask, and stirred. When the temperature was about 0℃, 54.67g of 3,4-epoxycyclohexyl methacrylate was started to be added dropwise. After the dropwise addition was completed, the temperature was increased to 20℃, and the reaction was continued for 5h. Then, 20mL of pure water was added into the system to terminate the reaction. After the liquid separation and rotary evaporation of the solvent, the alicyclic copolyether intermediate was obtained.

[0039] (2) 55.07g of the alicyclic copolyether intermediate, 12.74g of 3-mercaptopropionic acid, 0.71g of photoinitiator BDK, and 141.98g of dichloromethane were added into a 500mL three-necked flask, and reacted under 300W, 365nm ultraviolet light for 20min. Then, the dichloromethane was removed by rotary evaporation to obtain the alkali-soluble alicyclic copolyether.

[0040] Example 3

[0041] The preparation method of the alkali-soluble alicyclic copolyether resin in the embodiment comprises the following steps:

[0042] (1) 0.62g of 1,4-butanediol, 0.93g of boron trifluoride etherate, 7.21g of tetrahydrofuran, and 123.76g of dichloromethane were added into a 500mL three-necked flask, and stirred. When the temperature was about 0℃, 54.67g of 3,4-epoxycyclohexyl methacrylate was started to be added dropwise. After the dropwise addition was completed, the temperature was increased to 20℃, and the reaction was continued for 5h. Then, 20mL of pure water was added into the system to terminate the reaction. After the liquid separation and rotary evaporation of the solvent, the alicyclic copolyether intermediate was obtained.

[0043] (2) 55.07g of the alicyclic copolyether intermediate, 12.74g of 3-mercaptopropionic acid, 0.71g of photoinitiator BDK, and 141.98g of dichloromethane were added into a 500mL three-necked flask, and reacted under 300W, 365nm ultraviolet light for 20min. Then, the dichloromethane was removed by rotary evaporation to obtain the alkali-soluble alicyclic copolyether.

[0044] Example 4

[0045] The preparation method of the alkali-soluble alicyclic copolyether resin of the embodiment comprises the following steps:

[0046] (1) 0.62 g of 1,4-butanediol, 0.93 g of boron trifluoride etherate, 7.21 g of tetrahydrofuran, and 123.76 g of dichloromethane were added to a 500 mL three-necked flask, stirred, and cooled. When the temperature was about 0°C, 54.67 g of 3,4-epoxycyclohexyl methacrylate was added dropwise. After the dropwise addition was completed, the temperature was increased to 20°C, and the reaction was continued for 5 h. Then, 20 mL of pure water was added to the system to terminate the reaction. After separation and rotary evaporation of the solvent, the alicyclic copolyether intermediate was obtained.

[0047] (2) 55.07 g of the alicyclic copolyether intermediate, 15.92 g of 3-mercaptopropionic acid, 0.71 g of a photoinitiator BDK, and 141.98 g of dichloromethane were added to a 500 mL three-necked flask, and the mixture was reacted under ultraviolet light of 300 W and 365 nm for 20 min. Then, the dichloromethane was removed by rotary evaporation to obtain the alkali-soluble alicyclic copolyether.

[0048] Example 5

[0049] The preparation method of the alkali-soluble alicyclic copolyether resin of the embodiment comprises the following steps:

[0050] (1) 0.62 g of 1,4-butanediol, 0.93 g of boron trifluoride etherate, 7.21 g of tetrahydrofuran, and 123.76 g of dichloromethane were added to a 500 mL three-necked flask, stirred, and cooled. When the temperature was about 0°C, 54.67 g of 3,4-epoxycyclohexyl methacrylate was added dropwise. After the dropwise addition was completed, the temperature was increased to 20°C, and the reaction was continued for 5 h. Then, 20 mL of pure water was added to the system to terminate the reaction. After separation and rotary evaporation of the solvent, the alicyclic copolyether intermediate was obtained.

[0051] (2) 55.07 g of the alicyclic copolyether intermediate, 15.92 g of 3-mercaptopropionic acid, 0.71 g of a photoinitiator BDK, and 141.98 g of dichloromethane were added to a 500 mL three-necked flask, and the mixture was reacted under ultraviolet light of 300 W and 365 nm for 20 min. Then, the dichloromethane was removed by rotary evaporation to obtain the alkali-soluble alicyclic copolyether.

[0052] Next, the alkali-soluble alicyclic copolyether resins prepared in Examples 1-5 were tested for performance.

[0053] First, the molecular weight of the alkali-soluble alicyclic copolyether resins prepared in Examples 1-5 was determined using a Waterse2695 gel chromatograph. The test results are shown in Table 1.

[0054] Table 1 Molecular weight of the alkali-soluble alicyclic copolyether resins prepared in Examples 1-5

[0055]

[0056] Then, the photosensitive dry film prepared from the alkali-soluble alicyclic copolyether resin prepared in Examples 1-5 was subjected to performance testing, and the testing method was as follows:

[0057] (1) Photosensitivity: The materials of the examples in Table 2 were mixed uniformly and coated on copper-clad plates by a coating machine, respectively, baked at 75°C for 20 minutes, and exposed and developed under an LED light source, with the 21-step light gradient scale placed above the film layer, with the time for the film layer to remain 7 steps as the standard.

[0058] (2) Minimum line width: tested according to the method for light imaging plating resist for printed boards in GB / T 29846-2013.

[0059] (3) Etching resistance evaluation: the etching resistance was tested according to the method for light imaging plating resist for printed boards in GB / T 29846-2013, and the etching after-observation pattern was complete, the line edge was neat, there was no wrinkling, peeling or dog-tooth shape, which was excellent, no peeling was good, and peeling was poor.

[0060] (4) Hardness evaluation: the dry film prepared in the application examples was tested for hardness according to GB / T 1730-93.

[0061] (5) Flexibility evaluation: after the film was pasted, exposed and developed, the dry film prepared was folded 20 times from different angles, and whether the dry film cracked was observed, the cracking times were counted, and the greater the value, the better the flexibility of the dry film.

[0062] Table 2 Components of application examples

[0063]

[0064] In Table 2, the weight of each component was calculated according to the solid content, and the solvent component was not included in the overall content of the composition (the mass percentage of the solvent was calculated with the solvent as the numerator and the composition as the denominator). The photoinitiator used was diphenyl (2,4,6-trimethyl) phosphine oxide (photoinitiator TPO), the active diluent was bisphenol A dimethyl acrylate, the defoaming agent was a siloxane copolymer defoaming agent, and the leveling agent was a polyacrylate. The test results of each index are shown in Table 3.

[0065] Table 3 Performance test results of alkali-soluble alicyclic copolyether resin of Examples 1-5

[0066]

[0067] As shown in Table 3, the alkali-soluble alicyclic copolyether resin has excellent photosensitivity, etching resistance, hardness, flexibility and other properties, and meets the application requirements of the photosensitive dry film.

[0068] The above merely describes some embodiments of the present application. For those skilled in the art, without departing from the concept of the present application, several modifications and improvements can be made, which are within the protection scope of the present application.

Claims

1. A method for preparing an alkali-soluble alicyclic copolyether resin, characterized in that: The steps include: S1. Mix a solvent, a polyol, tetrahydrofuran, and a catalyst, add 3,4-epoxycyclohexyl methacrylate dropwise at 0-5°C, then raise the temperature to 15-25°C, react for 4-6 hours, add water to terminate the reaction, and then remove the solvent to obtain an alicyclic copolyether intermediate; the molar ratio of the 3,4-epoxycyclohexyl methacrylate to the tetrahydrofuran is (2-5):1, and the catalyst is boron trifluoride etherate, and the amount thereof is 0.5-3 wt% of the total mass of the 3,4-epoxycyclohexyl methacrylate and the tetrahydrofuran; S2. Mix the alicyclic copolyether intermediate prepared in S1 with 3-mercaptopropionic acid, an organic solvent, and a photoinitiator, and react under ultraviolet light for 10-30 minutes, then remove the solvent to obtain an alkali-soluble alicyclic copolyether; wherein the molar ratio of the double bond in the alicyclic copolyether intermediate to the thiol group of the 3-mercaptopropionic acid is 1:(0.4-0.6).

2. The method for preparing the alkali-soluble alicyclic copolyether resin according to claim 1, wherein The solvent in step S1 is one or more of acetone, dichloromethane, butanone, and toluene, and its amount is 1-3 times the total mass of the 3,4-epoxycyclohexyl methacrylate and the tetrahydrofuran.

3. The method for preparing the alkali-soluble alicyclic copolyether resin according to claim 1 or 2, wherein: The polyol in step S1 is one or more of ethylene glycol, propylene glycol, butylene glycol, glycerol, trimethylolpropane and trimethylolethane, and its amount is 0.5-2wt% of the total mass of the 3,4-epoxycyclohexyl methacrylate and the tetrahydrofuran.

4. The method for preparing the alkali-soluble alicyclic copolyether resin according to claim 1, wherein The organic solvent in step S2 is at least one of acetone, dichloromethane, butanone, and toluene, and its amount is 1-3 times the total mass of the alicyclic copolyether intermediate and the 3-mercaptopropionic acid; the photoinitiator in step S2 is any cleavage-type free radical photoinitiator, and its amount is 0.5-2 wt% of the total mass of the alicyclic copolyether intermediate and the 3-mercaptopropionic acid.

5. An alkali-soluble alicyclic copolyether resin prepared by the method for preparing an alkali-soluble alicyclic copolyether resin according to any one of claims 1 to 4.

6. Use of the alkali-soluble alicyclic copolyether resin according to claim 5 in the preparation of photosensitive dry films.

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