Resin composition with multi-time photocuring performance as well as preparation method and application thereof

Abstract

The invention relates to a resin composition with multi-time photocuring performance and a preparation method and application thereof, and the preparation method of the resin composition with the multi-time photocuring performance comprises the following steps: mixing an acrylate monomer with a solvent to obtain a solution A; mixing an initiator with a solvent to obtain a solution B; uniformly mixing a part of the solution A and a part of the solution B, carrying out a preliminary reaction, respectively adding the remaining solutions of the solution A and the solution B into a reaction system at a constant speed in the reaction process, and continuing the reaction to obtain a resin prepolymer; uniformly mixing the resin prepolymer, acrylic acid and an accelerant, and reacting to obtain resin with photocuring activity; uniformly mixing the resin with the photocuring activity, an acidic catalyst and an acidity regulator, and reacting to obtain acidic photocuring resin; and uniformly mixing the acidic light-cured resin with a curing agent, and reacting to obtain the resin composition with the multi-time light curing performance.

Description

Technical Field

[0001] The present invention relates to the technical field of resin compositions, and particularly to a resin composition with multiple photocuring properties, a preparation method thereof, and an application thereof. Background Art

[0002] Lithography technology is a common process in the LCD industry, and photoresist is an essential material for the lithography process. Under the irradiation of a light beam, it can undergo crosslinking curing or degradation reactions. Since the photoresist has the property of not being eroded by the etching solution after undergoing a photo-crosslinking curing reaction, it is often used in the patterning etching process of display panels and can also be retained as a direct material in the panel. Taking negative photoresist as an example, the process of forming a pattern with the photoresist is as follows: in the exposure stage, ultraviolet light is used to irradiate the photoresist, causing the photoinitiator therein to generate free radicals, promoting the crosslinking reaction of monomers or resins in the light-receiving area and being retained after the subsequent development process, while the area not irradiated by ultraviolet light is dissolved by the developer in the subsequent development process, thereby forming the required photoresist pattern.

[0003] Adding conductive silver paste to the photoresist for printing circuits enables it to transmit electrical signals smoothly. CN114089599A discloses a photoresist composition based on metal nanoparticles and its application. The photoresist composition has good film-forming properties and excellent patterning imaging capabilities. Through ultraviolet, electron beam, or extreme ultraviolet exposure, photolithography patterns with different resolutions can be obtained. After heat treatment, the formed patterns have good conductivity and can be directly used for the processing of micro-nano devices. However, the linear structure of slurry printing will directly affect the strength of the transmitted electrical signal, and thus affect the resistance of the material. Moreover, in flexible displays, due to the bendable situation of the screen, the resistance will fluctuate to a certain extent with different bending effects. To solve this problem, when printing a photoresist containing conductive silver powder, printing a stepped linear structure will reduce the fluctuation range of the resistance, making the electrical signal transmission of the product more stable. In the conventional preparation field, to achieve a stepped structure, multiple printing and exposure development are required, and the process is cumbersome and the pattern edges are not regular enough, which affects the popularization and use of this technology.

[0004] Therefore, how to obtain a photoresist that can reduce the fluctuation range of the resistance, make the electrical signal transmission of the product more stable, avoid multiple printing and exposure development, has a simple process, and has clear and regular etched pattern edges has become an urgent problem to be solved at present. Summary of the Invention

[0005] To solve the above technical problems, the present invention provides a resin composition with multiple photocuring properties. By introducing two structures with completely different photocuring efficiencies and selectivities, namely allyl groups and acrylate groups, the resin composition has the property of being curable multiple times. The cured resin composition has excellent anti-ultraviolet aging performance and flexibility, and can be applied in the field of photoresists. A photoresist with a stepped structure can be obtained by only one printing and multiple exposures.

[0006] To achieve this purpose, the present invention adopts the following technical solutions:

[0007] In the first aspect, the present invention provides a preparation method of a resin composition with multiple photocuring properties. The preparation method of the resin composition with multiple photocuring properties includes the following steps:

[0008] (1) Mix acrylate monomers with a solvent to obtain solution A; mix an initiator with a solvent to obtain solution B;

[0009] (2) After uniformly mixing a part of solution A and a part of solution B, carry out a preliminary reaction. During the reaction, the remaining solutions of solution A and solution B are uniformly added to the reaction system at a constant speed, and continue the reaction to obtain a resin prepolymer;

[0010] (3) Uniformly mix the above resin prepolymer, acrylic acid and a promoter, and carry out a reaction to obtain a resin with photocuring activity;

[0011] (4) Uniformly mix the above resin with photocuring activity, an acidic catalyst and an acidity regulator, and carry out a reaction to obtain an acidic photocuring resin;

[0012] (5) Uniformly mix the above acidic photocuring resin with a curing agent, and carry out a reaction to obtain the resin composition with multiple photocuring properties.

[0013] The resin composition with multiple photocuring properties prepared by the present invention has two structures with completely different photocuring efficiencies and selectivities, namely olefin groups and acrylate groups. During the exposure process of acrylate groups, the reaction is rapid, while the olefin groups have a relatively low photocuring conversion rate. In the application of photoresists, a photoresist with a stepped linear structure can be formed without secondary printing. The addition of a blocked isocyanate curing agent further crosslinks with the remaining hydroxyl groups in the resin, further forming a stepped linear curing structure with clearer edges.

[0014] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the purpose and beneficial effects of the present invention can be better achieved and realized.

[0015] Preferably, the acrylic monomers in step (1) include glycidyl methacrylate, isobornyl methacrylate, methyl methacrylate, and n-butyl methacrylate.

[0016] Preferably, the mass ratio of glycidyl methacrylate, isobornyl methacrylate, methyl methacrylate, and n-butyl methacrylate is (1 - 1.5):(0.5 - 0.8):(3.5 - 5):(2 - 3).

[0017] Among them, "1 - 1.5" can be 1, 1.1, 1.2, 1.3, 1.4, or 1.5; "0.5 - 0.8" can be 0.5, 0.6, 0.7, or 0.8; "3.5 - 5" can be 3.5, 3.8, 4, 4.2, 4.4, 4.5, 4.8, or 5; "2 - 3" can be 2, 2.2, 2.4, 2.6, 2.8, or 3.

[0018] Preferably, the solvent in step (1) includes any one or a combination of at least two of diethylene glycol monobutyl ether, diethylene glycol methyl ether acetate, or dipropylene glycol methyl ether acetate.

[0019] Preferably, the initiator includes azobisisobutyronitrile.

[0020] Preferably, the addition amount of the initiator is 0.4 - 0.8 wt.% of the addition amount of the acrylic monomers, and for example, it can be 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, or 0.8 wt.%.

[0021] Preferably, the solid content of solution B in step (1) is 30 - 40%, and for example, it can be 30%, 32%, 34%, 36%, 38%, or 40%.

[0022] Preferably, the partial solution A in step (2) is 20 - 40 wt.% of solution A in step (1), and for example, it can be 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, or 40 wt.%.

[0023] Preferably, the partial solution B in step (2) is 20 - 40 wt.% of solution B in step (1), and for example, it can be 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, or 40 wt.%.

[0024] Preferably, the temperatures of the preliminary reaction and the continuous reaction in step (2) are both 105 - 115°C, and for example, they can be 105°C, 106°C, 108°C, 110°C, 112°C, 114°C, or 115°C.

[0025] Preferably, the addition time for the uniform addition in step (2) is 4 - 5 h, and it can be, for example, 4 h, 4.2 h, 4.4 h, 4.6 h, 4.8 h or 5 h.

[0026] Preferably, the reaction time for the continued reaction in step (2) is 3 - 9 h, and it can be, for example, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h or 9 h.

[0027] By controlling the partial addition of solution A and solution B and the uniform addition of the remaining parts, the resin composition prepared by the present invention has a suitable cross - linking density, avoiding too high or too low local cross - linking density, thereby affecting the subsequent multiple curing processes of the resin composition.

[0028] Preferably, the mass ratio of the acrylic acid in step (3) to the acrylate monomer in step (1) is 1:(10 - 21), and it can be, for example, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20 or 1:21.

[0029] Preferably, the accelerator includes N,N - dimethylbenzylamine.

[0030] Preferably, the addition amount of the accelerator is 0.3 - 0.9 wt.% of the sum of the addition amounts of the acrylic acid monomer and the acrylic acid, and it can be, for example, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.% or 0.9 wt.%.

[0031] Preferably, the acid value of the resin with photocuring activity is ≤3 mgKOH / g, and it can be, for example, 0.5 mgKOH / g, 1 mgKOH / g, 1.5 mgKOH / g, 2 mgKOH / g, 2.5 mgKOH / g or 3 mgKOH / g.

[0032] Preferably, the temperature of the reaction in step (3) is 100 - 110 °C, and it can be, for example, 101 °C, 102 °C, 104 °C, 106 °C, 108 °C or 110 °C.

[0033] Preferably, the reaction time in step (3) is 3 - 9 h, and it can be, for example, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h or 9 h.

[0034] Preferably, the acidic catalyst in step (4) includes p - toluenesulfonic acid.

[0035] Preferably, the addition amount of the acidic catalyst is 0.1 - 0.5 wt.% of the sum of the addition amounts of the acrylic acid monomer and the acrylic acid, and it can be, for example, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.% or 0.5 wt.%.

[0036] Preferably, the acidity regulator includes maleic anhydride.

[0037] Preferably, the addition amount of the acidity regulator is 6.2 - 8.2 wt.% of the sum of the addition amounts of acrylic acid monomer and acrylic acid, and can be, for example, 6.2 wt.%, 6.5 wt.%, 7 wt.%, 7.5 wt.%, 8 wt.% or 8.2 wt.%.

[0038] Preferably, the temperature of the reaction in step (4) is 85 - 95 °C, and can be, for example, 85 °C, 86 °C, 88 °C, 90 °C, 92 °C, 94 °C or 95 °C.

[0039] Preferably, the reaction time in step (4) is 3 - 9 h, and can be, for example, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h or 9 h.

[0040] Preferably, the acid value of the acidic photocurable resin is 60 - 80 mgKOH / g, and can be, for example, 60 mgKOH / g, 65 mgKOH / g, 70 mgKOH / g, 75 mgKOH / g or 80 mgKOH / g.

[0041] Preferably, the mass ratio of the acidic photocurable resin to the curing agent in step (5) is 1:(0.03 - 0.06), and can be, for example, 1:0.03, 1:0.04, 1:0.05 or 1:0.06.

[0042] Preferably, the curing agent includes a blocked isocyanate curing agent.

[0043] Preferably, the temperature of the reaction in step (5) is 20 - 30 °C, and can be, for example, 20 °C, 22 °C, 24 °C, 26 °C, 28 °C or 30 °C.

[0044] Preferably, the blocked isocyanate curing agent can be selected from any one or a combination of at least two of HF - 4268 and HF - 9069 of Haoyi New Materials, K60X of Asahi Kasei of Japan, and 3175 of Covestro.

[0045] In a second aspect, the present invention provides a resin composition prepared by the preparation method of the resin composition having multiple photocuring performances as described in the first aspect.

[0046] In a third aspect, the present invention provides a photoresist, and the photoresist includes the resin composition as described in the second aspect.

[0047] Preferably, the photoresist further includes a conductive agent.

[0048] The photoresist prepared in the third aspect of the present invention can be used to form printed circuits in a printing manner. The resin composition obtained in the second aspect of the present invention is combined with a conductive agent to obtain a photoresist with conductive function. The photoresist is baked at 70 - 80 °C for 30 - 60 min. After the solvent is dried, the desired printed pattern is shielded from light, and then the first exposure is carried out. After alkali washing, the desired pattern shape is obtained. At this time, the printed shape is triangular or trapezoidal, and the main cross-linking group during the first exposure is the acrylate group. After drying the alkali washing solution, the second exposure is carried out to further cross-link the remaining allyl groups. At this time, a certain degree of depression will appear at the hypotenuse of the trapezoid or triangle. To make the depression more obvious, a photoresist with a stepped structure is formed.

[0049] The present invention also introduces a blocked isocyanate curing agent, and the system is further baked at 150 - 170 °C for 30 - 90 min. The curing agent makes the final cross-linking with the residual hydroxyl groups in the resin. Due to a certain shrinkage after the resin cross-links, the depression will deepen or even collapse, forming a stepped linear curing structure with clearer edges.

[0050] Compared with the prior art, the present invention has at least the following beneficial effects:

[0051] The present invention prepares a resin composition with multiple photocuring properties. By introducing two structures with completely different photocuring efficiencies and selectivities, namely allyl groups and acrylate groups, the resin composition has the property of being curable multiple times. The cured resin composition has excellent anti-ultraviolet aging performance and flexibility, and can be applied to the field of photoresists. A photoresist with a stepped structure can be obtained only by one printing and multiple exposures, which can reduce the fluctuation range of resistance and make the product's electrical signal transmission more stable. Detailed Embodiments

[0052] To facilitate the understanding of the present invention, the following examples are listed. Those skilled in the art should understand that the examples are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0053] The sources of raw materials used in the following examples and comparative examples are as follows:

[0054] 1. Glycidyl methacrylate, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0055] 2. Isobornyl methacrylate, purchased from Shanghai Macklin Biochemical Technology Co., Ltd.;

[0056] 3. Methyl methacrylate, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0057] 4. n-Butyl methacrylate, purchased from Shanghai Macklin Biochemical Co., Ltd.;

[0058] 5. 2,2'-Azobis(2-methylpropionitrile), purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0059] 6. N,N-Dimethylbenzylamine, purchased from Shanghai Macklin Biochemical Co., Ltd.;

[0060] 7. p-Toluenesulfonic acid, purchased from Shanghai Macklin Biochemical Co., Ltd.;

[0061] 8. Maleic anhydride, purchased from Shanghai Macklin Biochemical Co., Ltd.;

[0062] 9. Blocked isocyanate curing agent, HF-4268, purchased from Haoyi New Materials;

[0063] 10. Blocked isocyanate curing agent, HF-9069, purchased from Haoyi New Materials;

[0064] 11. Blocked isocyanate curing agent, K60X, purchased from Asahi Kasei of Japan.

[0065] Example 1

[0066] A preparation method of a resin composition having multi-time photocuring performance, the preparation method of the resin composition having multi-time photocuring performance includes the following steps:

[0067] (1) Mix glycidyl methacrylate, isobornyl methacrylate, methyl methacrylate and n-butyl methacrylate (mass ratio of 1:0.5:3.5:2) as acrylic monomers with an equal mass of diethylene glycol monobutyl ether to obtain solution A; mix 2,2'-azobis(2-methylpropionitrile) (its addition amount is 0.4 wt.% of the addition amount of acrylic monomers) with diethylene glycol monobutyl ether (mass ratio of 2,2'-azobis(2-methylpropionitrile) to diethylene glycol monobutyl ether is 3:7) to obtain solution B, and the solid content of solution B is 30%;

[0068] (2) Take a part of solution A (accounting for 30% of the total mass of solution A) and a part of solution B (accounting for 30% of the total mass of solution B), and uniformly mix them, then carry out a preliminary reaction at 110 °C. During the reaction, the remaining solutions of solution A and solution B are uniformly added to the reaction system at a constant speed. After controlling the addition to be completed uniformly in 4 h, continue the reaction for 4 h to obtain a resin prepolymer;

[0069] (3) Uniformly mix the above resin prepolymer, acrylic acid (mass ratio to the acrylate monomer described in step (1) is 1:14) and N,N-dimethylbenzylamine (its addition amount is 0.3% of the sum of the addition amounts of acrylic monomers and acrylic acid), and react at 100 °C for 4 h to obtain a resin with photocuring activity;

[0070] (4) The above resin with photocuring activity, p-toluenesulfonic acid (the addition amount is 0.1 wt.% of the sum of the addition amounts of acrylic monomers and acrylic acid), and maleic anhydride (the addition amount is 6.2 wt.% of the sum of the addition amounts of acrylic monomers and acrylic acid) are uniformly mixed and reacted at 90 °C for 4 h to obtain an acidic photocuring resin.

[0071] (5) The acidic photocuring resin and the blocked isocyanate curing agent HF-4268 with a mass ratio of 1:0.03 are uniformly mixed at 25 °C to obtain the resin composition with multiple photocuring performances.

[0072] Example 2

[0073] A preparation method of a resin composition with multiple photocuring performances, the preparation method of the resin composition with multiple photocuring performances includes the following steps:

[0074] (1) Acrylic monomers (glycidyl methacrylate, isobornyl methacrylate, methyl methacrylate, and n-butyl methacrylate with a mass ratio of 1.25:0.7:4.5:2.5) are mixed with an equal mass of diethylene glycol monobutyl ether to obtain solution A; azobisisobutyronitrile (the addition amount is 0.6 wt.% of the addition amount of acrylic monomers) and diethylene glycol monobutyl ether (the mass ratio of azobisisobutyronitrile to diethylene glycol monobutyl ether is 3.5:6.5) are mixed to obtain solution B, and the solid content of solution B is 35%.

[0075] (2) Take a part of solution A (accounting for 20% of the total mass of solution A) and a part of solution B (accounting for 20% of the total mass of solution B), and after uniformly mixing them, conduct a preliminary reaction at 105 °C. During the reaction process, the remaining solutions of solution A and solution B are added to the reaction system at a constant speed. After controlling the completion of the uniform addition in 4.5 h, continue the reaction for 6 h to obtain a resin prepolymer.

[0076] (3) The above resin prepolymer, acrylic acid (the mass ratio to the acrylate monomer described in step (1) is 1:10), and N,N-dimethylbenzylamine (the addition amount is 0.6 wt.% of the sum of the addition amounts of acrylic monomers and acrylic acid) are uniformly mixed and reacted at 105 °C for 6 h to obtain a resin with photocuring activity.

[0077] (4) The above resin with photocuring activity, p-toluenesulfonic acid (the addition amount is 0.3 wt.% of the sum of the addition amounts of acrylic monomers and acrylic acid), and maleic anhydride (the addition amount is 7.2 wt.% of the sum of the addition amounts of acrylic monomers and acrylic acid) are uniformly mixed and reacted at 85 °C for 6 h to obtain an acidic photocuring resin.

[0078] (5) Mix the acid-curable resin and the blocked isocyanate curing agent HF-9069 with a mass ratio of 1:0.04 evenly at 20 °C to obtain the resin composition with multiple photocuring properties.

[0079] Example 3

[0080] A preparation method of a resin composition with multiple photocuring properties, the preparation method of the resin composition with multiple photocuring properties includes the following steps:

[0081] (1) Mix the acrylic monomers (glycidyl methacrylate, isobornyl methacrylate, methyl methacrylate, n-butyl methacrylate with a mass ratio of 1.5:0.8:5:3) with an equal mass of diethylene glycol monobutyl ether to obtain solution A; mix azobisisobutyronitrile (the addition amount is 0.8 wt.% of the addition amount of acrylic monomers) with diethylene glycol monobutyl ether (the mass ratio of azobisisobutyronitrile to diethylene glycol monobutyl ether is 4:6) to obtain solution B, and the solid content of solution B is 40%;

[0082] (2) Take a part of solution A (accounting for 30% of the total mass of solution A) and a part of solution B (accounting for 30% of the total mass of solution B), and after mixing them evenly, carry out a preliminary reaction at 115 °C. During the reaction, the remaining solutions of solution A and solution B are added to the reaction system at a constant speed respectively. After controlling the addition to be completed at a constant speed for 5 h, continue to react for 9 h to obtain a resin prepolymer;

[0083] (3) Mix the above resin prepolymer, acrylic acid (the mass ratio to the acrylate monomer described in step (1) is 1:20) and N,N-dimethylbenzylamine (the addition amount is 0.9 wt.% of the sum of the addition amounts of acrylic monomers and acrylic acid) evenly, and react at 110 °C for 9 h to obtain a resin with photocuring activity;

[0084] (4) Mix the above resin with photocuring activity, p-toluenesulfonic acid (the addition amount is 0.5 wt.% of the sum of the addition amounts of acrylic monomers and acrylic acid) and maleic anhydride (the addition amount is 8.2 wt.% of the sum of the addition amounts of acrylic monomers and acrylic acid) evenly, and react at 95 °C for 9 h to obtain an acid-curable resin;

[0085] (5) Mix the acid-curable resin and the blocked isocyanate curing agent K60X with a mass ratio of 1:0.06 evenly at 28 °C to obtain the resin composition with multiple photocuring properties.

[0086] Example 4

[0087] A preparation method of a resin composition with multiple photocuring properties, which is different from Example 1 in that: the addition amount of azobisisobutyronitrile in step (1) is 0.1 wt.% of the addition amount of acrylic monomers.

[0088] Example 5

[0089] A preparation method of a resin composition with multiple photocuring properties, which is different from Example 1 in that: the addition amount of azobisisobutyronitrile in step (1) is 1 wt.% of the addition amount of acrylic monomers.

[0090] Example 6

[0091] A preparation method of a resin composition with multiple photocuring properties, which is different from Example 1 in that: the addition amount of maleic anhydride in step (4) is 5.2 wt.% of the sum of the addition amounts of acrylic monomers and acrylic acid.

[0092] Example 7

[0093] A preparation method of a resin composition with multiple photocuring properties, which is different from Example 1 in that: the addition amount of maleic anhydride in step (4) is 10 wt.% of the sum of the addition amounts of acrylic monomers and acrylic acid.

[0094] Comparative Example 1

[0095] A preparation method of a resin composition, the preparation method of the resin composition includes the following steps:

[0096] (1) Mix glycidyl methacrylate, isobornyl methacrylate, methyl methacrylate, and n-butyl methacrylate (with a mass ratio of 1:0.5:3.5:2) as acrylic monomers with an equal mass of diethylene glycol monobutyl ether to obtain solution A; mix azobisisobutyronitrile (the addition amount thereof is 0.4 wt.% of the addition amount of acrylic monomers) with diethylene glycol monobutyl ether (the mass ratio of azobisisobutyronitrile to diethylene glycol monobutyl ether is 3:7) to obtain solution B, and the solid content of solution B is 30%;

[0097] (2) Take a part of solution A (accounting for 30% of the total mass of solution A) and a part of solution B (accounting for 30% of the total mass of solution B), and uniformly mix them, then carry out a preliminary reaction at 110 °C. During the reaction, the remaining solutions of solution A and solution B are respectively added to the reaction system at a constant speed. After controlling the addition to be completed in 4 h at a constant speed, continue the reaction for 4 h to obtain a resin prepolymer;

[0098] (3) The above resin prepolymer, p-toluenesulfonic acid (the addition amount thereof is 0.1 wt.% of the addition amount of acrylic monomers), and maleic anhydride (the addition amount thereof is 6.2 wt.% of the addition amount of acrylic monomers) are uniformly mixed and reacted at 90 °C for 4 h to obtain an acidic resin;

[0099] (4) The acidic resin and the blocked isocyanate curing agent HF-4268 with a mass ratio of 1:0.03 are uniformly mixed at 25 °C to obtain a resin composition.

[0100] Comparative Example 2

[0101] A preparation method of a resin composition, the preparation method of the resin composition comprising the following steps:

[0102] (1) The acrylic monomers (glycidyl methacrylate, isobornyl methacrylate, methyl methacrylate, n-butyl methacrylate with a mass ratio of 1:0.5:3.5:2) are mixed with an equal mass of diethylene glycol monobutyl ether to obtain Solution A; azobisisobutyronitrile (the addition amount thereof is 0.4 wt.% of the addition amount of acrylic monomers) and diethylene glycol monobutyl ether (the mass ratio of azobisisobutyronitrile to diethylene glycol monobutyl ether is 3:7) are mixed to obtain Solution B, and the solid content of Solution B is 30%;

[0103] (2) Take a part of Solution A (accounting for 30% of the total mass of Solution A) and a part of Solution B (accounting for 30% of the total mass of Solution B), and after uniformly mixing them, conduct a preliminary reaction at 110 °C. During the reaction process, the remaining solutions of Solution A and Solution B are uniformly added to the reaction system at a constant speed. After controlling the completion of the uniform addition in 4 h, continue the reaction for 4 h to obtain a resin prepolymer;

[0104] (3) The above resin prepolymer, acrylic acid (the molar ratio thereof to the acrylate monomer described in step (1) is 1:0.95), and N,N-dimethylbenzylamine (the addition amount thereof is 0.3% of the sum of the addition amounts of acrylic monomers and acrylic acid) are uniformly mixed and reacted at 100 °C for 4 h to obtain a resin with photocuring activity;

[0105] (4) The above resin with photocuring activity, p-toluenesulfonic acid (the addition amount thereof is 0.1 wt.% of the sum of the addition amounts of acrylic monomers and acrylic acid), and maleic anhydride (the addition amount thereof is 6.2 wt.% of the sum of the addition amounts of acrylic monomers and acrylic acid) are uniformly mixed and reacted at 90 °C for 4 h to obtain the resin composition.

[0106] Comparative Example 3

[0107] The resin composition with multiple photocuring performances prepared in Example 1 is replaced with Sartomer photocuring resin CN2203 in equal mass.

[0108] Testing method

[0109] Take the resin compositions with multi - photo - curing performance prepared in Examples 1 - 7 and Comparative Examples 1 - 3, and make a photoresist with conductive function by combining with a photo - initiator and conductive copper powder. Coat the photoresist on a PET film, then bake it at 80 °C for 50 min. After the solvent is dried, shade the required serpentine pattern, conduct the first exposure, and then obtain the required pattern shape after alkali washing. Then dry the alkali washing solution and conduct the second exposure. Bake the photoresist after the second exposure at 160 °C for 60 min to form a stepped linear photoresist with clearer edges, and conduct the following tests.

[0110] Yellowness index Δb (UV60KWh): Test according to the test method provided in 《ASTM E313 - 2010》;

[0111] Linear resistance: Use a micro - ohmmeter to test the linear resistance at the ends of the serpentine screen;

[0112] Linear resistance test after bending:

[0113] Use a folding resistance tester to test. The folding area is the center line of the serpentine piece, conduct folding from 0° to 180°, set the rotation radius R to 1 mm, and stop for 2 s each time; folding from 0° to 180° clockwise and then returning to 0° is counted as 1 time. After 20 consecutive times, use a micro - ohmmeter to test the linear resistance.

[0114] Test results

[0115] Table 1

[0116]

[0117] It can be seen from the test results that:

[0118] (1) Through the performance tests of Examples 1 - 7, it can be known that when the resin composition with multi - photo - curing performance prepared by the present invention is used as the matrix resin of the photoresist, after the photoresist resistance is bent multiple times, the increase can be controlled within 30%, and there is no obvious yellowing of the photoresist.

[0119] (2) Through the performance tests of Examples 4 - 5, it can be known that when the content of the initiator is too low, the molecular weight of the resin composition with multi - photo - curing performance will be too high, making the photoresist difficult to develop, and the edge is rough after development, thus increasing the resistance; while when the content of the initiator is too high, the molecular weight of the resin composition with multi - photo - curing performance is low, over - development occurs, resulting in the linear structure not presenting a relatively clear stepped shape, also leading to an increase in resistance.

[0120] (3) It can be seen from the performance tests of Examples 6-7 that when the anhydride content is too low, it also causes difficult development and an increase in resistance; when the anhydride content is too high, there are too many carboxyl groups in the anhydride, which affects conductivity and causes an increase in resistance.

[0121] (4) It can be seen from Example 1 and Comparative Example 1 that when the resin composition lacks allyl groups, it cannot be effectively developed by secondary exposure to form a relatively obvious stepped structure, and the resistance fluctuates greatly before and after bending, with the resistance increase exceeding 50%.

[0122] (5) It can be seen from Example 1 and Comparative Example 1 that when the resin composition lacks a blocked crosslinking agent, the linear stepped structure is not clear enough. After the photoresist is bent, the linear difference is relatively obvious, and the resistance fluctuates greatly before and after bending, with the resistance increase exceeding 50%.

[0123] (6) Comparative Example 3 is a commercially available resin product with photocuring properties. Compared with the product prepared in Example 1 of the present invention, the resistance fluctuates greatly before and after bending, with the resistance increase exceeding 50%.

[0124] The applicant declares that the above description is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by any person skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A method for preparing a resin composition having multi - light - curing performance, characterized in that, The preparation method of the resin composition with multiple photocuring properties comprises the following steps: (1) Mix acrylate monomers with a solvent to obtain solution A; mix an initiator with a solvent to obtain solution B; (2) Uniformly mix a part of solution A and a part of solution B, carry out a preliminary reaction, and during the reaction, uniformly add the remaining solutions of solution A and solution B to the reaction system at a constant speed, and continue the reaction to obtain a resin prepolymer; (3) Uniformly mix the above resin prepolymer, acrylic acid and a promoter, and carry out a reaction to obtain a resin with photocuring activity; (4) Uniformly mix the above resin with photocuring activity, an acidic catalyst and an acidity regulator, and carry out a reaction to obtain an acidic photocuring resin; (5) Uniformly mix the above acidic photocuring resin with a curing agent, and carry out a reaction to obtain the resin composition with multiple photocuring properties.

2. The preparation method of the resin composition having multiple photocuring properties according to claim 1, characterized in that, The acrylate monomers described in step (1) include glycidyl methacrylate, isobornyl methacrylate, methyl methacrylate and n-butyl methacrylate; Preferably, the mass ratio of glycidyl methacrylate, isobornyl methacrylate, methyl methacrylate and n-butyl methacrylate is (1 - 1.5):(0.5 - 0.8):(3.5 - 5):(2 - 3).

3. The preparation method of the resin composition having multiple photocuring properties according to claim 1 or 2, characterized in that, The solvent described in step (1) includes any one or a combination of at least two of diethylene glycol monobutyl ether, diethylene glycol methyl ether acetate or dipropylene glycol methyl ether acetate.

4. The preparation method of the resin composition with multiple photocuring properties according to any one of claims 1-3, characterized in that, The initiator includes azobisisobutyronitrile; Preferably, the addition amount of the initiator is 0.4 - 0.8 wt.% of the addition amount of acrylate monomers; Preferably, the solid content of solution B in step (1) is 30 - 40%.

5. The preparation method of the resin composition having multi - light - curing performance according to any one of claims 1 - 4, characterized in that, The part of solution A in step (2) is 20 - 40 wt.% of solution A in step (1); Preferably, the part of solution B in step (2) is 20 - 40 wt.% of solution B in step (1); Preferably, the temperatures of the preliminary reaction and the continued reaction in step (2) are both 105 - 115 °C; Preferably, the addition time for the uniform addition in step (2) is 4 - 5 h; Preferably, the reaction time for the continued reaction in step (2) is 3 - 9 h.

6. The preparation method of the resin composition with multiple photocuring properties according to any one of claims 1-5, characterized in that, The mass ratio of acrylic acid to the acrylate monomers described in step (1) in step (3) is 1:(10 - 21); Preferably, the promoter includes N,N-dimethylbenzylamine; Preferably, the addition amount of the promoter is 0.3 - 0.9 wt.% of the sum of the addition amounts of acrylate monomers and acrylic acid; Preferably, the acid value of the resin with photocuring activity is ≤ 3 mgKOH / g; Preferably, the temperature of the reaction in step (3) is 100 - 110 °C; Preferably, the reaction time in step (3) is 3 - 9 h.

7. The preparation method of the resin composition with multiple photocuring performances according to any one of claims 1-6, characterized in that, The acidic catalyst in step (4) includes p-toluenesulfonic acid; Preferably, the addition amount of the acidic catalyst is 0.1 - 0.5 wt.% of the sum of the addition amounts of acrylate monomers and acrylic acid; Preferably, the acidity regulator includes maleic anhydride; Preferably, the addition amount of the acidity regulator is 6.2 - 8.2 wt.% of the sum of the addition amounts of acrylic acid monomer and acrylic acid; Preferably, the temperature of the reaction in step (4) is 85 - 95 °C; Preferably, the reaction time in step (4) is 3 - 9 h; Preferably, the acid value of the acidic photocurable resin is 60 - 80 mgKOH / g.

8. The preparation method of the resin composition having multi - photocuring performance according to any one of claims 1 - 7, characterized in that, In step (5), the mass ratio of the acidic photocurable resin to the curing agent is 1:(0.03 - 0.06); Preferably, the curing agent includes a blocked isocyanate curing agent; Preferably, the temperature of the reaction in step (5) is 20 - 30 °C.

9. A resin composition prepared by the preparation method of the resin composition with multiple photocuring performances according to any one of claims 1 - 8.

10. A photoresist, characterized in that, The photoresist includes the resin composition according to claim 9.

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