Resin, resin composition and application thereof

Abstract

The invention provides a resin, a resin composition and application of the resin composition. The resin is composed of the following structural units: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16 R1 is selected from aliphatic groups with 1-18 carbon atoms; r < 2 > is selected from CH2CH (OH) CH2 and CH2C6H9 (OH), and R < 12 > is selected from CH2CH (OH) CH2 and CH2C6H9 (OH); r < 3 > is shown in the description, R < 13 >, R < 14 > and R < 15 > are independently selected from alkoxy with 1-3 carbon atoms or alkyl with 1-3 carbon atoms, R < 13 >, R < 14 > and R < 15 > cannot be alkyl at the same time, and R < 16 > is selected from-C2H4 <-> or-CH2CH2OCH2CH (OH) CH2 <->; r4 is shown in the specification, and R5 is-H; and R6, R7, R8, R9, R10 and R11 are respectively and independently selected from-H or-CH3. According to the resin provided by the invention, the adhesive force, the light sensitivity, the weather resistance, the yellowing resistance and the like of an existing product can be remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of photosensitive resin technology, and more particularly to a resin, a resin composition, and its application. Background Technology

[0002] Photolithography utilizes the properties of photosensitive materials to create intricate patterns in electronic components through steps such as exposure and development. Currently, photosensitive materials are widely used in printed circuit boards (PCBs), integrated circuits (ICs), liquid crystal displays (LCDs), and microelectromechanical systems (MEMS) for fabricating materials such as photoresists and protective or insulating layers in electronic components. Due to the trend towards miniaturization and high integration, the requirements for photosensitive materials are becoming increasingly stringent. Therefore, to meet the demands for high resolution and improve product reliability and yield, photosensitive materials must possess characteristics such as high photosensitivity, high light transmittance, high surface hardness, high heat resistance, high flatness, high corrosion resistance, low thermal expansion, and high adhesion to substrates (e.g., indium tin oxide (ITO) in LCD and touch panels). Although many improvements have been made to photosensitive resins, to meet the needs of the glass substrate industry, there is still a pressing need for resin materials that possess high adhesion, aging resistance, and excellent photosensitivity. Summary of the Invention

[0003] In a first aspect, the present invention provides a resin that significantly improves the adhesion, photosensitivity, weather resistance, and yellowing resistance of existing products.

[0004] Specifically, the resin provided by the present invention is composed of the following structural units: , , , and ; R1 is selected from aliphatic groups with 1-18 carbon atoms; R2 is , where R 12 Selected from CH2CH(OH)CH2 and CH2C6H9(OH); R3 is , where R 13 R 14 R 15 Each is independently selected from an alkoxy group with 1-3 carbon atoms or an alkyl group with 1-3 carbon atoms, and R 13 R 14 R 15 Cannot be alkyl at the same time, R 16Selected from -C2H4- or -CH2CH2OCH2CH(OH)CH2-; R4 is ; R5 is -H; R6, R7, R8, R9, R 10 R 11 Each can be selected independently from -H or -CH3.

[0005] According to the resin provided by the present invention, the structural unit of Formula 1 serves as the main component of the resin, and polymers with different softening points and molecular weights are obtained by polymerization with different types of (meth)acrylate monomers. The structural units of Formula 2 and Formula 4 are obtained by grafting reactions based on the structural unit of Formula 5, which can improve photosensitivity and alkali solubility, while the structural unit of Formula 3 provides excellent adhesion. Simultaneously, by employing resins composed of structural units of Formulas 1 to 5, the structural units synergistically enhance each other, working together to further improve the resin's photosensitivity, anti-aging properties, and adhesion.

[0006] In some embodiments of the present invention, R1 is selected from at least one of methyl, ethyl, propyl, butyl, tert-butyl, hydroxyethyl, hydroxypropyl, and isobornyl.

[0007] In some embodiments of the present invention, R 13 R 14 R 15 Each is independently selected from at least one of methoxy, ethoxy, propoxy, methyl, ethyl, or propyl, and R 13 R 14 R 15 It cannot be an alkyl group at the same time.

[0008] In some embodiments of the present invention, based on the total number of moles of structural units of Formula 1, Formula 2, Formula 3, Formula 4 and Formula 5, the molar percentage of structural unit of Formula 3 is 5-10%.

[0009] In some embodiments of the present invention, based on the total number of moles of structural units of Formula 1, Formula 2, Formula 3, Formula 4 and Formula 5, the molar percentage of structural unit of Formula 4 is 5-10%.

[0010] In some embodiments of the present invention, the molar ratio of the structural unit of Formula 1, the structural unit of Formula 2, the structural unit of Formula 3, the structural unit of Formula 4 and the structural unit of Formula 5 is (70~120):(5~20):(5~15):(5~15):(5~20).

[0011] As an example, the structure of the resin is as follows: .

[0012] According to the resin provided by the present invention, the acid value of the resin is 60 mg KOH / g to 210 mg KOH / g, preferably 90 mg KOH / g to 120 mg KOH / g. For example, the acid value is 60 mg KOH / g, 80 mg KOH / g, 100 mg KOH / g, 120 mg KOH / g, 140 mg KOH / g, 160 mg KOH / g, 180 mg KOH / g, 210 mg KOH / g, etc., or any range between the above two values. If the acid value of the resin exceeds this range, the ideal alkaline development characteristics cannot be achieved. That is, if the resin acid value is less than 60 mg KOH / g, the solubility relative to the alkaline developer may be insufficient, affecting the presentation of the developed pattern; if the resin acid value exceeds 210 mg KOH / g, the hydrophilicity is too strong, affecting the product performance.

[0013] According to the resin provided by the present invention, the weight-average molecular weight Mw (measured by light scattering method) of the resin is 8000-30000, more preferably 15000-25000. For example, the weight-average molecular weight is 8000, 10000, 12000, 15000, 20000, 25000, 30000, etc., or any range between the above two values. If the weight-average molecular weight of the resin is less than 8000, the film-forming properties are poor; if the weight-average molecular weight of the resin exceeds 30000, the probability of carboxyl group reaction decreases, and some residue will remain after thermosetting, affecting the product performance.

[0014] According to the resin provided by the present invention, the double bond equivalent of the resin is 400~1900 g / mol, preferably 600~900 g / mol. For example, the double bond equivalent of the resin is 400 g / mol, 600 g / mol, 800 g / mol, 1000 g / mol, 1200 g / mol, 1400 g / mol, 1600 g / mol, 1800 g / mol, 1900 g / mol, etc., or any range between the above two values. Controlling the double bond equivalent of the resin within the above range can provide suitable sensitivity while maintaining a certain degree of flexibility.

[0015] In some embodiments of the present invention, the resin is prepared as follows: (1) Polymerize (meth)acrylate monomers, (meth)acrylic acid, and (meth)acrylate oxysilane monomers under the action of a free radical initiator to obtain a main chain resin; (2) The main chain resin is grafted with glycidyl methacrylate under the action of a catalyst to obtain a photosensitive resin; (3) The photosensitive resin is mixed with 3,4-cyclohexene dianone to undergo a substitution reaction to obtain the resin.

[0016] (Meth)acrylate monomers, (meth)acrylic acid, and (meth)acrylate oxysilane monomers polymerize by double bond breakage under the action of a free radical initiator, forming a main-chain resin containing R3 and R5 groups. The main-chain resin is then grafted with glycidyl (meth)acrylate under the action of a catalyst to obtain R2 groups. Finally, the obtained photosensitive resin is mixed with 3,4-cyclohexene dianone to undergo a substitution reaction, yielding R4 groups.

[0017] In some embodiments of the present invention, in step (1), the (meth)acrylate monomers include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, hydroxyethyl (meth)acrylate, isobornyl (meth)acrylate, etc.

[0018] In some embodiments of the present invention, in step (1), the temperature of the system in which the polymerization reaction occurs is maintained at 62-67°C for 3-4 hours, and then the temperature is raised to 72-77°C for 2-3 hours.

[0019] In some embodiments of the present invention, in step (1), the initiator includes, but is not limited to, one or more of 2,2'-azobisisobutyronitrile (AIBN), azobisisoheptanenitrile (ABVN), and benzoyl peroxide (BPO), preferably 2,2'-azobisisobutyronitrile (AIBN). Further, based on the total mass of the reactants in step (1), the amount of initiator added is 1-10% of the total mass of the reactants.

[0020] In some embodiments of the present invention, in step (1), the polymerization reaction is carried out in a solvent, which includes, but is not limited to, one or more of propylene glycol methyl ether acetate, isopropanol, and butanone, with propylene glycol methyl ether acetate (PMA) being particularly preferred. Further, based on the total mass of the solution, the mass percentage of the solvent is preferably about 50%.

[0021] In some embodiments of the present invention, in step (2), the system in which the grafting reaction occurs reacts at a temperature of 105-115°C for 3.5-4.5 h.

[0022] In some embodiments of the present invention, in step (2), the catalyst includes, but is not limited to, at least one of triphenylphosphine and methoxyphenol.

[0023] In some embodiments of the present invention, in step (3), the system in which the substitution reaction occurs reacts at a temperature of 105-115°C for 1.5-2.5 h.

[0024] The present invention also provides a resin composition containing the aforementioned resin. Due to the presence of the resin, this composition exhibits significant advantages in terms of adhesion, photosensitivity, weather resistance, and resistance to yellowing.

[0025] Preferably, based on the total mass of the resin composition, the mass percentage of the resin is 40-70%, more preferably 55-65%.

[0026] Preferably, the composition further includes auxiliary alkali-soluble photosensitive resin, monomer reactive diluent, epoxy thermosetting agent, photopolymerization initiator, antioxidant, and ultraviolet absorber.

[0027] The resin composition provided by this invention has the characteristics of high sensitivity, good adhesion to substrates, and resistance to yellowing. It can be applied in the field of transparent displays and has good adhesion to glass, ceramic substrates, etc.

[0028] The present invention also provides the application of the above-described resin or resin composition in printed circuits, integrated circuits, display panels or microelectromechanical systems. Detailed Implementation

[0029] Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this invention.

[0030] Example 1 This embodiment provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, add 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 40 parts by weight of methyl methacrylate (MMA), 25 parts by weight of methacrylic acid (MAA), 40 parts by weight of ethyl methacrylate (EMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 50 parts by weight of trimethacryloyloxypropylmethyldimethoxysilane (siloxane structure). After replacing with nitrogen, start stirring rapidly and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the main chain resin. (2) In an air atmosphere, add 30 parts by weight of glycidyl methacrylate, 0.5 parts by weight of triphenylphosphine and 0.3 parts by weight of methoxyphenol to the system obtained in step (1) and react at 110°C for 4 h.

[0031] (3) Add 8 parts by weight of 3,4-cyclohexene dianone to the system obtained in step (2) and continue the reaction for 2 hours to obtain the resin.

[0032] The resin prepared in this embodiment was tested and found to have a solid component acid value of 80 mgKOH / g, a double bond equivalent of 600 g / mol, and a weight-average molecular weight of 21000.

[0033] Resin Chinese-style 1 structural unit ( Formula 2 structural unit ( Formula 3 structural unit ( Formula 4 structural unit ( ) and Equation 5 structural unit ( The molar ratio of ) is 80:16:13:5:8, where n, m, and j are integers greater than or equal to 0.

[0034] Example 2 This embodiment provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, add 2 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 40 parts by weight of methyl methacrylate (MMA), 25 parts by weight of methacrylic acid (MAA), 40 parts by weight of ethyl methacrylate (EMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 50 parts by weight of trimethacryloyloxypropylmethyldimethoxysilane (siloxane structure). After replacing with nitrogen, start stirring rapidly and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the main chain resin; (2) In an air atmosphere, add 30 parts by weight of glycidyl methacrylate, 0.5 parts by weight of triphenylphosphine and 0.3 parts by weight of methoxyphenol to the system obtained in step (1) and react at 110°C for 4 h.

[0035] (3) Add 8 parts by weight of 3,4-cyclohexene dianone to the system obtained in step (2) and continue the reaction for 2 hours to obtain the resin.

[0036] The resin prepared in this embodiment was tested and found to have a solid component acid value of 80 mgKOH / g, a double bond equivalent of 600 g / mol, and a weight-average molecular weight of 14000.

[0037] The structural units of Formula 1, Formula 2, Formula 3, Formula 4 and Formula 5 in Embodiment 2 are the same as those in Embodiment 1.

[0038] The molar ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4 and structural unit 5 in the resin is 80:9:13:5:15.

[0039] Example 3 This embodiment provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, add 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 40 parts by weight of methyl methacrylate (MMA), 25 parts by weight of methacrylic acid (MAA), 40 parts by weight of ethyl methacrylate (EMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 50 parts by weight of trimethacryloyloxypropylmethyldimethoxysilane (siloxane structure). After replacing with nitrogen, start stirring rapidly and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the main chain resin; (2) In an air atmosphere, add 20 parts by weight of glycidyl methacrylate, 0.5 parts by weight of triphenylphosphine and 0.3 parts by weight of methoxyphenol to the system obtained in step (1) and react at 110°C for 4 h.

[0040] (3) Add 8 parts by weight of 3,4-cyclohexene dianone to the system obtained in step (2) and continue the reaction for 2 hours to obtain the resin.

[0041] The resin prepared in this embodiment was tested and found to have a solid component acid value of 120 mgKOH / g, a double bond equivalent of 1050 g / mol, and a weight-average molecular weight of 21000.

[0042] The structural units of Formula 1, Formula 2, Formula 3, Formula 4 and Formula 5 in Embodiment 3 are the same as those in Embodiment 1.

[0043] The molar ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4 and structural unit 5 in the resin is 80:9:13:5:15.

[0044] Example 4 This embodiment provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, add 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 40 parts by weight of methyl methacrylate (MMA), 25 parts by weight of methacrylic acid (MAA), 40 parts by weight of ethyl methacrylate (EMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 50 parts by weight of trimethacryloyloxypropylmethyldimethoxysilane (siloxane structure). After replacing with nitrogen, start stirring rapidly and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the main chain resin; (2) In an air atmosphere, add 30 parts by weight of glycidyl methacrylate, 0.5 parts by weight of triphenylphosphine and 0.3 parts by weight of methoxyphenol to the system obtained in step (1) and react at 110°C for 4 h.

[0045] (3) Add 12 parts by weight of 3,4-cyclohexene dianone to the system obtained in step (2) and continue the reaction for 2 hours to obtain the resin.

[0046] The resin prepared in this embodiment was tested and found to have a solid component acid value of 100 mgKOH / g, a double bond equivalent of 750 g / mol, and a weight-average molecular weight of 21000. The structural units of Formula 1, Formula 2, Formula 3, Formula 4 and Formula 5 in Embodiment 4 have the same structure as those in Embodiment 1.

[0047] The molar ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4 and structural unit 5 in the resin is 80:13:13:8:8.

[0048] Example 5 This embodiment provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN) and 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA) were added. Then, 40 parts by weight of methyl methacrylate (MMA), 47 parts by weight of methacrylic acid (MAA), 30 parts by weight of ethyl methacrylate (EMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 56 parts by weight of trimethacryloyloxypropylmethyldimethoxysilane (siloxane structure) were added. After purging with nitrogen, the mixture was stirred rapidly and the temperature was maintained at 65°C for 3.5 hours. Then, the temperature was raised to 75°C for 2.5 hours to obtain the main chain resin. (2) In an air atmosphere, add 50 parts by weight of glycidyl methacrylate, 0.5 parts by weight of triphenylphosphine and 0.3 parts by weight of methoxyphenol to the system obtained in step (1) and react at 110°C for 4 hours.

[0049] (3) Add 24 parts by weight of 3,4-cyclohexene dianone to the system obtained in step (2) and continue the reaction for 2 hours to obtain the resin.

[0050] The resin prepared in this embodiment was tested and found to have a solid component acid value of 210 KOH / g, a double bond equivalent of 400 g / mol, and a weight-average molecular weight of 21000.

[0051] The structural units of Formula 1, Formula 2, Formula 3, Formula 4 and Formula 5 in Embodiment 5 are the same as those in Embodiment 1.

[0052] The molar ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4 and structural unit 5 in the resin is 70:20:15:15:20.

[0053] Example 6 This embodiment provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, add 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 60 parts by weight of methyl methacrylate (MMA), 13 parts by weight of methacrylic acid (MAA), 50 parts by weight of ethyl methacrylate (EMA), 30 parts by weight of isobornyl methacrylate (IBOMA), and 20 parts by weight of trimethacryloyloxypropylmethyldimethoxysilane (siloxane structure). After replacing with nitrogen, start stirring rapidly and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the main chain resin; (2) In an air atmosphere, add 14 parts by weight of glycidyl methacrylate, 0.5 parts by weight of triphenylphosphine and 0.3 parts by weight of methoxyphenol to the system obtained in step (1) and react at 110°C for 4 hours.

[0054] (3) Add 8 parts by weight of 3,4-cyclohexene dianone to the system obtained in step (2) and continue the reaction for 2 hours to obtain the resin.

[0055] The alkali-soluble photosensitive resin prepared in this embodiment was tested and found to have a solid component acid value of 60 KOH / g, a double bond equivalent of 1900 g / mol, and a weight-average molecular weight of 21000.

[0056] The structural units of Formula 1, Formula 2, Formula 3, Formula 4 and Formula 5 in Embodiment 6 are the same as those in Embodiment 1.

[0057] The molar ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4 and structural unit 5 in the resin is 120:5:5:5:5.

[0058] Example 7 This embodiment provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, add 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 40 parts by weight of methyl methacrylate (MMA), 22 parts by weight of methacrylic acid (MAA), 40 parts by weight of ethyl methacrylate (EMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 75 parts by weight of trimethacryloyloxypropylmethyldimethoxysilane (siloxane structure). After replacing with nitrogen, start stirring rapidly and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the main chain resin; (2) In an air atmosphere, add 28 parts by weight of glycidyl methacrylate, 0.5 parts by weight of triphenylphosphine and 0.3 parts by weight of methoxyphenol to the system obtained in step (1) and react at 110°C for 4 hours.

[0059] (3) Add 9 parts by weight of 3,4-cyclohexene dianone to the system obtained in step (2) and continue the reaction for 2 hours to obtain the resin.

[0060] The resin prepared in this embodiment was tested and found to have a solid component acid value of 130 KOH / g, a double bond equivalent of 700 g / mol, and a weight-average molecular weight of 21,000.

[0061] The structural units of Formula 1, Formula 2, Formula 3, Formula 4 and Formula 5 in Embodiment 7 are the same as those in Embodiment 1.

[0062] The molar ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4 and structural unit 5 in the resin is 75:14:12:6:13.

[0063] Example 8 This embodiment provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, add 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 40 parts by weight of methyl methacrylate (MMA), 43 parts by weight of methacrylic acid (MAA), 40 parts by weight of ethyl methacrylate (EMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 22 parts by weight of 3-methacryloyloxypropylmethyldimethoxysilane (siloxane structure). After replacing with nitrogen, start stirring rapidly and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the main chain resin; (2) In an air atmosphere, add 48 parts by weight of glycidyl methacrylate, 0.5 parts by weight of triphenylphosphine and 0.3 parts by weight of methoxyphenol to the system obtained in step (1) and react at 110°C for 4 hours.

[0064] (3) Add 32 parts by weight of 3,4-cyclohexene dianone to the system obtained in step (2) and continue the reaction for 2 hours to obtain the resin.

[0065] The resin prepared in this embodiment was tested and found to have a solid component acid value of 210 KOH / g, a double bond equivalent of 700 g / mol, and a weight-average molecular weight of 21000.

[0066] The structural units of Formula 1, Formula 2, Formula 3, Formula 4 and Formula 5 in Embodiment 8 are the same as those in Embodiment 1.

[0067] The molar ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4 and structural unit 5 in the resin is 75:14:6:12:13.

[0068] Example 9 This embodiment provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, add 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 50 parts by weight of methyl methacrylate (MMA), 26 parts by weight of methacrylic acid (MAA), 20 parts by weight of ethyl methacrylate (EMA), 26 parts by weight of hydroxyethyl methacrylate (HEMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 37 parts by weight of trimethacryloyloxypropylmethyldimethoxysilane (siloxane structure). After replacing with nitrogen, start stirring rapidly and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the main chain resin; (2) In an air atmosphere, add 28 parts by weight of glycidyl methacrylate, 0.5 parts by weight of triphenylphosphine and 0.3 parts by weight of methoxyphenol to the system obtained in step (1) and react at 110°C for 4 hours.

[0069] (3) Add 16 parts by weight of 3,4-cyclohexene dianone to the system obtained in step (2) and continue the reaction for 2 hours to obtain the resin.

[0070] The resin prepared in this embodiment was tested and found to have a solid component acid value of 120 KOH / g, a double bond equivalent of 950 g / mol, and a weight-average molecular weight of 23,000.

[0071] The structural units of Formula 2, Formula 3, Formula 4, and Formula 5 in Embodiment 9 have the same structure as those in Embodiment 1, and the structural unit of Formula 1 is... In the formula, k, n, m, and l are integers greater than or equal to 0.

[0072] The molar ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4 and structural unit 5 in the resin is 90:10:10:10:10.

[0073] Example 10 This embodiment provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, add 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 50 parts by weight of methyl methacrylate (MMA), 26 parts by weight of methacrylic acid (MAA), 22 parts by weight of propyl methacrylate (PMA), 26 parts by weight of hydroxyethyl methacrylate (HEMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 37 parts by weight of trimethacryloyloxypropylmethyldimethoxysilane (siloxane structure). After purging with nitrogen, start rapid stirring and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the main chain resin; (2) In an air atmosphere, add 28 parts by weight of glycidyl methacrylate, 0.5 parts by weight of triphenylphosphine and 0.3 parts by weight of methoxyphenol to the system obtained in step (1) and react at 110°C for 4 hours.

[0074] (3) Add 16 parts by weight of 3,4-cyclohexene dianone to the system obtained in step (2) and continue the reaction for 2 hours to obtain the resin.

[0075] The resin prepared in this embodiment was tested and found to have a solid component acid value of 120 KOH / g, a double bond equivalent of 950 g / mol, and a weight-average molecular weight of 23,000.

[0076] The structural units of Formula 2, Formula 3, Formula 4, and Formula 5 in Example 10 have the same structure as those in Example 1, and the structural unit of Formula 1 is... In the formula, k, n, m, and l are integers greater than or equal to 0.

[0077] The molar ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4 and structural unit 5 in the resin is 90:10:10:10:10.

[0078] Example 11 This embodiment provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, add 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 50 parts by weight of methyl methacrylate (MMA), 26 parts by weight of methacrylic acid (MAA), 40 parts by weight of ethyl methacrylate (EMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 37 parts by weight of trimethacryloyloxypropylmethyldimethoxysilane (siloxane structure). After replacing with nitrogen, start stirring rapidly and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the main chain resin; (2) In an air atmosphere, add 28 parts by weight of 3,4-epoxycyclohexyl methacrylate (ECHMMA), 0.5 parts by weight of triphenylphosphine and 0.3 parts by weight of methoxyphenol to the system obtained in step (1), and react at 110°C for 4 hours.

[0079] (3) Add 16 parts by weight of 3,4-cyclohexene dianone to the system obtained in step (2) and continue the reaction for 2 hours to obtain the resin.

[0080] The resin prepared in this embodiment was tested and found to have a solid component acid value of 120 KOH / g, a double bond equivalent of 950 g / mol, and a weight-average molecular weight of 23,000.

[0081] The structural units of Formula 1, Formula 3, Formula 4, and Formula 5 in Example 11 are the same as those in Example 1, and the structural unit of Formula 2 is... .

[0082] The molar ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4 and structural unit 5 in the resin is 90:10:10:10:10.

[0083] Example 12 This embodiment provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, add 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 50 parts by weight of methyl methacrylate (MMA), 26 parts by weight of methacrylic acid (MAA), 40 parts by weight of ethyl methacrylate (EMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 38 parts by weight of 3-methacryloyloxypropyltrimethoxysilane (siloxane structure). After purging with nitrogen, start rapid stirring and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the resin; (2) In an air atmosphere, add 42 parts by weight of glycidyl methacrylate, 0.5 parts by weight of triphenylphosphine and 0.3 parts by weight of methoxyphenol to the system obtained in step (1) and react at 110°C for 4 hours.

[0084] (3) Add 16 parts by weight of 3,4-cyclohexene dianone to the system obtained in step (2) and continue the reaction for 2 hours to obtain the resin.

[0085] The resin prepared in this embodiment was tested and found to have a solid component acid value of 120 KOH / g, a double bond equivalent of 950 g / mol, and a weight-average molecular weight of 23,000.

[0086] The structural units of Formula 1, Formula 2, Formula 4, and Formula 5 in Example 12 are the same as those in Example 1, and the structural unit of Formula 3 is... .

[0087] The molar ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4 and structural unit 5 in the resin is 90:10:10:10:10.

[0088] Example 13 This embodiment provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, add 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 50 parts by weight of methyl methacrylate (MMA), 26 parts by weight of methacrylic acid (MAA), 40 parts by weight of ethyl methacrylate (EMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 40 parts by weight of trimethacryloyloxypropylmethyldiethoxysilane (siloxane structure). After replacing with nitrogen, start stirring rapidly and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the main chain resin; (2) In an air atmosphere, add 42 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate (ECHMMA), 0.5 parts by weight of triphenylphosphine, and 0.3 parts by weight of methoxyphenol to the system obtained in step (1), and react at 110°C for 4 hours.

[0089] (3) Add 16 parts by weight of 3,4-cyclohexene dianone to the system obtained in step (2) and continue the reaction for 2 hours to obtain the resin.

[0090] The resin prepared in this embodiment was tested and found to have a solid component acid value of 120 KOH / g, a double bond equivalent of 950 g / mol, and a weight-average molecular weight of 23,000.

[0091] The structural units of Formula 1, Formula 2, Formula 4, and Formula 5 in Example 13 are the same as those in Example 1. The structural unit of Formula 3 is... .

[0092] The molar ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4 and structural unit 5 in the resin is 90:10:10:10:10.

[0093] Comparative Example 1 This comparative example provides a resin and its preparation method. Compared with Example 1, the difference in this comparative example lies in the selection of polymerizable monomers. Specifically, equimolar amounts of hydroxyethyl methacrylate (HEMA) are used to replace acrylates with siloxane structures.

[0094] (1) In a flask equipped with a condenser and a stirrer, add 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 40 parts by weight of methyl methacrylate (MMA), 25 parts by weight of methacrylic acid (MAA), 40 parts by weight of ethyl methacrylate (EMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 18 parts by weight of hydroxyethyl methacrylate (HEMA). After purging with nitrogen, start stirring rapidly and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the main chain resin; (2) In an air atmosphere, add 30 parts by weight of glycidyl methacrylate, 0.5 parts by weight of triphenylphosphine and 0.3 parts by weight of methoxyphenol to the system obtained in step (1) and react at 110°C for 4 hours.

[0095] (3) Add 8 parts by weight of 3,4-cyclohexene dianone to the system obtained in step (2) and continue the reaction for 2 hours to obtain the resin.

[0096] The resin prepared in this comparative example was tested and found to have a solid component acid value of 80 mgKOH / g, a double bond equivalent of 600 g / mol, and a weight-average molecular weight of 19000.

[0097] The molar ratio of structural units of Formula 1, Formula 2, Formula 3, Formula 4, and Formula 5 in the resin is 80:16:0:5:8:. The structure of structural unit of Formula 1 in Comparative Example 1 is as follows: The structure of the structural unit in Equation 2-5 is the same as that in Example 1.

[0098] Comparative Example 2 This comparative example provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, add 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 40 parts by weight of methyl methacrylate (MMA), 25 parts by weight of methacrylic acid (MAA), 40 parts by weight of ethyl methacrylate (EMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 50 parts by weight of trimethacryloyloxypropylmethyldimethoxysilane (siloxane structure). After replacing with nitrogen, start stirring rapidly and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the main chain resin. The resin prepared in this embodiment was tested and found to have a solid component acid value of 170 KOH / g, a double bond equivalent of 0 g / mol, and a weight-average molecular weight of 17000.

[0099] In Comparative Example 2, the structural units of Formula 1, Formula 3, and Formula 5 in the resin are the same as those in Example 1.

[0100] The molar ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4 and structural unit 5 in the resin is 80:0:13:0:29.

[0101] Comparative Example 3 This comparative example provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, add 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 40 parts by weight of methyl methacrylate (MMA), 25 parts by weight of methacrylic acid (MAA), 40 parts by weight of ethyl methacrylate (EMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 50 parts by weight of trimethacryloyloxypropylmethyldimethoxysilane (siloxane structure). After replacing with nitrogen, start stirring rapidly and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the main chain resin. (2) In an air atmosphere, add 30 parts by weight of glycidyl methacrylate, 0.5 parts by weight of triphenylphosphine and 0.3 parts by weight of methoxyphenol to the system obtained in step (1), and react at 110°C for 4 hours to obtain the resin.

[0102] The resin prepared in this embodiment was tested and found to have a solid component acid value of 60 KOH / g, a double bond equivalent of 500 g / mol, and a weight-average molecular weight of 20,000.

[0103] In Comparative Example 3, the structural units of Formula 1, Formula 2, Formula 3 and Formula 5 in the resin are the same as those in Example 1.

[0104] The molar ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4 and structural unit 5 in the resin is 80:21:13:0:8.

[0105] Comparative Example 4 This comparative example provides a resin and its preparation method. The specific preparation process of the resin is as follows: (1) In a flask equipped with a condenser and a stirrer, add 1.5 parts by weight of the thermal free radical initiator 2,2'-azobisisobutyronitrile (AIBN), 200 parts by weight of the solvent propylene glycol methyl ether acetate (PMA), then add 40 parts by weight of methyl methacrylate (MMA), 40 parts by weight of ethyl methacrylate (EMA), 10 parts by weight of isobornyl methacrylate (IBOMA), and 50 parts by weight of trimethacryloyloxypropylmethyldimethoxysilane (siloxane structure). After purging with nitrogen, start rapid stirring and maintain the temperature at 65°C for 3.5 hours, then raise the temperature to 75°C for 2.5 hours to obtain the main chain resin.

[0106] The resin prepared in this embodiment was tested and found to have a weight-average molecular weight of 15,000.

[0107] The resin structural units of Formula 1 and Formula 3 in Comparative Example 4 are the same as those in Example 1.

[0108] The molar ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4 and structural unit 5 in the resin is 80:0:13:0:0.

[0109] Experimental Example 1 This experimental example verifies the performance of the resins prepared in the above examples and comparative examples. Resin compositions were prepared using the above resins, and then the practical application performance of the resin compositions was tested. The formulations of the resin compositions in the examples and comparative examples are as follows: Alkali-soluble photosensitive resin: 20 parts by weight of the main resin * 1, and 5 parts by weight of the propylene copolymer modified resin. Acrylic monomers: 2 parts by weight of SR238*3, 2 parts by weight of SR502*4, and 2 parts by weight of SR344*5; Epoxy curing agent: 3 parts by weight of hydrogenated epoxy*6, 2 parts by weight of TTA-21P*7; Photoinitiator: 0.2 parts by weight of TPO*8, 0.2 parts by weight of 184*9, and 0.1 parts by weight of 1173*10; Additives: 0.1 parts by weight of 1010*11, 0.02 parts by weight of 168*12, and 0.1 parts by weight of light stabilizer*13.

[0110] Wherein, *1: the main resin is the resin synthesized in the examples and comparative examples.

[0111] *2: Propylene copolymer modified resin (Daicel, acid value: 80 mg KOH / g, solid content: 45%).

[0112] *3: SR238 is 1,6-hexanediol diacrylate (Sartoma).

[0113] *4: SR502 is 9-ethoxylated trimethylolpropane triacrylate (Sartoma).

[0114] *5: SR344 is polyethylene glycol (400) diacrylate (Sardoma).

[0115] *6: Hydrogenated epoxy is hydrogenated bisphenol A epoxy resin with an epoxy equivalent of 210-230 g / eq (Hunan Servi).

[0116] *7: TTA21P is an alicyclic epoxy resin with an epoxy equivalent of 126~135 g / eq (Jiangsu Taiter).

[0117] *8: The photoinitiator TPO is diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (Jiuri New Materials).

[0118] *9: Photoinitiator 184 is 1-hydroxycyclohexylphenyl ketone (IGM).

[0119] *10: Photoinitiator 1173 is 2-hydroxy-2-methyl-1-phenyl-1-propanone (IGM).

[0120] *11: Antioxidant 1010 is pentaerythritol 4-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (BASF).

[0121] *12: Antioxidant 168 is tris(2,4-di-tert-butylphenyl) phosphite (BASF).

[0122] *13: The light stabilizer is 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (BASF).

[0123] Test method: 1. Photosensitivity: Photosensitivity was evaluated using a 41-level exposure scale on a film. The number of frames of the adhesive layer retained under the same substrate, exposure, and development conditions was used as the evaluation standard. The higher the number of frames of the adhesive layer retained, the better the photosensitivity.

[0124] 2. Adhesion: The adhesion is evaluated using the cross-cut adhesion test. After light curing and heat curing, the cross-cut adhesion test is performed, and the number of cells retained is observed as the evaluation standard. The more cells retained, the better the adhesion (5B is the best, and 0B is the worst).

[0125] 3. Weather resistance: After light curing and heat curing, the double 85 test is carried out for 168 hours, and the adhesion is evaluated by the cross-cut adhesion test (5B is the best, 0B is the worst).

[0126] 4. Yellowing resistance: Place the sample in a special test chamber and irradiate it for a specified time with a sun lamp or ultraviolet lamp under certain temperature and humidity conditions. Observe the color change of the irradiated part of the sample (confirm yellowing based on the change of b value).

[0127] 5. Flexibility: According to GB / T1731 standard, the flexibility tester accepts a set of steel rods of varying diameters. The coating is bent 180° to check for cracking. During the test, rods of different diameters, such as 1mm, 2mm, 3mm, 4mm, 5mm, 10mm, and 15mm, are used for 180° bending. The smallest rod diameter that does not cause coating damage is used to represent the coating's flexibility.

[0128] The performance test results of the resin compositions in the examples and comparative examples are shown in Table 1.

[0129] Table 1

[0130] Note: ※ indicates that exposure and development cannot be performed.

[0131] Exposure conditions: High-pressure mercury lamp exposure machine was used for exposure, and the exposure energy was uniformly 200mJ. The mixture was allowed to stand for 1 hour before development.

[0132] Developing conditions: 1 wt% NaHCO3 aqueous solution, temperature 30℃, water pressure 1.5Kg / CM2, developing time 45S.

[0133] Comparative Example 3 experienced slower development due to a lower acid value. As shown in Table 2, Example 1 exhibits excellent overall performance. Compared to Example 1, Example 2, due to its lower molecular weight, shows reduced adhesion and decreased flexibility after weathering tests. Example 3, with its larger double bond equivalent value (i.e., lower double bond content), suffers from decreased sensitivity. Example 4, with its increased acid value, experiences a slight decrease in weather resistance. Examples 5-8 show an imbalance in the proportion of each structural unit, resulting in a slight decrease in overall performance. Examples 9-13 involve replacing some structural units within the same series, with minimal impact on performance. Comparative Example 1, lacking the addition of a siloxane structure, shows a significant decrease in adhesion after weathering tests. Comparative Example 2, without grafting double bonds, cannot undergo photocuring crosslinking. Comparative Example 3, without further acid modification, suffers from development difficulties, severely impacting practical use. Comparative Example 4, by not introducing acrylic acid during the polymerization stage, cannot be developed with a 1wt% NaHCO3 solution and also cannot undergo grafting reactions to introduce double bonds.

[0134] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A resin, characterized in that, The resin is composed of the following structural units: , , , and ; R1 is selected from aliphatic groups consisting of 1-18 carbon atoms; R2 is , where R 12 Selected from CH2CH(OH)CH2 and CH2C6H9(OH); R3 is , where R 13 R 14 R 15 Each is independently selected from an alkoxy group with 1-3 carbon atoms or an alkyl group with 1-3 carbon atoms, and R 13 R 14 R 15 Cannot be alkyl at the same time, R 16 Selected from -C2H4- or -CH2CH2OCH2CH(OH)CH2-; R4 is ; R5 is -H; R6, R7, R8, R9, R 10 R 11 Each can be independently selected from -H or -CH3.

2. The resin according to claim 1, characterized in that, R1 is selected from at least one of methyl, ethyl, propyl, butyl, tert-butyl, hydroxyethyl, hydroxypropyl, and isobornyl.

3. The resin according to claim 1, characterized in that, R 13 R 14 R 15 Each is independently selected from at least one of methoxy, ethoxy, propoxy, methyl, ethyl, or propyl, and R 13 R 14 R 15 It cannot be an alkyl group at the same time.

4. The resin according to claim 1, characterized in that, Based on the total number of moles of the structural units of Formula 1, Formula 2, Formula 3, Formula 4, and Formula 5, the molar percentage of the structural unit of Formula 3 is 5% to 10%. And / or, based on the total number of moles of the structural unit of Formula 1, the structural unit of Formula 2, the structural unit of Formula 3, the structural unit of Formula 4 and the structural unit of Formula 5, the molar percentage of the structural unit of Formula 4 is 5~10%.

5. The resin according to claim 1, characterized in that, The molar ratio of the structural unit of Formula 1, Formula 2, Formula 3, Formula 4 and Formula 5 is (70~120):(5~20):(5~15):(5~15):(5~20).

6. The resin according to any one of claims 1-5, characterized in that, The acid value of the resin is 60 mg KOH / g to 210 mg KOH / g, preferably 90 mg KOH / g to 120 mg KOH / g.

7. The resin according to any one of claims 1-5, characterized in that, The weight-average molecular weight of the resin is 8,000-30,000, more preferably 15,000-25,000.

8. The resin according to any one of claims 1-5, characterized in that, The double bond equivalent of the resin is 400~1900 g / mol, preferably 600~900 g / mol.

9. A resin composition, characterized in that, Includes the resin described in any one of claims 1-8; Preferably, the resin accounts for 40-70% of the total mass of the resin composition.

10. The use of the resin of any one of claims 1-8 or the resin composition of claim 9 in printed circuits, integrated circuits, display panels or microelectromechanical systems.

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