Photosensitive resin composition and preparation method and application thereof

Abstract

The invention discloses a photosensitive resin composition as well as a preparation method and application thereof, the composition comprises alkali-soluble resin, modified methacrylate and a photoinitiator, and the modified methacrylate is prepared from the following components in parts by weight: 95-105 parts of Daexid FM1D, 0.1-0.3 part of sodium methoxide and 0.01-0.03 part of antioxidant. And 100-200 parts of a mixed solution of ethylene oxide and propylene oxide. According to the invention, a defoaming agent is not used, so that the developing solution generates less foam in the use process, the defoaming agent is not required to be used in the developing and stripping processes, and the dissolution promoter is also added, so that the resin is completely dissolved in the developing solution, and the generation of aggregates is reduced.

Description

Technical Field

[0001] The present invention relates to a resin composition, specifically a photosensitive resin composition, a preparation method thereof, and an application thereof. Background Art

[0002] Patterning of substrates such as circuit boards, carbon plates, metals, and glasses can be achieved by photolithography. Photolithography is a method of coating a photocurable resin composition on a substrate, exposing it through a mask film pattern, partially curing the photocurable resin composition, removing the uncured part with a developer, forming a resist pattern on the substrate, then performing etching or electroplating to form a corresponding pattern, and finally stripping the resist layer on the substrate to obtain a pattern on the substrate.

[0003] In photolithography, when coating a photocurable resin composition on a substrate, the following methods can be used: directly coating a photoresist solution on the substrate for use, or coating a photoresist solution on a support and transferring the coating layer to the substrate through the support. Currently, most methods choose to use the method of transferring the coating layer to the substrate through the support to achieve patterning.

[0004] First, peel off the polyolefin protective layer on the photocurable resin laminate. Using a laminator, laminate in the order of the substrate, photocurable resin laminate, and support; combine a photomask, expose the photocurable resin laminate, polymerize and cure the exposed part, and peel off the support (generally polyethylene terephthalate); dissolve or disperse and remove the unexposed part of the photocurable resin laminate with a weakly alkaline aqueous solution to form a resist pattern on the substrate. In this process section, the photocurable resin composition is not completely dissolved in the developer. Within a certain period, the dissolved components and undissolved components of the developer increase, and finally aggregates are generated. The generation of aggregates is one of the reasons for the final short circuit of the circuit. The formed resist pattern is used as a protective mask for known etching treatment or pattern plating treatment. Finally, peel off the resist pattern from the substrate to manufacture a substrate with a certain pattern.

[0005] In the above process, each process is particularly important. For example, the foam generated in the developing tank during the developing stage is one of the technical difficulties faced in the industry. Patent JP7376712B2 mentions that in order to solve the problem of overflowing the chamber when too much foam is generated, an antifoaming agent for suppressing foam is used in the alkaline solution at a ratio of 0.1% to 3%. Patent CN115167076A shows that the leveling agent and the antifoaming agent interact to ensure that the photosensitive resin composition forms a flat, smooth, and uniform film, can effectively reduce the surface tension of the photosensitive resin composition, improve its leveling property and uniformity, and prevent the generation of too much foam from affecting the use performance of the photosensitive resin composition.

[0006] When too much defoamer is used, there are problems of increased production cost and reduced productivity. When the defoamer is overused, it is likely to combine with the components of the dry film to produce scum insoluble in water, resulting in etching failure or electroplating failure. Therefore, there is an increasing demand for dry films that generate less foam and do not require the use of defoamers during the development and stripping processes. Summary of the Invention

[0007] The purpose of the present invention is precisely to overcome the above-mentioned deficiencies of the prior art and provide a photosensitive resin composition, a preparation method thereof, and an application.

[0008] A photosensitive resin composition, the composition comprising an alkali-soluble resin, a modified methacrylate, and a photoinitiator, wherein the modified methacrylate has the following compound structure:

[0009]

[0010] In the formula, R4 is H or CH3, m is an integer from 0 to 4, n is an integer from 1 to 5, n is an integer from 1 to 5, o and p are both from 2 to 50, and o + P = 10 - 50.

[0011] The compound structure of the alkali-soluble resin is:

[0012]

[0013] The modified methacrylate is composed of the following components by weight:

[0014] 95 - 105 parts of Daicel FM1D, 0.1 - 0.3 parts of sodium methoxide, 0.01 part - 0.03 part of antioxidant, 100 - 200 parts of a mixed liquid of ethylene oxide and propylene oxide.

[0015] The modified methacrylate is prepared according to the following steps:

[0016] Weigh each component according to the set dosage ratio,

[0017] Put Daicel FM1D, sodium methoxide, and antioxidant into a flask, heat to 95 - 100 °C under a nitrogen atmosphere, maintain for 2 - 3 hours, and dropwise add the mixed liquid of ethylene oxide and propylene oxide. After dropping, continuously stir at 95 - 100 °C for 5 - 6 hours. After the reaction is completed, add a set amount of phosphoric acid, and filter to obtain the modified methacrylate monomer.

[0018] The alkali-soluble resin is composed of the following components by weight:

[0019] 95 - 105 parts of methyl ethyl ketone, 15 - 25 parts of methacrylic acid, 45 - 55 parts of methyl methacrylate, 15 - 25 parts of methyl methacrylate, 25 - 35 parts of modified methacrylate monomer, 1 - 2 parts of azobisisobutyronitrile.

[0020] The alkali - soluble resin is prepared according to the following steps:

[0021] Weigh each component according to the set dosage ratio;

[0022] Put methyl ethyl ketone into a flask, heat it to 75 - 80 °C under a nitrogen atmosphere, and dropwise add methacrylic acid, methyl methacrylate, methyl methacrylate, modified methacrylate monomer and azobisisobutyronitrile within 2 - 3 hours; after dropping, continuously stir at 75 - 80 °C for 10 - 12 hours. After the reaction ends, dilute the obtained resin solution with methyl ethyl ketone to obtain a binder polymer solution with a structural unit of methacrylic acid, and the solid content is 50% by mass.

[0023] A method for preparing a photosensitive resin composition, characterized by comprising the following steps:

[0024] Prepare a modified methacrylate, and weigh according to parts by weight:

[0025] 95 - 105 parts of Daicel FM1D, 0.1 - 0.3 parts of sodium methoxide, 0.01 - 0.03 parts of antioxidant, 100 - 200 parts of a mixed liquid of ethylene oxide and propylene oxide;

[0026] Put Daicel FM1D, sodium methoxide and antioxidant into a flask, heat it to 95 - 100 °C under a nitrogen atmosphere, maintain the temperature and dropwise add the mixed liquid of ethylene oxide and propylene oxide within 2 - 3 hours. After dropping, continuously stir at 95 - 100 °C for 5 - 6 hours. After the reaction ends, add a set amount of phosphoric acid, and filter to obtain the modified methacrylate monomer;

[0027] Prepare an alkali - soluble resin:

[0028] Weigh according to parts by weight: 95 - 105 parts of methyl ethyl ketone, 15 - 25 parts of methacrylic acid, 15 - 55 parts of methyl methacrylate, 25 - 35 parts of modified methacrylate monomer, 0 - 30 parts of styrene, 1 - 2 parts of azobisisobutyronitrile;

[0029] Put methyl ethyl ketone into a flask, heat it to 75 - 80 °C under a nitrogen atmosphere, and dropwise add methacrylic acid, methyl methacrylate, styrene, modified methacrylate monomer and azobisisobutyronitrile within 2 - 3 hours; after dropping, continuously stir at 75 - 80 °C for 10 - 12 hours. After the reaction ends, dilute the obtained resin solution with methyl ethyl ketone to obtain a binder polymer solution with a structural unit of methacrylic acid, and the solid content is 50%;

[0030] A photosensitive resin composition is obtained by mixing a modified methacrylate, an alkali-soluble resin, and a photoinitiator.

[0031] Compared with the prior art, the present invention has the following beneficial technical effects:

[0032] No defoaming agent is used so that less foam is generated during the use of the developer and no defoaming agent is required during the development and stripping processes. Moreover, a solubilizer is added to dissolve all the resin in the developer, reducing the formation of aggregates. Detailed implementation manners

[0033] To further understand the features, technical means, specific purposes, and functions achieved by the present invention, the present invention will be further described in detail below in conjunction with the specific implementation manners.

[0034] A photosensitive resin composition, the composition comprising an alkali-soluble resin, a modified methacrylate, and a photoinitiator, wherein the modified methacrylate has the following compound structure:

[0035]

[0036] In the formula, R4 is H or CH3, m is an integer from 0 to 4, n is an integer from 1 to 5, n is an integer from 1 to 5, o and p are both from 2 to 50, and o + p = 10 to 50. By taking different values, corresponding combinations can be achieved. The m link is because the raw material basically has only this structure. The n link provides a certain hydrophobic chain segment and flexible segment, providing support for the toughness in the later film properties. The o link is the hydrophilic part, and p is the hydrophobic part, which also reduces the viscosity of the glue solution during the coating of the film and promotes leveling. The combination of m, o, and p reduces the generation of foam.

[0037] The compound structure of the alkali-soluble resin is:

[0038]

[0039] The modified methacrylate is composed of the following components by weight:

[0040] 95 - 105 parts of Daicel FM1D, 0.1 - 0.3 parts of sodium methoxide, 0.01 part - 0.03 part of antioxidant, 100 - 200 parts of a mixed solution of ethylene oxide and propylene oxide.

[0041] The modified methacrylate is prepared according to the following steps:

[0042] Weigh each component according to the set dosage ratio.

[0043] Charge Celanese FM1D, sodium methoxide, and antioxidant into a flask. Heat it to 95 - 100 °C under a nitrogen atmosphere and maintain for 2 - 3 hours. Then, slowly add a mixed liquid of ethylene oxide and propylene oxide dropwise. After the addition, continuously stir at 95 - 100 °C for 5 - 6 hours. After the reaction is completed, add a set amount of phosphoric acid, and filter to obtain the modified methacrylate monomer. No defoamer is used in the whole component, which solves the problems of increased production cost and reduced productivity when using too much defoamer. When the defoamer is overused, it is easy to combine with the components of the dry film to produce scum insoluble in water, resulting in etching failure or electroplating failure. After application, no defoamer is required during the development and stripping processes, and a solubilizer is also added to completely dissolve the resin in the developer, reducing the formation of aggregates.

[0044] The alkali-soluble resin is composed of the following components by weight:

[0045] 95 - 105 parts of methyl ethyl ketone, 15 - 25 parts of methacrylic acid, 45 - 55 parts of methyl methacrylate, 15 - 25 parts of methyl methacrylate, 25 - 35 parts of modified methacrylate monomer, 1 - 2 parts of azobisisobutyronitrile.

[0046] The alkali-soluble resin is prepared according to the following steps:

[0047] Weigh each component according to the set dosage ratio;

[0048] Charge methyl ethyl ketone into a flask. Heat it to 75 - 80 °C under a nitrogen atmosphere and add methacrylic acid, methyl methacrylate, methyl methacrylate, modified methacrylate monomer, and azobisisobutyronitrile dropwise for 2 - 3 hours. After the addition, continuously stir at 75 - 80 °C for 10 - 12 hours. After the reaction is completed, dilute the obtained resin solution with methyl ethyl ketone to obtain a binder polymer solution of the structural unit of methacrylic acid, with a solid content of 50% by mass.

[0049] A method for preparing a photosensitive resin composition, characterized by comprising the following steps:

[0050] Prepare modified methacrylate, and weigh according to the following parts by weight:

[0051] 95 - 105 parts of Celanese FM1D, 0.1 - 0.3 parts of sodium methoxide, 0.01 - 0.03 parts of antioxidant, 100 - 200 parts of a mixed liquid of ethylene oxide and propylene oxide;

[0052] Add Daicel FM1D, sodium methoxide and antioxidant into a flask, heat to 95-100°C under nitrogen atmosphere, maintain for 2-3 hours, dropwise add ethylene oxide and propylene oxide mixed liquid, continue stirring at 95-100°C for 5-6 hours after dropwise addition, add a set amount of phosphoric acid after the reaction is completed, and filter to obtain a modified methacrylate monomer;

[0053] Preparation of alkali soluble resin:

[0054] Weigh the following according to weight: 95-105 parts of methyl ethyl ketone, 15-25 parts of methacrylic acid, 15-55 parts of methyl methacrylate, 0-30 parts of styrene, 25-35 parts of modified methacrylate monomer, and 1-2 parts of azobisisobutyronitrile;

[0055] Add methyl ethyl ketone into a flask, raise the temperature to 75-80° C. under a nitrogen atmosphere, and drop methacrylic acid, methyl methacrylate, methyl methacrylate, modified methacrylate monomer and azobisisobutyronitrile over 2-3 hours; after the dropwise addition, continue stirring at 75-80° C. for 10-12 hours. After the reaction is completed, dilute the obtained resin solution with methyl ethyl ketone to obtain a binder polymer solution of a methacrylic acid structural unit with a solid content of 50%;

[0056] The modified methacrylate, the alkali-soluble resin and the photoinitiator are mixed to obtain a photosensitive resin composition.

[0057] It should be noted that the above description is not a limitation of the present invention. Without departing from the creative concept of the present invention, any obvious replacement is within the protection scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that The composition comprises an alkali-soluble resin, a modified methacrylate and a photoinitiator, wherein the modified methacrylate has the following compound structure: In the formula, R4 is H or CH3, m=an integer of 0-4, n=an integer of 1-5, o and p are both 2-50, and o+P=10-50.

2. The photosensitive resin composition according to claim 1, characterized in that The compound structure of the alkali-soluble resin is:

3. The photosensitive resin composition according to claim 2, characterized in that: The modified methacrylate is composed of the following components in parts by weight: 95-105 parts of Daicel FM1D, 0.1-0.3 parts of sodium methoxide, 0.01-0.03 parts of antioxidant, 100-200 parts of ethylene oxide and propylene oxide mixture.

4. The photosensitive resin composition according to claim 3, characterized in that: The modified methacrylate is prepared according to the following steps: Weigh each component according to the set dosage ratio. Add Daicel FM1D, sodium methoxide and antioxidant into a flask, heat to 95-100°C under nitrogen atmosphere, maintain for 2-3 hours, dropwise add ethylene oxide and propylene oxide mixed liquid, continue stirring at 95-100°C for 5-6 hours after the dropwise addition, add a set amount of phosphoric acid after the reaction is completed, and obtain the modified methacrylate monomer after filtering.

5. The photosensitive resin composition according to claim 4, characterized in that: The alkali-soluble resin is composed of the following components in parts by weight: 95-105 parts of methyl ethyl ketone, 15-25 parts of methacrylic acid, 15-55 parts of methyl methacrylate, 25-35 parts of modified methacrylate monomer, 0-30 parts of styrene, 1-2 parts of azobisisobutyronitrile.

6. The photosensitive resin composition according to claim 5, characterized in that: The alkali-soluble resin is prepared according to the following steps: Weigh each component according to the set dosage ratio; Methyl ethyl ketone is added to a flask, and the temperature is raised to 75-80° C. under a nitrogen atmosphere. Methacrylic acid, methyl methacrylate, methyl methacrylate, modified methacrylate monomer and azobisisobutyronitrile are added dropwise over 2-3 hours. After the addition, stirring is continued at 75-80° C. for 10-12 hours. After the reaction is completed, the obtained resin solution is diluted with methyl ethyl ketone to obtain a binder polymer solution of a methacrylic acid structural unit, and the solid content is 50% by mass.

7. A method for preparing the photosensitive resin composition according to claim 6, characterized in that: The following steps are involved: To prepare modified methacrylate, weigh the following in parts by weight: 95-105 parts of Daicel FM1D, 0.1-0.3 parts of sodium methoxide, 0.01-0.03 parts of antioxidant, 100-200 parts of ethylene oxide and propylene oxide mixture; Add Daicel FM1D, sodium methoxide and antioxidant into a flask, heat to 95-100°C under nitrogen atmosphere, maintain for 2-3 hours, dropwise add ethylene oxide and propylene oxide mixed liquid, continue stirring at 95-100°C for 5-6 hours after dropwise addition, add a set amount of phosphoric acid after the reaction is completed, and filter to obtain a modified methacrylate monomer; Preparation of alkali soluble resin: Weigh the following according to weight: 95-105 parts of methyl ethyl ketone, 15-25 parts of methacrylic acid, 45-55 parts of methyl methacrylate, 15-25 parts of methyl methacrylate, 25-35 parts of modified methacrylate monomer, and 1-2 parts of azobisisobutyronitrile; Add methyl ethyl ketone into a flask, raise the temperature to 75-80° C. under a nitrogen atmosphere, and drop methacrylic acid, methyl methacrylate, styrene, modified methacrylate monomer and azobisisobutyronitrile over 2-3 hours; after the dropwise addition, continue stirring at 75-80° C. for 10-12 hours. After the reaction is completed, dilute the obtained resin solution with methyl ethyl ketone to obtain a binder polymer solution of a methacrylic acid structural unit, with a solid content of 50% by mass; The modified methacrylate, the alkali-soluble resin and the photoinitiator are mixed to obtain a photosensitive resin composition.

8. Use of the photosensitive resin composition according to claim 6.

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