Polyamic acid resin and preparation method thereof, positive photosensitive resin composition

Abstract

The present application relates to a polyamic acid resin, the structural formula of which is as follows: #imgabs0# wherein R1 is selected from H or CF3, the structures of X and Y each independently contain an imide structure, x+y=1, and n=5 to 200. In the structure of the above polyamic acid resin, the dissolution rate of the polyamic acid in an alkaline aqueous developer can be adjusted by controlling the ratio of imide to amic acid in the polyamic acid resin, which is beneficial to increase the difference in dissolution rate between the exposed area and the non-exposed area, prolong the development time, improve the resolution of the developed pattern, and solve the problem that the development process is difficult to accurately control.

Description

Technical Field

[0001] The present application relates to the technical field of functional polymer materials, and in particular to a polyamic acid resin and a preparation method thereof, and a positive photosensitive resin composition. Background Art

[0002] Polyimide has excellent electrical insulation, heat resistance, chemical resistance and mechanical properties, and can be widely used in the semiconductor field, such as interlayer insulation, surface passivation and packaging materials for electronic and electrical components of microelectronic chips. Traditional polyimide materials do not have photosensitivity and are mostly insoluble. To obtain the required pattern, it is necessary to use traditional etching processes for pattern transfer, form the pattern at the prepolymer polyamic acid stage, remove the photoresist, and form the polyimide pattern at high temperature, which is a relatively complicated process. If polyimide is given a photosensitive function and directly exposed and developed, the processing process will be greatly simplified. Photosensitive polyimide (PSPI for short) is a polymer material with photosensitivity. This material is different from ordinary photoresists. After forming the pattern, it must be permanently left in the structure of the chip to play the role of dielectric and buffer.

[0003] Positive PSPI is photodegradable, and the resulting photolithographic pattern is the same as the mask. At present, commercial positive photosensitive polyimide resins mainly use polyimide precursors (polyamic acid, PAA), which have the following advantages: positive photosensitive polyimide has better resolution than negative photosensitive polyimide, a relatively small light radiation area, a lower probability of defects, a wider source of monomers, and can be developed in alkaline solutions (2.38wt% tetramethylammonium hydroxide aqueous solution, TMAH), which is environmentally friendly. However, the dissolution rate of pure polyamic acid resin in alkaline developer is extremely fast, the development time is short, the difference in dissolution rate between the exposed area and the non-exposed area is small, the pattern resolution is low, and the development process is difficult to accurately control.

[0004] To solve the above problems, in actual application, polyamic acid needs to be esterified or chemically imidized to reduce its dissolution rate in alkaline solution. However, after the synthesis of polyamic acid, the degree of further esterification or chemical imidization is difficult to accurately control. Currently, only a few companies have the technology to accurately control the development process, and the technology monopoly situation is relatively severe. In order to break this monopoly, more and more research focuses on the development of new positive photosensitive polyimide resin products.

[0005] For example, Japanese Patent Application Publication Nos. 52-13315 and 62-135824 disclose a method of generating a pattern by mixing polyamic acid as a polyimide precursor and naphthoquinone diazide as a dissolution inhibitor with each other and utilizing the solubility difference between the exposed portion and the non-exposed portion. However, the method has the disadvantage that the solubility difference between the exposed portion and the non-exposed portion is small, and it is difficult to obtain a pattern with high resolution.

[0006] For example, Japanese Patent Application Publication No. 64-60630 discloses a method of mixing a soluble polyimide having one hydroxyl group with naphthoquinone diazide. However, this method has problems in that the amount of photosensitizer added is large, the structure of the polyimide precursor is limited, and its physical properties are poor.

[0007] For example, Japanese Patent Application Publication No. 60-37550 discloses a method of ester-bonding an o-nitrobenzyl ester group as a photosensitive group to a precursor. However, this method has a disadvantage in that it is difficult to improve the thickness of the layer due to low product strength.

[0008] For example, Japanese Patent Application Publication Nos. 7-33874 and 7-134414 disclose a chemical amplification composition prepared by mixing a resin obtained by replacing a carboxyl group with an acetal group dissociated by an acid with a photoacid generating agent. However, the method has the disadvantage that, although the composition has an excellent residual layer ratio, the layer shrinks greatly after curing and has poor physical properties.

[0009] It can be seen that although there have been some latest achievements in positive photosensitive polyimide resins in the current research progress, the overall effect is not ideal. It is still necessary to develop a new positive photosensitive polyimide resin product to solve the problems of extremely fast dissolution rate of the resin in alkaline developer, short development time, small difference in dissolution rate between exposed and non-exposed areas, low pattern resolution, and difficulty in precise control of the development process. Summary of the invention

[0010] Based on this, it is necessary to provide a polyamic acid resin and a preparation method thereof, and a positive photosensitive resin composition that are easy to control the dissolution rate of the resin in an alkaline developer, can prolong the development time, improve the pattern resolution, and the development process is easier to accurately control.

[0011] An embodiment of the present application provides a polyamic acid resin, the structural formula of which is shown below:

[0012]

[0013] Wherein, R1 is selected from H or CF3, the structures of X and Y each independently contain an imide structure, x+y=1, and n=5-200.

[0014] In one embodiment, the structure of X is selected from at least one of the following structures:

[0015]

[0016] In one embodiment, the structure of Y is selected from at least one of the following structures:

[0017]

[0018] In one embodiment, the relative viscosity of the polyamic acid resin is 0.35-0.45.

[0019] An embodiment of the present application provides a method for preparing a polyamic acid resin, comprising the following steps:

[0020] In a protective gas atmosphere, a diamine containing an imide structure, a dianhydride containing an imide structure, and 1,3-bis(3-aminopropyl)tetramethyldisiloxane are mixed in a first solvent for reaction;

[0021] The structural formula of the diamine containing an imide structure is: H2N-X-NH2, wherein X contains an imide structure;

[0022] The structural formula of the dianhydride containing the imide structure is: wherein Y comprises an imide structure;

[0023] The structural formula of the 1,3-bis(3-aminopropyl)tetramethyldisiloxane is:

[0024]

[0025] In one embodiment, the step of mixing a diamine containing an imide structure, a dianhydride containing an imide structure, and 1,3-bis(3-aminopropyl)tetramethyldisiloxane comprises:

[0026] The diamine containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane are first mixed in the first solvent, and then the dianhydride containing an imide structure is added under ice bath conditions.

[0027] In one embodiment, the molar ratio of the diamine containing an imide structure to 1,3-bis(3-aminopropyl)tetramethyldisiloxane is (15-25):1;

[0028] The ratio of the mole number of the dianhydride containing an imide structure to the total mole number of the diamine containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane is (0.99-1.02):1.

[0029] In one embodiment, after the diamine containing an imide structure, the dianhydride containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane are mixed in the first solvent, the total concentration of the diamine containing an imide structure, the dianhydride containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the reaction system is 12 wt % to 17 wt %.

[0030] In one embodiment, the reaction time is 12 h to 24 h.

[0031] In one embodiment, the step of precipitating, washing and drying the reaction product is also included;

[0032] Optionally, during the precipitation process, the precipitant is a mixture of ethanol and water, and the volume ratio of ethanol to water is 1:(3-5);

[0033] Optionally, during the drying process, the drying conditions include a vacuum degree of -0.09 MPa to -0.1 MPa, a temperature of 70° C. to 90° C., and a time of not less than 12 hours.

[0034] In one embodiment, the first solvent is selected from one or more of N, N'-dimethylformamide, N, N'-dimethylacetamide, γ-butyrolactone and N-methyl-2-pyrrolidone.

[0035] In one embodiment, the preparation method of the diamine containing an imide structure and the dianhydride containing an imide structure comprises the following steps:

[0036] Mixing unequal amounts of diamine monomer and dianhydride monomer in a second solvent, performing polymerization reaction at room temperature, and then thermal imidization;

[0037] When the equivalent ratio of the diamine monomer to the dianhydride monomer is greater than 1, the diamine containing an imide structure is obtained;

[0038] When the equivalent ratio of the diamine monomer to the dianhydride monomer is less than 1, the dianhydride containing an imide structure is obtained;

[0039] Optionally, the diamine monomer is selected from one or more of 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylpropane, 2,2'-trifluoromethyl-4,4'-benzidine, 1,3-bis(4,4'-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane;

[0040] Optionally, the dianhydride monomer is selected from one or more of biphenyltetracarboxylic acid dianhydride, oxydiphthalic anhydride, bisdicarboxyphenoxydiphenyl ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and isopropylidene diphenoxydiphthalic anhydride;

[0041] Optionally, the second solvent is selected from one or more of cyclohexanone and dimethylacetamide;

[0042] Optionally, the polymerization reaction time is 12h to 36h;

[0043] Optionally, the thermal imidization time is 1 h to 4 h, and the temperature is 150° C. to 300° C.

[0044] An embodiment of the present application further provides a use of a polyamic acid resin as described in any of the above embodiments or a polyamic acid resin prepared by the method for preparing a polyamic acid resin as described in any of the above embodiments in positive photosensitive development.

[0045] An embodiment of the present application also provides a positive photosensitive resin composition, the components of which include a polyamic acid resin as described in any of the above embodiments or a polyamic acid resin prepared by the preparation method of the polyamic acid resin as described in any of the above embodiments, a photosensitizer, a coupling agent and a third solvent.

[0046] In one embodiment, the components of the positive photosensitive resin composition include the following components in parts by weight:

[0047]

[0048] Optionally, the photosensitizer includes one or both of 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate and 2,3,4,4'-tetrahydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate;

[0049] Optionally, the coupling agent includes one or more of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyl and γ-aminopropyltrimethoxysilane;

[0050] Optionally, the third solvent includes organic solvent A and organic solvent B;

[0051] The organic solvent A is an organic solvent having a boiling point of 100° C. to 160° C. at atmospheric pressure;

[0052] The organic solvent B is an organic solvent having a boiling point of 180° C. to 240° C. at atmospheric pressure;

[0053] More optionally, the weight of the organic solvent A accounts for 5% to 20% of the total weight of the third solvent.

[0054] In the structure of the above-mentioned polyamic acid resin, X and Y independently contain an imide structure, and the dissolution rate of the polyamic acid in the alkaline aqueous developer can be adjusted by controlling the ratio of the imide structure to the amic acid structure in the polyamic acid resin structure, which is beneficial to increase the difference in dissolution rate between the exposed area and the non-exposed area, prolong the development time, improve the resolution of the developed pattern, and solve the problem that the development process is difficult to accurately control.

[0055] Furthermore, the preparation method of the polyamic acid resin has mild reaction conditions, does not require a catalyst, has readily available raw materials, is low in cost, is easy to scale up for production, and is suitable for large-scale promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 The positive photosensitive resin composition developed pattern of Example 1 (optical microscope);

[0057] Figure 2 The heat resistance test result (DSC) of the positive photosensitive resin composition of Example 1;

[0058] Figure 3 The positive photosensitive resin composition developed pattern of Example 2 (optical microscope);

[0059] Figure 4 The heat resistance test result (DSC) of the positive photosensitive resin composition of Example 2;

[0060] Figure 5 The positive photosensitive resin composition developed pattern of Example 3 (optical microscope);

[0061] Figure 6 The heat resistance test result (DSC) of the positive photosensitive resin composition of Example 3 is shown. DETAILED DESCRIPTION

[0062] For ease of understanding of the application, the application is described more fully below in conjunction with embodiments and accompanying drawings. The application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the application more thorough and comprehensive.

[0063] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present application belongs. The terms used herein in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0064] The terms "first", "second", "third", "fourth", etc. (if any) used in this application are used to distinguish similar objects and are only used for descriptive purposes, and are not necessarily used to describe a specific order or sequence, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" or "second" may explicitly or implicitly include at least one of the features. In the description of the present invention, the meaning of "multiple" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0065] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0066] One embodiment of the present application provides a polyamic acid resin, the structural formula of which is shown below:

[0067]

[0068] Wherein, R1 is selected from H or CF3, the structures of X and Y each independently contain an imide structure, x+y=1, and n=5-200.

[0069] It can be understood that the imide structure refers to a structure in which a N atom is connected to two carbonyl groups, and its structure can be represented as follows:

[0070] The polyamic acid resin is used as a precursor of polyimide. In the structure of the polyamic acid resin, X and Y independently contain an imide structure. The dissolution rate of the polyamic acid in the alkaline aqueous developer can be adjusted by controlling the ratio of the imide structure to the amic acid structure in the polyamic acid resin structure, which is beneficial to increase the difference in dissolution rate between the exposed area and the non-exposed area, prolong the development time, improve the resolution of the developed pattern, and solve the problem that the development process is difficult to accurately control.

[0071] In one embodiment, the structure of X is selected from at least one of the following structures:

[0072]

[0073] In one embodiment, the structure of Y is selected from at least one of the following structures:

[0074]

[0075] In one embodiment, the relative viscosity of the polyamic acid resin is 0.35 to 0.45. If the relative viscosity of the polyamic acid resin is too large, it is not convenient to operate in actual use; if the relative viscosity of the polyamic acid resin is too small, it is difficult to form a film during the development process. The relative viscosity of the polyamic acid resin within this range can ensure that the development process is easy to operate, easy to evenly coat, and easy to form a film. It can be understood that the relative viscosity of the polyamic acid resin can be, for example, but not limited to, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, and the like.

[0076] An embodiment of the present application provides a method for preparing a polyamic acid resin, comprising the following steps:

[0077] In a protective gas atmosphere, a diamine containing an imide structure, a dianhydride containing an imide structure, and 1,3-bis(3-aminopropyl)tetramethyldisiloxane are mixed in a first solvent for reaction;

[0078] The structural formula of the diamine containing an imide structure is: H2N-X-NH2, wherein X contains an imide structure;

[0079] The structural formula of the dianhydride containing the imide structure is: wherein Y comprises an imide structure;

[0080] The structural formula of 1,3-bis(3-aminopropyl)tetramethyldisiloxane is:

[0081]

[0082] In one embodiment, the step of mixing a diamine containing an imide structure, a dianhydride containing an imide structure, and 1,3-bis(3-aminopropyl)tetramethyldisiloxane comprises:

[0083] Firstly, a diamine containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane are mixed in a first solvent, and then a dianhydride containing an imide structure is added under ice bath conditions.

[0084] In one embodiment, the molar ratio of the diamine containing an imide structure to 1,3-bis(3-aminopropyl)tetramethyldisiloxane is (15-25):1. On the one hand, 1,3-bis(3-aminopropyl)tetramethyldisiloxane is beneficial to improving the bonding performance of the polyamic acid resin, but if the amount of 1,3-bis(3-aminopropyl)tetramethyldisiloxane is too high, it will cause the mechanical properties of the resin to decrease. Controlling the molar ratio of the diamine containing an imide structure to 1,3-bis(3-aminopropyl)tetramethyldisiloxane within this range can ensure that the resin has good bonding properties while also having good mechanical properties. Furthermore, the raw material cost of 1,3-bis(3-aminopropyl)tetramethyldisiloxane is relatively expensive, and controlling the use of a lower amount of 1,3-bis(3-aminopropyl)tetramethyldisiloxane as much as possible can reduce production costs. It can be understood that the molar ratio of the diamine containing an imide structure to 1,3-bis(3-aminopropyl)tetramethyldisiloxane can be, for example but not limited to, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, etc.

[0085] In one embodiment, the ratio of the molar number of the dianhydride containing an imide structure to the total molar number of the diamine containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane is (0.99-1.02): 1. It can be understood that 1,3-bis(3-aminopropyl)tetramethyldisiloxane is also a compound having a diamine structure. The ratio of the molar number of the dianhydride containing an imide structure to the total molar number of the diamine containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane refers to the ratio of the molar number of the dianhydride structure to the molar number of the diamine structure. Controlling the molar number of the dianhydride structure and the diamine structure in a relatively close range is conducive to the polymerization to obtain a polyamic acid resin with a relatively moderate molecular weight. It can be understood that the ratio of the molar number of the dianhydride containing an imide structure to the total molar number of the diamine containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane can be, for example but not limited to, 0.99:1, 1:1, 1.01:1, 1.02:1, etc.

[0086] In one embodiment, after the diamine containing an imide structure, the dianhydride containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane are mixed in the first solvent, the total concentration of the diamine containing an imide structure, the dianhydride containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the reaction system is 12wt% to 17wt%. Controlling the total concentration of these three raw materials in the reaction system within this range can ensure that the polymerization reaction has a suitable reaction rate and a high yield. It can be understood that the total concentration of the diamine containing an imide structure, the dianhydride containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the reaction system can be, for example, but not limited to, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, and the like.

[0087] In one embodiment, the reaction time is 12 hours to 24 hours. It is understandable that the reaction time can be, for example but not limited to, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, etc.

[0088] In one embodiment, the protective gas may be, for example but not limited to, nitrogen, argon, etc.

[0089] In one embodiment, the method further includes the steps of precipitating, washing and drying the reaction product.

[0090] Optionally, during the precipitation process, the precipitant is a mixture of ethanol and water, and the volume ratio of ethanol to water is 1:(3-5). It can be understood that the volume ratio of ethanol to water can be, for example but not limited to, 1:3, 1:4, 1:5, etc.

[0091] Optionally, during the washing process, the washing liquid is water.

[0092] Optionally, during the drying process, the drying conditions include a vacuum degree of -0.090 MPa to -0.1 MPa, a temperature of 70° C. to 90° C., and a time of not less than 12 hours.

[0093] In one embodiment, the first solvent is selected from one or more of N, N'-dimethylformamide, N, N'-dimethylacetamide, γ-butyrolactone and N-methyl-2-pyrrolidone.

[0094] In one embodiment, the preparation method of the diamine containing an imide structure and the dianhydride containing an imide structure comprises the following steps:

[0095] Mixing unequal amounts of diamine monomer and dianhydride monomer in a second solvent, performing polymerization reaction at room temperature, and then thermal imidization;

[0096] When the equivalent ratio of the diamine monomer to the dianhydride monomer is greater than 1, a diamine containing an imide structure is obtained;

[0097] When the equivalent ratio of the diamine monomer to the dianhydride monomer is less than 1, the dianhydride containing an imide structure is obtained.

[0098] Diamines containing an imide structure and dianhydrides containing an imide structure are key monomers for synthesizing polyamic acid resins. The diamines containing an imide structure and the dianhydrides containing an imide structure prepared by the above method have the advantages of high yield and easy purification. The structures of the two key monomers contain an imide structure, so that the ratio of imide to amic acid in polyamic acid can be controlled, thereby adjusting the dissolution rate of polyamic acid in alkaline water developer, which is beneficial to prolonging the development time, and the developed pattern has higher resolution and better heat resistance.

[0099] It can be understood that the diamine containing an imide structure and the dianhydride containing an imide structure are not limited to being prepared by the above method, and can also be prepared by other methods.

[0100] Optionally, the diamine monomer is selected from one or more of 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylpropane, 2,2'-trifluoromethyl-4,4'-benzidine, 1,3-bis(4,4'-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

[0101] Optionally, the dianhydride monomer is selected from one or more of biphenyltetracarboxylic dianhydride, oxydiphthalic anhydride, bis(dicarboxyphenoxy)diphenyl ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and isopropylidene diphenoxydiphthalic anhydride.

[0102] Optionally, the second solvent is selected from one or more of cyclohexanone and dimethylacetamide.

[0103] Optionally, the polymerization reaction time is 12 h to 36 h.

[0104] Optionally, the thermal imidization time is 1 h to 4 h, and the temperature is 150° C. to 300° C.

[0105] Furthermore, the preparation method of the polyamic acid resin has mild reaction conditions, does not require a catalyst, has readily available raw materials, is low in cost, is easy to scale up for production, and is suitable for large-scale promotion and application. In the structure of the polyamic acid resin prepared by the above method, the key monomers all contain a certain imide structure, and the ratio of imide to amic acid in the polyamic acid resin can be controlled to thereby adjust the dissolution rate of the polyamic acid in the alkaline aqueous developer, which is beneficial to increase the difference in dissolution rate between the exposed area and the non-exposed area, extend the development time, improve the resolution of the developed pattern, and solve the problem of the difficulty in precise control of the development process.

[0106] One embodiment of the present application further provides a use of a polyamic acid resin as in any of the above embodiments or a polyamic acid resin prepared by the method for preparing a polyamic acid resin as in any of the above embodiments in positive photosensitive development.

[0107] One embodiment of the present application also provides a positive photosensitive resin composition, the components of which include a polyamic acid resin as in any of the above embodiments or a polyamic acid resin prepared by the preparation method of a polyamic acid resin as in any of the above embodiments, a photosensitizer, a coupling agent, and a third solvent.

[0108] In one embodiment, the components of the positive photosensitive resin composition include, by weight:

[0109]

[0110]

[0111] In one embodiment, the components of the positive photosensitive resin composition include, by weight:

[0112]

[0113] In one embodiment, the photosensitizer comprises a quinonediazide compound.

[0114] Optionally, the quinonediazide compound is selected from one or both of 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate and 2,3,4,4′-tetrahydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate.

[0115] Further, the structural formula of 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate is:

[0116] Wherein, R2, R3 and R4 are each independently selected from H or

[0117] Further, the structural formula of 2,3,4,4'-tetrahydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate is:

[0118] Wherein, R5, R6, R7 and R8 are each independently selected from H or

[0119] In one embodiment, the coupling agent includes a silane coupling agent.

[0120] Optionally, the silane coupling agent is selected from one or more of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyl and γ-aminopropyltrimethoxysilane.

[0121] In one embodiment, the third solvent includes organic solvent A and organic solvent B, wherein organic solvent A is an organic solvent having a boiling point of 100° C. to 160° C. at atmospheric pressure; and organic solvent B is an organic solvent having a boiling point of 180° C. to 240° C. at atmospheric pressure.

[0122] The third solvent is a mixture of two organic solvents with different boiling points, which is beneficial for the positive photosensitive resin composition to gradually volatilize the solvent to completely volatilize in a more appropriate manner to form a layer pattern during the development process, and the pattern effect is better.

[0123] Optionally, the organic solvent A is selected from one or more of toluene, xylene, ethyl lactate, ethyl acetate and propyl acetate.

[0124] Optionally, the organic solvent B is selected from one or more of N,N'-dimethylformamide, N,N'-dimethylacetamide, diethylene glycol butyl ether, dipropylene glycol butyl ether, γ-butyrolactone and N-methyl-2-pyrrolidone.

[0125] Optionally, the weight of the organic solvent A accounts for 5% to 20% of the total weight of the third solvent. It is understandable that the weight of the organic solvent A accounts for the total weight of the third solvent, for example, but not limited to, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc. Further, the weight of the organic solvent A accounts for 10% to 15% of the total weight of the third solvent.

[0126] One embodiment of the present application further provides a method for preparing a positive photosensitive resin composition as in any of the above embodiments, comprising the following steps:

[0127] The polyamic acid resin, the photosensitizer and the coupling agent are mixed in the third solvent.

[0128] An embodiment of the present application also provides a method for positive photosensitive development, comprising the following steps:

[0129] Applying the positive photosensitive resin composition in any of the above embodiments on a substrate to form a film layer;

[0130] The film layer is pre-baked, exposed, developed, cleaned and cured in sequence.

[0131] In one embodiment, the substrate is a dry hard substrate. Further, the substrate is a silicon wafer.

[0132] In one embodiment, the pre-baking conditions include: a temperature of 100° C. to 110° C. and a time of 150 s to 200 s.

[0133] In one embodiment, the exposure conditions include: i-line exposure with an exposure dose of 180 mJ / cm 2 ~400mJ / cm 2 .

[0134] In one embodiment, the developing conditions include: alkaline solution development, and the developing time is 80s to 100s. Further, the alkaline solution is a 2.38wt% TMAH solution.

[0135] In one embodiment, the curing conditions include: soft baking first and hard baking later. Further, the soft baking conditions include: temperature of 100°C to 120°C and time of 10 min to 15 min. Further, the hard baking conditions include: temperature of 330°C to 350°C and time of 3 h to 4 h.

[0136] In one embodiment, the method of positive photosensitive development comprises the following steps:

[0137] Mix the positive photosensitive resin composition on a mixer for 12 to 24 hours, and filter and degas;

[0138] Applying the defoamed positive photosensitive resin composition on a hard substrate to form a film layer;

[0139] Place the film layer on a hot plate at 100℃~110℃ for pre-baking for 150s~200s to form a dry film;

[0140] The dry film was exposed to i-line with an exposure dose of 180 mJ / cm 2 ~400mJ / cm 2 ;

[0141] The exposed dry film is developed with alkaline solution for 80s to 100s;

[0142] The pattern film obtained by development is placed on a hot plate at 100-120° C. for curing for 10-15 minutes, then placed in a high-temperature vacuum oven and stepwise heated to 330-350° C. for curing for 3-4 hours to obtain a cured positive photosensitive development pattern.

[0143] An embodiment of the present application further provides a positive photosensitive development pattern, which is obtained by the positive photosensitive development method in the above embodiment.

[0144] One embodiment of the present application also provides a method for positive photosensitive development as in the above embodiment or an application of a positive photosensitive development pattern as in the above embodiment in manufacturing semiconductor materials. For example, it can be used as, but not limited to, an interlayer insulating layer of a microelectronic chip, a surface passivation layer, and a packaging material for electronic and electrical components.

[0145] The polyamic acid resin, positive photosensitive resin composition and preparation method and application of the present application are further described in detail below in combination with specific examples and comparative examples. It can be understood that in the specific examples, unless otherwise specified, all raw materials can be sourced from common commercial sources.

[0146] Example 1

[0147] 1. Preparation of polyamic acid resin

[0148] 1.1 Synthesis of key monomers with imide structure:

[0149] Biphenyltetracarboxylic acid dianhydride and 4,4'-diaminodiphenyl ether are polymerized in a solvent N,N'-dimethylacetamide at room temperature for 24 hours in a molar ratio of 2:1, thermal imidization is performed at a temperature of 150°C for 2 hours, and purification is performed to form a dianhydride containing an imide structure;

[0150] Biphenyltetracarboxylic acid dianhydride and 4,4'-diaminodiphenyl ether are polymerized in a solvent N,N'-dimethylacetamide at room temperature for 24 hours in a molar ratio of 1:2, thermally imidized at 150°C for 2 hours, and purified to form a diamine containing an imide structure.

[0151] 1.2 Synthesis of polyamic acid resin:

[0152] Under nitrogen atmosphere, the diamine containing an imide structure prepared in step 1.1 and 1,3-bis(3-aminopropyl)tetramethyldisiloxane were blended in a molar ratio of 15:1 and dissolved in N,N'-dimethylformamide solvent, and the dianhydride containing an imide structure prepared in step 1.1 was added under ice-water bath conditions, the ratio of the mole number of the dianhydride containing an imide structure to the total mole number of the diamine containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane was 1.01:1, and the total concentration of the diamine containing an imide structure, the dianhydride containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the reaction system was 12wt%.

[0153] The reaction was stirred for 12 hours, and then the solution was poured into a precipitant consisting of a mixture of ethanol and water, with the volume ratio of ethanol to water being 1:3. The precipitated solid was washed with pure water and dried in a vacuum oven at 70°C for 12 hours to obtain a polyamic acid resin. The relative viscosity of the resin was 0.35 as characterized by an Ubbelohde viscometer.

[0154] 2. Preparation of positive photosensitive resin composition:

[0155] By weight, 100 parts of the polyamic acid resin prepared in step 1, 26 parts of 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate, and 1 part of γ-(2,3-epoxypropoxy)propyltrimethoxysilane are stirred and mixed in 20 parts of ethyl lactate and 180 parts of γ-butyrolactone to uniformly mix.

[0156] 3. Positive photosensitive development

[0157] 3.1 The positive photosensitive resin composition prepared in step 2 was mixed on a mixer for 12 hours, and filtered to remove bubbles;

[0158] 3.2 Spin-coat the positive photosensitive resin composition treated in step 3.1 onto a hard substrate silicon wafer to form a film layer;

[0159] 3.3 Place the film layer formed in step 3.2 on a hot plate at 100°C for pre-baking for 200 seconds to form a dry film;

[0160] 3.4 The dry film formed in step 3.3 was exposed to i-line with an exposure dose of 180 mJ / cm 2 ;

[0161] 3.5 The dry film treated in step 3.4 is developed with a 2.38wt% TMAH solution for 100s, and then washed with ultra-clear water to form a positive pattern;

[0162] 3.6 Place the positive pattern formed in step 3.5 on a 100°C hot plate for curing for 15 minutes, then place it in a high-temperature vacuum oven and cure it at a temperature step of 120°C / 1h+180°C / 1h+280°C / 1h+330°C / 1h to obtain a cured positive photosensitive polyimide development pattern.

[0163] Example 2

[0164] 1. Preparation of polyamic acid resin

[0165] 1.1 Synthesis of key monomers with imide structure:

[0166] 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and 2,2'-diaminodiphenylpropane are polymerized in a solvent N,N'-dimethylacetamide at a molar ratio of 2:1 at room temperature for 24 hours, thermally imidized at 250°C for 2 hours, and purified to form a dianhydride containing an imide structure;

[0167] 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and 2,2'-diaminodiphenylpropane are polymerized in a solvent N,N'-dimethylacetamide at a molar ratio of 1:2 at room temperature for 24 hours, thermally imidized at 250° C. for 2 hours, and purified to form a diamine containing an imide structure.

[0168] 1.2 Synthesis of polyamic acid resin:

[0169] Under nitrogen atmosphere, the diamine containing an imide structure prepared in step 1.1 and 1,3-bis(3-aminopropyl)tetramethyldisiloxane are blended in a molar ratio of 18:1 and dissolved in N,N'-dimethylformamide solvent, and the dianhydride containing an imide structure prepared in step 1.1 is added under ice-water bath conditions, the ratio of the mole number of the dianhydride containing an imide structure to the total mole number of the diamine containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane is 1:1, and the total concentration of the diamine containing an imide structure, the dianhydride containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the reaction system is 14wt%.

[0170] The reaction was stirred for 13 hours, and then the solution was poured into a precipitant consisting of a mixture of ethanol and water, with the volume ratio of ethanol to water being 1:4. The precipitated solid was washed with pure water and dried in a vacuum oven at 90°C for 12 hours to obtain a polyamic acid resin. The relative viscosity of the resin was 0.40 as characterized by an Ubbelohde viscometer.

[0171] 2. Preparation of positive photosensitive resin composition:

[0172] By weight, 100 parts of the polyamic acid resin prepared in step 1, 29 parts of 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate, and 3 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane are stirred and mixed in 45 parts of toluene, 200 parts of γ-butyrolactone, and 55 parts of N-methyl-2-pyrrolidone, and the mixture is uniformly stirred.

[0173] 3. Positive photosensitive development

[0174] 3.1 The positive photosensitive resin composition prepared in step 2 was mixed on a mixer for 15 hours, and filtered to remove bubbles;

[0175] 3.2 Spin-coat the positive photosensitive resin composition treated in step 3.1 onto a hard substrate silicon wafer to form a film layer;

[0176] 3.3 Place the film layer formed in step 3.2 on a hot plate at 110°C for pre-baking for 180 seconds to form a dry film;

[0177] 3.4 The dry film formed in step 3.3 was exposed to i-line with an exposure dose of 280 mJ / cm 2 ;

[0178] 3.5 The dry film treated in step 3.4 is developed with a 2.38wt% TMAH solution for 90s, and then washed with ultra-clear water to form a positive pattern;

[0179] 3.6 Place the positive pattern formed in step 3.5 on a 110°C hot plate for curing for 12 minutes, then place it in a high-temperature vacuum oven for curing at a temperature step of 150°C / 30min+200°C / 1h+250°C / 1h+340°C / 1h to obtain a cured positive photosensitive polyimide development pattern.

[0180] Example 3

[0181] 1. Preparation of polyamic acid resin

[0182] 1.1 Synthesis of key monomers with imide structure:

[0183] Isopropylidene diphenoxy diphthalic anhydride and 1,3-bis(4-aminophenoxy)benzene are polymerized in a solvent N,N'-dimethylacetamide at a molar ratio of 2:1 at room temperature for 24 hours, thermally imidized at 300°C for 2 hours, and purified to form a dianhydride containing an imide structure;

[0184] Isopropylidene diphenoxy diphthalic anhydride and 1,3-bis(4-aminophenoxy)benzene are polymerized in a solvent N,N'-dimethylacetamide at a molar ratio of 1:2 at room temperature for 24 hours, thermally imidized at 300°C for 2 hours, and purified to form a diamine containing an imide structure.

[0185] 1.2 Synthesis of polyamic acid resin:

[0186] Under nitrogen atmosphere, the diamine containing an imide structure prepared in step 1.1 and 1,3-bis(3-aminopropyl)tetramethyldisiloxane were blended in a molar ratio of 20:1 and dissolved in N,N'-dimethylformamide solvent, and the dianhydride containing an imide structure prepared in step 1.1 was added under ice-water bath conditions, the ratio of the mole number of the dianhydride containing an imide structure to the total mole number of the diamine containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane was 0.99:1, and the total concentration of the diamine containing an imide structure, the dianhydride containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the reaction system was 17wt%.

[0187] The reaction was stirred for 12 hours, and then the solution was poured into a precipitant consisting of a mixture of ethanol and water, with the volume ratio of ethanol to water being 1:4. The precipitated solid was washed with pure water and dried in a vacuum oven at 80°C for 15 hours to obtain a polyamic acid resin. The relative viscosity of the resin was 0.38 as characterized by an Ubbelohde viscometer.

[0188] 2. Preparation of positive photosensitive resin composition:

[0189] By weight, 100 parts of the polyamic acid resin prepared in step 1, 30 parts of 2,3,4,4'-tetrahydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate, and 5 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane are stirred and mixed in 30 parts of ethyl lactate, 30 parts of toluene, and 340 parts of γ-butyrolactone to uniformly mix.

[0190] 3. Positive photosensitive development

[0191] 3.1 The positive photosensitive resin composition prepared in step 2 was mixed on a mixer for 12 hours, and filtered to remove bubbles;

[0192] 3.2 Spin-coat the positive photosensitive resin composition treated in step 3.1 onto a hard substrate silicon wafer to form a film layer;

[0193] 3.3 Place the film layer formed in step 3.2 on a 120°C hot plate for pre-baking for 150 seconds to form a dry film;

[0194] 3.4 The dry film formed in step 3.3 was exposed to i-line with an exposure dose of 400 mJ / cm2 ;

[0195] 3.5 The dry film treated in step 3.4 is developed with a 2.38wt% TMAH solution for 80s, and then washed with ultra-clear water to form a positive pattern;

[0196] 3.6 Place the positive pattern formed in step 3.5 on a 120°C hot plate for curing for 10 minutes, then place it in a high-temperature vacuum oven for curing at 180°C / 1h+280°C / 1h+300°C / 30min+350°C / 30min to obtain a cured positive photosensitive polyimide development pattern.

[0197] It can be seen from the positive development methods of Examples 1 to 3 that the development time of Examples 1 to 3 is 80s to 100s, the development time is longer, and the development process is easier to control.

[0198] like Figures 1 to 6 As shown, the developed pattern resolution of the positive photosensitive resin composition of Examples 1 to 3 is 5 μm to 20 μm, which is high in resolution; the glass transition temperature is 260° C. to 285° C., which is good in heat resistance.

[0199] The technical features of the above embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0200] The above embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the inventive concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the attached claims.

Claims

1. A method for preparing a polyamic acid resin, characterized in that: The steps include: In a protective gas atmosphere, a diamine containing an imide structure, a dianhydride containing an imide structure, and 1,3-bis(3-aminopropyl)tetramethyldisiloxane are mixed in a first solvent for reaction; The preparation method of the diamine containing an imide structure and the dianhydride containing an imide structure comprises the following steps: Mixing unequal amounts of diamine monomer and dianhydride monomer in a second solvent, performing polymerization reaction at room temperature, and then thermal imidization; When the equivalent ratio of the diamine monomer to the dianhydride monomer is greater than 1, the diamine containing an imide structure is obtained; When the equivalent ratio of the diamine monomer to the dianhydride monomer is less than 1, the dianhydride containing an imide structure is obtained; The diamine monomer is selected from one or more of 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylpropane, 2,2'-trifluoromethyl-4,4'-benzidine, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane; The dianhydride monomer is selected from one or more of biphenyltetracarboxylic acid dianhydride, oxydiphthalic anhydride, bis(dicarboxy)phenoxydiphenyl ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and isopropylidene diphenoxydiphthalic anhydride; The molar ratio of the diamine containing an imide structure to 1,3-bis(3-aminopropyl)tetramethyldisiloxane is (15-25):1, and the ratio of the molar number of the dianhydride containing an imide structure to the total molar number of the diamine containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane is (0.99-1.02):

1.

2. The method for preparing a polyamic acid resin according to claim 1, wherein The step of mixing a diamine including an imide structure, a dianhydride including an imide structure, and 1,3-bis(3-aminopropyl)tetramethyldisiloxane comprises: The diamine containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane are first mixed in the first solvent, and then the dianhydride containing an imide structure is added under ice bath conditions.

3. The method for preparing a polyamic acid resin according to any one of claims 1 to 2, characterized in that: After the diamine containing an imide structure, the dianhydride containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane are mixed in the first solvent, the total concentration of the diamine containing an imide structure, the dianhydride containing an imide structure and 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the reaction system is 12 wt % to 17 wt %.

4. The method for preparing a polyamic acid resin according to any one of claims 1 to 2, characterized in that: The reaction time is 12h~24h.

5. The method for preparing a polyamic acid resin according to any one of claims 1 to 2, characterized in that: The method also includes the steps of precipitating, washing and drying the reaction product.

6. The method for preparing the polyamic acid resin according to claim 5, characterized in that: During the precipitation process, the precipitant is a mixture of ethanol and water, and the volume ratio of ethanol to water is 1: (3~5).

7. The method for preparing the polyamic acid resin according to claim 5, characterized in that: During the drying process, the drying conditions include vacuum degree -0.09Mpa~-0.1Mpa, temperature 70℃~90℃, and time not less than 12h.

8. The method for preparing a polyamic acid resin according to any one of claims 1 to 2, characterized in that: The first solvent is selected from one or more of N, N'-dimethylformamide, N, N'-dimethylacetamide, γ-butyrolactone and N-methyl-2-pyrrolidone.

9. The method for preparing a polyamic acid resin according to any one of claims 1 to 2, characterized in that: The second solvent is selected from one or more of cyclohexanone and dimethylacetamide.

10. The method for preparing a polyamic acid resin according to any one of claims 1 to 2, characterized in that: The polymerization reaction time is 12h~36h.

11. The method for preparing a polyamic acid resin according to any one of claims 1 to 2, characterized in that: The thermal imidization time is 1h~4h, and the temperature is 150℃~300℃.

12. A polyamic acid resin, characterized in that: It is prepared by the preparation method according to any one of claims 1 to 11.

13. Use of the polyamic acid resin according to claim 12 or the polyamic acid resin prepared by the preparation method of the polyamic acid resin according to any one of claims 1 to 11 in positive photosensitive development.

14. A positive photosensitive resin composition, characterized in that: The components of the positive photosensitive resin composition include the polyamic acid resin according to claim 12 or the polyamic acid resin prepared by the preparation method of the polyamic acid resin according to any one of claims 1 to 11, a photosensitizer, a coupling agent and a third solvent.

15. The positive photosensitive resin composition according to claim 14, characterized in that: The components of the positive photosensitive resin composition include, by weight: 100 parts of the polyamic acid resin, 1 to 55 parts of the photosensitizer, 200 to 400 parts of the third solvent, and The coupling agent is 1 to 20 parts.

16. The positive photosensitive resin composition according to claim 15, characterized in that: The photosensitizer includes one or both of 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate and 2,3,4,4'-tetrahydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate.

17. The positive photosensitive resin composition according to claim 15, characterized in that: The coupling agent includes one or more of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane.

18. The positive photosensitive resin composition according to claim 15, characterized in that: The third solvent includes organic solvent A and organic solvent B; The organic solvent A is an organic solvent having a boiling point of 100° C. to 160° C. at atmospheric pressure; The organic solvent B is an organic solvent having a boiling point of 180° C. to 240° C. at atmospheric pressure.

19. The positive photosensitive resin composition according to claim 18, characterized in that: The weight of the organic solvent A accounts for 5% to 20% of the total weight of the third solvent.

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