TWI571481B - Polymer, method for preparing the same, and a photosensitive resin composition thereof - Google Patents

Description

Polymer, method for producing the same, and photosensitive resin composition containing the same

The present invention relates to a polymer, a method for producing the same, and a photosensitive resin composition comprising the same.

Polyimide (PI) is widely used in the semiconductor and display industries due to its excellent thermal stability and good mechanical, electrical and chemical properties, for example, as a semiconductor wafer protective film or as an insulating layer on a display. Driven by the demand for high-performance functions such as increased computing speed, reduced product size, and reduced power consumption in today's electronic products, packaging trends are moving toward three-dimensional stacking and increasing the degree of accumulation. As a result, low curing temperatures and low temperatures are caused. The material requirements for stress. However, the conventional photosensitive polytheneamine needs to be imidized at a high temperature of 350 ° C in order to achieve excellent thermal stability and good mechanical, electrical and chemical properties. Further, the conventional photosensitive polyimidonide easily forms a film layer having high internal stress after curing at a high temperature, resulting in bending deformation, cracking, or delamination of the underlying substrate, and damage of the semiconductor element.

Based on the above, the industry needs a polymer material with low curing temperature and low stress to meet current semiconductor and display processes.

The present invention discloses a polymer having the structure represented by formula (I)

Wherein R ₁ is -OH, or -COOH; A ₁ is , ,or ; A ₂ is independent , , or ;A ₃ series is independent , ,or ;A ₄ series ,or ;Z series -O-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, , , ,or m is an integer greater than 1, such as an integer between 2 and 100; n is an integer greater than 1, such as an integer between 2 and 100; i is an integer between 1 and 5; and, j is between 1 An integer up to 20, such as an integer between 1 and 10.

The polymer of the present invention may have a repeating unit And repeating units Where the repeating unit And the repeating unit Can be arranged in an orderly or random manner.

According to some embodiments of the present invention, there is provided a method of producing a polymer comprising: subjecting a composition to a polymerization to obtain the above polymer of the present invention. Wherein the composition comprises at least one acid anhydride having the formula (II), at least one diamine having the formula (III), at least one diamine having the formula (IV), and at least one compound having the formula (V):

H ₂ NA ₂ -NH ₂ Formula (IV) H ₂ NA ₃ -R ₁ Formula (V)

Wherein R ₁ is -OH, or -COOH; A ₁ is , ,or ; A ₂ is independent , , or ;A ₃ series is independent , ,or ;A ₄ series ,or ;Z series -O-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, , , ,or m is an integer greater than 1, such as an integer between 2 and 100; n is an integer greater than 1, such as an integer between 2 and 100; i is an integer between 1 and 5; j is between 1 and 20 An integer, such as an integer between 1 and 10.

According to an embodiment of the present invention, the present invention also provides a photosensitive resin composition comprising the following components uniformly dispersed in a solvent: component (A) the above polymer having the formula (I); and component (B) having a phenol group (phenol) Group) of compounds; and, component (C) sensitizer.

The above and other objects, features, and advantages of the present invention will become more apparent and understood.

According to an embodiment of the present invention, the present invention provides a polymer obtained by introducing a phenylbenzoxazole structure into a polymer main chain and designing a structure having a hydroxyl group or a carboxyl group by an terminal blocking group. The polymer is soluble in organic solvents. The polymer may be further blended with a phenolic hardener and a photosensitive agent to prepare a photosensitive resin composition of the present invention. It is to be noted that the photosensitive resin composition of the present invention can be cross-linked and cured at a baking temperature equal to or lower than about 230 ° C after the yellow light lithography process, and has good developability and resolution. Degree, electrical characteristics, and chemical resistance.

According to an embodiment of the present invention, the polymer of the present invention may have the structure represented by the formula (I) Formula (I)

Wherein R ₁ may be -OH or -COOH; A ₁ may be , ,or ; A ₂ can be independent , , or ; A ₃ can be independent , ,or ; A ₄ can be ,or ;Z can be -O-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, , , ,or m may be an integer greater than 1, such as an integer between 2 and 100; n may be an integer greater than 1, such as an integer between 2 and 100; i may be an integer between 1 and 5; j may be an integer from 1 to 20, for example, may be an integer from 1 to 10.

According to an embodiment of the present invention, the polymer of the present invention may have a repeating unit And repeating units Where the repeating unit And the repeating unit Can be arranged in an orderly or random manner.

According to some embodiments of the invention, the polymer may comprise m Repetitive unit of structure, and n have A repeating unit of structure wherein the value of m/(m+n) is between about 0.05 and 0.9, for example between 0.1 and 0.4. When the value of m/(m+n) is less than 0.05 or more than 0.9, the resulting cured layer is inferior in developability and chemical resistance. In one embodiment, when the compound of the formula (I) of the present invention has a m/(m+n) value of between 0.1 and 0.4, the photosensitive resin composition containing the same can be exposed after exposure and development. Curing is carried out at a temperature of about 230 ° C or below (for example, about 180 ° C to 230 ° C), and the resulting cured layer has excellent developability (that is, the unexposed coating hardly remains after development), and is resistant. Chemical. According to some embodiments of the invention, the inherent viscosity (IV) of the polymer may range from 0.15 dL/g to 0.35 dL/g.

According to some embodiments of the present invention, there is provided a process for the preparation of a polymer for the preparation of a polymer of the above formula (I). The method comprises subjecting a composition to a polymerization reaction. Wherein the composition is prepared by uniformly dispersing at least one diamine having the formula (III), at least one diamine having the formula (IV), and at least one acid anhydride having the formula (II) in a solvent. And adding at least one compound having the formula (V):

H ₂ NA ₂ -NH ₂ Formula (IV) H ₂ NA ₃ -R ₁ Formula (V)

Wherein R ₁ may be -OH or -COOH; A ₁ may be , ,or ; A ₂ can be independent , , or ; A ₃ can be independent , ,or ; A ₄ can be ,or ;Z can be -O-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, , , ,or m may be an integer greater than 1, such as an integer between 2 and 100; n may be an integer greater than 1, such as an integer between 2 and 100; i may be an integer between 1 and 5; It is an integer from 1 to 20, for example, may be an integer from 1 to 10. According to an embodiment of the invention, the composition may be subjected to a heating process to effect the polymerization, wherein the temperature of the heating process may be between about 100 and 220 °C. According to an embodiment of the present invention, the solvent may be, for example, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), xylene, Or a combination thereof.

According to an embodiment of the present invention, the preparation method of the polymer of the present invention may comprise the following steps. An appropriate amount of an acid anhydride having the formula (II) and a diamine having the formula (III) and the formula (IV) are dissolved in a solvent (for example, N-methyl-2-pyrrolidone (NMP)). And stirring for a few hours (for example, about 1-10 hours) at a temperature lower than room temperature (for example, 0 to 10 ° C). A compound of formula (V) is used as an endcapped agent. After stirring for several hours (for example, about 1-10 hours), a solvent (for example, xylene) is added and heated to reflux (the heating temperature depends on the boiling point of the solvent, for example, between about 100 and 220 ° C). After the reaction is completed (for example, the reaction is about 1-10 hours), it is cooled to obtain a polymer solution having a hydroxyl group or a carboxyl group at the end of the main chain, wherein the polymer solution is further added with a solvent to dilute the solution to a desired concentration for use. . The photosensitive resin composition of the present invention can be prepared by taking an appropriate amount of the above polymer solution.

According to an embodiment of the present invention, the acid anhydride having the formula (II) may be used in an amount of about 1 mole, and the diamine having the formula (III) may be used in an amount of about 0.2 to 0.5 mole, and the formula (IV) The diamine may be used in an amount of from about 0.4 to 0.9 moles, and the compound of formula (V) may be used in an amount of from about 0.1 to 0.4 moles. Further, the molar number of the compound of the formula (V) having the formula (III) and the molar amount of the diamine having the formula (IV) plus half times the molar amount of the compound of the formula (V) coefficient ratio between about 0.7 to 1.6, i.e. the molar number of the diamine having the formula (III), M _1, of a diamine having the formula (IV) in molar M _2, having the formula ( The molar number M ₃ of the compound of V) and the molar number M ₄ of the anhydride having the formula (II) satisfy the following equation: 0.7 [(M ₁ +M ₂ +M ₃ /2)/M ₄ ] 1.6. According to another embodiment of the present invention, the molar number of the compound of the formula (V) having the formula (III) and the molar amount of the diamine having the formula (IV) plus half times the formula (II) The ratio of the molar number of the anhydride may be between about 0.8 and 1.2, that is, the molar number M ₁ of the diamine having the formula (III), and the molar number M ₂ of the diamine having the formula (IV) The molar number M ₃ of the compound of the formula (V) and the molar number M ₄ of the anhydride having the formula (II) satisfy the following equation: 0.8 [(M ₁ +M ₂ +M ₃ /2)/M ₄ ] 1.2.

In another aspect, the ratio of the molar number of the diamine having the formula (III) to the total number of moles of the diamine having the formula (III) and the formula (IV) may be between 0.05 and 0.9, that is, The molar number M ₁ of the diamine having the formula (III) and the molar number M ₂ of the diamine having the formula (IV) satisfy the following equation: 0.05 [M ₁ /(M ₁ +M ₂ )] 0.9. According to another embodiment of the present invention, in order to make the photosensitive resin composition containing the polymer subsequently, the cured film layer has better developability and chemical resistance, and the molar number of the diamine having the formula (III) is The ratio of the molar ratio of the diamines of the formula (III) and the formula (IV) may be between 0.1 and 0.4, that is, the molar number M ₁ of the diamine having the formula (III), and the The molar number M ₂ of the diamine having the formula (IV) conforms to the following equation: 0.1 [M ₁ /(M ₁ +M ₂ )] 0.4.

Furthermore, according to an embodiment of the present invention, in order to make the photosensitive resin composition containing the polymer subsequently, the cured layer can be raised with a crosslinking agent (phenol-based compound) during hard baking under the condition of developing characteristics. a cross-linking reaction, the ratio of the molar number of the compound having the formula (V) to the molar number of the anhydride having the formula (II) may be between 0.1 and 0.3, that is, the compound having the formula (V) The molar number M ₃ and the molar number M ₄ of the anhydride having the formula (II) conform to the following equation: 0.1 (M ₃ /M ₄ )] 0.3. If it is less than 0.1, the photosensitive resin composition containing the polymer later is hard to develop clean; if it is more than 0.3, the photosensitive resin composition containing the polymer later is less resistant to the developer.

According to another embodiment of the present invention, the present invention provides a photosensitive resin composition which can be developed in a short time with an alkaline aqueous solution, and has high light sensitivity, good resolution, low hard baking temperature, and high film thickness retention. And high chemical resistance. Further, the photosensitive resin composition of the present invention has good storage properties at room temperature.

The photosensitive resin composition of the present invention comprises the following components uniformly dispersed in a solvent: (A) the polymer of the formula (I) of the present invention; (B) a compound having a phenol group; and (C) photosensitive Agent. Wherein the content of the component (A) may be about 100 parts by weight, the content of the component (B) may be about 1 to 50 parts by weight (for example, about 5 to 25 parts by weight), and the content of the component (C) may be about 1-50 parts by weight (for example, about 5-25 parts by weight).

According to an embodiment of the present invention, the component (B) has a phenol group compound, and may be, for example, , , , Or a combination of the above.

According to an embodiment of the present invention, the component (C) sensitizer may comprise quinonediazide. For example, the component (C) sensitizer can be Or a combination of the above. Among them, D is independent of -OH, , ,or And in the same compound, at least one of D is not -OH.

According to an embodiment of the present invention, the solvent may be, for example, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), or a combination thereof.

The photosensitive resin composition of the present invention can be subjected to a lithography process by: (i) coating a photosensitive resin composition on a suitable substrate; (ii) pre-baking; (iii) exposure; Iv) development; and (v) hard roasting. In the above step (i), the substrate may be, for example, a crucible substrate, glass, or ITO glass, and the substrate may be Any desired film layer has been formed. The method of applying the photosensitive resin composition may be, for example, a spin coating, a roller coating, a screen coating, or a curtain coating. , dip coating, or spray coating, but is not limited to the above coating method. In the embodiment of the present invention, the film formed by coating may be pre-baked for several minutes at about 60-120 ° C to distill off the solvent therein. Then, the coated substrate is exposed to actinic radiation under a mask, such as X-ray, electron beam, ultraviolet, visible, or other sources that can be used as actinic rays. Wait. After exposure, the coated substrate is subsequently developed by an alkaline aqueous developer to wash away the exposed portions of the film to obtain a pattern. The above alkaline aqueous developer comprises an alkaline aqueous solution, which may be an inorganic base (for example: potassium hydroxide or sodium hydroxide), a primary amine (for example, ethylamine), a secondary amine (for example, diethylamine), An aqueous solution of a tertiary amine (for example, triethylamine) or a quaternary ammonium salt (for example, tetramethylammonium hydroxide) is preferred, and an aqueous solution containing tetramethylammonium hydroxide is preferred. Development can be accomplished by soaking, spraying or laminating or using other known development methods. The developed photoresist pattern is then washed with deionized water. Since the photosensitive resin composition has the specific polymer (i.e., the polymer having the formula (I)) of the present invention, it can be hard at a temperature of about 230 ° C or below (for example, about 180 ° C to 230 ° C). Bake, and obtain a cured layer having high developability, resolution, electrical properties, and chemical resistance.

The above-described and other objects, features and advantages of the present invention will become more apparent from the claims.

Preparation of polymer having the structure of formula (I)

Example 1 :

A reaction flask is provided, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, BisAPAF is added under nitrogen, and the structure thereof is (57.5 mmol), 5-amino-2-(4-aminophenyl)benzoxazole, 5-ABO, the structure of which is (20 mmol), 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldioxane (1,3-bis(3-aminopropyl-1,1) , 3,3-tetramethyldisiloxane) (siloxane 248), the structure of which ) (10 millimoles), and ethylene glycol bisanhydrotrimellitate (TMEG) (100 mmol) in a reaction flask, and 200 g of N-methyl-2-pyrrolidone (NMP) was added as a solvent. Next, after the solution was cooled to 0 ° C and stirred for 4 hours, 3-aminophenol (3-aminophenol) was added. (25 mmol) as a blocking agent and stirred at room temperature for a further 4 hours. Next, 80 g of xylene was added, and the mixture was heated to 180 ° C and stirred for 3 hours. After cooling, a viscous polymer solution (I) was obtained. Referring to Table 1, the components and contents used in Example 1 and the ratio of the repeating unit are shown. Finally, the intrinsic viscosity of the polymer of the polymer solution (I) was measured, and the intrinsic viscosity obtained was 0.21 dL/g.

Example 2 :

A reaction flask was provided, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF) (57.5) was added under nitrogen. M-mole), 6-amino-2-(4-aminophenyl)benzoxazole, 6-ABO, the structure of which is (20 mmol), 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldioxane (1,3-bis(3-aminopropyl-1,1) , 3,3-tetramethyldisiloxane) (siloxane 248) (10 mmol), and ethylene glycol bisanhydrotrimellitate (TMEG) (100 mmol) in a reaction flask, and added 200 g of N -Methyl-2-pyrrolidone (NMP) as a solvent. Then, after cooling the above solution to 0 ° C and stirring for 4 hours, 3-aminophenol was added (25 Mol) as a blocking agent, and stirred at room temperature for another 4 hours. Then, after adding 80 g of xylene, the temperature was raised to 180 ° C and stirred for 3 hours. After cooling, a viscous polymer solution (II) was obtained. Referring to Table 1, the composition and content used in Example 2 and the ratio of the re-fraction unit are shown. Finally, the intrinsic viscosity of the polymer of the polymer solution (II) is measured, and the intrinsic viscosity obtained is 0.22. dL/g.

Example 3 :

A reaction flask was provided and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF) (57.5) was added under nitrogen. Milliamine, 5-amino-2-(4-aminophenyl)benzoxazole (5-ABO) (20 mmol), 1, 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (1,3-bis(3-aminopropyl-1,1,3,3-tetramethyldisiloxane) (siloxane 248 ) (10 mmol) and 4,4'-oxydiphthalic dianhydride (ODA), the structure of which is (100 mmol) in a reaction flask, and 200 g of N-methyl-2-pyrrolidone (NMP) was added as a solvent. Next, after the solution was cooled to 0 ° C and stirred for 4 hours, 3-aminophenol (25 mmol) was added as a blocking agent, and stirred at room temperature for further 4 hours. Next, 80 g of xylene was added, and the mixture was heated to 180 ° C and stirred for 3 hours. After cooling, a viscous polymer solution (III) was obtained. Referring to Table 1, the components and contents used in Example 3 and the ratio of the repeating unit are shown. Finally, the intrinsic viscosity of the polymer of the polymer solution (III) was measured, and the intrinsic viscosity obtained was 0.25 dL/g.

Example 4 :

A reaction flask was provided, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF) (57.5) was added under nitrogen. 6-Amino-2-(4-aminophenyl)benzoxazole (6-ABO) (20 mmol) Ear), 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldioxane (1,3-bis(3-aminopropyl-1,1,3,3- Tetramethyldisiloxane) (siloxane 248) (10 mmol) and 4,4'-Oxydiphthalic dianhydride (ODPA) (100 mmol) in a reaction flask and added 200 g of N-methyl-2-pyrrolidone (NMP) was used as a solvent. Then, after the solution was cooled to 0 ° C and stirred for 4 hours, 3-aminophenol was added. (25 mmol) as a blocking agent, and stirred at room temperature for another 4 hours. Then, after adding 80 g of xylene, the temperature was raised to 180 ° C and stirred for 3 hours. After cooling, a viscous polymer solution was obtained. (IV). Referring to Table 1, the composition and content used in Example 4, and the ratio of the repeating unit are shown. Finally, the intrinsic viscosity of the polymer of the polymer solution (IV) is measured, and the inherent viscosity is obtained. The value is 0.24 dL/g.

Example 5 :

A reaction flask was provided, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF) (52.5) was added under nitrogen. Mole, 6-Amino-2-(4-aminophenyl)benzoxazole (6-ABO) (35 mmol), and 4 4'-Oxydiphthalic dianhydride (ODPA) (100 mmol) in a reaction flask and 200 g of N-methyl-2-pyrrolidone (N-methyl-) 2-pyrrolidone, NMP) as a solvent. Next, after the solution was cooled to 0 ° C and stirred for 4 hours, 3-aminophenol (25 mmol) was added as a blocking agent, and stirred at room temperature for further 4 hours. Next, after adding 80 g of xylene, the temperature was raised to 180 ° C and stirred. hour. After cooling, a viscous polymer solution (V) was obtained. Referring to Table 1, the components and contents used in Example 5 and the ratio of the repeating unit are shown. Finally, the intrinsic viscosity of the polymer of the polymer solution (V) was measured, and the intrinsic viscosity obtained was 0.3 dL/g.

Example 6 :

A reaction flask was provided, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF) (57.5) was added under nitrogen. Milliamine, 5-amino-2-(4-aminophenyl)benzoxazole (5-ABO) (20 mmol), 1, 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (1,3-bis(3-aminopropyl-1,1,3,3-tetramethyldisiloxane) (siloxane 248 ) (10 mmol), and bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicyclo[2.2.2] oct-7-ene-2,3 , 5,6-tetracarboxylic dianhydride, B1317, the structure of which is (100 mmol) in a reaction flask, and 200 g of N-methyl-2-pyrrolidone (NMP) was added as a solvent. Next, after the solution was cooled to 0 ° C and stirred for 4 hours, 3-aminophenol (25 mmol) was added as a blocking agent, and stirred at room temperature for further 4 hours. Next, 80 g of xylene was added, and the mixture was heated to 180 ° C and stirred for 3 hours. After cooling, a viscous polymer solution (VI) was obtained. Referring to Table 1, the components and contents used in Example 6 and the ratio of the repeating unit are shown. Finally, the intrinsic viscosity of the polymer of the polymer solution (VI) was measured, and the intrinsic viscosity obtained was 0.21 dL/g.

Example 7 :

A reaction flask was provided, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF) (57.5) was added under nitrogen. ,6-Amino-2-(4-aminophenyl)benzoxazole (6-ABO) (20 mmol), 1, 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (1,3-bis(3-aminopropyl-1,1,3,3-tetramethyldisiloxane) (siloxane 248 ) (10 mmol), and bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicyclo[2.2.2] oct-7-ene-2,3 5,6-tetracarboxylic dianhydride, B1317) (100 mmol) in a reaction flask, and 200 g of N-methyl-2-pyrrolidone (NMP) was added as a solvent. After the solution was cooled to 0 ° C and stirred for 4 hours, 3-aminophenol (25 mmol) was added as a blocking agent, and stirred at room temperature for further 4 hours. Then, 80 g of the solution was added. After xylene, the mixture was heated to 180 ° C and stirred for 3 hours. After cooling, a viscous polymer solution (VII) was obtained. Referring to Table 1, the components and contents used in Example 7 and the repeated sheets were shown. Ratio. Finally, the inherent viscosity of the polymer measured polymer solution (VII), the a value obtained from intrinsic viscosity of 0.2dL / g.

Comparative Example 1 :

A reaction flask was provided, and 2,2-bis(3-amino-4-hydroxyphenyl) (2,2-bis-4-hydroxy-4-hydroxyphenyl) was added under nitrogen. Hexafluoropropane) (BisAPAF) (77.5 mmol), 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldioxane (1,3-bis(3-aminopropyl) -1,1,3,3-tetramethyldisiloxane) (siloxane 248) (10 mmol), and ethylene glycol bisanhydrotrimellitate (TMEG) (100 mmol) in a reaction flask, and 200 g of N-methyl-2-pyrrolidone (NMP) was added as a solvent. Then, after the solution was cooled to 0 ° C and stirred for 4 hours, 3-aminophenyl alcohol (3- Aminophenol) (25 mmol) was used as a blocking agent and stirred at room temperature for further 4 hours. Then, 80 g of xylene was added, and the mixture was heated to 180 ° C for 3 hours. After cooling, a polymer solution was obtained ( VIII). Referring to Table 1, the composition and content of the comparative example 1 and the ratio of the repeating unit are shown. Finally, the intrinsic viscosity of the polymer of the polymer solution (VIII) is measured, and the inherent viscosity is obtained. The value is 0.28 dL/g.

Comparative Example 2 :

A reaction vial was provided and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF) (43.75) was added under nitrogen. Milliamine), 5-amino-2-(4-aminophenyl)benzoxazole (5-ABO) (43.75 millimolar), and Ethylene glycol bisanhydrotrimellitate (TMEG) (100 mmol) was placed in a reaction flask, and 200 g of N-methyl-2-pyrrolidone (NMP) was added as a solvent. . Next, after cooling the above solution to 0 ° C and stirring for 4 hours, 3-aminophenol (25 mmol) was added as a blocking agent at room temperature. Stir for another 4 hours. Next, 80 g of xylene was added, and the mixture was heated to 180 ° C and stirred for 3 hours. After cooling, a viscous polymer solution (IX) was obtained. Referring to Table 1, the components and contents used in Comparative Example 2 and the ratio of the repeated units are shown. Finally, the intrinsic viscosity of the polymer of the polymer solution (IX) was measured, and the intrinsic viscosity obtained was 0.39 dL/g.

Remark: m/(m+n) is substituted into m with a millimolar of a diamine of the formula (IV), and is obtained by substituting n with the millimolar of the diamine of the formula (III).

Example 8 :

A reaction flask is provided, and 3,3'-dihydroxy-4,4'-biphenyldiamine (3,3'-Dihydroxybenzidine, P-HAB) is added under nitrogen. (55 mmol), 5-amino-2-(4-aminophenyl)benzoxazole, 5-ABO, the structure of which is (20 mmol), 2,2'-bis(trifluoromethyl)benzidine, TFMB, the structure of which is ) (10 millimoles), and ethylene glycol bisanhydrotrimellitate (TMEG) (100 mmol) in a reaction flask, and 200 g of N-methyl-2-pyrrolidone (NMP) was added as a solvent. Next, after the solution was cooled to 0 ° C and stirred for 4 hours, 3-aminophenol (3-aminophenol) was added. (30 mmol) as a blocking agent and stirred at room temperature for a further 4 hours. Next, 80 g of xylene was added, and the mixture was heated to 180 ° C and stirred for 3 hours. After cooling, a viscous polymer solution (X) was obtained. Referring to Table 2, the components and contents used in Example 8 and the ratio of the repeating unit are shown. Finally, the intrinsic viscosity of the polymer of the polymer solution (X) was measured, and the intrinsic viscosity obtained was 0.19 dL/g.

Example 9 :

A reaction flask was provided, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF) was added under nitrogen. for (55 mmol), 5-amino-2-(4-aminophenyl)benzoxazole, 5-ABO, the structure of which is (20 mmol), 2,2'-bis[4-(4-aminophenoxyphenyl)propane (2,2-Bis[4-(4-aminophenoxy)phenyl]propane, BAPP), Its structure is ) (10 millimoles), and ethylene glycol bisanhydrotrimellitate (TMEG) (100 mmol) in a reaction flask, and 200 g of N-methyl-2-pyrrolidone (NMP) was added as a solvent. Next, after the solution was cooled to 0 ° C and stirred for 4 hours, 3-aminophenol (3-aminophenol) was added. (30 mmol) as a blocking agent and stirred at room temperature for a further 4 hours. Next, 80 g of xylene was added, and the mixture was heated to 180 ° C and stirred for 3 hours. After cooling, a viscous polymer solution (XI) was obtained. Referring to Table 2, the components and contents used in Example 9 and the ratio of the repeating unit are shown. Finally, the intrinsic viscosity of the polymer of the polymer solution (XI) was measured, and the intrinsic viscosity obtained was 0.22 dL/g.

Example 10:

A reaction flask was provided, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF) (52.5) was added under nitrogen. Milliamine, 5-amino-2-(4-aminophenyl)benzoxazole (5-ABO) (25 mmol), 4, 4'-Bis(4-aminophenoxy)phenyl]Sulfone, m-BAPS, the structure of which is ) (10 mmol) and 4,4'-oxydiphthalic dianhydride (ODA), the structure of which is (100 mmol) in a reaction flask, and 200 g of N-methyl-2-pyrrolidone (NMP) was added as a solvent. Next, after the solution was cooled to 0 ° C and stirred for 4 hours, 3-aminophenol (25 mmol) was added as a blocking agent, and stirred at room temperature for further 4 hours. Next, 80 g of xylene was added, and the mixture was heated to 180 ° C and stirred for 3 hours. After cooling, a viscous polymer solution (XII) was obtained. Referring to Table 2, the components and contents used in Example 10 and the ratio of the repeating unit are shown. Finally, the intrinsic viscosity of the polymer of the polymer solution (XII) was measured, and the intrinsic viscosity obtained was 0.21 dL/g.

Example 11

A reaction vial was provided and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF) was added under nitrogen (55 Milliamine, 5-amino-2-(4-aminophenyl)benzoxazole (5-ABO) (20 mmol), 4, 4'-diaminodiphenyl ether 4,4'-Oxydianiline, ODA, its structure is ) (10 mmol), and bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicyclo[2.2.2] oct-7-ene-2,3 , 5,6-tetracarboxylic dianhydride, B1317, the structure of which is (100 mmol) in a reaction flask, and 200 g of N-methyl-2-pyrrolidone (NMP) was added as a solvent. Next, after cooling the above solution to 0 ° C and stirring for 4 hours, 3-aminophenol (30 mmol) was added as a blocking agent, and further stirred at room temperature for 4 hours. Next, 80 g of xylene was added, and the mixture was heated to 180 ° C and stirred for 3 hours. After cooling, a viscous polymer solution (XIII) was obtained. Referring to Table 2, the components and contents used in Example 11 and the ratio of the repeating unit are shown. Finally, the intrinsic viscosity of the polymer of the polymer solution (XIII) was measured, and the intrinsic viscosity obtained was 0.23 dL/g.

Example 12

A reaction flask was provided, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF) (52.5) was added under nitrogen. Milliamine, 5-amino-2-(4-aminophenyl)benzoxazole (5-ABO) (25 mmol), 1, 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (1,3-bis(3-aminopropyl-1,1,3,3-tetramethyldisiloxane) (siloxane 248 ) (10 mmol) and 4,4'-oxydiphthalic dianhydride (ODA), the structure of which is (100 mmol) in a reaction flask, and 200 g of N-methyl-2-pyrrolidone (NMP) was added as a solvent. Then, after the solution was cooled to 0 ° C and stirred for 4 hours, 3-aminobenzoic acid (3-Aminobenzoic acid) was added. (25 mmol) as a blocking agent and stirred at room temperature for a further 4 hours. Next, 80 g of xylene was added, and the mixture was heated to 180 ° C and stirred for 3 hours. After cooling, a viscous polymer solution (XIV) was obtained. Referring to Table 2, the components and contents used in Example 12 and the ratio of the repeating unit are shown. Finally, the intrinsic viscosity of the polymer of the polymer solution (XIV) was measured, and the intrinsic viscosity obtained was 0.22 dL/g.

Example 13

A reaction vial was provided and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF) was added under nitrogen (55 Milliamine, 5-amino-2-(4-aminophenyl)benzoxazole (5-ABO) (20 mmol), 1, 4-bis(4-aminophenoxy)phenyl (1,4-Bis(4-aminophenoxy)benzene, TPE-Q, the structure of which is ) (10 mmol) and 4,4'-oxydiphthalic dianhydride (ODA), the structure of which is (100 mmol) in a reaction flask, and 200 g of N-methyl-2-pyrrolidone (NMP) was added as a solvent. Then, after the solution was cooled to 0 ° C and stirred for 4 hours, 3-aminobenzoic acid (3-Aminobenzoic acid) was added. (30 mmol) as a blocking agent and stirred at room temperature for a further 4 hours. Next, 80 g of xylene was added, and the mixture was heated to 180 ° C and stirred for 3 hours. After cooling, a viscous polymer solution (XV) was obtained. Referring to Table 2, the components and contents used in Example 13 and the ratio of the repeating unit are shown. Finally, the intrinsic viscosity of the polymer of the polymer solution (XV) was measured, and the resulting intrinsic viscosity was 0.19 dL/g.

Photosensitive resin composition

Example 14

Take 50 grams of polymer solution (I) and add 3.28 grams of PAC-4 (structure is , where D is , manufactured and sold by Sambo, 1.96 g of 2,6-bis(hydroxymethyl)-p-cresol (2,6-Bis(hydroxymethyl)-p-cresol, DML-PC), mixed evenly, available Photosensitive resin composition (I). Next, the photosensitive resin composition (I) was applied onto a wafer by a spin coating method, and subjected to a soft bake process (pre-bake) at 110 ° C for 2 minutes to obtain a film thickness of about 2 μm. film. Next, the film was irradiated with an unfiltered mercury arc lamp (having a wavelength of 250 to 400 nm measured), and an energy of about 150 mJ/cm ^{2 was applied} thereto, followed by exposure. Next, development was carried out with a tetramethylammonium hydroxide (TMAH) aqueous solution (2.38% by weight) of a developer, and the development time was 60 seconds. The cured layer (I) was then obtained in a hot air circulating oven at 230 ° C for 60 minutes by post-cure. The developability and chemical resistance of the obtained cured layer (I) were measured, and the results are shown in Table 3. This developability was evaluated by observing the residual state of the photosensitive resin composition in the developing region by a scanning electron microscopy (SEM) after development, and the residue was recorded as O, and the residual was recorded as X. The chemical resistance was evaluated by immersing the cured layer in TOK-106 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) heated to 70 ° C for 10 minutes, and then rinsing with water for 5 minutes to observe the film of the cured layer treated therewith. Whether the thickness and shape were changed, the film thickness and shape were recorded as O without significant change, and the film thickness and shape change were recorded as X.

Example 15

The preparation of the photosensitive resin composition was carried out in the same manner as described in Example 14, except that the polymer solution (I) was changed to the polymer solution (II) to obtain a photosensitive resin composition (II). Then, the photosensitive resin composition was formed into a cured layer in the same manner as described in Example 14, except that the photosensitive resin composition (I) was changed to the photosensitive resin composition (II) to obtain a cured layer (II). The developability and chemical resistance of the obtained cured layer (II) were measured, and the results are shown in Table 3.

Example 16

Take 50 grams of polymer solution (III), add 3.12 grams of PAC-4, 1.875 grams of 2,6-bis(hydroxymethyl)-p-cresol (2,6-Bis(hydroxymethyl)-p-cresol, DML- After PC), the mixture is uniformly mixed to obtain a photosensitive resin composition (III). Next, the photosensitive resin composition (III) was applied onto a wafer by a spin coating method, and subjected to a soft baking process (pre-bake) at 110 ° C for 2 minutes to obtain a film thickness of about 2 μm. film. Next, the film was irradiated with an unfiltered mercury arc lamp (having a wavelength of 250 to 400 nm measured), and an energy of about 150 mJ/cm ^{2 was applied} thereto, followed by exposure. Next, development was carried out with a tetramethylammonium hydroxide (TMAH) aqueous solution (2.38% by weight) of a developer, and the development time was 60 seconds. The cured layer (III) was then obtained in a hot air circulating oven at 230 ° C for 60 minutes by post-cure. The developability and chemical resistance of the obtained cured layer (III) were measured, and the results are shown in Table 3.

Example 17-20

Example 17-20 The preparation of the photosensitive resin composition was carried out in the same manner as described in Example 16, except that the polymer solution (III) was changed to the polymer solutions (IV) to (VII), respectively, to obtain a photosensitive resin composition. (IV)-(VII). Next, in Example 17-20, the photosensitive resin composition was formed into a cured layer in the same manner as described in Example 16, except that the photosensitive resin composition (III) was changed to the photosensitive resin composition (IV)-(VII), respectively. ), the cured layer (IV)-(VII) is obtained. The developability and chemical resistance of the obtained cured layers (IV) to (VII) were measured, and the results are shown in Table 3.

Comparative Example 3

Take 50 grams of polymer solution (VIII), add 3.4 grams of PAC-4, 2.03 grams of 2,6-bis(hydroxymethyl)-p-cresol (2,6-Bis(hydroxymethyl)-p-cresol, DML- After PC), the mixture is uniformly mixed to obtain a photosensitive resin composition (VIII). Next, the photosensitive resin composition (VIII) was applied onto a wafer by a spin coating method, and pre-bake was performed at 110 ° C for 2 minutes to obtain a film thickness of about 2 μm. film. Next, the film was irradiated with an unfiltered mercury arc lamp (having a wavelength of 250 to 400 nm measured), and an energy of about 150 mJ/cm ^{2 was applied} thereto, followed by exposure. Next, development was carried out with a tetramethylammonium hydroxide (TMAH) aqueous solution (2.38% by weight) of a developer, and the development time was 60 seconds. The cured layer (VIII) was then obtained in a hot air circulating oven at 230 ° C for 60 minutes by post-cure. The developability and chemical resistance of the obtained cured layer (VIII) were measured, and the results are shown in Table 3.

Comparative Example 4

The preparation of the photosensitive resin composition was carried out in the same manner as in Comparative Example 3 except that the polymer solution (VIII) was changed to the polymer solution (IX) to obtain a photosensitive resin composition (IX). Then, the photosensitive resin composition was formed into a cured layer in the same manner as described in Example 8, except that the photosensitive resin composition (VIII) was changed to the photosensitive resin composition (IX) to obtain a cured layer (IX). The developability and chemical resistance of the obtained cured layer (IX) were measured, and the results are shown in Table 3.

It can be seen from Table 3 that when the compound of the formula (I) of the present invention has a m/(m+n) value of between 0.1 and 0.4, the photosensitive resin composition containing the same is obtained after exposure and development. The cured layer has excellent developability (i.e., the unexposed coating does not remain after development), and chemical resistance. On the other hand, when the value of m/(m+n) is less than 0.1 and less than 0.1, the cured layer is inferior in chemical resistance, and when it is 0.5 or more, its workability and developability are inferior.

Example 21-26

Examples 21-26 The preparation of the photosensitive resin composition was carried out in the same manner as described in Example 16, except that the polymer solution (III) was changed to the polymer solution (X)-(XV), respectively, to obtain a photosensitive resin composition. (X)-(XV). Subsequently, in Examples 21-26, the photosensitive resin composition was formed into a cured layer in the same manner as described in Example 16, except that the photosensitive resin composition (III) was changed to a photosensitive resin composition (X)-(XV), respectively. ), a cured layer (X) - (XV) is obtained. The developability and chemical resistance of the obtained cured layers (X) to (XV) were measured, and the results are shown in Table 4.

Although the embodiments of the present invention and its advantages are disclosed above, it should be understood that those skilled in the art can make modifications, substitutions, and refinements without departing from the spirit and scope of the invention. In addition, the scope of the present invention is not limited to the processes, machines, manufacture, compositions, devices, methods, and steps in the specific embodiments described in the specification. Any one of ordinary skill in the art can. The processes, machines, fabrications, compositions, devices, methods, and procedures that are presently or in the future are understood to be used in accordance with the present invention as long as they can perform substantially the same function or achieve substantially the same results in the embodiments described herein. Accordingly, the scope of the invention includes the above-described processes, machines, manufactures, compositions, devices, methods, and steps. In addition, the scope of each of the claims constitutes an individual embodiment, and the scope of the invention also includes the combination of the scope of the application and the embodiments.

Claims (14)

a polymer having the structure represented by formula (I) Wherein R ₁ is -OH, or -COOH; A ₁ is , ,or ; A ₂ is independent , , or ;A ₃ series is independent , ,or ;A ₄ series ,or ;Z series -O-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, , , ,or m is an integer greater than 1; n is an integer greater than 1; i is an integer between 1 and 3; and j is an integer between 1 and 20; and the repeating unit And the repeating unit They are arranged in a random manner, where the value of m/(m+n) is between 0.1 and 0.4. The polymer of claim 1, wherein the value of m/(m+n) is between 0.05 and 0.9. A method for producing a polymer comprising: polymerizing a composition to obtain a polymer according to claim 1, wherein the composition comprises an acid anhydride having the formula (II), a formula ( a diamine of III), a diamine of formula (IV), and a compound of formula (V) H ₂ N - A ₂ -NH ₂ Formula (IV) H ₂ NA ₃ -R ₁ Formula (V) wherein R ₁ is -OH, or -COOH; A ₁ system, , ,or ; A ₂ is independent , , or ;A ₃ series is independent , ,or ;A ₄ series ,or ;Z series -O-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, , , ,or i is an integer from 1 to 3; and j is an integer from 1 to 20, wherein the molar number of the diamine having the formula (III) and the formula (III) and (IV) The ratio of the total number of moles of diamine is between 0.1 and 0.4. The method for producing a polymer according to claim 3, wherein the acid anhydride having the formula (II) is used in an amount of 1 part by mole, and the diamine having the formula (III) is used in an amount of 0.2 to 0.5 mole. The diamine having the formula (IV) is used in an amount of from 0.4 to 0.9 mol parts, and the compound having the formula (V) is used in an amount of from 0.1 to 0.4 mol parts. The method for producing a polymer according to claim 3, wherein the molar amount of the diamine having the formula (III) and the diamine having the formula (IV) plus half of the compound of the formula (V) The ratio of the molar number to the molar number of the anhydride having the formula (II) is between 0.7 and 1.6. The method for producing a polymer according to claim 3, wherein the molar amount of the diamine having the formula (III) and the diamine having the formula (IV) is added to a half-fold of the compound having the formula (V) The ratio of the number of ears to the number of moles of the anhydride having the formula (II) is between 0.8 and 1.2. The method for producing a polymer according to claim 3, wherein the molar number of the diamine having the formula (III) and the total number of moles of the diamine having the formula (III) and the formula (IV) The ratio of the combination is between 0.05 and 0.9. The method for producing a polymer according to claim 3, wherein the ratio of the molar number of the compound having the formula (V) to the molar number of the anhydride having the formula (II) is from 0.1 to Between 0.3. A photosensitive resin composition comprising the following components uniformly dispersed in a solvent: (A) the polymer of claim 1; (B) a compound having a phenol group; and (C) a sensitizer. The photosensitive resin composition according to claim 9, wherein the component (A) content is 100 parts by weight, the component (B) content is 1 to 50 parts by weight, and the component (C) content is 1 to 50 parts by weight. Share. The photosensitive resin composition according to claim 9, wherein the component (B) is a compound having a phenol group , , Or a combination thereof. The photosensitive resin composition according to claim 9, wherein the component (C) comprises a sulfonium sulfonate. The photosensitive resin composition according to claim 9, wherein the component (C) is a sensitizer , , Or a combination of the above, wherein the D system is independently -OH, , ,or And at least one D is not -OH. The photosensitive resin composition according to claim 9, wherein the solvent is N-methyl-2-pyrrolidone, γ-butyrolactone, or a combination thereof.