Polymer, photosensitive composition, dry film photoresist, and lithography method

Abstract

To provide a novel photoresist composition for use in PCB processes, aimed at forming positive photoresists developable using sodium carbonate solutions.SOLUTION: A polymer is formed by the reaction of a specific phenolic epoxy resin or a specific bisphenol epoxy resin with carboxylic acid. The carboxylic acid has any of chemical structures below, a combination of them. (In the formula, Ar is benzene or naphthalene, X is a hydroxy group, an alkoxy group, or an alkyl group, and at least one X is a hydroxy group, with m=1 to 3. R2 is a C3-7 alkyl group).SELECTED DRAWING: None

Description

Technical Field

[0001] This technical field relates to polymers, and more particularly to the application of polymers to photosensitive compositions.

Background Art

[0002] Photoresists used in lithography processes are generally classified into positive photoresists and negative photoresists. Most positive photoresists are applied using a wet process and developed using a tetramethylammonium hydroxide (TMAH) solution, and cannot be used in printed circuit board (PCB) processes. Negative photoresists can be made into dry film photoresists and developed using a sodium carbonate solution. Therefore, negative photoresists can be used in PCB processes, but the resolution after development is poor.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] There is a need for a novel photoresist composition to form a positive photoresist that can be developed using a sodium carbonate solution and is used in PCB processes.

Means for Solving the Problems

[0005] One embodiment of the present disclosure provides a polymer formed by the reaction of a phenolic epoxy resin or a bisphenol epoxy resin with a carboxylic acid. The phenolic epoxy resin has the following chemical structure.

[0006] [Chemical formula]

[0007] In the formula, W is H, an alkyl group, or a halogen, and R 1 is methylene, dimethylenediphenyl, dimethylenebenzene, tetrahydrodicyclopentadiene, or [Chemical formula] and n = 1 to 8.

[0008] The bisphenol epoxy resin has the following chemical structure.

[0009] [Chemical formula]

[0010] In the formula, Z is H or an alkyl group, and R 4 is methylene, methylmethylene, dimethylmethylene, ethylmethylmethylene, bis(trifluoromethyl)methylene, fluorenylidene, or a sulfonyl group, and p = 1 to 10.

[0011] The carboxylic acid has any of the following chemical structures, or a combination thereof.

[0012] [Chemical formula]

[0013] In the formula, Ar is benzene or naphthalene, X is a hydroxy group, an alkoxy group, or an alkyl group, and at least one X is a hydroxy group, and m = 1 to 3. R 2 is a C 3-7 alkyl group.

[0014] One embodiment of the present disclosure provides a photosensitive composition containing 100 parts by weight of a polymer and 15 to 90 parts by weight of a photosensitive compound.

[0015] One embodiment of the present disclosure provides a dry film photoresist including a photosensitive film interposed between a support film and a protective film, and the photosensitive film contains a photosensitive composition.

[0016] One embodiment of the present disclosure provides a lithography method including the steps of preparing a material layer, forming a photoresist layer on the material layer, the photoresist layer containing a photosensitive composition, exposing the photoresist layer so that the photoresist layer has an exposed portion and an unexposed portion, and developing the photoresist layer using an alkaline solution to remove the exposed portion of the photoresist layer while leaving the unexposed portion of the photoresist layer, thereby exposing a part of the material layer.

Advantages of the Invention

[0017] The positive photoresist of the present disclosure can be developed with a sodium carbonate solution and can be used in a PCB process.

[0018] A detailed description will be given in the following embodiments.

Modes for Carrying Out the Invention

[0019] In the following detailed description, for the purpose of explanation, numerous specific details are set forth in order to provide a more thorough understanding of the disclosed embodiments. However, it will be apparent that one or more embodiments may be practiced without these specific details.

[0020] One embodiment of the present disclosure provides a polymer formed by the reaction of a phenolic epoxy resin or a bisphenol-type epoxy resin with a carboxylic acid. The phenolic epoxy resin has the following chemical structure.

[0021]

Chemical formula

[0022] In the formula, W is H, an alkyl group, or a halogen. R 1 is methylene (-CH2-), dimethylenediphenyl (

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0023]

Chemical formula

[0024] In the formula, Z is H or an alkyl group. R 4is methylene, methylmethylene (-CH(CH3)-), dimethylmethylene (-C(CH3)2-), ethylmethylmethylene (-C(CH3)(C2H5)-), bis(trifluoromethyl)methylene (-C(CF3)2-), fluorenylidene ( [Chemical formula] ), or a sulfonyl group (-SO2-). p ranges from 1 to 10. If p is too large, the solubility and development resolution of the photosensitive composition containing the polymer will decrease. The carboxylic acid has any of the following chemical structures, or a combination thereof.

[0025] [Chemical formula]

[0026] Ar is benzene or naphthalene. X is a hydroxy group, an alkoxy group, or an alkyl group, and at least one X is a hydroxy group. m ranges from 1 to 3, and R 2 is a C 3-7 alkyl group. If there is no hydroxy group in Ar, the image on the mask cannot be transferred to the polymer used as a positive dry film photoresist. If the number of carbon atoms of R 2 is too small or too large, the image on the mask cannot be transferred to the polymer used as a positive dry film photoresist.

[0027] In some embodiments, the phenolic epoxy resin is a cresol-based phenolic epoxy resin, a bis-cresol-based phenolic epoxy resin, a tricresol-based phenolic epoxy resin, or a combination thereof. In some embodiments, the bisphenol epoxy resin is a bisphenol A epoxy resin, a bisphenol E epoxy resin, a bisphenol F epoxy resin, a bisphenol B epoxy resin, a bisphenol AF epoxy resin, a bisphenol S epoxy resin, or a combination thereof. In some embodiments, the carboxylic acid is a hydroxy aromatic acid, such as hydroxybenzoic acid, dihydroxybenzoic acid, trihydroxybenzoic acid, hydroxynaphthoic acid, or a combination thereof.

[0028] In some embodiments, the polymer has any of the following chemical structures.

[0029]

Chem.

Chem.

[0030] wherein, R 11 is methylene, dimethylenediphenyl, dimethylenebenzene, tetrahydrodicyclopentadiene, or

Chem.

Chem.

[0031] In some embodiments, the polymer is further reacted with an anhydride to form a modified polymer. The anhydride has the following chemical structure.

[0032] [Chemical formula]

[0033] wherein Y is [Chemical formula] or a combination thereof, and the acid value of the modified polymer is from 0 to 100 mg KOH / g. If the acid value of the modified polymer is too high, the photosensitive composition will not be able to withstand development. In some embodiments, the anhydride is hexahydrophthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride or a combination thereof. In some embodiments, the weight average molecular weight of the polymer or the modified polymer is from 2000 to 50000. If the weight average molecular weight of the polymer or the modified polymer is too low, the photosensitive composition cannot be formed into a film.

[0034] In some embodiments, the modified polymer has any of the following chemical structures.

[0035] [Chemical formula] [Chemical formula]

[0036] In the formula, R 21 is methylene, dimethylenediphenyl, methylenebenzene, tetrahydrodicyclopentadiene, or [Chemical formula] and R 22 is methylene, dimethylenediphenyl, methylenebenzene, tetrahydrodicyclopentadiene, or [Chemical formula] and R 23 is methylene, dimethylenediphenyl, methylenebenzene, tetrahydrodicyclopentadiene, or [Chemical formula] and R 3 is [Chemical formula] and so on.

[0037] One embodiment of the present disclosure provides a photosensitive composition including 100 parts by weight of a polymer and 15 to 90 parts by weight of a photosensitive compound. If the amount of the photosensitive compound is too small, the photosensitivity of the photosensitive composition becomes insufficient, and the photosensitive composition cannot withstand development. If the amount of the photosensitive compound is too large, the solubility and developability of the photosensitive composition deteriorate. In some embodiments, the photosensitive compound includes a diazonaphthoquinone-based compound.

[0038] In some embodiments, the photosensitive composition further comprises 200 to 1000 parts by weight of a solvent. If the amount of the solvent is too small, the polymer and the photosensitive compound may not be uniformly dispersed in the solvent, and the composition of the photoresist layer (formed by applying and drying the photosensitive composition) may become non-uniform. If the amount of the solvent is too large, the cost for removing the solvent later increases, and it becomes difficult to form a thick photoresist layer. In some embodiments, the solvent includes propylene glycol monomethyl ether acetate, n-butyl acetate, ethyl acetate, γ-butyrolactone, cyclohexanone, or a combination thereof.

[0039] In some embodiments, the photosensitive composition may further include 40 to 200 parts by weight of a phenol resin. The phenol resin can be cresol-based, biscresol-based, tricresol-based, or a combination thereof. If the amount of the phenol resin is too large, the developability of the photosensitive composition deteriorates. The weight average molecular weight of the phenol resin may be from 5000 to 50000. If the weight average molecular weight of the phenol resin is too low, the photosensitive composition cannot be formed into a film. If the weight average molecular weight of the phenol resin is too high, the photosensitive composition cannot be developed.

[0040] One embodiment of the present disclosure provides a dry film photoresist including a photosensitive film interposed between a support film and a protective film, and the photosensitive film includes a photosensitive composition. The release force of the support film is from 150 g to 500 g, and the release force of the protective film is from 1 g to 100 g. In some embodiments, the thickness of the photosensitive film can be from 6 micrometers to 18 micrometers, which is determined by the thickness required for the photoresist layer in the actual lithography process.

[0041] For example, a solution of a photosensitive composition can be applied to a support film and dried, and a protective film can be attached to the dried photosensitive composition (photosensitive film), whereby a positive dry film photoresist is formed. In the transfer process, the protective film is peeled off, and the dried photosensitive composition (photosensitive film) is attached to a material layer such as, for example, a wafer or a copper-clad laminate. Pressure is applied to the support film using a heated roller to transfer the dried photosensitive composition (photosensitive film) onto the material layer. Next, the support film is peeled off, and subsequent exposure and development processes are performed.

[0042] One embodiment of the present disclosure provides a lithography method including a step of preparing a material layer and a step of forming a photoresist layer on the material layer, the photoresist layer including a photosensitive composition. The method of forming the photoresist layer can be wet coating or transfer of the photoresist film in the positive dry film photoresist onto the material layer. The photoresist layer is exposed so that the photoresist layer surely has exposed portions and unexposed portions. The photoresist layer is developed using an alkaline solution to expose a part of the material layer while leaving the unexposed portions of the photoresist layer and removing the exposed portions of the photoresist layer. In some embodiments, the alkaline solution is a sodium carbonate solution, a sodium hydroxide solution, a potassium hydroxide solution, or a combination thereof. Note that prior to the present disclosure, there was no positive dry film photoresist that could be developed using a sodium carbonate solution. In some embodiments, the method further includes a step of etching the exposed portion of the material layer, a step of implanting into the exposed portion of the material layer, or a step of depositing another material layer on the exposed portion of the material layer. For example, the material layer may be a substrate material or a conductive layer, a dielectric layer, or a semiconductor layer formed on the substrate.

[0043] Exemplary embodiments are described in detail below so that those of ordinary skill in the art can easily understand them. The concept of the present invention can be embodied in various forms without being limited to the exemplary embodiments shown herein. For clarity, descriptions of well-known parts are omitted, and like reference numerals throughout indicate like components.

Example

[0044] In the following examples, the phenolic epoxy resin was assumed to be commercially available from Nippon Kayaku. The bisphenol-type epoxy resin was EPON 828 (commercially available from Shell Chemical). The catalyst was chromium(III) acetylacetonate-triphenyl phosphite. The inhibitor was hydroquinone (abbreviated as HQ). The weight-average molecular weight of the polymer was measured by GPC, and the standard sample was polystyrene. The photosensitive compound was 2,3,4-trihydroxybenzophenone naphthoquinone-1,2-diazide-5-sulfonate (abbreviated as DNQ).

[0045] To form a positive dry film photoresist, the support film was a PET film (commercially available from Nanya Plastics Co. or Shinkong Synthetic Fibers Co.) with a release force of 300 g, and the protective film was a PET film (commercially available from Nanya Plastics Co. or Shinkong Synthetic Fibers Co.) with a release force of 30 g. A solution of the photosensitive composition was applied to the support film and then dried to form a photosensitive film (i.e., the dried photosensitive composition). Then, the protective film was attached to the photosensitive film to form a positive dry film photoresist. In the transfer process, the protective film was peeled off, the photosensitive film was attached to the wafer, and it was rolled at 95 °C with a pressure of 2.5 kg / cm 2Pressure was applied to the support film so that the photosensitive film was transferred onto the wafer. Subsequently, the support film was peeled off and subsequent exposure and development processes were performed.

[0046] Example 1 24.4 g of phenolic epoxy resin EPPN-502H (commercially available from Nippon Kayaku), 20.1 g of 4-hydroxybenzoic acid (4-HBA), 0.13 g of catalyst, 0.04 g of HQ, and 47 g of propylene glycol monomethyl ether acetate (PGMEA) were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Subsequently, 8.3 g of hexahydrophthalic anhydride was added to the reaction flask and then stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 83 mg KOH / g and the weight average molecular weight was 6,500. The above phenolic epoxy resin EPPN-502H has the following chemical structure.

[0047]

Chemical formula

[0048] n = 1 to 3.

[0049] When 23 parts by weight of the modified polymer, 6.9 parts by weight of DNQ, and 70.1 parts by weight of a solvent (PGMEA and n-butyl acetate (BA), v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure amount 100 mJ / cm 2 ), and developed for 20 to 40 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0050] Example 2 25.0 g of phenolic epoxy resin EPPN-502H, 20.6 g of 4-HBA, 0.14 g of catalyst, 0.04 g of HQ, and 48 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Then, 6.2 g of hexahydrophthalic anhydride was added to the reaction flask and stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 58 mg KOH / g, and the weight average molecular weight was 5200.

[0051] When 23 parts by weight of the modified polymer, 6.9 parts by weight of DNQ, and 70.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). The solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed to ghi-ray (exposure dose 100 mJ / cm 2 ), and developed with 1% sodium carbonate solution for 30 to 50 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0052] Example 3 25.7 g of phenolic epoxy resin EPPN-502H, 21.2 g of 4-HBA, 0.14 g of catalyst, 0.04 g of HQ, and 49.4 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Then, 3.5 g of hexahydrophthalic anhydride was added to the reaction flask and stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 50 mg KOH / g, and the weight average molecular weight was 5300.

[0053] When 23 parts by weight of a modified polymer, 8 parts by weight of DNQ, and 69 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visible visually). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure dose 100 mJ / cm 2 ), it was developed with a 1% sodium carbonate solution for 30 to 50 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0054] Example 4 30.0 g of a phenol-type epoxy resin EPPN-502H, 24.8 g of 4-HBA, 0.03 g of a catalyst, 0.06 g of HQ, and 45 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 27 mg KOH / g, and the weight average molecular weight was 5700.

[0055] When 23 parts by weight of a polymer, 6.9 parts by weight of DNQ, and 70.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visible visually). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure dose 200 mJ / cm 2 ), it was developed with a 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0056] Example 5 27.3 g of a phenol-type epoxy resin EPPN-502H, 22.5 g of 4-HBA, 0.14 g of a catalyst, 0.04 g of HQ, and 50 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 0 mg KOH / g, and the weight average molecular weight was 5500.

[0057] When 23 parts by weight of a polymer, 6.0 parts by weight of DNQ, and 71 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure amount 200 mJ / cm 2 ), it was developed for 30 to 50 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0058] Example 6 24.6 g of a phenolic epoxy resin EPPN-502H, 20.3 g of 3-hydroxybenzoic acid (3-HBA), 0.13 g of a catalyst, 0.04 g of HQ, and 45.2 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Then, 9.8 g of hexahydrophthalic anhydride was added to the reaction flask and then stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 80 mg KOH / g and the weight average molecular weight was 2900.

[0059] When 23 parts by weight of the modified polymer, 6.0 parts by weight of DNQ, and 71 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure amount 100 mJ / cm 2 ), it was developed for 20 to 40 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0060] Example 7 24.5 g of phenol-type epoxy resin EPPN-502H, 20.2 g of 3-HBA, 0.13 g of catalyst, 0.04 g of HQ, and 47.2 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Then, 8.0 g of hexahydrophthalic anhydride was added to the reaction flask and then stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 65 mg KOH / g, and the weight-average molecular weight was 3300.

[0061] When 23 parts by weight of the modified polymer, 6.0 parts by weight of DNQ, and 71 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed to ghi-ray (exposure dose 100 mJ / cm 2 ), and developed with a 1% sodium carbonate solution for 30 to 50 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0062] Example 8 26.2 g of phenol-type epoxy resin EPPN-502H, 21.6 g of 3-HBA, 0.14 g of catalyst, 0.04 g of HQ, and 48 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Then, 4.0 g of hexahydrophthalic anhydride was added to the reaction flask and then stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 37 mg KOH / g, and the weight-average molecular weight was 2700.

[0063] When 23 parts by weight of a modified polymer, 3.5 parts by weight of DNQ, and 73.5 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure dose 100 mJ / cm 2 ), it was developed for 60 to 80 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0064] Example 9 30 g of phenol-type epoxy resin EPPN-502H, 24.8 g of 3-HBA, 0.03 g of a catalyst, 0.06 g of HQ, and 45 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 7 mg KOH / g and the weight average molecular weight was 3000.

[0065] When 23 parts by weight of a polymer, 5.1 parts by weight of DNQ, and 71.9 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure dose 100 mJ / cm 2 ), it was developed for 100 to 120 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0066] Example 10 27.3 g of phenol-type epoxy resin EPPN-502H, 22.5 g of 3-HBA, 0.14 g of a catalyst, 0.04 g of HQ, and 50 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 0 mg KOH / g and the weight average molecular weight was 2800.

[0067] When 23 parts by weight of a polymer, 6.9 parts by weight of DNQ, and 70.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed to ghi rays (exposure dose: 200 mJ / cm 2 ), it was developed for 40 to 60 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0068] Example 11 24.5 g of phenol-type epoxy resin EPPN-502H, 20.2 g of 2-hydroxybenzoic acid (2-HBA), 0.13 g of a catalyst, 0.04 g of HQ, and 47.2 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Then, 8.0 g of hexahydrophthalic anhydride was added to the reaction flask and then stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 88 mg KOH / g, and the weight average molecular weight was 3500.

[0069] When 23 parts by weight of the modified polymer, 6.9 parts by weight of DNQ, and 70.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was poor (a precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed to ghi rays (exposure dose: 1000 mJ / cm 2 ), it was developed for 100 to 150 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 50 micrometers was obtained.

[0070] Example 12 26 g of phenolic epoxy resin EPPN-502H, 23.8 g of 2,6-dihydroxybenzoic acid (2,6-DHBA), 0.14 g of catalyst, 0.04 g of HQ, and 50 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 7 mg KOH / g and the weight average molecular weight was 46,000.

[0071] When 23 parts by weight of the polymer, 6.9 parts by weight of DNQ, and 70.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed to ghi-ray (exposure amount 1000 mJ / cm 2 ), it was developed with 1% sodium carbonate solution for 100 to 150 seconds. As a result, a pattern with a resolution of 50 micrometers was obtained.

[0072] Example 13 26 g of phenolic epoxy resin EPPN-502H, 23.8 g of 2,4-dihydroxybenzoic acid (2,4-DHBA), 0.14 g of catalyst, 0.04 g of HQ, and 50 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 49 mg KOH / g and the weight average molecular weight was 11,000.

[0073] When 23 parts by weight of the polymer, 6.0 parts by weight of DNQ, and 71 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed to ghi-ray (exposure amount 200 mJ / cm 2 ), it was developed with 1% sodium carbonate solution for 90 to 120 seconds. As a result, a pattern with a resolution of 50 micrometers was obtained.

[0074] Example 14 26 g of phenol-type epoxy resin EPPN-502H, 23.8 g of 3,5-dihydroxybenzoic acid (3,5-DHBA), 0.14 g of catalyst, 0.04 g of HQ, and 50 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140°C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 9 mg KOH / g and the weight average molecular weight was 3,000.

[0075] When 23 parts by weight of the polymer, 5.1 parts by weight of DNQ, and 71.9 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed to ghi-ray (exposure amount 200 mJ / cm 2 ), it was developed with 1% sodium carbonate solution for 90 to 120 seconds. As a result, a pattern with a resolution of 50 micrometers was obtained.

[0076] Example 15 23.5 g of phenol-type epoxy resin EPPN-502H, 26.3 g of 3-hydroxy-2-naphthoic acid (3H2NA), 0.12 g of catalyst, 0.04 g of HQ, and 50 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140°C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 52 mg KOH / g and the weight average molecular weight was 11,800.

[0077] When 23 parts by weight of the polymer, 6.9 parts by weight of DNQ, and 70.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was poor (a precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed to ghi-ray (exposure amount 1000 mJ / cm 2) It was developed for 100 to 150 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 50 micrometers was obtained.

[0078] Example 16 40.2 g of phenol-type epoxy resin EPPN-502H, 24.5 g of pentanoic acid, 0.06 g of catalyst, 0.07 g of HQ, and 35.2 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 25 mg KOH / g, and the weight average molecular weight was 2400.

[0079] When 12 parts by weight of the polymer, 10.2 parts by weight of phenol resin PR56001 (weight average molecular weight is 5000, commercially available from Sumitomoto Bakelite), 6.7 parts by weight of DNQ, and 71.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visible visually). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure amount 400 mJ / cm 2 ) It was developed for 60 to 90 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0080] Example 17 When 7.5 parts by weight of the polymer synthesized in Example 16, 15 parts by weight of phenol resin PR56001 (weight average molecular weight is 5000), 6.7 parts by weight of DNQ, and 70.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visible visually). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure amount 400 mJ / cm 2 ) It was developed for 60 to 90 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0081] Example 18 When 15 parts by weight of the polymer synthesized in Example 16, 7.5 parts by weight of phenol resin PR56001 (weight average molecular weight: 5000), 3.5 parts by weight of DNQ, and 74.3 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure dose: 400 mJ / cm 2 ), it was developed with 1% sodium carbonate solution for 60 to 90 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0082] Example 19 36.4 g of phenol-type epoxy resin EPPN-502H, 22.2 g of pentanoic acid, 0.19 g of catalyst, 0.07 g of HQ, and 35.0 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Then, 6.1 g of hexahydrophthalic anhydride was added to the reaction flask and stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 61 mg KOH / g, and the weight average molecular weight was 2500.

[0083] When 12 parts by weight of the modified polymer, 10.2 parts by weight of phenol resin PR56032 (weight average molecular weight: 50000, commercially available from Sumitomoto Bakelite), 8 parts by weight of DNQ, and 69.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure dose: 400 mJ / cm 2 ), it was developed with 1% sodium carbonate solution for 60 to 90 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0084] Example 20 When 7.5 parts by weight of the polymer synthesized in Example 19, 15 parts by weight of phenol resin PR56032 (weight average molecular weight: 50,000), 6.7 parts by weight of DNQ, and 70.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed with ghi-ray (exposure dose: 400 mJ / cm 2 ), it was developed with 1% sodium carbonate solution for 60 to 90 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0085] Example 21 When 15 parts by weight of the polymer synthesized in Example 19, 7.5 parts by weight of phenol resin PR56032 (weight average molecular weight: 50,000), 6.7 parts by weight of DNQ, and 70.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed with ghi-ray (exposure dose: 400 mJ / cm 2 ), it was developed with 1% sodium carbonate solution for 60 to 90 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0086] Example 22 40.2 g of phenol-type epoxy resin EPPN-502H, 17.7 g of propanoic acid, 0.21 g of catalyst, 0.07 g of HQ, and 35.0 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react to form a polymer. Then, 6.7 g of hexahydrophthalic anhydride was added to the reaction flask and stirred for 3 hours to react to form a modified polymer. The acid value of the modified polymer was 55 mg KOH / g and the weight average molecular weight was 2,700.

[0087] When 12 parts by weight of a modified polymer, 10.2 parts by weight of a phenolic resin PR56001 (weight average molecular weight: 5000), 6.7 parts by weight of DNQ, and 71.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, but it was not possible to transfer it onto a wafer to form a photoresist layer.

[0088] Example 23 When 12 parts by weight of the modified polymer synthesized in Example 22, 10.2 parts by weight of a phenolic resin PR56032 (weight average molecular weight: 50000), 6.7 parts by weight of DNQ, and 71.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, but it was not possible to transfer it onto a wafer to form a photoresist layer.

[0089] Example 24 29 g of a phenolic epoxy resin EPPN-502H, 21.1 g of benzoic acid, 0.15 g of a catalyst, 0.06 g of HQ, and 40.0 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Then, 9.7 g of hexahydrophthalic anhydride was added to the reaction flask and stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 80 mg KOH / g and the weight average molecular weight was 2500.

[0090] When 12 parts by weight of a modified polymer, 10.2 parts by weight of a phenolic resin PR56001 (weight average molecular weight: 5000), 6.7 parts by weight of DNQ, and 71.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, but it could not be transferred onto a wafer to form a photoresist layer.

[0091] Example 25 When 12 parts by weight of the modified polymer synthesized in Example 24, 10.2 parts by weight of a phenolic resin PR56032 (weight average molecular weight: 50000), 6.7 parts by weight of DNQ, and 71.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, but it could not be transferred onto a wafer to form a photoresist layer.

[0092] Example 26 31.5 g of a phenol-type epoxy resin EPPN-502H, 22.9 g of benzoic acid, 0.16 g of a catalyst, 0.07 g of HQ, and 40.0 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Then, 5.3 g of hexahydrophthalic anhydride was added to the reaction flask and stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 46 mg KOH / g, and the weight average molecular weight was 2500.

[0093] When 12 parts by weight of a modified polymer, 10.2 parts by weight of a phenolic resin PR56032 (weight average molecular weight: 50000), 6.7 parts by weight of DNQ, and 71.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, but it could not be transferred onto a wafer to form a photoresist layer.

[0094] Example 27 28.8 g of phenolic epoxy resin EPPN-201 (commercially available from Nippon Kayaku), 21 g of 4-HBA, 0.13 g of catalyst, 0.04 g of HQ, and 50 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react to form a polymer. The acid value of the polymer was 0 mg KOH / g and the weight average molecular weight was 5200. The above phenolic epoxy resin EPPN-201 has the following chemical structure.

[0095] [Chemical formula]

[0096] n ≒ 6.

[0097] When 23 parts by weight of the polymer, 6.0 parts by weight of DNQ, and 71 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure amount 100 mJ / cm 2 ), and developed for 70 to 90 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0098] Example 28 30.1 g of phenolic epoxy resin EOCN-102S (commercially available from Nippon Kayaku), 19.8 g of 4-HBA, 0.13 g of catalyst, 0.04 g of HQ, and 50 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react to form a polymer. The acid value of the polymer was 3 mg KOH / g and the weight average molecular weight was 5600. The above phenolic epoxy resin EOCN-102S has the following chemical structure.

[0099] [Chemical]

[0100] n is approximately from 4 to 6.

[0101] When 23 parts by weight of a polymer, 6.0 parts by weight of DNQ, and 71 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure dose 100 mJ / cm 2 ), and developed for 70 to 90 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0102] Example 29 33.2 g of a phenol-type epoxy resin BREN-105 (commercially available from Nippon Kayaku), 16.7 g of 4-HBA, 0.11 g of a catalyst, 0.04 g of HQ, and 50 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 5 mg KOH / g, and the weight average molecular weight was 5900. The above phenol-type epoxy resin BREN-105 has the following chemical structure.

[0103] [Chemical]

[0104] n is approximately 2.

[0105] When 23 parts by weight of a polymer, 5.1 parts by weight of DNQ, and 71.9 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visible by visual inspection). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed to ghi rays (exposure dose 100 mJ / cm 2 ), it was developed for 70 to 90 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0106] Example 30 33.2 g of a phenolic epoxy resin XD-1000 (commercially available from Nippon Kayaku), 17.7 g of 4-HBA, 0.11 g of a catalyst, 0.04 g of HQ, and 50 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 5 mg KOH / g and the weight average molecular weight was 5700. The above phenolic epoxy resin XD-1000 has the following chemical structure.

[0107] [Chemical formula]

[0108] n is from 1 to 3.

[0109] When 23 parts by weight of a polymer, 6.0 parts by weight of DNQ, and 71 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visible by visual inspection). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed to ghi rays (exposure dose 200 mJ / cm 2 ), it was developed for 60 to 80 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0110] Example 31 31.4 g of phenol-type epoxy resin NC-2000-L (commercially available from Nippon Kayaku), 18.5 g of 4-HBA, 0.12 g of catalyst, 0.04 g of HQ, and 50 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react to form a polymer. The acid value of the polymer was 3 mg KOH / g and the weight average molecular weight was 5100. The above phenol-type epoxy resin NC-2000-L has the following chemical structure.

[0111] [Chemical formula]

[0112] n is from 1 to 3.

[0113] When 23 parts by weight of the polymer, 6.0 parts by weight of DNQ, and 71 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure dose 200 mJ / cm 2 ), and developed with 1% sodium carbonate solution for 60 to 80 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0114] Example 32 33.0 g of phenol-type epoxy resin NC-3000-L (commercially available from Nippon Kayaku), 16.9 g of 4-HBA, 0.11 g of catalyst, 0.04 g of HQ, and 50 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 5 mg KOH / g and the weight average molecular weight was 6000. The above phenol-type epoxy resin NC-3000-L has the following chemical structure.

[0115]

Chemical Structure

[0116] n ranges from 1 to 3.

[0117] When 23 parts by weight of the polymer, 6.9 parts by weight of DNQ, and 70.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visible by visual inspection). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure dose 200 mJ / cm 2 ), and developed with 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0118] Example 33 30.2 g of phenol-type epoxy resin NC-7300L (commercially available from Nippon Kayaku), 19.6 g of 4-HBA, 0.13 g of catalyst, 0.04 g of HQ, and 50 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 4 mg KOH / g and the weight average molecular weight was 5800. The above phenol-type epoxy resin NC-7300L has the following chemical structure.

[0119]

Chem.

[0120] n is from 1 to 3.

[0121] When 23 parts by weight of a polymer, 6.9 parts by weight of DNQ, and 70.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed to ghi-ray (exposure amount 200 mJ / cm 2 ), it was developed for 40 to 60 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0122] Example 34 26.5 g of a phenolic epoxy resin EPPN-502H, 19.3 g of 4-HBA, 0.12 g of a catalyst, 0.04 g of HQ, and 46.0 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Then, 8 g of hexahydrophthalic anhydride was added to the reaction flask and stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 82 mg KOH / g, and the weight average molecular weight was 6100.

[0123] When 23 parts by weight of the modified polymer, 6.0 parts by weight of DNQ, and 71 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed to ghi-ray (exposure amount 100 mJ / cm 2) It was developed for 70 to 90 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0124] Example 35 27.8 g of phenol-type epoxy resin EOCN-102S, 18.3 g of 4-HBA, 0.12 g of catalyst, 0.04 g of HQ, and 46.2 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Then, 7.5 g of hexahydrophthalic anhydride was added to the reaction flask and then stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 83 mg KOH / g and the weight average molecular weight was 6500.

[0125] When 23 parts by weight of the modified polymer, 6.0 parts by weight of DNQ, and 71 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visible visually). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi rays (exposure dose 100 mJ / cm 2 ) It was developed for 70 to 90 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0126] Example 36 31.1 g of phenol-type epoxy resin BREN-105, 15.6 g of 4-HBA, 0.10 g of catalyst, 0.04 g of HQ, and 46.8 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Then, 6.4 g of hexahydrophthalic anhydride was added to the reaction flask and then stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 80 mg KOH / g and the weight average molecular weight was 5900.

[0127] When 23 parts by weight of a modified polymer, 5.1 parts by weight of DNQ, and 71.9 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visible by visual inspection). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure dose 100 mJ / cm 2 ), it was developed for 70 to 90 seconds using a 1% sodium carbonate solution. Thereby, a pattern with a resolution of 8 micrometers was obtained.

[0128] Example 37 30.0 g of a phenol-type epoxy resin XD-1000, 16.5 g of 4-HBA, 0.11 g of a catalyst, 0.04 g of HQ, and 46.6 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react to form a polymer. Then, 6.8 g of hexahydrophthalic anhydride was added to the reaction flask and then stirred for 3 hours to react to form a modified polymer. The acid value of the modified polymer was 80 mg KOH / g and the weight average molecular weight was 6700.

[0129] When 23 parts by weight of a modified polymer, 6.0 parts by weight of DNQ, and 71 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visible by visual inspection). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure dose 200 mJ / cm 2 ), it was developed for 60 to 80 seconds using a 1% sodium carbonate solution. Thereby, a pattern with a resolution of 8 micrometers was obtained.

[0130] Example 38 29.2 g of phenol-type epoxy resin NC-2000-L, 17.2 g of 4-HBA, 0.11 g of catalyst, 0.04 g of HQ, and 46.4 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Then, 7.1 g of hexahydrophthalic anhydride was added to the reaction flask and then stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 82 mg KOH / g and the weight average molecular weight was 6300.

[0131] When 23 parts by weight of the modified polymer, 6.0 parts by weight of DNQ, and 71 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed to ghi-ray (exposure dose 200 mJ / cm 2 ), and developed with 1% sodium carbonate solution for 60 to 80 seconds. Thereby, a pattern with a resolution of 8 micrometers was obtained.

[0132] Example 39 30.8 g of phenol-type epoxy resin NC-3000-L, 15.8 g of 4-HBA, 0.10 g of catalyst, 0.04 g of HQ, and 46.8 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Then, 6.5 g of hexahydrophthalic anhydride was added to the reaction flask and then stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 78 mg KOH / g and the weight average molecular weight was 6500.

[0133] When 23 parts by weight of a modified polymer, 6.9 parts by weight of DNQ, and 70.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed to ghi-ray (exposure dose 200 mJ / cm 2 ), it was developed with a 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0134] Example 40 28.0 g of a phenolic epoxy resin NC-7300L, 18.2 g of 4-HBA, 0.12 g of a catalyst, 0.04 g of HQ, and 46.2 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react to form a polymer. Then, 7.5 g of hexahydrophthalic anhydride was added to the reaction flask and stirred for 3 hours to react to form a modified polymer. The acid value of the modified polymer was 77 mg KOH / g, and the weight average molecular weight was 6600.

[0135] When 23 parts by weight of a modified polymer, 6.9 parts by weight of DNQ, and 70.1 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed to ghi-ray (exposure dose 200 mJ / cm 2 ), it was developed with a 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0136] Example 41 34.5 g of bisphenol type epoxy resin EPON828, 25.3 g of 4-HBA, 0.18 g of catalyst, 0.07 g of HQ, and 40.0 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 3 mg KOH / g and the weight average molecular weight was 2100.

[0137] When 17.4 parts by weight of the polymer, 8.7 parts by weight of phenolic resin PR56001 (weight average molecular weight: 5000), 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed to ghi-ray (exposure dose: 100 mJ / cm 2 ), it was developed with a 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0138] Example 42 When 18.3 parts by weight of the polymer of Example 41, 9.1 parts by weight of phenolic resin PR56001 (weight average molecular weight: 5000), 4.8 parts by weight of DNQ, and 67.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed to ghi-ray (exposure dose: 200 mJ / cm 2 ), it was developed with a 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0139] Example 43 17.4 parts by weight of the polymer of Example 41, 8.7 parts by weight of phenol resin PR56032 (weight average molecular weight is 50,000), 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, and the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure amount 100 mJ / cm 2 ), and developed with 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0140] Example 44 18.3 parts by weight of the polymer of Example 41, 9.1 parts by weight of phenol resin PR56032 (weight average molecular weight is 50,000), 4.8 parts by weight of DNQ, and 67.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, and the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure amount 200 mJ / cm 2 ), and developed with 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0141] Example 45 26.1 parts by weight of the polymer of Example 41, 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, and the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure amount 100 mJ / cm 2 ), and developed with 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0142] Example 46 When 27.4 parts by weight of the polymer of Example 41, 4.8 parts by weight of DNQ, and 67.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure amount 200 mJ / cm 2 ), and developed for 20 to 40 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0143] Example 47 28.2 g of bisphenol type epoxy resin EPON828, 20.7 g of 4-HBA, 0.15 g of catalyst, 0.07 g of HQ, and 40.0 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. Then, 10.9 g of hexahydrophthalic anhydride was added to the reaction flask and then stirred for 3 hours to react and form a modified polymer. The acid value of the modified polymer was 81 mg KOH / g, and the weight average molecular weight was 2,800.

[0144] When 17.4 parts by weight of the modified polymer, 8.7 parts by weight of phenolic resin PR56001 (weight average molecular weight is 5,000), 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure amount 100 mJ / cm 2 ), and developed for 40 to 60 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0145] Example 48 18.3 parts by weight of the modified polymer of Example 47, 9.1 parts by weight of phenol resin PR56032 (weight average molecular weight: 50,000), 4.8 parts by weight of DNQ, and 67.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed. As a result, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure dose: 200 mJ / cm 2 ), and developed with 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0146] Example 49 26.1 parts by weight of the modified polymer of Example 47, 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed. As a result, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure dose: 100 mJ / cm 2 ), and developed with 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0147] Example 50 34.5 g of bisphenol type epoxy resin EPON828, 25.3 g of 3-HBA, 0.18 g of catalyst, 0.07 g of HQ, and 40.0 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140°C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 0 mg KOH / g, and the weight average molecular weight was 2300.

[0148] When 17.4 parts by weight of a polymer, 8.7 parts by weight of a phenol resin PR56001 (weight average molecular weight: 5000), 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure dose 100 mJ / cm 2 ), it was developed for 40 to 60 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0149] Example 51 When 18.3 parts by weight of the polymer of Example 50, 9.1 parts by weight of a phenol resin PR56032 (weight average molecular weight: 50000), 4.8 parts by weight of DNQ, and 67.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure dose 200 mJ / cm 2 ), it was developed for 40 to 60 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0150] Example 52 When 26.1 parts by weight of the polymer of Example 50, 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure dose 100 mJ / cm 2 ), it was developed for 40 to 60 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0151] Example 53 28.2 g of bisphenol type epoxy resin EPON828, 20.7 g of 3-HBA, 0.15 g of catalyst, 0.07 g of HQ, and 40.0 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react to form a polymer. Then, 10.9 g of hexahydrophthalic anhydride was added to the reaction flask and stirred for 3 hours to react to form a modified polymer. The acid value of the modified polymer was 77 mg KOH / g, and the weight average molecular weight was 2900.

[0152] When 17.4 parts by weight of the modified polymer, 8.7 parts by weight of phenol resin PR56001 (weight average molecular weight: 5000), 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed to ghi-ray (exposure amount: 100 mJ / cm 2 ), and developed with 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0153] Example 54 When 18.3 parts by weight of the modified polymer of Example 53, 9.1 parts by weight of phenol resin PR56032 (weight average molecular weight: 50000), 4.8 parts by weight of DNQ, and 67.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed to ghi-ray (exposure amount: 200 mJ / cm 2 ), and developed with 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0154] Example 55 When 26.1 parts by weight of the modified polymer of Example 53, 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure amount 100 mJ / cm 2 ), it was developed for 40 to 60 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0155] Example 56 33.5 g of bisphenol type epoxy resin EPON828, 27.3 g of 2,6-DHBA, 0.18 g of catalyst, 0.07 g of HQ, and 38.9 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 0 mg KOH / g and the weight average molecular weight was 2500.

[0156] When 17.4 parts by weight of the polymer, 8.7 parts by weight of phenol resin PR56001 (weight average molecular weight is 5000), 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure amount 100 mJ / cm 2 ), it was developed for 40 to 60 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0157] Example 57 18.3 parts by weight of the polymer of Example 56, 9.1 parts by weight of phenolic resin PR56032 (weight average molecular weight: 50,000), 4.8 parts by weight of DNQ, and 67.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, and the solubility of DNQ was good (no precipitate was visible by visual inspection). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi rays (exposure dose: 200 mJ / cm 2 ), and developed with a 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0158] Example 58 26.1 parts by weight of the polymer of Example 56, 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, and the solubility of DNQ was good (no precipitate was visible by visual inspection). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi rays (exposure dose: 100 mJ / cm 2 ), and developed with a 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0159] Example 59 33.5 g of bisphenol type epoxy resin EPON828, 27.3 g of 2,4-DHBA, 0.18 g of catalyst, 0.07 g of HQ, and 38.9 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 2 mg KOH / g, and the weight average molecular weight was 2,600.

[0160] 17.4 parts by weight of a polymer, 8.7 parts by weight of a phenolic resin PR56001 (weight average molecular weight: 5000), 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, and the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure dose 100 mJ / cm 2 ), it was developed for 40 to 60 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0161] Example 60 18.3 parts by weight of the polymer of Example 59, 9.1 parts by weight of a phenolic resin PR56032 (weight average molecular weight: 50000), 4.8 parts by weight of DNQ, and 67.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, and the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure dose 200 mJ / cm 2 ), it was developed for 40 to 60 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0162] Example 61 26.1 parts by weight of the polymer of Example 59, 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, and the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After exposing the photoresist layer with ghi-ray (exposure dose 100 mJ / cm 2 ), it was developed for 40 to 60 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0163] Example 62 33.5 g of bisphenol type epoxy resin EPON828, 27.3 g of 3,5-DHBA, 0.18 g of catalyst, 0.07 g of HQ, and 38.9 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react and form a polymer. The acid value of the polymer was 3 mg KOH / g and the weight average molecular weight was 2300.

[0164] When 17.4 parts by weight of the polymer, 8.7 parts by weight of phenol resin PR56001 (weight average molecular weight: 5000), 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure dose 100 mJ / cm 2 ), and developed with 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0165] Example 63 When 18.3 parts by weight of the polymer of Example 62, 9.1 parts by weight of phenol resin PR56032 (weight average molecular weight: 50000), 4.8 parts by weight of DNQ, and 67.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure dose 200 mJ / cm 2 ), and developed with 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0166] Example 64 When 26.1 parts by weight of the polymer of Example 62, 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed with ghi-ray (exposure dose 100 mJ / cm 2 ), it was developed for 40 to 60 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0167] Example 65 31.6 g of bisphenol type epoxy resin EPON828, 31.6 g of 3H2NA, 0.17 g of catalyst, 0.07 g of HQ, and 36.6 g of PGMEA were mixed in a reaction flask. The mixture was heated to 140 °C and stirred for 7 hours to react to form a polymer. The acid value of the polymer was 0 mg KOH / g and the weight average molecular weight was 2800.

[0168] When 17.4 parts by weight of the polymer, 8.7 parts by weight of phenol resin PR56001 (weight average molecular weight is 5000), 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. After the photoresist layer was exposed with ghi-ray (exposure dose 100 mJ / cm 2 ), it was developed for 40 to 60 seconds using a 1% sodium carbonate solution. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0169] Example 66 18.3 parts by weight of the polymer of Example 65, 9.1 parts by weight of phenolic resin PR56032 (weight average molecular weight is 50000), 4.8 parts by weight of DNQ, and 67.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, and the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure amount 200 mJ / cm 2 ), and developed with 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0170] Example 67 26.1 parts by weight of the polymer of Example 65, 6.3 parts by weight of DNQ, and 67.6 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, and the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, and then transferred onto a wafer to form a photoresist layer. The photoresist layer was exposed with ghi-ray (exposure amount 100 mJ / cm 2 ), and developed with 1% sodium carbonate solution for 40 to 60 seconds. As a result, a pattern with a resolution of 8 micrometers was obtained.

[0171] Comparative Example 1 22.5 parts by weight of phenolic resin PR56001 (weight average molecular weight is 5000), 6.7 parts by weight of DNQ, and 70.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, and the solubility of DNQ was good (no precipitate was visually observed). A solution of the photosensitive composition was prepared into a positive dry film photoresist, but it could not be transferred onto a wafer to form a photoresist layer.

[0172] Comparative Example 2 When 22.5 parts by weight of phenolic resin PR56032 (weight average molecular weight: 50,000), 6.7 parts by weight of DNQ, and 70.8 parts by weight of a solvent (PGMEA and BA, v / v = 9 / 1) were mixed, the solubility of DNQ was good (no precipitate was visible visually). A solution of the photosensitive composition was prepared into a positive dry film photoresist, but it was not possible to transfer it onto a wafer to form a photoresist layer.

[0173] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed methods and materials. The specification and examples are intended to be regarded as illustrative, and the true scope of the disclosure is indicated by the following claims and their equivalents.

Claims

1. A polymer formed by the reaction of a phenolic epoxy resin and a carboxylic acid, wherein the phenolic epoxy resin has the following chemical structure, 【Chemical 1】 (wherein W is H, an alkyl group, or a halogen, and R 1 is dimethylene benzene or [Chemical 2] where n = 1 to 8. ) The carboxylic acid has any of the following chemical structures, or a combination thereof, [Chemical Formula 4] (In the formula, Ar is benzene or naphthalene, X is a hydroxy group, an alkoxy group, or an alkyl group, and at least one X is a hydroxy group, and m = 1 to 3. R 2 is a C4 alkyl group.) Polymer.

2. The polymer according to claim 1 having any of the following chemical structures. [Chemical Formula 5] (wherein, R 11 is dimethylene benzene or 【Chemical Formula 7】 and R 12 is dimethylenebenzene or 【Chemical 8】 and R 13 is dimethylene benzene or 【Chemical Formula 9】 It is. )

3. Further reacting with an anhydride to form a modified polymer, the anhydride having the following chemical structure, 【Chemical Formula 10】 (where Y is 【Chemical Formula 11】 Or a combination thereof. ) And the acid value of the modified polymer is greater than 0 mg KOH / g and less than or equal to 100 mg KOH / g, the polymer according to claim 1.

4. The polymer according to claim 3, wherein the modified polymer has any of the following chemical structures. 【Chemical Formula 12】 (wherein, R 21 is dimethylene benzene or 【Chemical 14】 and R 22 is dimethylenebenzene or 【Chemical Formula 15】 and R 23 is dimethylenebenzene or 【Chemical 16】 and R 3 is 【Chemical 17】 It is. )

5. 100 parts by weight of the polymer according to claim 1, 15 to 90 parts by weight of a photosensitive compound A photosensitive composition containing.

6. The photosensitive composition according to claim 5, wherein the photosensitive compound contains a diazonaphthoquinone-based compound.

7. The photosensitive composition according to claim 5, further containing 200 to 1000 parts by weight of a solvent.

8. The solvent contains propylene glycol monomethyl ether acetate, n-butyl acetate, ethyl acetate, γ-butyrolactone, cyclohexanone or a combination thereof, the photosensitive composition according to claim 7.

9. The photosensitive composition according to claim 5, further containing 40 to 200 parts by weight of a phenol resin.

10. A dry film photoresist containing a photosensitive film interposed between a support film and a protective film, the photosensitive film containing the photosensitive composition according to claim 5, a dry film photoresist.

11. A lithography method, Preparing a material layer step, Forming a photoresist layer on the material layer, the photoresist layer containing the photosensitive composition according to claim 5, step, Exposing the photoresist layer so that the photoresist layer has an exposed portion and an unexposed portion, Developing the photoresist layer with an alkaline solution, and removing the exposed portion of the photoresist layer while leaving the unexposed portion of the photoresist layer to expose a part of the material layer, A lithography method including.

12. The method of lithography according to claim 11, wherein the alkali solution is a sodium carbonate solution, a sodium hydroxide solution, a potassium hydroxide solution, or a combination thereof.

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