Polymer, positive photoresist composition, and method for forming patterned photoresist layer

Abstract

To provide a polymer, a positive photoresist composition, and a method for forming a patterned photoresist layer.SOLUTION: The polymer includes a first repeating unit and a second repeating unit. The first repeating unit has a structure of Formula (I) and the second repeating unit has a structure of Formula (II) wherein R1, R2, R3, R4, Q, Ar, n, m, and i are as defined in the specification.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to polymers, positive photoresist compositions, and methods for forming patterned photoresist layers. [Background technology]

[0002] With the continuous advancement of integrated circuit manufacturing and packaging technology, printed circuit boards (PCBs) are being developed to achieve high-density wiring, miniaturization, high electrical properties, high dimensional stability, high resolution, and lower costs. There is also an increasing demand for smaller hole diameters and multilayer technologies with higher alignment accuracy. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] US Patent Application Publication No. 2006 / 0110679 Summary of the Invention [Problem to be solved by the invention]

[0004] In the manufacturing process of printed circuit boards, to achieve high-density wiring and high resolution, it is necessary to further reduce the line width or pitch of the photosensitive patterned photoresist layer (e.g., 10 μm or less). It is also important to reduce the manufacturing cost of the photoresist layer (e.g., by using a weak alkaline developer such as a 1% aqueous sodium carbonate solution). Therefore, there is a strong demand for a photosensitive photoresist material that has high resolution, low manufacturing cost, and can be exposed to near-ultraviolet light and developed with a weak alkaline developer.

[0005] Although liquid photoresist compositions can form light-sensitive photoresist material patterns with better resolution, the process of forming these patterns becomes more complex and difficult as the substrate size increases, resulting in higher manufacturing costs. Furthermore, liquid photoresist compositions are generally used in ultra-fine processing (e.g., semiconductor manufacturing) and are developed with aqueous tetramethylammonium chloride solutions. Liquid photoresist compositions cannot be used in printed circuit board manufacturing processes because they are insoluble in weak alkaline developers (e.g., 1% aqueous sodium carbonate solutions).

[0006] Negative photoresists are suitable for dry film technology for large-scale, low-resolution device fabrication, but the poor resolution of negative dry film photoresists limits the use of dry film technology for high-resolution applications.

[0007] Therefore, there is a need for new photoresist compositions suitable for low-cost, high-performance, and high-resolution printed circuit board manufacturing to solve the above-mentioned problems. [Means for solving the problem]

[0008] The present disclosure provides a polymer. According to an embodiment of the present disclosure, the polymer includes a first repeating unit and a second repeating unit. The first repeating unit has a structure of formula (I), and the second repeating unit has a structure of formula (II). [ka] In the formula, R 1 , R 2 and R 3 are independently hydrogen or a C1-C4 alkyl group. Ar is a substituted or unsubstituted C6-C12 aryl group. m hydrogens are replaced with hydroxyl groups. R 4 is hydrogen, a C1-C8 alkyl group, or a substituted or unsubstituted C6-C12 aryl group. Q is a single bond or TIFF2025129010000002.tif1416. n is 0, 1, 2, 3, or 4. m is 1, 2, or 3. i is 0, 1, 2, 3, or 4.

[0009] The present disclosure provides a positive photoresist composition for use in forming a patterned photoresist layer. According to an embodiment of the present disclosure, the positive photoresist composition comprises a polymer of the present disclosure and a photoacid generator.

[0010] The present disclosure provides a method for forming a patterned photoresist layer. According to an embodiment of the present disclosure, the method includes the following steps: subjecting a positive photoresist layer to an exposure process; and fabricating the positive photoresist layer by subjecting the positive photoresist composition of the present disclosure to a drying process. After the exposure process, the positive photoresist layer is subjected to a development process using a developer to obtain the patterned photoresist layer of the present disclosure. [Effects of the Invention]

[0011] The present disclosure provides a polymer, a positive photoresist composition using the same, and a method for forming a patterned photoresist layer. Due to its alkali solubility (e.g., soluble in aqueous sodium carbonate (Na2CO3) solution), the polymer of the present disclosure can be used in a positive photoresist composition used to prepare high-resolution positive dry film photosensitive layers (e.g., forming patterns with line widths of 10 μm or less). The positive photoresist composition of the present disclosure and the dry film photosensitive layer prepared therefrom have good photosensitivity and light transmittance, allowing for the achievement of wiring patterns with high clarity and precision. Furthermore, the pattern has good adhesion to the substrate during pattern formation and is easily releasable from the substrate after pattern formation, simplifying the wiring pattern formation process. In addition, compared to conventional photosensitive phenolic resin compositions, positive photoresist compositions containing the disclosed polymer can be developed in aqueous sodium carbonate (Na2CO3) solution, making them highly suitable for use in printed circuit board processes (e.g., high-resolution printed circuit boards). [Brief explanation of the drawings]

[0012] The present disclosure can be more fully understood from the following detailed description and examples, taken in conjunction with the accompanying drawings.

[0013] [Figure 1] 1 is a flow chart illustrating a method 10 for forming a patterned photoresist layer according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0014] The polymers, positive photoresist compositions, and methods for forming patterned photoresist layers of the present disclosure are described in detail in the following description. In the following detailed description, for purposes of explanation, numerous specific details and embodiments are set forth in order to provide a thorough understanding of the present disclosure. Specific elements and configurations are set forth in the following detailed description to clearly explain the present disclosure. However, it will be apparent that the exemplary embodiments set forth herein are used for illustrative purposes only, and that the concept of the present invention can be embodied in various forms without being limited to these exemplary embodiments. As used herein, the term "about" in terms relating to quantity refers to an amount plus or minus an amount that is common and reasonable to one of ordinary skill in the art.

[0015] Furthermore, in this disclosure, the use of ordinal terms, such as "first," "second," "third," etc., to modify elements does not imply any priority, precedence, or order of one claim element over another, or the chronological order in which they are formed, but rather is merely used as a label to distinguish one claim element having a certain name from another element having the same name (unless ordinal terms are used) to distinguish between claim elements.

[0016] According to embodiments of the present disclosure, a polymer may include a first repeat unit and a second repeat unit, wherein the first repeat unit has a structure of formula (I) and the second repeat unit has a structure of formula (II). [ka] wherein R1, R2, and R3 are independently hydrogen or a C1-C4 alkyl group. Ar may be a substituted or unsubstituted C6-C12 aryl group. m hydrogen atoms in the aryl group may be replaced with hydroxyl groups. R 4 may be hydrogen, a C1-C8 alkyl group, or a substituted or unsubstituted C6-C12 aryl group. Q is a single bond or TIFF2025129010000004.tif1618. n can be 0, 1, 2, 3 or 4. m can be 1, 2 or 3. i can be 0, 1, 2, 3 or 4.

[0017] According to an embodiment of the present disclosure, Q is When TIFF2025129010000005.tif1618, i can be 1, 2, 3 or 4.

[0018] According to an embodiment of the present disclosure, a substituted C6-C12 aryl group means that at least one hydrogen bonded to a carbon of the aryl group can be optionally substituted with fluorine, a C1-C8 alkyl group, a C1-C8 fluoroalkyl group, or a C1-C8 alkoxy group.

[0019] According to embodiments of the present disclosure, the polymer may include at least one of the first repeat units and at least one of the second repeat units, i.e., the polymer may include at least one repeat unit having the structure shown in formula (I) and at least one repeat unit having the structure shown in formula (II).

[0020] According to an embodiment of the present disclosure, the first repeat unit may have a structure represented by formula (Ia): [ka] In the formula, R 1 , R 2 , n and m are as defined above.

[0021] According to embodiments of the present disclosure, the first repeat unit may be any of the following: [ka] TIFF2025129010000008.tif82163

[0022] According to embodiments of the present disclosure, the second repeat unit may be any of the following: [ka] In the formula, R 3 is the same as defined above.

[0023] According to an embodiment of the present disclosure, the second repeat unit may be: [ka]

[0024] According to embodiments of the present disclosure, the alkyl group of the present disclosure may be a straight chain or branched alkyl group.

[0025] For example, the C1-C8 alkyl group can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or an isomer thereof.

[0026] According to embodiments of the present disclosure, the fluoroalkyl group of the present disclosure may be a straight-chain or branched alkyl group in which some or all of the hydrogen atoms bonded to the carbon atoms are replaced with fluorine atoms.

[0027] For example, the C1-C8 fluoroalkyl group can be fluoromethyl, fluoroethyl, fluoropropyl, fluorobutyl, fluoropentyl, fluorohexyl, fluoroheptyl, fluorooctyl, or an isomer thereof, wherein the fluoromethyl group can be monofluoromethyl, difluoromethyl, or trifluoromethyl, and the fluoroethyl group can be monofluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, or perfluoroethyl.

[0028] According to embodiments of the present disclosure, the alkoxy group of the present disclosure may be a straight-chain or branched alkoxy group.

[0029] For example, a C1-C8 alkoxy group can be methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy or an isomer thereof.

[0030] According to an embodiment of the present disclosure, the C6-C12 aryl group of the present disclosure may be a phenyl group, a biphenyl group, or a naphthyl group.

[0031] According to an embodiment of the present disclosure, the repeat unit of the polymer may consist of a first repeat unit and a second repeat unit. According to an embodiment of the present disclosure, the polymer does not include any repeat units other than the first repeat unit and the second repeat unit.

[0032] According to embodiments of the present disclosure, the first repeat unit and the second repeat unit may be arranged randomly or in a block manner.

[0033] According to an embodiment of the present disclosure, the ratio of the number of first repeat units to the number of second repeat units in the polymer of the present disclosure can be 9:1 to 1:9, for example, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, or 2:8. This allows a positive photoresist composition using the polymer of the present disclosure to be developable with a weak alkaline developer (e.g., aqueous sodium carbonate solution). Furthermore, the use of the polymer of the present disclosure allows the amount of photoacid generator to be reduced.

[0034] According to an embodiment of the present disclosure, when the polymer further comprises other repeat units in addition to the first repeat unit and the second repeat unit, the ratio of the total number of the first repeat unit and the second repeat unit to the total number of all repeat units is 90:100 to 99.9:100.

[0035] According to embodiments of the present disclosure, the weight average molecular weight of the polymer of the present disclosure may be 5,000 g / mol to 50,000 g / mol, for example, 6,000 g / mol, 7,000 g / mol, 8,000 g / mol, 9,000 g / mol, 10,000 g / mol, 15,000 g / mol, 20,000 g / mol, 25,000 g / mol, 30,000 g / mol, 35,000 g / mol, 40,000 g / mol, or 45,000 g / mol. The weight average molecular weight (Mw) of the polymer of the present disclosure can be measured by gel permeation chromatography (GPC) based on a polystyrene calibration curve.

[0036] The polymers of the present disclosure can be prepared from a first monomer and a second monomer by a polymerization reaction, wherein the first repeat unit in the polymer is derived from the first monomer and the second repeat unit is derived from the second monomer.

[0037] According to an embodiment of the present disclosure, the first monomer is [ka] and the second monomer may be [ka] may be In the formula, R 1 , R 2 , R 3 , R 4 , Q, Ar, n, m, and i are as defined above.

[0038] According to an embodiment of the present disclosure, the first monomer may be: [ka] In the formula, R 1 , R 2 , n, and m are as defined above.

[0039] The second monomer may be any of the following: [ka] In the formula, R 3 can be hydrogen or methyl, and i can be 1, 2, 3 or 4.

[0040] According to embodiments of the present disclosure, in producing the polymers of the present disclosure, the molar ratio of the first monomer to the second monomer may be from 9:1 to 1:9, for example, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, or 2:8.

[0041] The method for producing the polymer of the present disclosure is not limited. For example, a first monomer and a second monomer can be mixed and copolymerized in the presence of a chain transfer agent and / or a catalyst (reaction temperature: 50°C to 150°C, reaction time: 1 hour to 12 hours). Alternatively, the first monomer can be homopolymerized to obtain a first oligomer, and the second monomer can be homopolymerized to obtain a second oligomer. The first oligomer and the second oligomer are then mixed and copolymerized in the presence of a chain transfer agent and / or a catalyst (reaction temperature: 50°C to 150°C, reaction time: 1 hour to 12 hours). According to an embodiment of the present disclosure, the chain transfer agent and catalyst are not limited and may be any chain transfer agent and catalyst commonly used in copolymerization.

[0042] According to an embodiment of the present disclosure, the present disclosure also provides a positive photoresist composition. The positive photoresist composition may include the polymer of the present disclosure and a photoacid generator.

[0043] According to an embodiment of the present disclosure, the positive photoresist composition of the present disclosure has high photosensitivity, low dielectric constant, and high optical transparency, and therefore, a dry film prepared from the positive photoresist composition of the present disclosure can achieve a wiring pattern with high clarity and precision.

[0044] According to embodiments of the present disclosure, the weight ratio of the polymer of the present disclosure to the photoacid generator may be from 2:1 to 12:1, for example, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, or 11:1.

[0045] According to embodiments of the present disclosure, the photoacid generator may be an onium salt, a triarylsulfonium salt, an alkylarylsulfonium salt, a diaryl iodonium salt, a diaryl chloronium salt, a diaryl bromonium salt, a sulfonate salt, a diazonium salt, a diazonaphthoquinone sulfonate, or a combination thereof.

[0046] According to an embodiment of the present disclosure, in the positive photoresist composition of the present disclosure, the polymer and the photoacid generator of the present disclosure can be uniformly dissolved in an organic solvent.

[0047] According to embodiments of the present disclosure, the organic solvent may be benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene, decahydronaphthalene, dipentene, pentane, hexane, heptane, octane, nonane, decane, ethylcyclohexane, methylcyclohexane, p-menthane, dipropyl ether, dibutyl ether, anisole, ethyl acetate, butyl acetate, pentyl acetate, methyl isobutyl ketone, cyclohexylbenzene, cyclohexanone, cyclopentanone (CPN), triglyme, 1,3-dimethyl-2-imidazolidinone (DMI), N-methyl-2-pyrrolidone (NMP), methyl ethyl ketone (MEK), N,N-dimethylacetamide (DMAc), γ-butyrolactone (GBL), N,N-dimethylformamide (DMF), propylene glycol methyl ether acetate (PGMEA), dimethyl sulfoxide (DMSO), or a combination thereof.

[0048] According to an embodiment of the present disclosure, additives such as leveling agents, colorants, adhesion promoters, thixotropic agents, sensitizers, fillers, or combinations thereof can be optionally added to the composition so that the positive photoresist composition or the dry film formed therefrom has desired properties. According to an embodiment of the present disclosure, the amount of additives can be 0.1 wt % to 30 wt % based on the total weight of the polymer and the photoacid generator.

[0049] According to embodiments of the present disclosure, when a positive photoresist composition of the present disclosure includes an organic solvent, the solids content of the positive photoresist composition can be about 10% to 50% (e.g., 15%, 20%, 25%, 30%, 35%, 40%, or 45%). Solids content refers to the weight percent of all components in the positive photoresist composition, excluding the organic solvent, based on the total weight of the positive photoresist composition.

[0050] The present disclosure also provides a method for forming a patterned photoresist layer. As shown in the figure, the method 10 for forming a patterned photoresist layer of the present disclosure includes the following steps: an exposure process is performed on a positive photoresist layer (step 12). The positive photoresist layer is made from the positive photoresist composition of the present disclosure. Then, after the exposure process, the positive photoresist layer is subjected to a development process using a developer (step 14) to obtain a patterned photoresist layer.

[0051] According to an embodiment of the present disclosure, the light source used in the exposure process may be ultraviolet (UV) light (wavelength range 150 nm to 450 nm). The exposure dose of the exposure process is 10 mJ / cm. 2 to 500mJ / cm 2 (e.g., 20 mJ / cm 2 , 50 mJ / cm 2 , 70 mJ / cm 2 , 100mJ / cm 2 , 120mJ / cm 2 , 150 mJ / cm 2 , 200mJ / cm 2 , 250 mJ / cm 2, 300mJ / cm 2 , 350 mJ / cm 2 , 400mJ / cm 2 or 450 mJ / cm 2 ) may be.

[0052] According to an embodiment of the present disclosure, the developer may be an aqueous alkali metal salt solution, such as an aqueous sodium carbonate solution or an aqueous potassium carbonate solution, in which the amount of the alkali metal salt may be 0.1 wt % to 5 wt % based on the total weight of the aqueous alkali metal salt solution.

[0053] According to an embodiment of the present disclosure, the positive photoresist layer can be a dry film prepared by subjecting the positive photoresist composition of the present disclosure to a coating process and a drying process.

[0054] According to an embodiment of the present disclosure, the preparation and use of a positive dry film photoresist according to the present disclosure may include the following steps: First, a positive photoresist composition is applied to a carrier film. After drying, a protective film is laminated on the dried photoresist composition to form a positive dry film photoresist. During transfer printing, the protective film is removed, and the dried photoresist composition is transferred to a substrate by a transfer printing process. Then, the carrier film is removed, and an exposure process and a development process can be carried out.

[0055] The application method of the above-mentioned positive photoresist composition may include, but is not limited to, screen printing, spin coating, bar coating, blade coating, roller coating, dip coating, spray coating, or brush coating.

[0056] According to an embodiment of the present disclosure, the carrier film and the positive film may be a polyethylene terephthalate (PET) film, a polyethylene (PE) film, or an oriented polypropylene (OPP) film. According to an embodiment of the present disclosure, the substrate may be a wafer or a copper-clad laminate.

[0057] In order to facilitate understanding by those skilled in the art, exemplary embodiments will be described in detail below with reference to the accompanying drawings. The present invention is not limited to the exemplary embodiments shown herein, but may be embodied in various forms. For clarity, descriptions of well-known parts will be omitted, and similar reference numerals will refer to similar elements throughout.

[0058] Polymer manufacturing Manufacturing Examples 1 to 5 Glycidyl methacrylate (GMA) (375 g), 4-hydroxybenzoic acid (367.5 g), catalyst (triphenylphosphine) (1.88 g), and inhibitor (hydroquinone) (1.05 g) were added to a solvent (propylene glycol methyl ether acetate (PGMEA)) (320 g) to obtain a mixture. The mixture was stirred at 100° C. for 4 hours. After purification, Monomer (I) (having the following structure) was obtained. [ka]

[0059] Monomer (I), benzyl methacrylate (structure TIFF2025129010000016.tif1629), catalyst (2,2'-azobis(2-methylpropionitrile (AIBN)), chain transfer agent (1-dodecanethiol), and solvent (propylene glycol methyl ether acetate (PGMEA)) were mixed according to the amounts shown in Table 1. The resulting mixtures were heated to 90°C and stirred for 4 hours to obtain polymers (1) to (5), respectively. The weight-average molecular weights (Mw) of polymers (1) to (5) were measured by gel permeation chromatography (GPC). The results are shown in Table 1.

[0060] Manufacturing Examples 6-9 Monomer (I), styrene, catalyst (2,2'-azobis(2-methylpropionitrile (AIBN)), chain transfer agent (1-dodecanethiol), and solvent (propylene glycol methyl ether acetate (PGMEA)) were mixed according to the amounts shown in Table 1. The resulting mixture was heated to 90°C and stirred for 4 hours to obtain polymers (6) to (9), respectively. The weight-average molecular weights (Mw) of polymers (6) to (9) were measured by gel permeation chromatography (GPC). The results are shown in Table 1.

[0061] [Table 1]

[0062] Preparation of a positive photoresist composition Examples 1 to 3 Polymer (1), 2,3,4-trihydroxybenzophenone naphthoquinone-1,2-diazide-5-sulfonate (DNQ) (photoacid generator), butyl acetate (BA) (solvent), and propylene glycol methyl ether acetate (PGMEA) (solvent) were mixed in the amounts shown in Table 2. After thorough mixing, positive photoresist compositions (1) to (3) were obtained.

[0063] Examples 4 to 6 Polymer (2), 2,3,4-trihydroxybenzophenone naphthoquinone-1,2-diazide-5-sulfonate (DNQ) (photoacid generator), butyl acetate (BA) (solvent), and propylene glycol methyl ether acetate (PGMEA) (solvent) were mixed in the amounts shown in Table 2. After thorough mixing, positive photoresist compositions (4) to (6) were obtained.

[0064] Examples 7 to 9 Polymer (3), 2,3,4-trihydroxybenzophenone naphthoquinone-1,2-diazide-5-sulfonate (DNQ) (photoacid generator), butyl acetate (BA) (solvent), and propylene glycol methyl ether acetate (PGMEA) (solvent) were mixed in the amounts shown in Table 2. After thorough mixing, positive photoresist compositions (7) to (9) were obtained.

[0065] Examples 10 to 12 Polymer (4), 2,3,4-trihydroxybenzophenone naphthoquinone-1,2-diazide-5-sulfonate (DNQ) (photoacid generator), butyl acetate (BA) (solvent), and propylene glycol methyl ether acetate (PGMEA) (solvent) were mixed in the amounts shown in Table 2. After thorough mixing, positive photoresist compositions (10) to (12) were obtained.

[0066] Examples 13 to 15 Polymer (5), 2,3,4-trihydroxybenzophenone naphthoquinone-1,2-diazide-5-sulfonate (DNQ) (photoacid generator), butyl acetate (BA) (solvent), and propylene glycol methyl ether acetate (PGMEA) (solvent) were mixed in the amounts shown in Table 2. After thorough mixing, positive photoresist compositions (13) to (15) were obtained.

[0067] [Table 2]

[0068] Comparative Example 1 Phenol-formaldehyde resin (1) (purchased from Sumitomo Bakelite, product number PR56001) (weight average molecular weight (Mw) approximately 5,000) (22.5 g), 2,3,4-trihydroxybenzophenone naphthoquinone-1,2-diazide-5-sulfonate (DNQ) (photoacid generator) (6.7 g), butyl acetate (BA) (solvent) (7.08 g), and propylene glycol methyl ether acetate (PGMEA) (solvent) (63.72 g) were mixed. After thorough mixing, a positive photoresist composition (16) was obtained.

[0069] Comparative Example 2 Phenol-formaldehyde resin (2) (purchased from Sumitomo Bakelite, product number PR56032) (weight average molecular weight (Mw) approximately 50,000) (22.5 g), 2,3,4-trihydroxybenzophenone naphthoquinone-1,2-diazide-5-sulfonate (DNQ) (photoacid generator) (6.7 g), butyl acetate (BA) (solvent) (7.08 g), and propylene glycol methyl ether acetate (PGMEA) (solvent) (63.72 g) were mixed. After thorough mixing, a positive photoresist composition (17) was obtained.

[0070] Comparative Example 3 Poly(4-vinylphenol) (purchased from Sigma-Aldrich) (weight average molecular weight (Mw) approximately 11,000) (26.32 g), 2,3,4-trihydroxybenzophenone naphthoquinone-1,2-diazide-5-sulfonate (DNQ) (photoacid generator) (3.68 g), butyl acetate (BA) (7 g) (solvent), and propylene glycol methyl ether acetate (PGMEA) (63 g) (solvent) were mixed. After thorough mixing, a positive photoresist composition (18) was obtained.

[0071] Examples 16 to 23 Polymers (6) to (9), 2,3,4-trihydroxybenzophenone naphthoquinone-1,2-diazide-5-sulfonate (DNQ) (photoacid generator), butyl acetate (BA) (solvent), and propylene glycol methyl ether acetate (PGMEA) (solvent) were mixed in the amounts shown in Table 3. After thorough mixing, positive photoresist compositions (19) to (26) were obtained.

[0072] [Table 3]

[0073] Preparation of dry film photoresist layer Positive photoresist compositions (1) to (26) were each applied to a polyethylene terephthalate (PET) carrier film by blade coating. After drying at 80°C, the solvent was removed to obtain dry film photoresist layers (1) to (26) (approximately 6 μm thick). A polyethylene terephthalate (PET) protective film was then laminated onto each dry film photoresist layer.

[0074] Transfer print test The dry film photoresist layer on the carrier film was cut to obtain a test piece measuring 7 cm x 7 cm. After removing the protective film, the test piece was laminated onto a 10 cm x 10 cm wafer. Pressure was applied to the carrier film using a roller (approximately 2.5 kg / cm). 2 ). The roller temperature was 95°C and the roller speed was 0.2 m / min. This resulted in the transfer of the dry film photoresist layer to the wafer. After removing the carrier film, if the dry film photoresist layer was completely transferred to the wafer (no residue on the carrier film), it was recorded as ○. If the dry film photoresist layer was not completely transferred to the wafer (residue on the carrier film), it was recorded as ×. The results are shown in Table 4.

[0075] Resolution evaluation The dry film photoresist layers (1) to (26) used in the transfer printing test were exposed to full-spectrum UV light (pattern line width: 8 μm, line pitch: 8 μm). The dry film photoresist layers were then developed with aqueous sodium carbonate solution (approximately 60 to 90 seconds). The exposure dose and the concentration of the aqueous sodium carbonate solution are shown in Table 4. If the exposed and developed dry film photoresist layer produced a pattern with a line width and line pitch of 8 μm, it was recorded as ○; otherwise, it was recorded as ×.

[0076] [Table 4]

[0077] In addition, the dry film photoresist layers (16), (17) and (18) of Comparative Examples 1, 2 and 3 were exposed to a higher exposure dose (200 mJ / cm 2 The resist was exposed to a solution of sodium carbonate (the concentration was increased to 5%) and developed for a longer time (the development time was increased to 300 seconds), but no patterned photoresist layer was obtained.

[0078] As shown in Table 4, compared to conventional photosensitive phenolic resin compositions, the positive photoresist compositions containing the polymers of the present disclosure can be developed using aqueous sodium carbonate solutions, making the photoresist compositions of the present disclosure suitable for printed circuit board processing.

[0079] In summary, the alkali-solubility of the polymers disclosed herein allows them to be used in positive photoresist compositions for producing high-resolution, photosensitive, positive dry films. The positive photoresist compositions and dry films produced therefrom exhibit excellent photosensitivity and light transmittance, enabling the formation of highly defined and precise wiring patterns. Furthermore, the excellent adhesion of the pattern to the substrate during pattern formation and the excellent peelability of the pattern from the substrate after pattern formation simplify the wiring pattern process.

[0080] While the present disclosure has been described by way of example and in terms of preferred embodiments, it is to be understood that the present disclosure is not limited to the disclosed embodiments. Rather, it is intended to cover various modifications and similar arrangements (as would be apparent to those skilled in the art). Therefore, the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements. [Explanation of symbols]

[0081] 10...Method for forming a patterned photoresist layer 12, 14... steps

Claims

1. 1. A polymer comprising a first repeat unit and a second repeat unit, wherein the first repeat unit has a structure of Formula (Ia) and the second repeat unit has a structure of Formula (II): 【Chemical 1】 (In the formula, R 1 , R 2 and R 3 are independently hydrogen or a C1-C4 alkyl group. 4 is hydrogen, a C1-C8 alkyl group, or a substituted or unsubstituted C6-C12 aryl group. Q is a single bond or 【change】 n is 0, 1, 2, 3, or 4; m is 1, 2, or 3; and i is 0, 1, 2, 3, or 4.

2. 2. The polymer of claim 1, wherein the ratio of the number of first repeat units to the number of second repeat units is from 9:1 to 1:

9.

3. A polymer according to claim 1; a photoacid generator; A positive photoresist composition comprising:

4. 4. The positive photoresist composition of claim 3, wherein the weight ratio of said polymer to said photoacid generator is from 2:1 to 12:1.

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