Polymer, positive-type photoresist composition, and method for forming a patterned photoresist layer

Abstract

To provide a polymer for use in high-performance photoresist compositions suitable for manufacturing high-resolution printed circuit boards. [Solution] The polymer contains repeating units of the structures of formula (I) and formula (II). TIFF2026116717000038.tif119170 (In the formula, n is 0, 1, 2, 3, or 4, and m is 1, 2, or 3)

Description

[Technical Field]

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

[0002] Continuous advancements in integrated circuit manufacturing and packaging technology have led to the development of printed circuit boards (PCBs) that achieve high-density wiring, miniaturization, high electrical properties, high dimensional stability, high resolution, and cost reduction. Furthermore, there is a growing demand for multilayer technology that offers smaller pore sizes and higher alignment accuracy. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] U.S. Patent No. 6,743,563,B2 [Overview of the project] [Problems that the invention aims to solve]

[0004] In the manufacturing process of printed circuit boards, achieving high-density wiring and high resolution requires a further reduction (to 10 μm or less) in the width or line pitch of the formed photosensitive patterned photoresist layer. Furthermore, it is also important to reduce the manufacturing cost of the photoresist layer (for example, by using a weakly alkaline developer, e.g., a 1% sodium carbonate aqueous solution). Therefore, a photosensitive photoresist material that enables near-ultraviolet exposure, development with a weakly alkaline developer, high resolution, and low cost is highly desirable.

[0005] While liquid photoresist compositions can form photosensitive photoresist patterns with better resolution, the manufacturing process becomes increasingly complex as the substrate size increases. Furthermore, because liquid photoresist compositions cannot be dissolved in weakly alkaline solutions (such as a 1% sodium carbonate aqueous solution), applying them to PCB manufacturing processes is difficult.

[0006] Therefore, the industry still demands high-performance photoresist compositions suitable for the manufacture of high-resolution printed circuit boards. [Means for solving the problem]

[0007] This disclosure provides a polymer. According to embodiments of this disclosure, the polymer comprises a first repeating unit and a second repeating unit. The first repeating unit has the structure of formula (I), and the second repeating unit has the structure of formula (II). [ka] In the formula, R 1 , R 2 and R 3 R is independently hydrogen or a C1-C4 alkyl group, 4 is a branched C4-C10 alkyl group, a C5-C10 cycloalkyl group, or a substituted C5-C10 cycloalkyl group, Ar is a C6-C12 aryl group, or a C7-C18 alkylaryl group, where m hydrogens bonded to the carbon of Ar are substituted by hydroxyl groups, n is 0, 1, 2, 3, or 4, and m is 1, 2, or 3.

[0008] This disclosure provides a positive-type photoresist composition used for preparing a patterned photoresist layer. According to embodiments of this disclosure, the positive-type photoresist composition comprises the polymer of this disclosure and a photoacid generator.

[0009] 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. The positive photoresist layer is subjected to an exposure process, where the positive photoresist layer is obtained by drying the positive photoresist composition of the present disclosure. Further, the positive photoresist layer is subjected to a development process using a developer, and the patterned photoresist layer of the present disclosure is obtained.

Advantages of the Invention

[0010] The present disclosure provides a polymer, a positive photoresist composition using the polymer, and a method for forming a patterned photoresist layer. Since the polymer of the present disclosure has alkali solubility (such as being soluble in an aqueous sodium carbonate (Na2CO3) solution), it is applicable to a positive photoresist composition for preparing a high-resolution photosensitive positive dry film material (such as forming a pattern having a line width of 10 μm or less). The positive photoresist composition of the present disclosure and the dry film prepared therefrom have good photosensitivity and light transmittance, so that high clarity and a wiring pattern with high precision can be achieved. Further, during pattern formation, since it adheres closely to the substrate, the patterned photoresist layer exhibits excellent peeling characteristics from the substrate, thereby simplifying the process of forming a wiring pattern. Further, compared with a conventional photosensitive phenol resin composition, the positive photoresist composition containing the polymer of the present disclosure is developable in an aqueous sodium carbonate (Na2CO3) solution and is very suitable for use in the process of a printed wiring board (such as a high-resolution printed wiring board).

[0011] By referring to the accompanying drawings and reading the following detailed description and examples, the present disclosure can be understood more completely.

Brief Description of the Drawings

[0012] [Figure 1] It is a flowchart showing a method for forming a patterned photoresist layer according to an embodiment of the present disclosure. [Modes for carrying out the invention]

[0013] Polymers, positive photoresist compositions, and methods for forming patterned photoresist layers are described in detail below. Numerous specific details and embodiments are provided in the following detailed description to facilitate a full understanding of the disclosure. Specific elements and structures described in the following detailed description are provided to clearly illustrate the disclosure. However, the exemplary embodiments described herein are for illustrative purposes only, and it will become clear that the inventive concept can be embodied in various forms without being limited to these exemplary embodiments. Furthermore, drawings in various embodiments may use similar and / or corresponding figures to represent similar and / or corresponding elements in order to clearly illustrate the disclosure. However, the use of similar and / or corresponding figures in drawings of various embodiments does not imply any correlation between the various embodiments. As used herein, the term “about” in quantitative terms means that there is an increase or decrease from a quantity that is common and reasonable to those skilled in the art.

[0014] Furthermore, the use of sequential terms such as “first,” “second,” and “third” in the disclosure to modify elements does not in itself imply that any claimed element takes precedence, precedes, or is sequential to any other element, nor does it imply any temporal order in which they are formed. These terms are used merely as labels to distinguish a claimed element having a particular name from other elements having the same name (except for the use of sequential terms).

[0015] According to embodiments of the present disclosure, the polymer may include a first repeating unit and a second repeating unit, wherein the first repeating unit has the structure of formula (I) and the second repeating unit has the structure of formula (II). [Chemical formula] In the formula, R 1 , R 2 and R 3 are each independently hydrogen or a C1-C4 alkyl group, R 4 is a branched C4-C10 alkyl group, a C5-C10 cycloalkyl group, or a substituted C5-C10 cycloalkyl group, Ar is a C6-C12 aryl group, or a C7-C18 alkylaryl group, and in the formula, m hydrogen atoms bonded to the carbon of Ar are substituted by hydroxyl groups, n is 0, 1, 2, 3, or 4, and m is 1, 2, or 3. According to an embodiment of the present disclosure, R 4 is bonded to oxygen via a tertiary carbon atom.

[0016] According to an embodiment of the present disclosure, the C1-C4 alkyl group may be a straight-chain or branched alkyl group. For example, the C1-C4 alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl. According to an embodiment of the present disclosure, the branched C4-C10 alkyl group refers to a C4-C10 alkyl group containing a tertiary carbon atom, where the tertiary carbon is a carbon atom bonded to three other carbon atoms. For example, the branched C4-C10 alkyl group may be tert-butyl, tert-pentyl, or tert-hexyl.

[0017] According to an embodiment of the present disclosure, the C5-C10 cycloalkyl group may be a monocycloalkyl group or a polycycloalkyl group (such as a bicycloalkyl group or a tricycloalkyl group). The polycycloalkyl group may have a fused ring, a bridged ring, or a spiro ring system. For example, the C5-C10 cycloalkyl group may be cyclopentyl, cyclohexyl, cycloheptyl, cycloctyl, adamantyl, or norbornyl. According to an embodiment of the present disclosure, the substituted C5-C10 cycloalkyl group refers to a C5-C10 cycloalkyl group in which at least one hydrogen bonded to carbon can be optionally replaced by a C1-C4 alkyl group or a hydroxyl group.

[0018] According to embodiments of the present disclosure, the polymer may include at least one first repeating unit and at least one second repeating unit. That is, the polymer may include at least one repeating unit having a structure represented by formula (I) and at least one repeating unit having a structure represented by formula (II).

[0019] According to embodiments of this disclosure, the first repeating unit is: [ka] It can be, and in the formula, R 1 , R 2 n and m are the same as those defined above.

[0020] According to embodiments of this disclosure, the first repeating unit is: [ka] [ka] [ka] It can be.

[0021] According to embodiments of this disclosure, the second repeating unit is: [ka] [ka] It can be, and in the formula, R 3 is hydrogen or a C1-C4 alkyl group, R 5 is a C1-C4 alkyl group, and R 6 These are independently hydrogen, a C1-C4 alkyl group, or a hydroxyl group. For example, the second repeating unit is [ka] [ka] [ka] [ka] [ka] It can be.

[0022] According to embodiments of the present disclosure, the polymer may consist of a first repeating unit and a second repeating unit. According to embodiments of the present disclosure, the polymer does not contain any other repeating units other than the first and second repeating units.

[0023] According to embodiments of the present disclosure, the first repeating unit and the second repeating unit can be arranged randomly or in blocks.

[0024] According to embodiments of the present invention, in the polymer of the present disclosure, the ratio of the number of first repeating units to the number of second repeating units can be 100:20 to 100:150, for example, 100:25, 100:30, 100:40, 100:50, 100:60, 100:70, 100:80, 100:90, 100:100, 100:110, 100:120, 100:130, or 100:140. As a result, a positive-type photoresist composition containing the polymer of the present disclosure can be developed after exposure using a weakly alkaline developer (such as an aqueous sodium carbonate solution) to obtain a pattern with excellent resolution.

[0025] According to embodiments of the present disclosure, the polymer of the present disclosure further comprises a third repeating unit having the structure of formula (III), [ka] In the formula, R 7is hydrogen or a C1-C4 alkyl group, A 2 is a single bond or [ka] And R 8 i is a C6-C12 aryl group or a substituted C6-C12 aryl group, where i is 0, 1, 2, 3, or 4. According to embodiments of the present disclosure, a substituted C6-C12 aryl group refers to a C6-C12 aryl group in which at least one of the hydrogen atoms bonded to carbon may be optionally replaced by a C1-C4 alkyl group.

[0026] According to embodiments of this disclosure, the third repeating unit is: [ka] It can be, and in the formula, R 7 This is hydrogen or a C1-C4 alkyl group.

[0027] According to embodiments of this disclosure, the third repeating unit is: [ka] It can be.

[0028] According to embodiments of the present invention, in the polymer of the present disclosure, the ratio of the number of first repeating units to the number of third repeating units can be 100:1 to 100:50, for example, 100:2, 100:3, 100:5, 100:10, 100:20, 100:30, or 100:40. As a result, a positive-type photoresist composition containing the polymer of the present disclosure can be developed after exposure using a weakly alkaline developer (such as an aqueous sodium carbonate solution).

[0029] According to embodiments of the present disclosure, the polymer may consist of a first repeating unit and a second repeating unit. According to embodiments of the present disclosure, the polymer does not contain any other repeating units other than the first and second repeating units.

[0030] According to embodiments of the present disclosure, if the polymer of the present disclosure further includes other repeating units in addition to the first repeating units, the second repeating units, and the third repeating units, the ratio of the total number of the first, second, and third repeating units to the total number of all repeating units is 90:100 to 99.9:100.

[0031] According to embodiments of the present invention, the weight-average molecular weight of the polymers disclosed may be between 14,000 g / mol and 100,000 g / mol, for example, 15,000 g / mol, 18,000 g / mol, 20,000 g / mol, 25,000 g / mol, 30,000 g / mol, 35,000 g / mol, 40,000 g / mol, 45,000 g / mol, 50,000 g / mol, 55,000 g / mol, 60,000 g / mol, 65,000 g / mol, 70,000 g / mol, 75,000 g / mol, 80,000 g / mol, 85,000 g / mol, 90,000 g / mol, or 95,000 g / mol. The weight-average molecular weight (Mw) of the polymers of this disclosure can be measured by gel permeation chromatography (GPC) based on a polystyrene calibration curve. If the molecular weight of the polymer is too low, narrower patterns (less than 10 μm) formed by the positive photoresist composition containing the polymers of this disclosure will exhibit insufficient adhesion, making it difficult to form high-resolution pattern layers. If the molecular weight of the polymer is too high, the positive photoresist composition containing the polymers of this disclosure will have low solubility in weakly alkaline developers after exposure.

[0032] The polymers of the present disclosure can be obtained by polymerization of a first monomer and a second monomer. In the polymers of the present disclosure, the first repeating unit is derived from the first monomer, and the second repeating unit is derived from the second monomer.

[0033] According to embodiments of this disclosure, the first monomer is [ka] The second monomer can be [ka] It can be, and in the formula, R 1 , R 2 , R 3 , R 4 Ar, n, and m are the same as defined above.

[0034] According to embodiments of this disclosure, the first monomer is [ka] It can be, and in the formula, R 1 , R 2 n and m are the same as those defined above.

[0035] According to embodiments of the present invention, when the polymer of the present disclosure is obtained by polymerization of a first monomer and a second monomer, the molar ratio of the first monomer to the second monomer can be 100:10 to 100:150, for example, 100:10, 100:20, 100:30, 100:40, 100:50, 100:60, 100:70, 100:80, 100:90, 100:100, 100:110, 100:120, 100:130, or 100:140.

[0036] The polymers of this disclosure can be obtained by polymerization of a first monomer, a second monomer, and a third monomer. In the polymers of this disclosure, the first repeating unit is derived from the first monomer, the second repeating unit is derived from the second monomer, and the third repeating unit is derived from the third monomer.

[0037] According to embodiments of this disclosure, the third monomer is [ka] It can be. For example, the third monomer is [ka] It can be, R7 This is hydrogen or a C1-C4 alkyl group.

[0038] According to embodiments of the present invention, when the polymer of the present disclosure is obtained by polymerization of a first monomer, a second monomer, and a third monomer, the molar ratio of the first monomer to the third monomer can be 100:10 to 100:150, for example, 100:10, 100:20, 100:30, 100:40, 100:50, 100:60, 100:70, 100:80, 100:90, 100:100, 100:110, 100:120, 100:130, or 100:140.

[0039] The method for preparing the polymers of this disclosure is not particularly limited. For example, the first monomer and the second monomer can be mixed (or a third monomer can be further added), and subjected to copolymerization in the presence of a chain transfer agent and / or a catalyst (the reaction temperature can be in the range of 50°C to 150°C, and the reaction time can be in the range of 1 hour to 12 hours). According to embodiments of this disclosure, the molecular weight of the polymers of this disclosure can be controlled by adjusting the amount of chain transfer agent and / or catalyst, the reaction temperature, and the reaction time. According to embodiments of this disclosure, the first monomer can first undergo homopolymerization to obtain a first oligomer, the second monomer can first undergo homopolymerization to obtain a second oligomer, and / or the third monomer can first undergo homopolymerization to obtain a third oligomer. The obtained oligomers are then mixed with other monomers or oligomers and copolymerized in the presence of a chain transfer agent and / or a catalyst. According to embodiments of this disclosure, the chain transfer agent and catalyst are not particularly limited and can be conventional chain transfer agents and catalysts used in copolymerization.

[0040] According to embodiments 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.

[0041] According to embodiments of the present disclosure, the positive-type photoresist compositions of the present disclosure exhibit high photosensitivity and high light transmittance. As a result, dry films prepared from the positive-type photoresist compositions of the present disclosure can achieve high clarity and high precision of wiring patterns.

[0042] According to embodiments of the present disclosure, the weight ratio of the photoacid generator to the polymer can be 0.5:100 to 20:100, for example, 8:100, 10:100, 15:100, or 20:100.

[0043] According to embodiments of the present disclosure, the photoacid generator may be an onium salt, a triarylsulfonium salt, an alkylarylsulfonium salt, a diaryliodonium salt, a diarylchloronium salt, a diarylboronium salt, a sulfonate, a sulfonic acid ester, a fluorosulfonate ester, a diazonium salt, a diazonaphthoquinone sulfonate, or a combination thereof.

[0044] According to embodiments of the present disclosure, in the positive-type photoresist composition of the present disclosure, the polymer and the photoacid generator of the present disclosure can be uniformly dissolved in an organic solvent.

[0045] According to embodiments of this disclosure, the organic solvents include 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 (MEK ), cyclohexylbenzene, cyclohexanone, cyclopentanone (CPN), triglycerides, 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 combinations thereof.

[0046] According to embodiments of the present disclosure, one or more additives, such as polymerization inhibitors, leveling agents, colorants, adhesion promoters, thixotropic agents, sensitizers, and fillers, may be optionally added as needed to achieve desirable properties of the positive photoresist composition or the dry film formed therefrom. According to embodiments of the present disclosure, the amount of additives can range from 0.1% to 30% by weight, based on the total weight of the polymer and the photoacid generator.

[0047] According to embodiments of the present disclosure, if the positive photoresist composition of the present disclosure contains an organic solvent, the solid content of the positive photoresist composition may be about 10% to 50% (e.g., 15%, 20%, 25%, 30%, 35%, 40%, or 45%). The solid content refers to the weight percentage of all components in the composition, excluding the organic solvent, based on the total weight of the composition.

[0048] This 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 comprises the following steps: A positive photoresist layer is subjected to an exposure process (step 12), where the positive photoresist layer is obtained by drying the positive photoresist composition of this disclosure. Next, the positive photoresist layer is subjected to a development process (step 14) using a developer after exposure to obtain the patterned photoresist layer of this disclosure.

[0049] According to embodiments of this disclosure, the light source for the exposure process may be ultraviolet (UV) light (having wavelengths of 150 nm to 450 nm), and the exposure dose may be 10 mJ / cm². 2 ~500 mJ / cm 2 (For example, 20 mJ / cm²) 2 50 mJ / cm² 2 70 mJ / cm² 2 , 100 mJ / cm 2 , 120 mJ / cm 2 , 150 mJ / cm 2 , 200 mJ / cm 2 250 mJ / cm² 2 300 mJ / cm² 2 350 mJ / cm² 2 400 mJ / cm² 2 , or 450 mJ / cm² 2 It can be within the range of ).

[0050] According to embodiments of the present disclosure, the developer may be an aqueous solution of an alkali metal salt, such as an aqueous solution of sodium carbonate or an aqueous solution of potassium carbonate. According to embodiments of the present disclosure, the alkali salt content in the aqueous alkali metal salt solution may be 0.1% to 5% by weight, based on the total weight of the aqueous alkali metal salt solution.

[0051] According to embodiments of the present disclosure, the positive photoresist layer may be a dry film obtained by coating with the positive photoresist composition of the present disclosure and drying it.

[0052] According to embodiments of the present disclosure, a method for preparing a positive-type photoresist dry film and a method for using the same may include the following steps: First, a solution of a positive-type photoresist composition is coated onto a carrier film. After drying, a protective film is attached to the dried photoresist composition to form a positive-type photoresist dry film. During transfer printing, the protective film is peeled off and the dried photoresist composition is transferred onto a substrate by the transfer printing process. Next, the carrier film is peeled off and exposure and development processes are carried out.

[0053] The coating method for the positive-type photoresist composition is not limited and may include screen printing, spin coating, bar coating, blade coating, roller coating, dip coating, spray coating, or brush coating.

[0054] According to embodiments of the present disclosure, the carrier film and protective film may be polyethylene terephthalate (PET), polyethylene (PE) film, or stretched polypropylene (OPP) film. According to embodiments of the present disclosure, the substrate may be a wafer or a copper-clad laminate. [Examples]

[0055] The following describes exemplary embodiments in detail, which will be readily apparent to those skilled in the art. The inventive concept can be embodied in various forms, but is not limited to the exemplary embodiments described herein.

[0056] <Preparation of monomers> Preparation Example 1 Glycidyl methacrylate (GMA) (375 g), 4-hydroxybenzoic acid (367.5 g), catalyst (triphenylphosphine) (1.88 g), and polymerization inhibitor (hydroquinone) (1.05 g) were added to solvent (1-methoxy-2-propanol acetate, PGMEA) (320 g) to obtain a mixture. The mixture was stirred at 100°C for 4 hours. After purification, monomer (I) (having the structure shown in Chemical Formula 23 below) [ka] I obtained it.

[0057] <Preparation of polymers> Preparation Examples 2-8 Monomer (I), styrene, tert-butyl acrylate, catalyst (2,2'-azobis(2-methylpropionitrile), AIBN), chain transfer agent (1-dodecanethiol), and solvent (1-methoxy-2-propanol acetate, PGMEA) were mixed according to the ratios shown in Table 1. The resulting mixture was heated and stirred (at the reaction temperature and time shown in Table 1) to obtain polymers (1) to (7). The weight-average molecular weight (Mw) of polymers (1) to (7) was measured by gel permeation chromatography (GPC). The results are shown in Table 1. [Table 1]

[0058] Preparation Examples 9-13 Monomer (I), tert-butyl acrylate, catalyst (2,2'-azobis(2-methylpropionitrile), AIBN), chain transfer agent (1-dodecanethiol), and solvent (1-methoxy-2-propanol acetate, PGMEA) were mixed according to the ratios shown in Table 2. The resulting mixture was heated and stirred (at the reaction temperature and time shown in Table 2) to obtain polymers (8) to (12). The weight-average molecular weight (Mw) of polymers (8) to (12) was measured by gel permeation chromatography (GPC). The results are shown in Table 2. The alkaline dissolution rate of polymers (8) to (12) was evaluated, and the results are shown in Table 2. The method for evaluating the alkaline dissolution rate is described below. The polymer was dissolved in PGMEA, and a coating (10 μm thick) was formed using the resulting mixture. After drying for 3 minutes, the coating was baked at 110°C for 5 minutes and at 150°C for 10 minutes to obtain a film. Next, the film thickness (T1) was measured. Then, the film was immersed in a 1% sodium carbonate (Na2CO3) aqueous solution for 60 seconds. After removing and drying the film, the film thickness (T2) was measured. The alkaline dissolution rate was measured from the values ​​of T1 and T2. [Table 2]

[0059] As shown in Table 2, polymer (12) had an extremely high alkaline dissolution rate, and therefore readily dissolved in the developer. Consequently, polymer (12) was not used for subsequent verification of photoresist formation.

[0060] Preparation Example 14 Monomer (I), 1-ethylcyclohexyl methacrylate, catalyst (2,2'-azobis(2-methylpropionitrile), AIBN), chain transfer agent (1-dodecanethiol), and solvent (1-methoxy-2-propanol acetate, PGMEA) were mixed according to the ratios shown in Table 3. The resulting mixture was heated and stirred (at the reaction temperature and time shown in Table 3) to obtain polymer (13). The weight-average molecular weight (Mw) of polymer (13) was measured by gel permeation chromatography (GPC). The results are shown in Table 3.

[0061] Preparation Examples 15-17 Monomer (I), benzyl methacrylate (having the structure shown in chemical formula 24 below), [ka] The catalyst (2,2'-azobis(2-methylpropionitrile), AIBN), chain transfer agent (1-dodecanethiol), and solvent (1-methoxy-2-propanol acetate, PGMEA) were mixed according to the ratios shown in Table 3. The resulting mixture was heated and stirred (at the reaction temperature and time shown in Table 3) to obtain polymers (14) to (16). The weight-average molecular weight (Mw) of polymers (14) to (16) was measured by gel permeation chromatography (GPC). The results are shown in Table 3.

[0062] Preparation Example 18 Monomer (I), styrene, 1-ethylcyclohexyl methacrylate, catalyst (2,2'-azobis(2-methylpropionitrile), AIBN), chain transfer agent (1-dodecanethiol), and solvent (1-methoxy-2-propanol acetate, PGMEA) were mixed according to the ratios shown in Table 3. The resulting mixture was heated and stirred (at the reaction temperature and time shown in Table 3) to obtain polymer (17). The weight-average molecular weight (Mw) of polymer (17) was measured by gel permeation chromatography (GPC). The results are shown in Table 3. [Table 3]

[0063] <Preparation of positive-type photoresist composition> Examples 1-2 and Comparative Examples 1-6 Polymers (1) to (7) were mixed with a photoacid generator (1,1,2,2,3,3,4,4,4-nonafluoro-1,3-dioxo-1H-benzo[de]isoquinoline-2(3H)-yl ester), a polymerization inhibitor (trioctylamine), and a solvent (1,2-propylene glycol methyl ether acetate, PGMEA), respectively, according to the ratios shown in Table 4. After homogeneous mixing, positive-type photoresist compositions (1) to (8) were obtained. [Table 4]

[0064] Examples 3-9 and Comparative Example 7 Polymers (8) to (11) were mixed with a photoacid generator (1,1,2,2,3,3,4,4,4-nonafluoro-1,3-dioxo-1H-benzo[de]isoquinoline-2(3H)-yl ester), a polymerization inhibitor (trioctylamine), and a solvent (1,2-propylene glycol methyl ether acetate, PGMEA), respectively, according to the ratios shown in Table 5. After homogeneous mixing, positive-type photoresist compositions (9) to (16) were obtained. [Table 5]

[0065] Examples 10-17 and Comparative Example 8 Polymers (13) to (17) were mixed with phenolic resin (weight-average molecular weight: approximately 11,000, commercially available from Sigma-Aldrich), photoacid generator (1,1,2,2,3,3,4,4,4-nonafluoro-1,3-dioxo-1H-benzo[de]isoquinoline-2(3H)-yl ester), polymerization inhibitor (trioctylamine), and solvent (1,2-propylene glycol methyl ether acetate, PGMEA), respectively, according to the ratios shown in Table 6. After homogeneous mixing, positive-type photoresist compositions (17) to (25) were obtained. [Table 6]

[0066] Preparation of a dry film photoresist layer Positive-type photoresist compositions (1) to (25) were individually coated onto polyethylene terephthalate (PET) films by blade coating. After drying to 80°C and removing the solvent, dry film photoresist layers (1) to (25) with a thickness of approximately 6 μm were obtained. Next, polyethylene terephthalate (PET) protective films were attached to the dry film photoresist layers.

[0067] Transfer Printing Test The dry film photoresist layer on the carrier film was cut into a sample (7cm x 7cm in size). After removing the protective film, the sample was attached to a wafer (10cm x 10cm), and the carrier film was pressed down using a roller (roller temperature: 95°C, speed: 0.2m / min) under pressure (approximately 2.5kg / cm²). 2 The dry film was subjected to a transfer print onto the wafer. After removing the carrier film, a "○" was marked if the dry film was completely transferred to the wafer (no residue on the carrier film). A "×" was marked if the dry film was not completely transferred (residue was present on the carrier film). The results are shown in Table 7.

[0068] Resolution test The transferred dry film photoresist layers (1) to (25) were exposed to full-spectrum ultraviolet light (line width: 2 μm, line pitch: 2 μm). The exposed dry films were then developed with an aqueous sodium carbonate solution. The exposure amount, development time, and sodium carbonate solution concentration are listed in Table 7. If the developed dry film produced a pattern with a line width and pitch of 2 μm, it was marked with "○". Otherwise, it was marked with "×". The results are shown in Table 7. [Table 7]

[0069] As shown in Table 7, compared to conventional photosensitive phenolic resin compositions, the positive-type photoresist compositions (Examples 1-17) containing the polymers of this disclosure are developable using an aqueous sodium carbonate solution, making these positive-type photoresist compositions highly suitable for use in printed circuit board processes. Furthermore, if the polymer having a specific repeating unit of this disclosure has a weight-average molecular weight of less than 14,000 g / mol, the resulting positive-type photoresist compositions exhibit insufficient adhesion after exposure and development, making these positive-type photoresist compositions unsuitable for forming patterns with a resolution of less than 10 μm (i.e., the compositions are unsuitable for forming high-resolution patterns). Furthermore, compared to conventional photosensitive phenolic resin compositions, the positive-type photoresist compositions containing the polymers of this disclosure are developable using an aqueous sodium carbonate solution, making these positive-type photoresist compositions highly suitable for use in printed circuit board processes.

[0070] Therefore, due to the alkali solubility of the polymers disclosed herein, high-resolution photosensitive positive dry films can be prepared by using the polymers disclosed herein in a positive photoresist composition. The positive photoresist composition and the film prepared therefrom exhibit excellent light sensitivity and light transmittance, enabling the creation of highly clear and high-precision wiring patterns. Furthermore, the good adhesion to the substrate during pattern formation and the easy peelability after pattern formation simplify the wiring pattern formation process.

[0071] It will become clear that various modifications and variations can be applied to the disclosed methods and materials. The specification and examples are to be considered merely illustrative, and the true scope of this disclosure is intended to be shown by the following claims and their equivalents.

Claims

1. A polymer comprising a first repeating unit and a second repeating unit, wherein the first repeating unit has the structure of formula (I) and the second repeating unit has the structure of formula (II), 【Chemistry 1-1】 In the formula, R 1 , R 2 and R 3 R is independently hydrogen or a C1-C4 alkyl group. 4 A polymer in which is a branched C4-C10 alkyl group, a C5-C10 cycloalkyl group, or a substituted C5-C10 cycloalkyl group, Ar is a C6-C12 aryl group, or a C7-C18 alkylaryl group, where m hydrogens bonded to the carbon of Ar are substituted with hydroxyl groups, n is 0, 1, 2, 3, or 4, and m is 1, 2, or 3.

2. The polymer according to claim 1, wherein the ratio of the first repeating unit to the second repeating unit is 100:20 to 100:

150.

3. The second repeating unit is, 【Chemistry 2-1】 【Chemistry 2-2】 And in the formula, R 3 is hydrogen or a C1-C4 alkyl group, R 5 is a C1-C4 alkyl group, R 6 The polymer according to claim 1, wherein is independently hydrogen, a C1-C4 alkyl group, or a hydroxyl group.

4. The polymer further comprises a third repeating unit, the third repeating unit having the structure of formula (III), 【Chemistry 3-1】 In the formula, R 7 is hydrogen or a C1-C4 alkyl group, and A 2 is a single bond or 【Chemistry 4-1】 And R 8 The polymer according to claim 1, wherein is a C6-C12 aryl group or a substituted C6-C12 aryl group, and i is 0, 1, 2, 3, or 4.

5. The polymer according to claim 4, wherein the ratio of the first repeating unit to the third repeating unit is 100:1 to 100:

50.

6. The polymer according to claim 1, Photoacid generator, A positive-type photoresist composition comprising, A positive-type photoresist composition wherein the weight ratio of the photoacid generator to the polymer is 0.5:100 to 20:100.

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