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

Abstract

The present invention provides a polymer, a positive photoresist composition, and a method of forming a patterned photoresist layer. The polymer comprises a first repeating unit and a second repeating unit. The first repeating unit has a structure represented by Formula (I) and the second repeating unit has a structure represented by Formula (II), wherein R 1 , R 2 , R 3 , R 4 , Ar, n, and m are as defined in the specification.

Description

Technical Field

[0001] This invention relates to a polymer, a positive photoresist composition, and a method for forming a patterned photoresist layer. Background Technology

[0002] With the continuous advancement of integrated circuit processes and packaging technologies, printed circuit boards (PCBs) have been developing towards high-density wiring, thinness, high electrical characteristics, high dimensional stability, high resolution, and low cost. Furthermore, the requirements for layer addition technology with high aperture and high alignment accuracy are becoming increasingly stringent.

[0003] In printed circuit board (PCB) manufacturing, achieving high-density wiring and high resolution requires further reduction in the width or spacing of the formed photosensitive patterned photoresist layers (e.g., less than or equal to 10 μm). Furthermore, low photoresist layer manufacturing costs (e.g., using a weakly alkaline developer (1% sodium carbonate aqueous solution)) are also important. Therefore, photosensitive photoresist materials that can be exposed to near-ultraviolet light, can be developed with a weakly alkaline developer, offer high resolution, and are inexpensive are highly desirable.

[0004] While liquid photoresist compositions can form photosensitive photoresist patterns with good resolution, the process of forming such patterns becomes more complex as the substrate size increases. Furthermore, liquid photoresist compositions are difficult to apply in printed circuit board processes because they cannot be dissolved in weak alkalis (e.g., a 1% sodium carbonate aqueous solution).

[0005] The industry still needs a high-performance photoresist composition suitable for use in high-resolution printed circuit board processes. Summary of the Invention

[0006] This invention provides a polymer. According to an embodiment of the invention, the polymer comprises a first repeating unit and a second repeating unit. The first repeating unit has the structure shown in formula (I) and the second repeating unit has the structure shown in formula (II).

[0007] ,

[0008] Where R 1 R 2 and R 3 Independently hydrogen or C1-C4 alkyl; R 4Ar is a C4-C10 branched 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, wherein m hydrogens on Ar are replaced by hydroxyl groups; n is 0, 1, 2, 3, or 4; and m is 1, 2, or 3.

[0009] This invention provides a positive photoresist composition for forming a patterned photoresist layer. According to embodiments of the invention, the positive photoresist composition comprises the polymer described herein and a photoacid generator.

[0010] This invention provides a method for forming a patterned photoresist layer. According to an embodiment of the invention, the method includes the following steps: exposing a positive photoresist layer, wherein the positive photoresist layer is obtained by drying the positive photoresist composition described in this invention; and developing the exposed positive photoresist layer using a developer to obtain the patterned photoresist layer described in this invention. Attached Figure Description

[0011] Figure 1 A flowchart illustrating the steps of a method 10 for forming a patterned photoresist layer according to an embodiment of the present invention.

[0012] In the attached figures, the following labels are used:

[0013] 10. Methods for forming patterned photoresist layers; and

[0014] Steps 12 and 14. Detailed Implementation

[0015] The following provides a detailed description of the polymer, positive photoresist composition, and the formation of a patterned photoresist layer according to the present invention. It should be understood that the following description provides many different embodiments for implementing different variations of the invention. The specific components and arrangements described below are merely illustrative of the invention. Of course, these are only examples and not limitations of the invention. In this invention, the term "about" means an amount that can be increased or decreased by a size that is generally and reasonably understood by those skilled in the art.

[0016] The use of ordinal numbers such as "first," "second," "third," etc., in the specification and claims to modify the components of the claims does not imply or represent any prior ordinal number of the claimed component, nor does it represent the order of one claimed component with another, or the order of manufacturing methods. The use of these ordinal numbers is only to enable a claimed component with a certain name to be clearly distinguished from another claimed component with the same name.

[0017] The specific embodiments described are merely to illustrate particular ways in which the invention is used and are not intended to limit the invention. Unless otherwise defined, all terms used in this invention (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary knowledge in the art to which this invention pertains. It will be further understood that terms defined in common dictionaries should be interpreted as having the same meaning as they have in the relevant art and in the content of this invention, and that, unless explicitly defined herein, they will not be interpreted in an idealized or overly formal sense.

[0018] This invention provides a polymer, a positive photoresist composition comprising the polymer, and a method for forming a patterned photoresist layer. Because the polymer of this invention is alkali-soluble (e.g., soluble in an aqueous solution of sodium carbonate (Na₂CO₃), it can be applied to positive photoresist compositions for preparing high-resolution photosensitive positive dry film materials (e.g., forming patterns with a linewidth ≤ 10 μm). Since the positive photoresist composition of this invention and the dry film prepared using it have good photosensitivity and light transmittance, high-definition and high-precision wiring patterns can be achieved. Furthermore, the good adhesion to the substrate during pattern formation and good peelability from the substrate after pattern formation simplifies the wiring pattern formation process. Moreover, compared to conventional photosensitive phenolic resin compositions, the positive photoresist composition comprising the polymer of this invention can be developed in an aqueous solution of sodium carbonate (Na₂CO₃), making it highly suitable for use in printed circuit board (e.g., high-resolution printed circuit board) processes.

[0019] According to an embodiment of the present invention, the polymer may comprise a first repeating unit and a second repeating unit, wherein the first repeating unit has the structure shown in formula (I), and the second repeating unit has the structure shown in formula (II).

[0020] ,

[0021] Where R 1 R 2 and R 3 Independently hydrogen or C1-C4 alkyl; R 4Ar is a C4-C10 branched 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, wherein m hydrogens on Ar are replaced by hydroxyl groups; n is 0, 1, 2, 3, or 4; and m is 1, 2, or 3. According to embodiments of the present invention, R... 4 It is formed by the bonding of tertiary carbon atoms with oxygen.

[0022] According to embodiments of the present invention, the C1-C4 alkyl group can be a straight-chain or branched alkyl group. For example, the C1-C4 alkyl group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl. According to embodiments of the present invention, the C4-C10 branched 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 C4-C10 branched alkyl group can be tert-butyl, tert-pentyl, or tert-hexyl.

[0023] According to embodiments of the present invention, the C5-C10 cycloalkyl group can be a monocycloalkyl group or a polycycloalkyl group (e.g., a bicycloalkyl group or a tricycloalkyl group). The polycycloalkyl group can be a fused ring, a bridged ring, or a spiro ring system. For example, the C5-C10 cycloalkyl group can be cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantanly group, or norbornenyl group. According to embodiments of the present invention, a substituted C5-C10 cycloalkyl group refers to a C5-C10 cycloalkyl group in which at least one hydrogen atom on a carbon is replaced by a C1-C4 alkyl group or a hydroxyl group.

[0024] According to embodiments of the present invention, the polymer may comprise at least one of the first repeating units and at least one of the second repeating units. In other words, the polymer may comprise at least one repeating unit having the structure shown in formula (I) and at least one repeating unit having the structure shown in formula (II).

[0025] According to an embodiment of the present invention, the first repeating unit may be Where R 1 R 2 The definitions of , n, and m are the same as above.

[0026] According to an embodiment of the present invention, the first repeating unit may be

[0027]

[0028] According to an embodiment of the present invention, the second repeating unit may be:

[0029] Where R 3 It is hydrogen or C1-C4 alkyl; R 5 It is a C1-C4 alkyl group; and R 6 It can be independently hydrogen, C1-C4 alkyl (alkyl group), or hydroxyl (hydroxyl group). For example, the second repeating unit could be...

[0030]

[0031] According to embodiments of the present invention, the polymer may be composed of the first repeating unit and the second repeating unit. According to embodiments of the present invention, the polymer does not contain any other repeating units besides the first repeating unit and the second repeating unit.

[0032] According to an embodiment of the present invention, the first repeating unit and the second repeating unit may be repeated in a random manner or in a segmented manner.

[0033] According to embodiments of the present invention, the ratio of the number of the first repeating units to the number of the second repeating units in the polymer of the present invention can be from 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. In this way, the positive photoresist composition containing the polymer of the present invention can be developed using a weakly alkaline developer (e.g., an aqueous solution of sodium carbonate) after exposure, resulting in a pattern with excellent resolution.

[0034] According to an embodiment of the present invention, the polymer further comprises a third repeating unit, wherein the third repeating unit has the structure shown in formula (III).

[0035] ,

[0036] Where R 7 It is hydrogen or C1-C4 alkyl; A 2 For single key, or R 8 The alkyl group is a C6-C12 aromatic group or a substituted C6-C12 aromatic group; and i is 0, 1, 2, 3, or 4. According to embodiments of the present invention, a substituted C6-C12 aromatic group means that at least one hydrogen atom on a C6-C12 aromatic group is replaced by a C1-C4 alkyl group.

[0037] According to an embodiment of the present invention, the third repeating unit may be: Where R 7 It is hydrogen or C1-C4 alkyl.

[0038] According to an embodiment of the present invention, the third repeating unit may be:

[0039] According to embodiments of the present invention, the ratio of the number of the first repeating units to the number of the third repeating units in the polymer of the present invention can be from 100:1 to 100:50, for example 100:2, 100:3, 100:5, 100:10, 100:20, 100:30, or 100:40. In this way, the positive photoresist composition containing the polymer of the present invention can be developed using a weakly alkaline developer (e.g., an aqueous solution of sodium carbonate) after exposure.

[0040] According to embodiments of the present invention, the polymer may be composed of the first repeating unit and the second repeating unit. According to embodiments of the present invention, the polymer does not contain any other repeating units besides the first repeating unit and the second repeating unit.

[0041] According to embodiments of the present invention, if the polymer of the present invention further comprises other repeating units in addition to the first repeating unit, the second repeating unit, and the third repeating unit, the ratio of the total number of the first repeating unit, the second repeating unit, and the third repeating unit to the total number of all repeating units is 90:100 to 99.9:100.

[0042] According to embodiments of the present invention, the weight average molecular weight of the polymer can be from 14,000 g / mol to 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 polymer described in this invention can be measured by gel permeation chromatography (GPC) (using polystyrene as a standard to create a calibration curve). When the molecular weight of the polymer is too low, the pattern formed by the positive photoresist composition containing the polymer described in this invention has a narrow width (e.g., less than or equal to 10 μm) and poor adhesion, resulting in the inability to form a high-resolution pattern layer. When the molecular weight of the polymer is too high, the positive photoresist composition containing the polymer described in this invention is less soluble in a weakly alkaline developer after exposure.

[0043] The polymer of this invention can be obtained by polymerization of a first monomer and a second monomer. In the polymer of this invention, the first repeating unit is derived from the first monomer, and the second repeating unit is derived from the second monomer.

[0044] According to an embodiment of the present invention, the first monomer may be The second monomer can be Where R 1 R 2 R 3 R 4 The definitions of Ar, n, and m are the same as those above.

[0045] According to an embodiment of the present invention, the first monomer may be Where R 1 R 2 The definitions of , n, and m are the same as above.

[0046] According to embodiments of the present invention, when the polymer of the present invention is prepared by polymerization of the first monomer and the second monomer, the molar ratio of the first monomer to the second monomer can be from 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.

[0047] The polymer of the present invention can be obtained by polymerization of the first monomer, the second monomer, and a third monomer. In the polymer of the present invention, 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.

[0048] According to an embodiment of the present invention, the third monomer may be For example, the third monomer could be Where R 7 It is hydrogen or C1-C4 alkyl.

[0049] According to embodiments of the present invention, when the polymer of the present invention is prepared by polymerization of the first monomer, the second monomer, and a third monomer, the molar ratio of the first monomer to the third monomer can be from 100:1 to 100:50, for example 100:2, 100:3, 100:5, 100:10, 100:20, 100:30, or 100:40.

[0050] The preparation method of the polymer described in this invention is not particularly limited. For example, a first monomer and a second monomer can be mixed (or a third monomer can be further added), and a copolymerization reaction can be carried out in the presence of a chain transfer agent and / or catalyst (the reaction temperature can be from 50°C to 150°C, and the reaction time can be from 1 hour to 12 hours). According to embodiments of the present invention, the molecular weight of the polymer described in this invention can be controlled by adjusting the amount of chain transfer agent and / or catalyst added, the reaction temperature, and the reaction time. According to embodiments of the present invention, 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 resulting oligomers are then mixed with other monomers or oligomers and copolymerized in the presence of a chain transfer agent and / or catalyst. According to embodiments of the present invention, the chain transfer agent and catalyst are not particularly limited and can be any chain transfer agent and catalyst used in conventional copolymerization reactions.

[0051] According to embodiments of the present invention, a positive photoresist composition is also provided. This positive photoresist composition may comprise the polymer described in this invention, and a photoacid generator.

[0052] According to embodiments of the present invention, the positive photoresist composition of the present invention has high photosensitivity and high light transmittance. Therefore, the dry film prepared using the positive photoresist composition of the present invention can achieve high-definition and high-precision wiring patterns.

[0053] According to embodiments of the present invention, the weight ratio of the photoacid generator to the polymer can be from 0.5:100 to 20:100, for example 8:100, 10:100, 15:100, or 20:100.

[0054] According to embodiments of the present invention, the photoacid generator may be an onium salt, a triarylsulfonium salt, an alkylarylsulfonium salt, a diaryliodonium salt, a diarylchloronium salt, a diarylbromonium salt, a sulfonate salt, a sulfonate ester, a fluorosulfonate ester, a diazonium salt, a diazonaphthoquinone sulfonate, or a combination thereof.

[0055] According to an embodiment of the present invention, in the positive photoresist composition of the present invention, the polymer of the present invention and the photoacid generator can be uniformly dissolved in an organic solvent.

[0056] According to embodiments of the present invention, 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, ethylacetate, butyl acetate, pentyl acetate, or methylisobutyl ketone. Cyclohexylbenzene, cyclohexanone, cyclopentanone (CPN), triethylene glycol dimethyl ether, 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.

[0057] According to embodiments of the present invention, to achieve suitable properties in the positive photoresist composition or the dry film formed therefrom, an additive may be added as needed, such as an inhibitor, leveling agent, colorant, adhesion promoter, thixotropic agent, sensitizer, filler, etc. According to embodiments of the present invention, the amount of the additive may be from 0.1 wt% to 30 wt%, based on the total weight of the polymer and the photoacid generating agent.

[0058] According to embodiments of the present invention, when the positive photoresist composition of the present invention contains an organic solvent, the solid content of the positive photoresist composition may be from about 10% to 50% (e.g., 15%, 20%, 25%, 30%, 35%, 40%, or 45%). This solid content refers to the weight percentage of all components of the composition other than the organic solvent, based on the total weight of the composition.

[0059] This invention also provides a method for forming a patterned photoresist layer. Please refer to... Figure 1 The method 10 for forming a patterned photoresist layer according to the present invention includes the following steps: An exposure process (step 12) is performed on a positive photoresist layer, wherein the positive photoresist layer is obtained by drying the positive photoresist composition according to the present invention. Next, a development process (step 14) is performed on the exposed positive photoresist layer with a developer to obtain the patterned photoresist layer according to the present invention.

[0060] According to an embodiment of the present invention, the light source for this exposure process can be ultraviolet (UV) light (wavelength can be 150nm to 450nm), and the exposure dose can be 10mJ / cm². 2 Up to 500mJ / cm 2 (e.g., 20mJ / cm) 2 50mJ / cm 2 70mJ / cm 2 100mJ / cm 2 120mJ / cm 2 150mJ / cm 2 200mJ / cm 2 250mJ / cm 2 300mJ / cm 2 350mJ / cm 2 400mJ / cm 2 or 450mJ / cm 2 ).

[0061] According to embodiments of the present invention, the developer may be an aqueous solution of an alkali metal salt, such as an aqueous solution of sodium carbonate or potassium carbonate. According to embodiments of the present invention, the content of the alkali metal salt in the aqueous solution may be from 0.1 wt% to 5 wt%, based on the total weight of the aqueous solution.

[0062] According to an embodiment of the present invention, the positive photoresist layer can be a dry film obtained by coating and drying the positive photoresist composition described in the present invention.

[0063] According to embodiments of the present invention, the preparation method and usage of the positive dry film photoresist of the present invention may include the following steps. First, a solution of the positive photoresist composition is coated onto a carrier film, and after drying, a protective film is attached to the dried photoresist composition to form a positive dry film photoresist. During transfer printing, the protective film is peeled off, and the dried photoresist composition is attached to a substrate using a transfer process. Then, the carrier film is peeled off to perform the exposure and development processes.

[0064] The coating method of the above-mentioned positive photoresist composition is not limited, and can be screen printing, spin coating, bar coating, blade coating, roller coating, dip coating, spray coating, or brush coating.

[0065] According to embodiments of the present invention, the carrier film and protective film may be polyethylene terephthalate (PET) film, polyethylene (PE) film, or stretched polypropylene (OPP) film. According to embodiments of the present invention, the substrate may be a wafer or a copper foil substrate.

[0066] To make the above-mentioned and other objects, features and advantages of the present invention more apparent and understandable, preferred embodiments are described below in detail with reference to the accompanying drawings.

[0067] Preparation of monomers

[0068] Preparation Example 1

[0069] Glycidyl methacrylate (GMA) (375 g), 4-hydroxybenzoic acid (367.5 g), triphenylphosphine (1.88 g) as a catalyst, and hydroquinone (1.05 g) as an inhibitor were added to a solvent (1,2-propanediol methyl ether acetate, PGMEA) (320 g) to obtain a mixture. The mixture was stirred at 100 °C for 4 hours. After purification, monomer (I) (structure: [structure not provided]) was obtained.

[0070]

[0071] Polymer preparation

[0072] Preparation Examples 2-8

[0073] Monomer (I), styrene, tert-butyl acrylate, catalyst (azobisisobutyronitrile, 2,2'-azobis(2-methylpropionitrile), AIBN), chain transfer agent (dodecanethiol), and solvent (1,2-propanediol methyl ether acetate (PGMEA)) were mixed in the proportions described in Table 1. The resulting mixture was heated and stirred (reaction temperature and time are shown in Table 1) to obtain polymers (1)-(7). The weight-average molecular weight (Mw) of polymers (1)-(7) was determined by gel permeation chromatography (GPC), and the results are shown in Table 1.

[0074] Table 1

[0075]

[0076]

[0077] Preparation Examples 9 to 13

[0078] Monomer (I), tert-butyl acrylate, catalyst (azobis(2,2'-azobis(2-methylpropionitrile)), AIBN), chain transfer agent (dodecanethiol), and solvent (1,2-propanediol methyl ether acetate (PGMEA)) were mixed in the proportions described in Table 2. The resulting mixture was heated and stirred (reaction temperature and time are shown in Table 2) to obtain polymers (8) to (12). The weight-average molecular weight (Mw) of polymers (8) to (12) was determined by gel permeation chromatography (GPC), and 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 alkaline dissolution rate was evaluated as follows: the polymer was dissolved in 1,2-propanediol methyl ether acetate (PGMEA) to form a coating (10 μm thick). After drying for 3 minutes, the coating was baked at 110°C for 5 minutes and then at 150°C for 10 minutes to obtain a film. Next, the film thickness was measured (thickness T1). Then, the film was immersed in a 1% sodium carbonate (Na₂CO₃) aqueous solution for 60 seconds. After removal and drying, the film thickness was measured again (thickness T2). Finally, the alkali solubility rate was calculated from the obtained T1 and T2 values.

[0079] Table 2

[0080]

[0081]

[0082] As shown in Table 2, the alkali solubility rate of polymer (12) is too high, which makes it very easy to dissolve in the developer solution. Therefore, no further photoresist formulation verification was performed.

[0083] Preparation Example 14

[0084] Monomer (I), 1-ethylcyclohexyl methacrylate, catalyst (azobis(2,2'-azobis(2-methylpropionitrile)), AIBN), chain transfer agent (dodecanethiol), and solvent (1,2-propanediol methyl ether acetate (PGMEA)) were mixed in the proportions described in Table 3. The resulting mixture was heated and stirred (reaction temperature and time are shown in Table 3) to obtain polymer (13). The weight-average molecular weight (Mw) of polymer (13) was determined by gel permeation chromatography (GPC), and the results are shown in Table 3.

[0085] Preparation Examples 15-17

[0086] The monomer (I) and benzyl methacrylate (with the structure) were added. The following components were mixed in the proportions described in Table 3: tert-butyl acrylate, catalyst (azobisisobutyronitrile, 2,2'-azobis(2-methylpropionitrile), AIBN), chain transfer agent (dodecanethiol), and solvent (1,2-propanediol methyl ether acetate (PGMEA)). The resulting mixture was heated and stirred (reaction temperature and time are shown in Table 3) to obtain polymers (14) to (16). The weight-average molecular weight (Mw) of polymers (14) to (16) was determined by gel permeation chromatography (GPC), and the results are shown in Table 3.

[0087] Preparation Example 18

[0088] Monomer (I), styrene, 1-ethylcyclohexylmethacrylate, catalyst (azobis(2,2'-azobis(2-methylpropionitrile)), AIBN), chain transfer agent (dodecanethiol), and solvent (1,2-propanediol methyl ether acetate (PGMEA)) were mixed in the proportions described in Table 3. The resulting mixture was heated and stirred (reaction temperature and time are shown in Table 3) to obtain polymer (17). The weight-average molecular weight (Mw) of polymer (17) was determined by gel permeation chromatography (GPC), and the results are shown in Table 3.

[0089] Table 3

[0090]

[0091]

[0092] Preparation of positive photoresist compositions

[0093] Examples 1-2 and Comparative Examples 1-6

[0094] Polymers (1) to (7) were mixed with photoacid generator (1,1,2,2,3,3,4,4,4-nonafluoro-,1,3-dioxo-1H-benz[de]isoquinolin-2(3H)-yl ester), inhibitor (trioctylamine), and solvent (1,2-propanediol methyl ether acetate, PGMEA) in the amounts described in Table 4. After uniform mixing, positive photoresist compositions (1) to (8) were obtained.

[0095] Table 4

[0096]

[0097] Examples 3-9 and Comparative Example 7

[0098] Polymers (8) to (11) were mixed with photoacid generator (1,1,2,2,3,3,4,4,4-nonafluoro-,1,3-dioxo-1H-benz[de]isoquinolin-2(3H)-yl ester), inhibitor (trioctylamine), and solvent (1,2-propanediol methyl ether acetate, PGMEA) in the amounts described in Table 5. After uniform mixing, positive photoresist compositions (9) to (16) were obtained.

[0099] Table 5

[0100]

[0101] Examples 10-17 and Comparative Example 8

[0102] Polymers (13) to (17), phenolic resin (weight average molecular weight about 11,000) (purchased from Sigma-Aldrich), photoacid generator (1,1,2,2,3,3,4,4,4-nonafluoro-,1,3-dioxo-1H-benz[de]isoquinolin-2(3H)-yl ester, inhibitor (trioctylamine), and solvent (1,2-propanediol methyl ether acetate, PGMEA) were mixed in the amounts described in Table 6. After uniform mixing, positive photoresist compositions (17) to (25) were obtained.

[0103] Table 6

[0104]

[0105]

[0106] Preparation of dry film photoresist layer

[0107] Positive photoresist compositions (1)-(25) were coated onto a polyethylene terephthalate (PET) carrier film using a doctor blade coating method. After drying at 80°C to remove the solvent, dry film photoresist layers (1)-(25) (with a thickness of approximately 6 μm) were obtained. Next, a polyethylene terephthalate (PET) protective film was laminated onto the dry film photoresist layers.

[0108] Transfer test

[0109] The dry film photoresist layer, mounted on the carrier film, was cut into 7cm x 7cm pieces. After removing the protective film, the sample was attached to a 10cm x 10cm wafer, and pressure (approximately 2.5kg / cm²) was applied using rollers. 2 The dry film is transferred onto the wafer using a roller at a temperature of 95°C and a rotation speed of 0.2 m / min. After removing the carrier film, if some films are completely transferred onto the wafer (without any residue on the carrier film), it is recorded as O; if some films are not completely transferred onto the wafer (with residue on the carrier film), it is recorded as X. The results are shown in Table 7.

[0110] Resolution test

[0111] The dry film photoresist layers (1)-(25) that have undergone transfer testing were exposed to full-band ultraviolet light (the line width and line spacing of the pattern are 2 μm). Then, the dry film was developed with sodium carbonate aqueous solution. The exposure amount, development time, and sodium carbonate aqueous solution concentration are shown in Table 7. If the exposed and developed dry film can produce a pattern with a line width and line spacing of 2 μm, it is recorded as O; otherwise, it is recorded as X. The results are shown in Table 7.

[0112] Table 7

[0113]

[0114]

[0115]

[0116] As shown in Table 7, compared with conventional photosensitive phenolic resin compositions, the positive photoresist compositions (Examples 1-17) containing the polymers described in this invention can be developed in an aqueous sodium carbonate solution, making them highly suitable for use in printed circuit board processes. Furthermore, when the polymer having the specific repeating unit described in this invention has a weight-average molecular weight of less than 14,000 g / mol, the resulting positive photoresist compositions, after exposure and development, cannot form pattern layers with a resolution less than 10 μm due to poor pattern adhesion (i.e., this positive photoresist composition is not suitable for forming low-resolution pattern layers). Moreover, compared with conventional photosensitive phenolic resin compositions, the positive photoresist compositions containing the polymers described in this invention can be developed in an aqueous sodium carbonate solution, making them highly suitable for use in printed circuit board processes.

[0117] Based on the above, since the polymer described in this invention has alkali-soluble properties, it can be applied to positive photoresist compositions for preparing high-resolution photosensitive positive dry film materials. Because the positive photoresist composition of this invention and the dry film prepared using it have good photosensitivity and light transmittance, high-definition and high-precision wiring patterns can be achieved. Furthermore, due to the good adhesion to the substrate during pattern formation and the good peelability from the substrate after pattern formation, the wiring pattern formation process is simplified.

[0118] Although the present invention has been disclosed above with reference to several embodiments, it is not intended to limit the present invention. Anyone with common knowledge in the art can make any modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the scope defined in the appended claims.

Claims

1. A polymer comprising a first repeating unit and a second repeating unit, wherein the first repeating unit has the structure shown in formula (I), and the second repeating unit has the structure shown in formula (II). , Where R 1 R 2 and R 3 Independently hydrogen or C1-C4 alkyl; R 4 It is a C4-C10 branched alkyl, C5-C10 cycloalkyl, or substituted C5-C10 cycloalkyl; Ar is a C6-C12 aromatic or C7-C18 alkylaryl, where m hydrogens on Ar are replaced by hydroxyl groups; n is 0, 1, 2, 3, or 4; and m is 1, 2, or 3.

2. The polymer of claim 1, wherein the first repeating unit and the second repeating unit are repeated in a random or block manner.

3. 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.

4. The polymer according to claim 1, wherein the first repeating unit is R 1 and R 2 Independently, it is hydrogen or C1-C4 alkyl; n is 0, 1, 2, 3, or 4; and m is 1, 2, or 3.

5. The polymer according to claim 1, wherein the second repeating unit is Where R 3 It is hydrogen or C1-C4 alkyl; R 5 It is a C1-C4 alkyl group; and R 6 It can be hydrogen, C1-C4 alkyl, or hydroxyl.

6. The polymer according to claim 1, wherein the polymer further comprises a third repeating unit, wherein the third repeating unit has the structure shown in formula (III). ， Where R 7 It is hydrogen or C1-C4 alkyl; A 2 For single key, or R 8 It is a C6-C12 aromatic group or a substituted C6-C12 aromatic group; and i is 0, 1, 2, 3, or 4.

7. The polymer according to claim 6, wherein the ratio of the first repeating unit to the third repeating unit is 100:1 to 100:

50.

8. The polymer according to claim 6, wherein the third repeating unit is Where R 7 It is hydrogen or C1-C4 alkyl.

9. The polymer according to claim 6, wherein the third repeating unit is Where R 7 It is hydrogen or C1-C4 alkyl.

10. The polymer of claim 1, wherein the polymer has a weight average molecular weight of 14,000 g / mol to 100,000 g / mol.

11. A positive photoresist composition comprising: The polymer according to any one of claims 1 to 10; and Alumina generator.

12. The positive photoresist composition according to claim 11, wherein the weight ratio of the photoacid generator to the polymer is from 0.5:100 to 20:

100.

13. The positive photoresist composition according to claim 11, wherein the photoacid generator is an onium salt, a triarylsulfonium salt, an alkylarylsulfonium salt, a diarylsulfonium salt, a diaryl chloride salt, a diaryl bromide salt, a sulfonate, a sulfonate ester, a fluorosulfonate ester, a diazonium salt, a diazonium naphthoquinone sulfonate, or a combination thereof.

14. A method for forming a patterned photoresist layer, comprising the following steps: An exposure process is performed on a positive photoresist layer, wherein the positive photoresist layer is obtained by drying the positive photoresist composition of claim 11; and A patterned photoresist layer is obtained by developing an exposed positive photoresist layer using a developer.

15. The method for forming a patterned photoresist layer according to claim 14, wherein the developer is an aqueous solution of an alkali metal salt, wherein the content of the alkali metal salt in the aqueous solution of the alkali metal salt can be from 0.1 wt% to 5 wt%, based on the total weight of the aqueous solution of the alkali metal salt.

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