Photosensitive resin composition, and dry film photoresist, photosensitive element, circuit board, and display device using the same

Abstract

To provide a photosensitive resin composition capable of reducing undercut in pattern plating, achieving a pattern of high resolution, achieving improved plating resistance, and achieving excellent 1:1 resolution of 25 μ m or less.SOLUTION: There are provided a photosensitive resin composition, and a dry film photoresist, a photosensitive element, a circuit board, and a display device, each using the same, wherein the photosensitive resin composition uses an alkali developable binder resin comprising a repeating unit represented by a specific formula 1, a repeating unit represented by a specific formula 2, a repeating unit represented by a specific formula 3, and a repeating unit represented by a specific formula 4.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition and a dry film photoresist, a photosensitive element, a circuit board, and a display device using the same. [Background technology]

[0002] Photosensitive resin compositions are used in the form of dry film photoresist (DFR), liquid photoresist ink, etc., which are used in printed circuit boards (PCBs) and lead frames. Currently, dry film photoresists are widely used not only in the manufacture of printed circuit boards (PCBs) and lead frames, but also in the manufacture of rib barriers for plasma display panels (PDPs), ITO electrodes, bus address electrodes, and black matrices for other displays.

[0003] Generally, such dry film photoresists are often used for lamination on copper clad laminates. In the manufacturing process of a printed circuit board (PCB), a pre-treatment process is first carried out to laminate the copper clad laminate, which is the original material of the PCB. The pre-treatment process includes drilling, deburring, and surface preparation in the outer layer process, and surface preparation or pickling in the inner layer process. Bristle brush and jet pumice processes are mainly used in the surface preparation process, and pickling can involve soft etching and pickling with 5wt% sulfuric acid. To form a circuit on the copper-clad laminate that has been subjected to the pretreatment process, a dry film photoresist (hereinafter referred to as DFR) is generally laminated onto the copper layer of the copper-clad laminate. In this process, a laminator is used to laminate the photoresist layer of the DFR onto the copper surface while peeling off the protective film of the DFR. Generally, lamination is performed at a speed of 0.5 to 3.5 m / min, at a temperature of 100 to 130°C, and with a heating roll pressure of 10 to 90 psi. After the lamination process, the printed circuit board is left to stand for 15 minutes or more to stabilize the board, and then the photoresist of the DFR is exposed to light using a photomask with the desired circuit pattern formed on it. During this process, when the photomask is irradiated with UV light, the photoresist irradiated with UV light starts to polymerize in the irradiated areas due to the photoinitiator contained therein. First, the oxygen in the photoresist is consumed initially, then the activated monomer is polymerized and a crosslinking reaction occurs, and then the polymerization reaction continues as a large amount of monomer is consumed. Meanwhile, the unexposed areas remain in a state where no crosslinking reaction has occurred. Next, a development process is carried out to remove the unexposed parts of the photoresist, and in the case of alkaline-developable DFR, an aqueous solution of 0.8 to 1.2 wt% potassium carbonate and sodium carbonate is used as the developer. In this process, the unexposed parts of the photoresist are washed away in the developer due to a saponification reaction between the carboxylic acid of the binder polymer and the developer, and the hardened photoresist remains on the copper surface.

[0004] Next, circuits are formed through different processes depending on whether they are inner or outer layer processes. In the inner layer process, a circuit is formed on the board through etching and stripping processes, while in the outer layer process, a predetermined circuit is formed through plating and tenting processes, followed by etching and solder stripping. On the other hand, during the plating process, if the plating resistance of the dry film is insufficient, there is a limit to the occurrence of bubbles or the lifting or flowing of the hardened photoresist due to high pH. In particular, it is common for the lifting or flowing of the hardened photoresist to occur due to bubbles generated during nickel plating in the ENIG plating process. Therefore, there is an increased need for dry films with improved plating resistance. Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a photosensitive resin composition that can reduce undercutting during pattern plating and realize a high-resolution pattern. The present invention also provides a photosensitive resin composition that can realize improved plating resistance and excellent 1:1 resolution of 25 μm or less. The present invention also provides a dry film photoresist, a photosensitive element, a circuit board, and a display device using the photosensitive resin composition. [Means for solving the problem]

[0006] In order to achieve the above object, the present invention provides a photosensitive resin composition comprising an alkali-developable binder resin including a repeating unit represented by the following chemical formula 1, a repeating unit represented by the following chemical formula 2, a repeating unit represented by the following chemical formula 3, and a repeating unit represented by the following chemical formula 4, a photopolymerization initiator, and a photopolymerizable compound, and which satisfies either one of the following (a) or (b): (a) in a resist pattern obtained by exposing and developing a photosensitive resin layer containing a photosensitive resin composition, the maximum foot length of resist residue remaining on the bottom surface of a space between adjacent photosensitive resin layer lines is 1 μm or less; (b) when a film sample having a photosensitive resin layer containing the photosensitive resin composition laminated on a substrate is nickel-plated for 20 minutes or more using an aqueous solution containing nickel, the adhesion defined by the following formula 1 is 90% or more, [Formula 1] Adhesion (%) = (surface area of ​​the photosensitive resin layer containing the photosensitive resin composition in contact with the substrate after nickel plating / surface area of ​​the photosensitive resin layer containing the photosensitive resin composition in contact with the substrate before nickel plating) * 100 [ka] In the above Chemical Formula 1, R1 is hydrogen or an alkyl having 1 to 10 carbon atoms, R2 is an alkyl having 1 to 10 carbon atoms, Ar is an aryl having 6 to 20 carbon atoms, and n is an integer of 1 to 20; [ka] In the above formula 2, R3 is hydrogen or alkyl having 1 to 10 carbon atoms; [ka] In the above formula 3, R4 is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R5 is an alkyl group having 1 to 10 carbon atoms; [ka] In the above Chemical Formula 4, Ar is an aryl having 6 to 20 carbon atoms. The present invention also provides a dry film photoresist comprising a photosensitive resin layer containing the photosensitive resin composition.

[0007] The present invention also provides a photosensitive element comprising a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, and which satisfies either one of the following (a) or (b): (a) in a resist pattern obtained by exposing and developing the photosensitive resin layer, the maximum foot length of resist residue remaining on the bottom surface of a space between adjacent photosensitive resin layer lines is 1 μm or less; (b) when a film sample having the photosensitive resin layer laminated on a substrate is nickel-plated for 20 minutes or more in an aqueous solution containing nickel, the adhesion defined by the following formula 3 is 90% or more, [Formula 3] Adhesion (%) = (surface area of ​​the photosensitive resin layer of the photosensitive element in contact with the substrate after nickel plating / surface area of ​​the photosensitive resin layer of the photosensitive element in contact with the substrate before nickel plating) * 100 The present invention also provides a circuit board and a display device comprising a photosensitive resin layer containing the photosensitive resin composition. Hereinafter, a photosensitive resin composition according to a specific embodiment of the invention and a dry film photoresist, a photosensitive element, a circuit board, and a display device using the same will be described in more detail.

[0008] Unless otherwise expressly stated herein, the terminology used is for the purpose of referring to particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms include the plural forms unless the phrase clearly dictates to the contrary. As used herein, the meaning of "comprising" is to embody certain properties, regions, integers, steps, operations, elements, components and / or components, and does not exclude the presence or addition of other certain properties, regions, integers, steps, operations, elements, components and / or groups. In this specification, terms including ordinal numbers such as "first" or "second" are used for the purpose of distinguishing one component from another component, and are not limited by the terms. For example, a first component may be named as a second component, and similarly, a second component may be named as a first component, without departing from the scope of the present invention.

[0009] In this specification, examples of the substituents are described below, but are not limited to these. As used herein, the term "substituted" means that another functional group is bonded in place of a hydrogen atom in a compound, and the position of the substitution is not limited as long as it is a position at which a hydrogen atom is substituted, i.e., a position at which a substituent can be substituted, and when two or more substituents are substituted, the two or more substituents may be the same or different from each other. The term "substituted or unsubstituted" as used herein means that the group is substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, halogen, cyano, nitro, hydroxy, carbonyl, ester, imide, amide, primary amino, carboxy, sulfonic acid, sulfonamide, phosphine oxide, alkoxy, aryloxy, alkylthio, arylthio, alkylsulfoxy, arylsulfoxy, silyl, boron, alkyl, cycloalkyl, alkenyl, aryl, aralkyl, aralkenyl, alkylaryl, alkoxysilylalkyl, arylphosphine, or heterocyclic groups containing one or more of N, O, and S atoms, or that the group is substituted or unsubstituted with two or more of the above-listed substituents. For example, the "substituent with two or more substituents connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may also be interpreted as a substituent with two phenyl groups connected.

[0010] As used herein, TIFF0007607717000005.tif2119 or TIFF0007607717000006.tif1625 means a bond connected to another substituent, and a direct bond means that there is no other atom in the moiety represented by L. In this specification, (meth)acrylic means both acrylic and methacrylic. In this specification, an alkyl group is a monovalent functional group derived from an alkane, which may be linear or branched, and the number of carbon atoms in the linear alkyl group is not particularly limited, but is preferably 1 to 20. Also, the number of carbon atoms in the branched alkyl group is 3 to 20. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptan-4-yl, and the like. The alkyl group may be substituted or unsubstituted, and when substituted, examples of the substituents are as described above. In the present specification, the aryl group is a monovalent functional group derived from arene, and is preferably, but not limited to, a carbon number of 6 to 20, and may be a monocyclic aryl group or a polycyclic aryl group. The monocyclic aryl group may be, but is not limited to, a phenyl group, a biphenyl group, a terphenyl group, etc. The polycyclic aryl group may be, but is not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, etc. The aryl group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.

[0011] The present invention will now be described in more detail. 1. Photosensitive resin composition According to one embodiment of the invention, there may be provided a photosensitive resin composition comprising an alkali-developable binder resin including a repeating unit represented by the following chemical formula 1, a repeating unit represented by the following chemical formula 2, a repeating unit represented by the following chemical formula 3, and a repeating unit represented by the following chemical formula 4, a photopolymerization initiator, and a photopolymerizable compound, and which satisfies either one of the following (a) or (b): (a) in a resist pattern obtained by exposing and developing a photosensitive resin layer containing a photosensitive resin composition, the maximum foot length of resist residue remaining on the bottom surface of a space between adjacent photosensitive resin layer lines is 1 μm or less; (b) when a film sample having a photosensitive resin layer containing the photosensitive resin composition laminated on a substrate is nickel-plated for 20 minutes or more using an aqueous solution containing nickel, the adhesion defined by the following formula 1 is 90% or more, [Formula 1] Adhesion (%) = (surface area of ​​the photosensitive resin layer containing the photosensitive resin composition in contact with the substrate after nickel plating / surface area of ​​the photosensitive resin layer containing the photosensitive resin composition in contact with the substrate before nickel plating) * 100 [ka] In the above Chemical Formula 1, R1 is hydrogen or an alkyl having 1 to 10 carbon atoms, R2 is an alkyl having 1 to 10 carbon atoms, Ar is an aryl having 6 to 20 carbon atoms, and n is an integer of 1 to 20; [ka] In the above formula 2, R3 is hydrogen or alkyl having 1 to 10 carbon atoms; [ka] In the above formula 3, R4 is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R5 is an alkyl group having 1 to 10 carbon atoms; [ka] In the above Chemical Formula 4, Ar is an aryl having 6 to 20 carbon atoms. The present inventors have experimentally confirmed that the photosensitive resin composition of the embodiment includes a repeating unit represented by Chemical Formula 1 in an alkali developable binder resin, and that when a pattern is formed by exposure and development of a dry film photoresist using the photosensitive resin composition, the length of resist residue on a lower surface of the pattern can be minimized, thereby realizing a high-resolution fine pattern, and have completed the invention.

[0012] In addition, the present inventors have experimentally confirmed that the photosensitive resin composition of the embodiment contains a repeating unit represented by Chemical Formula 1 in an alkali developable binder resin, thereby improving the plating resistance of the alkali developable binder resin, thereby minimizing the lifting phenomenon caused by hydrogen bubbles during nickel plating of a dry film photoresist using the photosensitive resin composition, and have completed the invention. (1) Alkaline-developable binder resin The alkali-developable binder resin of the present invention may contain a repeating unit represented by Chemical Formula 1 above, a repeating unit represented by Chemical Formula 2 above, a repeating unit represented by Chemical Formula 3 above, and a repeating unit represented by Chemical Formula 4 above. Specifically, the alkali-developable binder resin may include a random copolymer of a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 2, a repeating unit represented by Chemical Formula 3, and a repeating unit represented by Chemical Formula 4. The alkaline developable binder resin contains a repeating unit represented by Chemical Formula 1, thereby increasing the hydrophobicity of the alkaline developable binder resin. This can suppress foam generation during a development process of a dry film photoresist using the photosensitive resin composition, thereby exhibiting excellent developability and improving adhesion to a substrate, thereby ensuring appropriate physical properties (resolution, fine line adhesion, etc.).

[0013] In the above Chemical Formula 1, R1 is any one of hydrogen and alkyl having 1 to 10 carbon atoms, and a specific example of the alkyl having 1 to 10 carbon atoms is methyl. In the above Chemical Formula 1, R2 is an alkyl group having 1 to 10 carbon atoms, and a specific example of the alkyl group having 1 to 10 carbon atoms is ethyl. In the above Chemical Formula 1, Ar is an aryl having 6 to 20 carbon atoms, and a specific example of the aryl having 6 to 20 carbon atoms is phenyl. The repeating unit represented by Chemical Formula 1 may be a repeating unit derived from a monomer represented by Chemical Formula 1-1 below. [ka] In the above Chemical Formula 1-1, R1 is hydrogen or an alkyl having 1 to 10 carbon atoms, R2 is an alkyl having 1 to 10 carbon atoms, Ar is an aryl having 6 to 20 carbon atoms, and n is an integer of 1 to 20. In the above Chemical Formula 1-1, the details regarding R1, R2, Ar, and n are the same as those described above in the above Chemical Formula 1.

[0014] A specific example of the monomer represented by Chemical Formula 1-1 is phenoxypolyethyleneoxyacrylate, more specifically, 2-phenoxyethyl methacrylate (PHEMA). The repeating unit represented by Chemical Formula 1 may be contained in an amount of 5 mol % to 40 mol %, or 5 mol % to 30 mol %, or 5 mol % to 25 mol %, or 10 mol % to 25 mol %, based on 100 mol % of the total molar content of repeating units contained in the alkali developable binder resin. In the above Chemical Formulae 2 to 4, R3 and R4 are the same or different and each independently represents hydrogen or alkyl having 1 to 10 carbon atoms, R5 represents alkyl having 1 to 10 carbon atoms, and Ar represents aryl having 6 to 20 carbon atoms. In the above Chemical Formulae 2 to 4, R3 and R4 are the same or different and each independently represent any one of hydrogen and alkyl having 1 to 10 carbon atoms. A specific example of the alkyl having 1 to 10 carbon atoms is methyl. R5 is alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms include methyl.

[0015] Ar is an aryl having 6 to 20 carbon atoms, and specific examples of the aryl having 6 to 20 carbon atoms include phenyl. The repeating unit represented by Chemical Formula 2 may be a repeating unit derived from a monomer represented by Chemical Formula 2-1 below. [ka] In the formula 2-1, R3 is hydrogen or an alkyl having 1 to 10 carbon atoms. The details regarding R3 in the formula 2-1 are the same as those described above in the formula 2. A specific example of the monomer represented by the formula 2-1 is methacrylic acid (MAA). The repeating unit represented by the above formula 3 may be a repeating unit derived from a monomer represented by the following formula 3-1. [ka] In the formula 3-1, R4 is hydrogen or an alkyl having 1 to 10 carbon atoms, and R5 is an alkyl having 1 to 10 carbon atoms. In the formula 3-1, the details of R4 and R5 are the same as those described above in the formula 3. A specific example of the monomer represented by the formula 3-1 is methylmethacrylate (MMA). The repeating unit represented by the above formula 4 may be a repeating unit derived from a monomer represented by the following formula 4-1. [ka] In the above Chemical Formula 4-1, Ar is an aryl having 6 to 20 carbon atoms. The details regarding Ar in the above Chemical Formula 4-1 are as described above in the above Chemical Formula 4. A specific example of the monomer represented by the above Chemical Formula 4-1 is styrene (SM). The alkali-developable binder resin may contain 20 mol % or more and 60 mol % or less of the repeating units represented by Chemical Formula 2, or 20 mol % or more and 50 mol % or less, or 30 mol % or more and 40 mol % or less, based on 100 mol % of the total molar content of the repeating units contained in the alkali-developable binder resin.

[0016] In addition, the alkali-developable binder resin may contain from 1 mol % to 30 mol %, or from 5 mol % to 30 mol % of the repeating units represented by Chemical Formula 3, and from 30 mol % to 60 mol %, or from 30 mol % to 50 mol %, or from 30 mol % to 40 mol % of the repeating units represented by Chemical Formula 4, based on 100 mol % of the total molar content of the repeating units contained in the alkali-developable binder resin. More specifically, the molar ratio of the repeating unit represented by Chemical Formula 3 to 100 moles of the repeating unit represented by Chemical Formula 4 may be 10 moles or more and 99 moles or less, or 15 moles or more and 95 moles or less, or 20 moles or more and 95 moles or less. As described above, as the content of the hydrophobic repeating unit represented by Formula 4 increases, the degree of hydrophobicity of the alkali developable binder resin also increases, and thus foam generation can be suppressed during the development process of the dry film photoresist using the photosensitive resin composition. The alkali developable binder resin may have a weight average molecular weight of 30,000 g / mol to 150,000 g / mol and a glass transition temperature of 20° C. to 150° C. This improves the coatability and conformability of the dry film photoresist, and the mechanical strength of the resist itself after circuit formation. In the present specification, the weight average molecular weight means a weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a commonly known analyzer, a detector such as a refractive index detector, and an analytical column are used, and commonly used temperature conditions, solvents, and flow rates can be applied. As a specific example of the measurement conditions, the alkali developable binder resin was dissolved in tetrahydrofuran to a concentration of 1.0 (w / w)% in THF (about 0.5 (w / w)% based on solid content), filtered using a syringe filter with a 0.45 μm pore size, and 20 μl was injected into the GPC. Tetrahydrofuran (THF) was used as the GPC mobile phase and was flowed at a flow rate of 1.0 mL / min. The columns were one Agilent PLgel 5 μm Guard (7.5×50 mm) and two Agilent PLgel 5 μm Mixed D (7.5×300 mm) connected in series, and the detector was an Agilent 1260 Infinity II system with an RI Detector, and the measurement was performed at 40° C.

[0017] The weight average molecular weight (Mw) of the alkali developable binder resin was calculated using a calibration curve formed by dissolving polystyrene having various molecular weights as follows in tetrahydrofuran at a concentration of 0.1 (w / w)% and filtering the polystyrene standard samples (STD A, B, C, D) with a 0.45μm pore size syringe filter and injecting the samples into GPC. STD A(Mp):791, 000 / 27, 810 / 945 STD B(Mp):282, 000 / 10, 700 / 580 STD C(Mp):126, 000 / 4, 430 / 370 STD D(Mp):51, 200 / 1, 920 / 162 The glass transition temperature was measured by comparing the reference and the binder polymer using a Differential Scanning Calorimeter (DSC) (Perkin-Elmer, DSC-7). The temperature was set to 20°C for 15 minutes, and then increased to 200°C at a rate of 1°C / min. The alkali developable binder resin may have an acid value of 120 mgKOH / g to 200 mgKOH / g, or 140 mgKOH / g to 160 mgKOH / g. The acid value was measured by dissolving about 1 g of the alkali developable binder resin in 50 ml of a mixed solvent (MeOH 20%, Acetone 80%), adding 2 drops of 1%-phenolphthalein indicator, and titrating with 0.1 N-KOH. The alkali-developable binder resin is contained in an amount of 20% by weight to 80% by weight based on the total weight of the photosensitive resin composition on the basis of the solid content. When the content of the alkali-developable binder resin is within the above range, it is possible to obtain an effect of enhancing fine line adhesion after circuit formation. The solid content based on the weight refers to the remaining components excluding the solvent from the photosensitive resin composition.

[0018] The content of the alkali developable binder resin of the present invention may be 40% by weight or more and 70% by weight or less based on the total weight of the photosensitive resin composition. If the content of the alkali developable binder resin is less than 40% by weight based on the total weight of the photosensitive resin composition, there is a disadvantage that contamination of the developed end occurs, resulting in defects such as short circuits, and if it exceeds 70% by weight, there is a problem that circuit physical properties such as adhesion and resolution are poor. Meanwhile, the alkali developable binder resin may further include a first alkali developable binder resin including a repeating unit represented by the following chemical formula 13, a repeating unit represented by the following chemical formula 14, a repeating unit represented by the following chemical formula 15, a repeating unit represented by the following chemical formula 16, and a repeating unit represented by the following chemical formula 17; and a second alkali developable binder resin including a repeating unit represented by the following chemical formula 14, a repeating unit represented by the following chemical formula 15, and a repeating unit represented by the following chemical formula 16: [ka] In the above Chemical Formula 13, R3'' is hydrogen; [ka] In the above Chemical Formula 14, R3' is an alkyl having 1 to 10 carbon atoms; [ka] In the above Chemical Formula 15, R4'' is an alkyl having 1 to 10 carbon atoms, and R5'' is an alkyl having 1 to 10 carbon atoms. [ka] In the above Chemical Formula 16, Ar is an aryl having 6 to 20 carbon atoms; [ka] In the above Chemical Formula 17, R4' is hydrogen; R5' is an alkyl group having 1 to 10 carbon atoms. Specifically, the first alkali-developable binder resin may include a random copolymer of the repeating unit represented by Chemical Formula 13, the repeating unit represented by Chemical Formula 14, the repeating unit represented by Chemical Formula 15, the repeating unit represented by Chemical Formula 16, and the repeating unit represented by Chemical Formula 17.

[0019] In the above Chemical Formulae 13 to 17, specific examples of the alkyl having 1 to 10 carbon atoms include methyl. Ar is an aryl having 6 to 20 carbon atoms, and specific examples of the aryl having 6 to 20 carbon atoms include phenyl. The repeating unit represented by the formula 14 may be a repeating unit derived from a monomer represented by the following formula 14-1. [ka] In the formula 14-1, R3″ is an alkyl having 1 to 10 carbon atoms. The details of R3″ in the formula 14-1 are the same as those described above in the formula 14. A specific example of the monomer represented by the formula 14-1 is methacrylic acid (MAA). The repeating unit represented by the above formula 15 may be a repeating unit derived from a monomer represented by the following formula 15-1. [ka] In the formula 15-1, R4" is an alkyl having 1 to 10 carbon atoms, and R5" is an alkyl having 1 to 10 carbon atoms. In the formula 15-1, the details of R4" and R5" are as described above in the formula 15. A specific example of the monomer represented by the formula 15-1 is methylmethacrylate (MMA).

[0020] The repeating unit represented by the formula 16 may be a repeating unit derived from a monomer represented by the following formula 16-1. [ka] In the above Chemical Formula 16-1, Ar is an aryl having 6 to 20 carbon atoms. The details regarding Ar in the above Chemical Formula 16-1 are as described above in the above Chemical Formula 16. A specific example of the monomer represented by the above Chemical Formula 16-1 is styrene (SM). The first alkali developable binder resin may have a weight average molecular weight of 30,000 g / mol to 150,000 g / mol and a glass transition temperature of 20° C. to 150° C. This improves the coating property and conformability of the dry film photoresist, and the mechanical strength of the resist itself after circuit formation. The first alkali developable binder resin may have an acid value of 140 mgKOH / g to 160 mgKOH / g. The second alkali developable binder resin may have a weight average molecular weight of 20,000 g / mol to 130,000 g / mol and a glass transition temperature of 30° C. to 160° C. This improves the coating property and conformability of the dry film photoresist, and the mechanical strength of the resist itself after the circuit is formed.

[0021] In the present specification, the weight average molecular weight means a weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a commonly known analyzer, a detector such as a refractive index detector, and an analytical column are used, and commonly used temperature conditions, solvents, and flow rates can be applied. As a specific example of the measurement conditions, the alkali developable binder resin was dissolved in tetrahydrofuran to a concentration of 1.0 (w / w)% in THF (about 0.5 (w / w)% based on solid content), filtered using a syringe filter with a 0.45 μm pore size, and 20 μl was injected into the GPC. Tetrahydrofuran (THF) was used as the GPC mobile phase and was flowed at a flow rate of 1.0 mL / min. The columns were one Agilent PLgel 5 μm Guard (7.5×50 mm) and two Agilent PLgel 5 μm Mixed D (7.5×300 mm) connected in series, and the detector was an Agilent 1260 Infinity II System with RI Detector, and the measurement was performed at 40° C. The weight average molecular weight (Mw) of the alkali developable binder resin was calculated using a calibration curve formed by dissolving polystyrene having various molecular weights in tetrahydrofuran at a concentration of 0.1 (w / w)% to obtain polystyrene standard samples (STD A, B, C, D) using a syringe filter with a 0.45μm pore size and then injecting the polystyrene into GPC. STD A(Mp):791, 000 / 27, 810 / 945 STD B(Mp):282, 000 / 10, 700 / 580 STD C(Mp):126, 000 / 4, 430 / 370 STD D(Mp):51, 200 / 1, 920 / 162 The glass transition temperature was measured by comparing the reference and the binder polymer using a Differential Scanning Calorimeter (DSC) (Perkin-Elmer, DSC-7). The temperature was set to 20°C for 15 minutes, and then increased to 200°C at a rate of 1°C / min.

[0022] The acid value of the alkali developable binder resin was measured by dissolving 1 g of the alkali developable binder resin in 50 ml of a mixed solvent (MeOH 20%, Acetone 80%), adding 2 drops of 1%-phenolphthalein indicator, and titrating with 0.1 N-KOH. The first alkali developable binder resin may have an acid value of 140 mgKOH / g to 160 mgKOH / g, and the second alkali developable binder resin may have an acid value of 160 mgKOH / g to 200 mgKOH / g. Specifically, the glass transition temperature ratio of the first alkali developable binder resin to the second alkali developable binder resin may be 1:1.5 or more and 1:5 or less, 1:1.5 or more and 1:3 or less, 1:1.5 or more and 1:2 or less, 1:1.5 or more and 1:1.8 or less, 1:1.5 or more and 1:75 or less, or 1:1.5 or more and 1:6 or less. In addition, the acid value ratio of the first alkali developable binder resin to the second alkali developable binder resin may be from 1:1.01 to 1:1.5, from 1:1.01 to 1:1.25, from 1:1.01 to 1:1.2, or from 1:1.01 to 1:1.1. Meanwhile, the first alkali-developable binder resin contained in the photosensitive resin composition of the embodiment may contain the repeating unit represented by Chemical Formula 4 in an amount of 1.2 mol to 3 mol, 1.2 mol to 2 mol, 1.5 mol to 2 mol, or 1.5 mol to 1.6 mol, per 1 mol of the repeating unit represented by Chemical Formula 3. The first alkali-developable binder resin contained in the photosensitive resin composition of the embodiment may contain the repeating unit represented by Chemical Formula 15 in an amount of 2 to 10 mols, 3 to 10 mols, 3 to 5 mols, or 4 to 5 mols, per 1 mol of the repeating unit represented by Chemical Formula 17.

[0023] Meanwhile, the second alkali developable binder resin may include a random copolymer of a repeating unit represented by the following Chemical Formula 14, a repeating unit represented by the following Chemical Formula 15, and a repeating unit represented by the following Chemical Formula 16: [ka] In the above Chemical Formula 14, R3' is an alkyl group having 1 to 10 carbon atoms. [ka] In the above Chemical Formula 15, R4″ is an alkyl group having 1 to 10 carbon atoms, and R5″ is an alkyl group having 1 to 10 carbon atoms. [ka] In the above Chemical Formula 16, Ar is an aryl having 6 to 20 carbon atoms. The repeating unit represented by the formula 14 may be a repeating unit derived from a monomer represented by the following formula 14-1. [ka] In the formula 14-1, R3″ is an alkyl having 1 to 10 carbon atoms. The details of R3″ in the formula 14-1 are the same as those described above in the formula 14. A specific example of the monomer represented by the formula 14-1 is methacrylic acid (MAA).

[0024] The repeating unit represented by the above formula 15 may be a repeating unit derived from a monomer represented by the following formula 15-1. [ka] In the formula 15-1, R4" is an alkyl having 1 to 10 carbon atoms, and R5" is an alkyl having 1 to 10 carbon atoms. In the formula 15-1, the details of R4" and R5" are as described above in the formula 15. A specific example of the monomer represented by the formula 15-1 is methylmethacrylate (MMA). The repeating unit represented by the formula 16 may be a repeating unit derived from a monomer represented by the following formula 16-1. [ka] In the above Chemical Formula 16-1, Ar is an aryl having 6 to 20 carbon atoms. The details regarding Ar in the above Chemical Formula 16-1 are as described above in the above Chemical Formula 6. A specific example of the monomer represented by the above Chemical Formula 16-1 is styrene (SM). Specifically, the first alkali-developable binder resin may contain the repeating unit represented by Chemical Formula 14:the repeating unit represented by Chemical Formula 15:the repeating unit represented by Chemical Formula 16 in a ratio of 1:(2 or more and 5 or less):(0.2 or more and 0.9 or less), 1:(2 or more and 3 or less):(0.5 or more and 0.9 or less), 1:(2.5 or more and 3 or less):(0.6 or more and 0.9 or less), or 1:(2.75 or more and 3 or less):(0.6 or more and 0.75 or less). In addition, the second alkali-developable binder resin may contain the repeating unit represented by Chemical Formula 14:the repeating unit represented by Chemical Formula 15:the repeating unit represented by Chemical Formula 16 in a ratio of 1:(1.1 or more and 2:(0.2 or more and 0.99 or less), 1:(1.5 or more and 2:(0.5 or more and 0.99 or less), or 1:(1.5 or more and 1.75 or less):(0.75 or more and 0.99 or less).

[0025] Meanwhile, the photosensitive resin composition according to one embodiment of the present invention may contain 500 parts by weight or more and 1,000 parts by weight or less, 600 parts by weight or more and 800 parts by weight or less, or 700 parts by weight or more and 800 parts by weight or less, of the second alkali-developable binder resin relative to 100 parts by weight of the first alkali-developable binder resin. As described above, by adding an excess of 500 parts by weight or more of the second alkaline developable binder resin relative to 100 parts by weight of the first alkaline developable binder resin, a hydrophobic function is imparted to the photosensitive resin, thereby increasing resistance to a developer, thereby achieving the technical effect of improving circuit properties.

[0026] (2) Photopolymerization initiator The photopolymerization initiator contained in the photosensitive resin composition according to the present invention is a substance that initiates a chain reaction of photopolymerizable monomers by UV or other radiation, and plays an important role in the curing of the dry film photoresist. Examples of compounds that can be used as the photopolymerization initiator include anthraquinone derivatives such as 2-methylanthraquinone and 2-ethylanthraquinone; and benzoin derivatives such as benzoin methyl ether, benzophenone, phenanthrenequinone, and 4,4'-bis-(dimethylamino)benzophenone. Other examples include 2,2'-bis(2-chlorophenyl)-4,4'-5,5'-tetraphenylbisimidazole, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-[4-morpholinophenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-[4-(2-hydroxymethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone, 1-(4-isopropylphenyl)2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 4 -Dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzyl ketone dimethyl acetal, benzyl ketone β-methoxydiethyl acetal, 1-phenyl-1,2-propyldioxime-o,o'-(2-carbonyl)ethoxy ether, methyl o-benzoylbenzoate, bis[4-dimethyl aminophenyl)ketone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, isobutoxybenzoin, tert-butoxybenzoin, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, α,A compound selected from α-dichloro-4-phenoxyacetophenone and pentyl 4-dimethylaminobenzoate is used as a photopolymerization initiator, but is not limited thereto.

[0027] The content of the photopolymerization initiator is 1% by weight or more and 10% by weight or less based on the total weight of the photosensitive resin composition, based on the solid content. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity can be obtained. The solid content based on the weight refers to the remaining components excluding the solvent from the photosensitive resin composition. If the content of the photopolymerization initiator is less than 1% by weight, the light efficiency is low and a large amount of exposure is required, resulting in a significant decrease in production efficiency. If the content of the photopolymerization initiator is more than 10% by weight, the film becomes brittle and the developer becomes highly contaminated, resulting in defects such as short circuits.

[0028] (3) Photopolymerizable compound The photopolymerizable compound of the present invention has resistance to a developer after exposure to UV light, making it possible to form a pattern. The photopolymerizable compound may include a difunctional (meth)acrylate compound. The difunctional (meth)acrylate compound may include an alkylene glycol di(meth)acrylate or a bisphenol di(meth)acrylate. As the alkylene glycol di(meth)acrylate, a compound represented by the following Chemical Formula 5 can be used. [ka] In the above Chemical Formula 5, l+n is an integer of 2 or 3, and m is an integer of 12-18. The compound represented by Formula 5 can improve the hydrophobicity of the photosensitive resin composition, significantly increase the resistance to a developer and a plating solution, and shorten the stripping time of the cured film. In the present invention, the compound represented by Chemical Formula 5 may be present in an amount of 10% by weight to 60% by weight, or 20% by weight to 40% by weight, based on the total weight of the solid content of the photosensitive resin composition. If the content of the compound represented by Chemical Formula 5 is less than 10 wt % based on the total weight of the solid content of the photosensitive resin composition, the effect of adding the compound represented by Chemical Formula 5 is insufficient, and if it exceeds 60 wt %, hydrophobicity increases, which may cause a problem of a rapid increase in development time in the post-exposure development process.

[0029] The bisphenol di(meth)acrylate may be a bisphenol di(meth)acrylate containing ethylene oxide. The bisphenol di(meth)acrylate containing ethylene oxide may include two types of bisphenol di(meth)acrylates: a bisphenol di(meth)acrylate containing 8 moles or less of ethylene oxide per molecule, and a bisphenol di(meth)acrylate containing more than 8 moles and 16 moles or less of ethylene oxide per molecule. Examples of the bisphenol-based di(meth)acrylate containing 8 moles or less of ethylene oxide include Miramer M244 (BPA(EO)3DA, Bisphenol A (EO)3 Diacrylate), Miramer M240 (BPA(EO)4DA, Bisphenol A (EO)4 Diacrylate), and Miramer M241 (Bisphenol A (EO)4 Dimethacrylate), both manufactured by Miwon Specialty Chemical Co., Ltd.

[0030] An example of the bisphenol di(meth)acrylate containing more than 8 moles and not more than 16 moles of ethylene oxide is Miramer M2100 (BPA(EO) 10 DA, Bisphenol A (EO) 10 diacrylate), Miramer M2200(BPA(EO) 20 DA, Bisphenol A (EO) 20 diacrylate), Miramer M2101(Bisphenol A(EO) 10Dimethacrylate, etc. can be used. On the other hand, the photopolymerizable compound may include a polyfunctional (meth)acrylate compound having three or more functional groups.

[0031] The tri- or higher functional polyfunctional (meth)acrylate compound may have a structure in which three or more alkylene oxide groups and (meth)acrylate functional groups, each having 1 to 10 carbon atoms, are bonded to a central group having 1 to 20 carbon atoms. The tri- or higher functional polyfunctional (meth)acrylate compound may include a compound represented by the following chemical formula 12. [ka] In the above formula 12, R 14 is hydrogen or alkyl having 1 to 10 carbon atoms, and R 15 is an alkylene having 1 to 10 carbon atoms, and R 16 is a functional group containing a central group having 1 to 20 carbon atoms, n12 is an integer of 1 to 20, and p is the R 16 is the number of functional groups substituted with , and is an integer of 3 to 10.

[0032] The photopolymerizable compound may further include a monofunctional (meth)acrylate compound. That is, the photosensitive resin composition according to an embodiment of the present invention may include a mixture of a monofunctional (meth)acrylate compound and a trifunctional or higher polyfunctional (meth)acrylate compound. The monofunctional (meth)acrylate compound may include a (meth)acrylate containing an alkylene oxide group having 1 to 10 carbon atoms. More specifically, the monofunctional (meth)acrylate compound may include a compound represented by the following Chemical Formula 11. [ka] In the above formula 11, R 11 is hydrogen or alkyl having 1 to 10 carbon atoms, and R 12 is an alkylene having 1 to 10 carbon atoms, and R 13is an alkyl group having 1 to 10 carbon atoms, and n11 is an integer of 1 to 20.

[0033] The product contains a monofunctional (meth)acrylate compound represented by the above chemical formula 11 and a trifunctional or higher polyfunctional (meth)acrylate compound represented by the above chemical formula 12, and has the same circuit properties as existing products. However, by increasing the photocuring speed, the time it takes for color to appear in the film is increased, and the contrast change time is improved for technical reasons to increase the amount of color change, ensuring excellent developability. Specifically, in the above-mentioned chemical formula 11, n11 is an integer of 1 to 20, an integer of 1 to 10, or an integer of 5 to 10. An example of the monofunctional (meth)acrylate compound represented by the above-mentioned chemical formula 11 is not particularly limited, and may be, for example, A040 (Methoxy propylene glycol

[0400] acrylate) represented by the following chemical formula A. [ka] The photosensitive resin composition of the embodiment includes the monofunctional (meth)acrylate compound represented by Chemical Formula 11, which can realize the effect of quickly realizing the color change of the film in the exposed area due to the technical reason of increasing the photocuring speed.

[0034] In addition, in the above Chemical Formula 12, n12 is an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to 5, and p is the above R 16 means the number of functional groups substituted with each other, and is an integer of 3 to 10, an integer of 3 to 5, or an integer of 3 to 4. That is, in the formula 12, the R 16 Since p, which means the number of functional groups substituted with , is an integer of 3 to 10, the compound may be a polyfunctional (meth)acrylate compound having three or more functional groups represented by Chemical Formula 12. Specifically, the tri- or higher functional (meth)acrylate compound is represented by the following chemical formula 12-1. [ka] In the above formula 12-1, R20 is a trivalent organic group, and R 21 ~R 23 are each independently an alkylene having 1 to 10 carbon atoms; R 24 ~R 26 each independently represents hydrogen or alkyl having 1 to 10 carbon atoms, and n to n5 each independently represents an integer of 1 to 20. In the above Chemical Formula 12-1, n13 to n15 are integers of 1 to 20, 1 to 10, or 1 to 5.

[0035] Examples of the tri- or higher functional polyfunctional (meth)acrylate compound represented by the above Chemical Formula 12 are not particularly limited, and may be, for example, T063 (Trimethylolpropane [EO]6triacrylate) represented by the following Chemical Formula B. [ka] The photosensitive resin composition according to the embodiment includes a polyfunctional (meth)acrylate compound having three or more functional groups represented by Chemical Formula 12. Compared with a monofunctional (meth)acrylate compound, the polyfunctional (meth)acrylate compound having three or more functional groups represented by Chemical Formula 12 has an increased cross-linking bond upon photocuring, and the reactive group can prevent deterioration of circuit properties due to various technical reasons and can realize an effect of increasing the amount of color change.

[0036] Meanwhile, the photosensitive resin composition of the embodiment may contain 110 parts by weight or more and 500 parts by weight or less, 110 parts by weight or more and 300 parts by weight or less, 110 parts by weight or more and 200 parts by weight or less, or 150 parts by weight or more and 200 parts by weight or less of the trifunctional or higher polyfunctional (meth)acrylate compound per 100 parts by weight of the monofunctional (meth)acrylate compound. The photosensitive resin composition of the embodiment contains an excess of the tri- or higher functional polyfunctional (meth)acrylate compound relative to the monofunctional (meth)acrylate compound, thereby achieving an effect of increasing the photocuring speed of the monofunctional (meth)acrylate compound represented by Chemical Formula 11 to realize a rapid color change of the film, and an effect of increasing the crosslinking during photocuring of the tri- or higher functional polyfunctional (meth)acrylate compound represented by Chemical Formula 12 to prevent a decrease in circuit properties that occurs when only a monofunctional material is added, and an effect of increasing the amount of reactive groups to increase the amount of color change. In the photosensitive resin composition of the embodiment, when the trifunctional or higher polyfunctional (meth)acrylate compound is contained in an amount of less than 100 parts by weight per 100 parts by weight of the monofunctional (meth)acrylate compound, technical problems such as circuit degradation and a decrease in the amount of color change may occur. The photopolymerizable compound may include a difunctional (meth)acrylate compound, a monofunctional (meth)acrylate compound represented by Chemical Formula 11, and a tri- or higher functional polyfunctional (meth)acrylate compound represented by Chemical Formula 12. That is, the photosensitive resin composition of the embodiment contains a photopolymerizable compound, and the photopolymerizable compound may contain a monofunctional (meth)acrylate compound, a trifunctional or higher polyfunctional (meth)acrylate compound, and a difunctional (meth)acrylate compound. Specifically, the photosensitive resin composition of the embodiment may contain 500 parts by weight or more and 1500 parts by weight or less, 500 parts by weight or more and 1000 parts by weight or less, 750 parts by weight or more and 1000 parts by weight or less, or 800 parts by weight or more and 900 parts by weight or less of the bifunctional (meth)acrylate compound relative to 100 parts by weight of the monofunctional (meth)acrylate compound. That is, the photosensitive resin composition of the embodiment may contain 110 parts by weight or more of the trifunctional or higher polyfunctional (meth)acrylate compound per 100 parts by weight of the monofunctional (meth)acrylate compound, and 500 parts by weight or more and 1500 parts by weight or less of the difunctional (meth)acrylate compound.

[0037] The photosensitive resin composition of the embodiment may contain 500 parts by weight or more and 1,000 parts by weight or less, 500 parts by weight or more and 800 parts by weight or less, 500 parts by weight or more and 750 parts by weight or less, 500 parts by weight or more and 700 parts by weight or less, or 500 parts by weight or more and 600 parts by weight or less of the bifunctional (meth)acrylate compound, relative to 100 parts by weight of the trifunctional or higher polyfunctional (meth)acrylate compound. As described above, the photosensitive resin composition of the embodiment contains a monofunctional (meth)acrylate compound, a trifunctional or higher polyfunctional (meth)acrylate compound, and a bifunctional (meth)acrylate compound in an amount that satisfies the above weight range, and is therefore capable of exhibiting appropriate circuit properties. 2 When the above amount of light is applied, the technical effect of rapid color development and color change in the exposed area can be realized. More specifically, the photosensitive resin composition of the embodiment may contain 100 parts by weight or less, 50 parts by weight or less, 1 part by weight or more and 100 parts by weight or less, or 1 part by weight or more and 50 parts by weight or less of the monofunctional (meth)acrylate compound represented by Chemical Formula 11 and the trifunctional or higher polyfunctional (meth)acrylate compound represented by Chemical Formula 12, relative to 100 parts by weight of the bifunctional (meth)acrylate compound. The content of the photopolymerizable compound is 10% by weight or more and 70% by weight or less based on the total weight of the photosensitive resin composition based on the solid content. When the content of the photopolymerizable compound is within the above range, it is possible to obtain the effect of enhancing photosensitivity, resolution, adhesion, etc. The solid content based on the weight refers to the remaining components excluding the solvent from the photosensitive resin composition.

[0038] (4) Photosensitive resin composition The photosensitive resin composition may satisfy either one of the following (a) or (b). (a) in a resist pattern obtained by exposing and developing a photosensitive resin layer containing a photosensitive resin composition, the maximum foot length of resist residue remaining on the bottom surface of a space between adjacent photosensitive resin layer lines is 1 μm or less; (b) when a film sample having a photosensitive resin layer containing the photosensitive resin composition laminated on a substrate is nickel-plated for 20 minutes or more using an aqueous solution containing nickel, the adhesion defined by the following formula 1 is 90% or more, [Formula 1] Adhesion (%) = (surface area of ​​the photosensitive resin layer containing the photosensitive resin composition in contact with the substrate after nickel plating / surface area of ​​the photosensitive resin layer containing the photosensitive resin composition in contact with the substrate before nickel plating) * 100 Specifically, for a resist pattern obtained by exposing and developing a photosensitive resin layer containing a photosensitive resin composition, the maximum foot length of resist residue remaining on the bottom surface of the space between adjacent photosensitive resin layer lines may be 1 μm or less, or 0.7 μm or less, or from 0.1 μm to 1 μm, or from 0.1 μm to 0.7 μm, or from 0.4 μm to 0.7 μm, or from 0.5 μm to 0.6 μm. The resist pattern can be formed by selectively exposing and developing the photosensitive resin composition, so that a portion of the photosensitive resin composition remains in the photosensitive resin layer to form photosensitive resin layer lines, and a portion of the photosensitive resin composition is removed by development to form spaces between the photosensitive resin layer lines. At this time, resist residues that are not completely removed by development may remain on the bottom of the spaces between adjacent photosensitive resin layer lines. If the foot length of such resist residues exceeds 1 μm, a footing phenomenon at the bottom of the pattern may occur excessively, making it difficult to achieve high resolution of the resist pattern.

[0039] Specifically, the foot length of the resist residue may be the shortest straight-line distance from a point on the boundary line formed by one side of the photosensitive resin layer line abutting the bottom surface and the resist residue to the intersection point where a cross-section of the resist residue in a plane formed by a perpendicular line from the point to the one side of the photosensitive resin layer line and a perpendicular line from the point to the bottom surface intersects with the boundary line formed by the bottom surface and the resist residue. To explain the foot length of the resist residue using the schematic cross-sectional view of the resist pattern in Figure 2, a point on the boundary line formed by one side of the photosensitive resin layer line abutting the bottom surface and the resist residue corresponds to the point indicated by d1, and the intersection point where the cross section of the resist residue along a plane formed by a perpendicular line from the point to one side of the photosensitive resin layer line and a perpendicular line from the point to the bottom surface meets the boundary line formed by the resist residue and the bottom surface corresponds to the point indicated by d2, and the shortest straight-line distance between d1 and d2 corresponds to the foot length of the resist residue. The foot length of the resist residue can be measured using an optical microscope (ZEISS AXIOPHOT Microscope) as shown in FIG. More specifically, the resist pattern used in measuring the foot length of the resist residue may have a ratio of the line width of the upper part of the photosensitive resin layer line to the interval between the upper parts of the adjacent photosensitive resin layer lines of 1:0.5 to 1:2, or 1:0.9 to 1:1.1. Specifically, the line width of the upper part of the photosensitive resin layer line corresponds to L in FIG. 2, and the interval between the upper parts of the adjacent photosensitive resin layer lines corresponds to S in FIG. 2. In addition, the line width of the upper part of the photosensitive resin layer line used for measuring the foot length of the resist residue may be 5 μm to 15 μm, or 9 μm to 11 μm. The line width of the upper part of the photosensitive resin layer line can be measured using an optical microscope. The thickness of the photosensitive resin layer used to measure the foot length of the resist residue may be 20 μm to 30 μm, or 24 μm to 26 μm. The thickness of the photosensitive resin layer corresponds to T in FIG. 2. The thickness of the photosensitive resin layer can be measured using an optical microscope.

[0040] When measuring the foot length of the resist residue, the exposure conditions were 35 mJ / cm using an exposure device. 2 More than 45mJ / cm 2 or less than 39 mJ / cm 2 More than 41mJ / cm 2 The ultraviolet light can be irradiated at the following exposure dose: The exposure time can be 1 minute or more and 10 minutes or less. When measuring the foot length of the resist residue, the development conditions may include an alkaline aqueous solution having a concentration of 0.5% by weight to 1.5% by weight, or 0.9% by weight to 1.1% by weight. The pH of the alkaline aqueous solution may be in the range of 9 to 11, and the temperature may be adjusted according to the developability of the photosensitive resin layer. Specific examples of the alkaline aqueous solution include an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, and an aqueous sodium hydroxide solution. The development may be performed by contacting the alkaline aqueous solution with the photosensitive resin layer, and specific examples of the contacting method include spraying or immersion. The development time may be from 1 minute to 10 minutes. Meanwhile, the photosensitive resin composition may have an adhesion defined by the following Equation 1 of 90% or more, or 90% or more and 100% or less, when a film sample having a photosensitive resin layer including the photosensitive resin composition laminated on a substrate is nickel-plated for 20 minutes or more in an aqueous solution containing nickel. [Formula 1] Adhesion (%) = (surface area of ​​the photosensitive resin layer containing the photosensitive resin composition in contact with the substrate after nickel plating / surface area of ​​the photosensitive resin layer containing the photosensitive resin composition in contact with the substrate before nickel plating) * 100 The adhesion defined by Equation 1 means a percentage ratio of a surface area of ​​the photosensitive resin layer including the photosensitive resin composition in contact with a substrate after nickel plating to a surface area of ​​the photosensitive resin layer including the photosensitive resin composition in contact with a substrate before nickel plating. The surface area for determining the degree of adhesion can be measured through an image of an optical microscope.

[0041] The specific conditions for the nickel plating are not particularly limited. For example, a film sample having a photosensitive resin layer including the photosensitive resin composition laminated on the substrate is immersed in an ICP NICORON GIB aqueous solution (a mixture of 100 cc of ICP NICORON GIB-M and 50 cc of ICP NICORON GIB-1 in 850 cc of distilled water) as an aqueous solution containing nickel, at a temperature of 50° C. to 100° C. for 20 minutes or more, or 20 minutes to 30 minutes, to perform plating. Prior to nickel plating, an immersion process in a catalytic aqueous solution must be performed before the immersion process in the aqueous solution containing nickel. The specific conditions for the immersion process in the catalytic aqueous solution are not particularly limited, but for example, a film sample having a photosensitive resin layer including the photosensitive resin composition laminated on the substrate can be immersed in a hydrochloric acid-based palladium catalyst ICP ACCERA H aqueous solution (a mixture of 90cc of 35% hydrochloric acid aqueous solution and 40cc of ICP ACCERA H in 870cc of distilled water) for 0.1 to 10 minutes under conditions of 10 to 40°C. In addition, if necessary, a step of immersing in an aqueous solution containing gold may be further performed after the step of immersing in the aqueous solution containing nickel. The specific conditions for the step of immersing in the aqueous solution containing gold are not particularly limited, but for example, a film sample having a photosensitive resin layer including the photosensitive resin composition laminated on the substrate may be immersed in the aqueous solution containing gold at a temperature of 70° C. to 100° C. for 1 minute to 20 minutes.

[0042] A specific example of the aqueous solution containing gold is an aqueous solution of IM GOLD IB MAKE UP SALT (a mixture of 80 g of IM GOLD IB MAKE UP SALT and 2.92 g of potassium gold cyanide in 1000 cc of distilled water). The film sample in which a photosensitive resin layer containing the photosensitive resin composition is laminated on a substrate may be a laminate in which a photosensitive resin layer containing the photosensitive resin composition is laminated on an arbitrary substrate, and an example of a substrate used in measuring the adhesion defined by the above mathematical formula 1 is a copper-clad laminate having a copper layer having a thickness of 10 μm or more and 100 mm or less located on a surface thereof. The photosensitive resin layer may include a dried or cured product of the photosensitive resin composition of the embodiment. The dried product means a material obtained through a drying process of the photosensitive resin composition of the embodiment. The cured product means a material obtained through a curing process of the photosensitive resin composition of the embodiment. The photosensitive resin layer may be in the form of a film without openings, or in the form of a pattern having openings. Examples of the method for forming the patterned photosensitive resin layer include a method in which a photosensitive resin layer of a dry film photoresist according to another embodiment described later is laminated on a substrate, followed by exposure and development, and a method in which a photosensitive resin layer of a photosensitive element according to another embodiment described later is laminated on a substrate, followed by exposure and development. When the dry film photoresist or photosensitive element of the other embodiment has a protective film on the photosensitive resin layer, a process of removing the protective film may be further performed before the photosensitive resin layer is laminated on a circuit board or a substrate for a display manufacturing device. In addition, when the dry film photoresist or photosensitive element of the other embodiment has a polymer substrate or substrate film laminated on one side of the photosensitive resin layer, a step of removing the polymer substrate or substrate film immediately after the exposure step can be further carried out. When measuring the adhesion defined by the above formula 1, the exposure conditions were 20 mJ / cm using an exposure device. 2 More than 200mJ / cm 2 or less than 50 mJ / cm 2 More than 100mJ / cm 2 The ultraviolet light can be irradiated at the following exposure dose: The exposure time can be from 1 second to 10 minutes, or from 1 second to 10 seconds.

[0043] When measuring the adhesion defined by the above formula 1, the development conditions may include an alkaline aqueous solution having a concentration of 0.5% by weight to 1.5% by weight, or 0.9% by weight to 1.1% by weight. The pH of the alkaline aqueous solution may be in the range of 9 to 11, and the temperature may be adjusted according to the developability of the photosensitive resin layer. Specific examples of the alkaline aqueous solution include an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, and an aqueous sodium hydroxide solution. The development is carried out by contacting the alkaline aqueous solution with the photosensitive resin layer, and specific examples of the contact method include spraying or immersion. The development time may be from 30 seconds to 10 minutes, or from 30 seconds to 2 minutes. The thickness of the photosensitive resin layer used to measure the adhesion defined by the above Equation 1 may be 20 μm to 80 μm, or 30 μm to 60 μm. In addition, the photosensitive resin layer used to measure the adhesion defined by the above Equation 1 has a cross-sectional area parallel to the ground of 0.10 m2. 2 More than 1.00m 2 Less than or equal to 0.15m 2 More than 0.30m 2 The thickness and cross-sectional area of ​​the photosensitive resin layer can be measured using an optical microscope. If the adhesion defined by the above formula 1 is excessively reduced to less than 90% due to bubbles generated during plating, undesired circuits will be formed in the final circuit board or display.

[0044] The photosensitive resin composition may contain, based on the solid content, 20% by weight or more and 80% by weight or less of an alkali developable binder resin, 1% by weight or more and 10% by weight or less of a photopolymerization initiator, and 10% by weight or more and 70% by weight or less of a photopolymerizable compound. The photosensitive resin composition may further include a solvent, which is generally selected from methyl ethyl ketone (MEK), methanol, THF, toluene, and acetone, and is not particularly limited, and the content of the solvent may be appropriately adjusted depending on the content of the photopolymerization initiator, the alkali developable binder resin, and the photopolymerizable compound. In addition, the photosensitive resin composition may further contain other additives as necessary. Examples of the other additives that can be used include plasticizers such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diallyl phthalate in the form of phthalic acid esters; triethylene glycol diacetate and tetraethylene glycol diacetate in the form of glycol esters; p-toluenesulfonamide, benzenesulfonamide, and n-butylbenzenesulfonamide in the form of acid amides; and triphenyl phosphate. In the present invention, a leuco dye or a coloring material can be added to improve the handling of the photosensitive resin composition. Examples of the leuco dye include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2-methylphenyl)methane, and fluoran dyes. Among them, leuco crystal violet is preferably used because it provides good contrast. When a leuco dye is included, the content may be 0.1% by weight or more and 10% by weight or less in the photosensitive resin composition. From the viewpoint of contrast development, 0.1% by weight or more is preferable, and from the viewpoint of maintaining storage stability, 10% by weight or less is preferable.

[0045] Examples of coloring substances include toluenesulfonic acid monohydrate, fuchsine, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green, Diamond Green, and Basic Blue 20. The amount of the coloring substance added when it is contained may be 0.001% by weight or more and 1% by weight or less based on the photosensitive resin composition. A content of 0.001% by weight or more has the effect of improving handleability, and a content of 1% by weight or less has the effect of maintaining storage stability. Other additives may further include a thermal polymerization inhibitor, a dye, a discoloring agent, an adhesion promoter, and the like. 2. Dry film photoresist According to another embodiment of the present invention, there is provided a dry film photoresist including a photosensitive resin layer including the photosensitive resin composition of the above embodiment. The content of the photosensitive resin composition includes all of the content described above in the above embodiment. Specifically, the photosensitive resin layer may include a dried or cured product of the photosensitive resin composition of the embodiment. The dried product means a substance obtained through a drying process of the photosensitive resin composition of the embodiment. The cured product means a substance obtained through a curing process of the photosensitive resin composition of the embodiment. The thickness of the photosensitive resin layer is not particularly limited, but can be appropriately adjusted within a range of, for example, 0.01 μm to 1 mm. For example, the photosensitive resin layer may include an alkali developable binder resin and a photopolymerizable compound, the alkali developable binder resin including the repeating unit represented by Chemical Formula 1, the repeating unit represented by Chemical Formula 2, the repeating unit represented by Chemical Formula 3, and the repeating unit represented by Chemical Formula 4. The alkali developable binder resin and the photopolymerizable compound including the repeating unit represented by Chemical Formula 1, the repeating unit represented by Chemical Formula 2, the repeating unit represented by Chemical Formula 3, and the repeating unit represented by Chemical Formula 4 include all of the details described above in the embodiment.

[0046] The thickness of the dry film photoresist is not particularly limited, and can be appropriately adjusted within a range of, for example, 0.01 μm to 1 mm. When the thickness of the dry film photoresist increases or decreases by a certain value, the physical properties measured for the dry film photoresist may also change by a certain value. The dry film photoresist may further include a base film and a protective film, which serves as a support for the photosensitive resin layer during the preparation of the dry film photoresist and facilitates handling of the photosensitive resin layer having adhesive strength during exposure. The base film may be any of various plastic films, including, for example, one or more plastic films selected from the group consisting of acrylic films, polyethylene terephthalate (PET) films, triacetyl cellulose (TAC) films, polynorbornene (PNB) films, cycloolefin polymer (COP) films, and polycarbonate (PC) films. The thickness of the base film is not particularly limited, but can be appropriately adjusted within the range of, for example, 0.01 μm to 1 mm. The protective film serves as a protective cover to prevent damage to the resist during handling and to protect the photosensitive resin layer from foreign matter such as dust, and is laminated on the back surface of the photosensitive resin layer on which the base film is not formed. The protective film serves to protect the photosensitive resin layer from the outside, and requires appropriate releasability and adhesion so that it can be easily removed when the dry film photoresist is applied to a post-process and does not come off during storage and distribution.

[0047] The protective film may be made of various plastic films, for example, one or more plastic films selected from the group consisting of acrylic films, polyethylene (PE) films, polyethylene terephthalate (PET) films, triacetyl cellulose (TAC) films, polynorbornene (PNB) films, cycloolefin polymer (COP) films, and polycarbonate (PC) films. The thickness of the protective film is not particularly limited, but can be appropriately adjusted within the range of, for example, 0.01 μm to 1 mm. The dry film photoresist may satisfy either one of the following (1) or (2). (a) in a resist pattern obtained by exposing and developing the photosensitive resin layer, the maximum foot length of resist residue remaining on the bottom surface of a space between adjacent photosensitive resin layer lines is 1 μm or less; (b) when a film sample having a photosensitive resin layer of the dry film photoresist laminated on a substrate is nickel-plated for 20 minutes or more in an aqueous solution containing nickel, the adhesion defined by the following formula 2 is 90% or more; [Formula 2] Adhesion (%) = (surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the substrate after nickel plating / surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the substrate before nickel plating) * 100 Specifically, for a resist pattern obtained by exposing and developing the photosensitive resin layer, the maximum foot length of resist residue remaining on the bottom surface of the space between adjacent photosensitive resin layer lines may be 1 μm or less, or 0.7 μm or less, or from 0.1 μm to 1 μm, or from 0.1 μm to 0.7 μm, or from 0.4 μm to 0.7 μm, or from 0.5 μm to 0.6 μm.

[0048] The resist pattern can be formed by selectively exposing and developing the photosensitive resin composition, so that a portion of the photosensitive resin composition remains in the photosensitive resin layer to form photosensitive resin layer lines, and a portion of the photosensitive resin composition is removed by development to form spaces between the photosensitive resin layer lines. At this time, resist residues that are not completely removed by development may remain on the bottom of the spaces between adjacent photosensitive resin layer lines. If the foot length of such resist residues exceeds 1 μm, a footing phenomenon at the bottom of the pattern may occur excessively, making it difficult to achieve high resolution of the resist pattern. Specifically, the foot length of the resist residue may be the shortest straight-line distance from a point on the boundary line formed by one side of the photosensitive resin layer line abutting the bottom surface and the resist residue to the intersection point where a cross-section of the resist residue in a plane formed by a perpendicular line from the point to the one side of the photosensitive resin layer line and a perpendicular line from the point to the bottom surface intersects with the boundary line formed by the bottom surface and the resist residue. To explain the foot length of the resist residue using the schematic cross-sectional view of the resist pattern in Figure 2, a point on the boundary line formed by one side of the photosensitive resin layer line abutting the bottom surface and the resist residue corresponds to the point indicated by d1, and the intersection point where the cross section of the resist residue along a plane formed by a perpendicular line from the point to one side of the photosensitive resin layer line and a perpendicular line from the point to the bottom surface meets the boundary line formed by the resist residue and the bottom surface corresponds to the point indicated by d2, and the shortest straight-line distance between d1 and d2 corresponds to the foot length of the resist residue. The foot length of the resist residue can be measured using an optical microscope (ZEISS AXIOPHOT Microscope) as shown in FIG. More specifically, the resist pattern used in measuring the foot length of the resist residue may have a ratio of the line width of the upper part of the photosensitive resin layer line to the interval between the upper parts of the adjacent photosensitive resin layer lines of 1:0.5 to 1:2, or 1:0.9 to 1:1.1. Specifically, the line width of the upper part of the photosensitive resin layer line corresponds to L in FIG. 2, and the interval between the upper parts of the adjacent photosensitive resin layer lines corresponds to S in FIG. 2.

[0049] The line width of the upper part of the photosensitive resin layer line used in measuring the foot length of the resist residue may be 5 μm or more and 15 μm or less, or 9 μm or more and 11 μm or less. The thickness of the photosensitive resin layer used for measuring the foot length of the resist residue may be 20 μm or more and 30 μm or less, or 24 μm or more and 26 μm or less. The thickness of the photosensitive resin layer corresponds to T in FIG. When measuring the foot length of the resist residue, the exposure conditions were 35 mJ / cm using an exposure device. 2 More than 45mJ / cm 2 or less than 39 mJ / cm 2 More than 41mJ / cm 2 The ultraviolet light can be irradiated at the following exposure dose: The exposure time can be 1 minute or more and 10 minutes or less. When measuring the foot length of the resist residue, the development conditions may include an alkaline aqueous solution having a concentration of 0.5% by weight to 1.5% by weight, or 0.9% by weight to 1.1% by weight. The pH of the alkaline aqueous solution may be in the range of 9 to 11, and the temperature may be adjusted according to the developability of the photosensitive resin layer. Specific examples of the alkaline aqueous solution include an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, and an aqueous sodium hydroxide solution. The development may be performed by contacting the alkaline aqueous solution with the photosensitive resin layer, and specific examples of the contacting method include spraying or immersion. The development time may be from 1 minute to 10 minutes. Meanwhile, the dry film photoresist may have an adhesion defined by the following Equation 2 of 90% or more, or 90% or more and 100% or less, when a film sample having a photosensitive resin layer of the dry film photoresist laminated on a substrate is nickel-plated for 20 minutes or more in an aqueous solution containing nickel. [Formula 2] Adhesion (%) = (surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the substrate after nickel plating / surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the substrate before nickel plating) * 100 The adhesion defined by Equation 2 means the percentage ratio of the surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the substrate after nickel plating to the surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the substrate before nickel plating. The surface area for determining the degree of adhesion can be measured through an image of an optical microscope.

[0050] The specific conditions for the nickel plating are not particularly limited. For example, a film sample having a photosensitive resin layer including the photosensitive resin composition laminated on the substrate is immersed in an ICP NICORON GIB aqueous solution (a mixture of 100 cc of ICP NICORON GIB-M and 50 cc of ICP NICORON GIB-1 in 850 cc of distilled water) as an aqueous solution containing nickel, at a temperature of 50° C. to 100° C. for 20 minutes or more, or 20 minutes to 30 minutes, to perform plating. Prior to nickel plating, an immersion process in a catalytic aqueous solution must be performed before the immersion process in the aqueous solution containing nickel. The specific conditions for the immersion process in the catalytic aqueous solution are not particularly limited, but for example, a film sample having a photosensitive resin layer including the photosensitive resin composition laminated on the substrate can be immersed in a hydrochloric acid-based palladium catalyst ICP ACCERA H aqueous solution (a mixture of 90cc of 35% hydrochloric acid aqueous solution and 40cc of ICP ACCERA H in 870cc of distilled water) for 0.1 to 10 minutes under conditions of 10 to 40°C. In addition, if necessary, a step of immersing in an aqueous solution containing gold may be further performed after the step of immersing in the aqueous solution containing nickel. The specific conditions for the step of immersing in the aqueous solution containing gold are not particularly limited, but for example, a film sample having a photosensitive resin layer including the photosensitive resin composition laminated on the substrate may be immersed in the aqueous solution containing gold at a temperature of 70° C. to 100° C. for 1 minute to 20 minutes. A specific example of the aqueous solution containing gold is an aqueous solution of IM GOLD IB MAKE UP SALT (a mixture of 80 g of IM GOLD IB MAKE UP SALT and 2.92 g of potassium gold cyanide in 1000 cc of distilled water). The film sample in which a photosensitive resin layer containing the photosensitive resin composition is laminated on the substrate may be a laminate in which a photosensitive resin layer containing the photosensitive resin composition is laminated on any substrate, and an example of a substrate used in measuring the adhesion defined by the mathematical formula 2 is a copper-clad laminate having a copper layer having a thickness of 10 μm or more and 100 mm or less located on the surface. The photosensitive resin layer may include a dried or cured product of the photosensitive resin composition of the embodiment. The dried product means a material obtained through a drying process of the photosensitive resin composition of the embodiment. The cured product means a material obtained through a curing process of the photosensitive resin composition of the embodiment.

[0051] The photosensitive resin layer may be in the form of a film without openings, or in the form of a pattern having openings. Examples of the method for forming the patterned photosensitive resin layer include a method in which the photosensitive resin layer of the dry film photoresist of the other embodiment is laminated on a substrate, followed by exposure and development, and a method in which the photosensitive resin layer of the photosensitive element of the other embodiment described below is laminated on a substrate, followed by exposure and development. When the dry film photoresist or photosensitive element of the other embodiment has a protective film on the photosensitive resin layer, a process of removing the protective film may be further performed before the photosensitive resin layer is laminated on a circuit board or a substrate for a display manufacturing device. In addition, when the dry film photoresist or photosensitive element of the other embodiment has a polymer substrate or substrate film laminated on one side of the photosensitive resin layer, a step of removing the polymer substrate or substrate film immediately after the exposure step can be further carried out. When measuring the adhesion defined by Equation 2, the exposure conditions were 20 mJ / cm using an exposure device. 2 More than 200mJ / cm 2 or less than 50 mJ / cm 2 More than 100mJ / cm 2The ultraviolet light can be irradiated at the following exposure dose: The exposure time can be from 1 second to 10 minutes, or from 1 second to 10 seconds. When measuring the adhesion defined by the above Equation 2, the development conditions may include an alkaline aqueous solution having a concentration of 0.5% by weight to 1.5% by weight, or 0.9% by weight to 1.1% by weight. The pH of the alkaline aqueous solution may be in the range of 9 to 11, and the temperature may be adjusted according to the developability of the photosensitive resin layer. Specific examples of the alkaline aqueous solution include an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, and an aqueous sodium hydroxide solution.

[0052] The development is carried out by contacting the alkaline aqueous solution with the photosensitive resin layer, and specific examples of the contact method include spraying or immersion. The development time may be from 30 seconds to 10 minutes, or from 30 seconds to 2 minutes. The thickness of the photosensitive resin layer used to measure the adhesion defined by the above Equation 2 may be 20 μm to 80 μm, or 30 μm to 60 μm. In addition, the photosensitive resin layer used to measure the adhesion defined by the above Equation 2 has a cross-sectional area parallel to the ground of 0.10 m2. 2 More than 1.00m 2 Less than or equal to 0.15m 2 More than 0.30m 2 The thickness and cross-sectional area of ​​the photosensitive resin layer can be measured using an optical microscope. If the adhesion defined by Equation 2 is excessively reduced to less than 90% due to bubbles generated during plating, undesired circuits will be formed in the final circuit board or display. The method for producing the dry film photoresist is not particularly limited, and for example, the photosensitive resin composition of the embodiment may be coated on a conventional base film such as polyethylene terephthalate using a conventional coating method, and then dried. A conventional protective film such as polyethylene may be laminated on the upper surface of the dried photosensitive resin layer to produce a dry film. The method for coating the photosensitive resin composition of the embodiment is not particularly limited, and for example, a coating bar method or the like may be used. The step of drying the coated photosensitive resin composition may be performed by a heating means such as a hot air oven, a hot plate, a hot air circulation oven, an infrared oven, etc., at a temperature of 50°C to 100°C.

[0053] 3. Photosensitive element According to yet another embodiment of the invention, there is provided a photosensitive element comprising a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, and satisfying either one of the following (a) or (b): (a) in a resist pattern obtained by exposing and developing the photosensitive resin layer, the maximum foot length of resist residue remaining on the bottom surface of a space between adjacent photosensitive resin layer lines is 1 μm or less; (b) when a film sample having the photosensitive resin layer laminated on a substrate is nickel-plated for 20 minutes or more in an aqueous solution containing nickel, the adhesion defined by the following formula 3 is 90% or more, [Formula 3] Adhesion (%) = (surface area of ​​the photosensitive resin layer of the photosensitive element in contact with the substrate after nickel plating / surface area of ​​the photosensitive resin layer of the photosensitive element in contact with the substrate before nickel plating) * 100 The details regarding the foot length and adhesion of the photosensitive resin layer and the resist residue include all of the details described above in the one embodiment and the other embodiments. That is, the photosensitive resin layer may include an alkali developable binder resin and a photopolymerizable compound, each of which includes a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 2, a repeating unit represented by Chemical Formula 3, and a repeating unit represented by Chemical Formula 4. The details regarding the alkali developable binder resin and the photopolymerizable compound including the repeating unit represented by Chemical Formula 1, the repeating unit represented by Chemical Formula 2, the repeating unit represented by Chemical Formula 3, and the repeating unit represented by Chemical Formula 4 include all the details described above in the above embodiment.

[0054] The polymer substrate may be made of various plastic films, for example, one or more plastic films selected from the group consisting of acrylic films, polyethylene terephthalate (PET) films, triacetyl cellulose (TAC) films, polynorbornene (PNB) films, cycloolefin polymer (COP) films, and polycarbonate (PC) films. The thickness of the polymer substrate is not particularly limited, but can be appropriately adjusted within the range of, for example, 0.01 μm to 1 mm. A specific example of the polymer substrate is a polyester film having an anti-blocking layer formed thereon by an in-line coating method in which an unstretched polyester film is uniaxially stretched, a liquid containing a binder resin and organic particles is applied to one side of the film, and the remaining film is uniaxially stretched. The polymer substrate does not contain an antiblocking agent, which is usually added in consideration of runnability and winding properties during production, but instead uses an in-line coating method and is provided with an organic particle layer using substitute particles that do not impair transparency. Examples of organic particles used here that take into consideration running properties and winding properties and do not impair transparency include acrylic particles such as methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, normal butyl methyl methacrylate, acrylic acid, and copolymers or terpolymers of methacrylic acid; olefin particles such as polyethylene, polystyrene, and polypropylene; acrylic and olefin copolymers; and organic particles such as multi-layered, multi-component particles in which a single polymer particle is formed and then a layer of a different type of monomer is coated on the polymer particle. Specifically, such organic particles must be spherical and have a refractive index different from that of the binder resin. Here, "spherical" means an ellipse with a ratio of the minor axis (a) to the major axis (b) of 0.5 or less.

[0055] The difference in refractive index between the organic particles and the binder resin is 0.05 or less. If the difference in refractive index is more than 0.05, the haze increases. This means that there is a lot of scattered light, and if there is a lot of scattered light, the smoothing effect of the sidewall decreases. This also depends on the size and amount of the organic particles. The organic particles preferably have an average particle size of about 0.5 μm to 5 μm. If the average particle size is smaller than this, the running characteristics and winding characteristics decrease, and if it is larger than 5 μm, it increases the haze and is not preferable in consideration of the occurrence of problems with falling off. The content of the organic particles is preferably 1 to 10% by weight based on the total amount including the binder resin. If the content of the organic particles is less than 1% by weight based on the total amount including the binder resin, the anti-blocking effect is insufficient, the film is vulnerable to scratches, and the winding properties and running properties are deteriorated. If the content of the organic particles is more than 10% by weight, there may be a problem that the haze increases and the transparency properties are deteriorated. Meanwhile, inorganic particles can be added in addition to the organic particles as described above. In this case, it is not preferable to add inorganic antiblocking agents that have been commonly used, and it is preferable to add colloidal silica with a particle size of 100 nm or less. The content is preferably 10 parts by weight or less per 100 parts by weight of binder resin. When the particle size and content are as described above, sidewall defects and crater-like grooves caused by the antiblocking layer during pattern formation using a dry film photoresist may not occur. ​As the binder resin that acts as an adhesive for applying such organic particles onto an unstretched polyester film, it is preferable to use one that is compatible with the organic particles. Examples of such resins include acrylic resins such as unsaturated polyester, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, normal butyl methyl methacrylate, acrylic acid, and copolymers or terpolymers of methacrylic acid; urethane resins; epoxy resins; and melamine resins, and acrylic resins are preferred. The solvent that can be used to prepare the solution from the binder resin and the organic particles is preferably water. In this way, the solution containing organic particles in the binder resin is applied to the uniaxially stretched film after uniaxially stretching the unstretched polyester film obtained by melt extrusion of PET pellets. The application can be performed on at least one side of the uniaxially stretched film, and the thickness is preferably about 30 nm to 200 nm based on the thickness after final drying. If the solution containing organic particles is applied to the uniaxially stretched film to a thickness of less than 30 nm, the organic particles are easily removed, the film is vulnerable to scratches, and there is a problem of white powder being generated, and if the solution is applied to a thickness of more than 200 nm, a coating line is generated in the coating direction in in-line coating with a high coating speed due to the increase in the viscosity of the solution.

[0056] The polymer substrate obtained by applying organic particles instead of a general antiblocking agent using the in-line coating method maintains winding and running properties due to the particle layer, and is a substrate film with excellent transparency due to the organic particles with excellent light transmittance. Since the photosensitive resin layer is laminated on the opposite side of the layer containing organic particles in the polymer substrate, the formation of the photosensitive resin layer on the opposite side of the layer containing organic particles in this way eliminates the crater-shaped scratches that would appear in the past when a substrate film containing an antiblocking agent is laminated. Particles such as silica are not only larger in size than organic particles, but are also distributed throughout the substrate film, so that even a slight effect of silica is apparent in the areas adjacent to the photosensitive resin layer. In contrast, the polymer substrate used in the present invention is made of organic particles with a size of 0.5 μm to 5 μm, and the organic particle layer is not adjacent to the photosensitive resin layer, so that the physical effect of the organic particles is not reached. In addition, by using organic particles with excellent light transmittance, the defects of the sidewall can be reduced, and other circuit physical properties are not impaired. The photosensitive element may further include a protective film formed on the photosensitive resin layer. The protective film serves as a protective cover to prevent damage to the photosensitive resin layer during handling and to protect the photosensitive resin layer from foreign matter such as dust, and is laminated on the back surface of the photosensitive resin layer on which the polymer substrate is not formed. The protective film serves to protect the photosensitive resin layer from the outside, and is required to have suitable releasability and adhesion so that it can be easily removed when the photosensitive element is applied to a post-process, but does not come off during storage and distribution.

[0057] The protective film may be made of various plastic films, for example, one or more plastic films selected from the group consisting of acrylic films, polyethylene (PE) films, polyethylene terephthalate (PET) films, triacetyl cellulose (TAC) films, polynorbornene (PNB) films, cycloolefin polymer (COP) films, and polycarbonate (PC) films. The thickness of the protective film is not particularly limited, but can be appropriately adjusted within the range of, for example, 0.01 μm to 1 mm. 4. Circuit boards, display devices According to yet another embodiment of the present invention, there is provided a circuit board or a display device, comprising a photosensitive resin layer including the photosensitive resin composition of the above embodiment. The content of the photosensitive resin composition includes all of the content described above in the above embodiment. The specific contents of the circuit board or the display device are not particularly limited, and various conventionally known technical configurations can be applied without any restrictions. The photosensitive resin layer included in the circuit board or display device may be in the form of a film without openings, or in the form of a pattern having openings. Examples of the method for forming the patterned photosensitive resin layer include a method in which the photosensitive resin layer of the dry film photoresist of the other embodiment is laminated on a circuit board or a substrate for display manufacturing equipment, and then exposed and developed. Also, a method in which the photosensitive resin layer of the photosensitive element of the other embodiment is laminated on a circuit board or a substrate for display manufacturing equipment, and then exposed and developed. When the dry film photoresist or photosensitive element of the other embodiment has a protective film on the photosensitive resin layer, a process of removing the protective film may be further performed before the photosensitive resin layer is laminated on a circuit board or a substrate for a display manufacturing device. In addition, when the dry film photoresist or photosensitive element of the other embodiment has a polymer substrate or substrate film laminated on one side of the photosensitive resin layer, a step of removing the polymer substrate or substrate film immediately after the exposure step can be further carried out. Thus, the photosensitive resin layer contained in the dry film photoresist or photosensitive element of the other embodiments may be included in the circuit board or display device. Effect of the Invention

[0058] According to the present invention, it is possible to provide a photosensitive resin composition capable of reducing undercut during pattern plating and realizing a high-resolution pattern, and a dry film photoresist, a circuit board, and a display device each using the same. Furthermore, according to the present invention, it is possible to provide a photosensitive resin composition capable of realizing improved plating resistance, and a dry film photoresist, a circuit board, and a display device using the same. [Brief description of the drawings]

[0059] [Figure 1] FIG. 1 shows an optical microscope image of the foot length measured in Example 1. [Diagram 2] FIG. 2 is a schematic cross-sectional view of the resist pattern obtained in Example 1. [Diagram 3] FIG. 13 is a diagram showing optical microscope images of the degree of adhesion between a substrate and a photosensitive resin layer measured in Examples 5 to 8. [Figure 4] FIG. 13 is a diagram showing an optical microscope image of the degree of adhesion between a substrate and a photosensitive resin layer measured in Comparative Example 3 (immersion for 20 minutes). [Diagram 5] FIG. 13 is a diagram showing optical microscope images of the adhesion between the substrate and the photosensitive resin layer measured in Comparative Example 3 (immersion for 30 minutes) and Comparative Example 4 (immersion for 20 minutes). [Figure 6] FIG. 13 is a diagram showing an optical microscope image of the degree of adhesion between a substrate and a photosensitive resin layer measured in Comparative Example 4 (immersion for 30 minutes). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0060] The present invention will be described in more detail in the following examples, but the following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention. <Production Examples and Comparative Production Examples: Production of Alkaline Developable Binder Resins> Manufacturing Example 1 A four-neck round-bottom flask was equipped with a mechanical stirrer and a reflux device, and the flask was purged with nitrogen. 68 g of methyl ethyl ketone (MEK) and 5 g of methanol (MeOH) were added to the nitrogen-purged flask, and then 0.9 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. A monomer mixture of 24g of methacrylic acid (MAA), 6g of methylmethacrylate (MMA), 30g of styrene (SM), and 40g of 2-phenoxyethyl methacrylate (PHEMA) was added thereto as monomers, heated to 80°C, and polymerized for 6 hours to produce an alkali developable binder resin (weight average molecular weight 68900g / mol, solid content 47.9wt%, acid value 154mgKOH / g). The alkali-developable binder resin prepared in the above Preparation Example was dissolved in tetrahydrofuran to a concentration of 1.0 (w / w)% in THF (about 0.5 (w / w)% based on solid content), filtered using a syringe filter with a 0.45 μm pore size, and 20 μl was injected into GPC. Tetrahydrofuran (THF) was used as the mobile phase for GPC, and the flow rate was 1.0 mL / min. The column consisted of one Agilent PLgel 5 μm Guard (7.5×50 mm) and two Agilent PLgel 5 μm Mixed D (7.5×300 mm) connected in series. The detection device was an Agilent 1260 InfinityII system and RII Detector, and the measurement was performed at 40° C. The acid value was measured by dissolving 1 g of the alkaline developable binder resin in 50 ml of a mixed solvent (MeOH 20%, Acetone 80%), adding 2 drops of 1%-phenolphthalein indicator, and then titrating with 0.1N-KOH. The solid content was measured by heating the alkali developable binder resin prepared in the above Preparation Example in an oven at 150° C. for 120 minutes and then measuring the weight percentage of the remaining solid content based on the weight of the alkali developable binder resin prepared in the above Preparation Example.

[0061] Manufacturing Example 2 A four-neck round-bottom flask was equipped with a mechanical stirrer and a reflux device, and the flask was purged with nitrogen. 68 g of methyl ethyl ketone (MEK) and 5 g of methanol (MeOH) were added to the nitrogen-purged flask, and then 0.9 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. A monomer mixture of 24g of methacrylic acid (MAA), 26g of methylmethacrylate (MMA), 30g of styrene (SM), and 20g of 2-phenoxyethyl methacrylate (PHEMA) was added thereto, heated to 80°C, and polymerized for 6 hours to produce an alkali developable binder resin (weight average molecular weight 52500g / mol, solid content 48.3wt%, acid value 154mgKOH / g). Production Example 3 A mechanical stirrer and a reflux device were attached to a four-neck round-bottom flask, and the flask was purged with nitrogen. 80g of methyl ethyl ketone (MEK) and 7.5g of methanol (MeOH) were added to the flask purged with nitrogen, and 0.45g of azobisisobutyronitrile (AIBN) was added and completely dissolved. A monomer mixture of 8g of acrylic acid (AA), 15g of methacrylic acid (MAA), 15g of butyl acrylate (BA), 52g of methyl methacrylate (MMA), and 10g of styrene (SM) was added as monomers, and the temperature was raised to 80°C, followed by polymerization for 6 hours to produce an alkali-developable binder resin. The alkaline developable binder resin had a measured weight average molecular weight of 71,538 g / mol, a glass transition temperature of 79° C., a solids content of 51.4 wt %, and an acid value of 156.3 mg KOH / g.

[0062] Production Example 4 A four-neck round-bottom flask was equipped with a mechanical stirrer and a reflux device, and the inside of the flask was purged with nitrogen. 110g of methyl ethyl ketone (MEK) and 10g of methanol (MeOH) were added to the nitrogen-purged flask, and then 1g of azobisisobutyronitrile (AIBN) was added and completely dissolved. A monomer mixture of 30g of methacrylic acid (MAA), 100g of methyl methacrylate (MMA), and 30g of styrene (SM) was added thereto, and the mixture was heated to 80°C and polymerized for 6 hours to produce an alkali-developable binder resin (weight average molecular weight 49852g / mol, glass transition temperature 125°C, solid content 48.5wt%, acid value 163.17mgKOH / g). Comparative Manufacturing Example 1 A four-neck round-bottom flask was equipped with a mechanical stirrer and a reflux device, and the inside of the flask was purged with nitrogen. 90g of methyl ethyl ketone (MEK) and 10g of PGMEA (Propylene Glycol Monomethyl Ether Acetate) were added to the nitrogen-purged flask, and then 0.8g of azobisisobutyronitrile (AIBN) was added and completely dissolved. A monomer mixture of 20g of methacrylic acid, 70g of methyl methacrylate, and 10g of styrene was added thereto, and the mixture was heated to 80°C and polymerized for 6 hours to produce an alkali-developable binder resin (weight average molecular weight 60,000g / mol). Comparative Manufacturing Example 2 A mechanical stirrer and a reflux device were attached to a 4-neck round-bottom flask Jaket set, and the inside of the flask was purged with nitrogen. 90g of methyl ethyl ketone (MEK) and 10g of methanol (MeOH) were added to the nitrogen-purged flask, and 0.8g of azobisisobutyronitrile (AIBN) was added and completely dissolved. A monomer mixture of 24g of methacrylic acid, 46g of methyl methacrylate, and 30g of styrene was added thereto, and the mixture was heated to 80°C and polymerized for 6 hours to produce an alkali-developable binder resin (weight average molecular weight 49000g / mol, solid content 50.0wt%, acid value 155mgKOH / g). <Examples and Comparative Examples: Production of Photosensitive Resin Composition and Dry Film Photoresist> According to the compositions shown in Table 1 (Table 1 consists of Tables 1A and 1B) and Table 2 below, photopolymerization initiators were dissolved in methyl ethyl ketone (MEK) as a solvent, and then photopolymerizable compounds and alkali developable binder resins were added and mixed using a mechanical stirrer for about 1 hour to prepare photosensitive resin compositions. The obtained photosensitive resin composition was coated on a 20 μm PET film using a coating bar. The coated photosensitive resin composition layer was dried using a hot air oven at a drying temperature of 80° C. for 5 minutes, and the thickness of the photosensitive resin composition layer after drying was 25 μm. After drying, a protective film (polyethylene) was laminated onto the photosensitive resin composition layer to prepare a dry film photoresist.

[0063] The PET film was produced by the following steps. PET was produced by carrying out an ester exchange reaction and a polycondensation reaction from ethylene glycol and terephthalic acid. The PET pellets were dried under reduced pressure at 120°C for 8 hours, then fed to an extruder and melted at 280°C. This was wrapped around a casting drum with a surface temperature of 20°C using an electrostatic casting method, cooled and solidified, and an unstretched film was produced. The extrusion rate of the extruder was adjusted to adjust the thickness of the unstretched film to 250 μm. After that, the unstretched film was stretched 4 times in the longitudinal direction, and a prepared solution of 4 g of acrylic resin and 0.1 g of polymethyl methacrylate as organic particles mixed with 95.9 g of water was applied to one side of the film using gravure to a thickness of 50 nm after final drying. The polymethyl methacrylate used here was coated on the surface with polystyrene, was spherical, and had a refractive index difference with the acrylic resin of 0.03. The uniaxially stretched film in the longitudinal direction, on which the liquid containing the organic particles was applied, was preheated at 120° C. and stretched four times in the transverse direction. The film was heat-set at a maximum temperature of 230° C. for 10 seconds at a specified length and then cooled to room temperature to obtain a polyester film with a total thickness of 20 μm and a coating layer thickness of 50 nm. [Table 1A] [Table 1B] [Table 2]

[0064] <Experimental Example> For the dry film photoresists produced in the above Examples and Comparative Examples, the physical properties were measured by the following methods. The results are shown in Tables 3 to 5. 1. Foot length (unit: μm) The protective films of the dry film photoresists prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were peeled off, and the photosensitive resin layer of the dry film photoresist was brought into contact with the copper layer surface of the copper-clad laminate having a thickness of 1.6 mm that had been subjected to a brush polishing treatment. The substrate preheat roll temperature was 120° C., the lamination roll temperature was 115° C., and the roll pressure was 4.0 kgf / cm. 2 The laminate was formed using a HAKUTO MACH 610i at a roll speed of 2.0 min / m. After removing the PET film that was the support for the dry film photoresist from the laminate, a photomask for circuit evaluation (opening width 10 μm, spacing between openings 10 μm) was used to perform photolithography at 40 mJ / cm using an EXM-1201 (parallel light exposure device) manufactured by ORC. 2 After irradiating with ultraviolet light until the exposure reached 1.0 wt% of the sample, the sample was left for 15 minutes. Then, the sample was sprayed with a 1.0 wt% aqueous solution of Na2CO3 at 30±1°C at a pressure of 1.5 kgf / cm 2 The resist pattern was developed for twice the minimum developing time under the developing conditions of the spray method, and as shown in FIG. 2, the ratio L / S of the line width (L) of the upper part of the photosensitive resin layer line to the space (S) between the photosensitive resin layer lines was 1:1, and the line width (L) of the upper part of the photosensitive resin layer line was 10 μm. Thereafter, as shown in FIG. 2, on the surface of the copper-clad laminate, which is the bottom of a space between adjacent photosensitive resin layer lines, the resist residue remaining undeveloped on the bottom and one side of the photosensitive resin layer line abutting therewith was measured using a ZEISS AXIOPHOT Microscope to determine the shortest straight line distance from a point (d1) on the boundary line between the one side of the photosensitive resin layer line abutting the bottom and the resist residue to an intersection point (d2) where a cross section of the resist residue on a plane formed by a perpendicular line from the point to the one side of the photosensitive resin layer line and a perpendicular line from the point to the bottom meets the boundary line between the bottom and the resist residue, and the shortest straight line distance was defined as a foot length (F), and the maximum value of the foot length was shown in Table 2 below. 2. Fine wire adhesion (unit: μm) The protective films of the dry film photoresists prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were peeled off, and the photosensitive resin layer of the dry film photoresist was brought into contact with the copper layer surface of the copper-clad laminate having a thickness of 1.6 mm that had been subjected to a brush polishing treatment. The substrate preheat roll temperature was 120° C., the lamination roll temperature was 115° C., and the roll pressure was 4.0 kgf / cm. 2 The laminate was formed using a HAKUTO MACH 610i at a roll speed of 2.0 min / m. After removing the PET film that was the support for the dry film photoresist from the laminate, the laminate was exposed to 40 mJ / cm using a photomask for circuit evaluation and an EXM-1201 (parallel light exposure device) manufactured by ORC. 2 After irradiating with ultraviolet light until the exposure reached 1.0 wt% of the sample, the sample was left for 15 minutes. Then, the sample was sprayed with a 1.0 wt% aqueous solution of Na2CO3 at 30±1°C at a pressure of 1.5 kgf / cm 2 The development was carried out under the jet type development conditions for twice the minimum development time. After the development was completed, the minimum line width of the photosensitive resin layer was measured using a ZEISS AXIOPHOT Microscope to evaluate the fine line adhesion. The smaller this value, the better the fine line adhesion.

[0065] 3.1:1 resolution (unit: μm) The protective films of the dry film photoresists prepared in Examples 1 to 4, Comparative Example 1, and Preparation Example 2 were peeled off, and the photosensitive resin layer of the dry film photoresist was brought into contact with the copper layer surface of the copper-clad laminate having a thickness of 1.6 mm that had been subjected to a brush polishing treatment. The substrate preheat roll temperature was 120° C., the lamination roll temperature was 115° C., and the roll pressure was 4.0 kgf / cm. 2 The laminate was formed using a HAKUTO MACH 610i at a roll speed of 2.0 min / m. After removing the PET film, which is the support of the dry film photoresist, from the laminate, a photomask for circuit evaluation was used so that the width of the circuit line after development and the space between the circuit lines were 1:1. Using an EXM-1201 (parallel light exposure device) manufactured by ORC, 40 mJ / cm 2 After irradiating with ultraviolet light until the exposure reached 1.0 wt% of the sample, the sample was left for 15 minutes. Then, the sample was sprayed with a 1.0 wt% aqueous solution of Na2CO3 at 30±1°C at a pressure of 1.5 kgf / cm 2 The development was carried out under the jet type development conditions for twice the minimum development time. After the development was completed, the minimum distance between the photosensitive resin layers of the laminate was measured using a ZEISS AXIOPHOT Microscope to evaluate the 1:1 resolution. The smaller this value is, the better the 1:1 resolution is. 4. Minimum development time (in seconds) The protective films of the dry film photoresists prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were peeled off, and the photosensitive resin layer of the dry film photoresist was brought into contact with the copper layer surface of the copper-clad laminate having a thickness of 1.6 mm that had been subjected to a brush polishing treatment. The substrate preheat roll temperature was 120° C., the lamination roll temperature was 115° C., and the roll pressure was 4.0 kgf / cm. 2 The laminate was formed using a HAKUTO MACH 610i at a roll speed of 2.0 min / m. Then, spray with a 1.0 wt% Na2CO3 solution at 30±1℃ under a pressure of 1.5 kgf / cm 2The film was developed under the development conditions of the jet method. The time required for the photosensitive resin layer on the copper-clad laminate to be completely removed by the developer (minimum developing time) was measured using a second clock. [Table 3] As can be seen from Table 3 above, the Examples maintained similar levels of development time, fine line adhesion, and resolution compared to the Comparative Examples, and were found to have excellent developability with a significantly shorter foot length.

[0066] 5. Plating resistance The protective films of the dry film photoresists prepared in Examples 5 to 8 and Comparative Examples 3 and 4 were peeled off, and the photosensitive resin layer of the dry film photoresist was brought into contact with the copper layer surface of the copper-clad laminate having a thickness of 1.6 mm that had been subjected to a brush polishing treatment. The substrate preheat roll temperature was 120° C., the lamination roll temperature was 115° C., and the roll pressure was 4.0 kgf / cm. 2 The laminate was formed using a HAKUTO MACH 610i at a roll speed of 2.0 min / m. After removing the PET film that was the support for the dry film photoresist from the laminate, the laminate was exposed to 80 mJ / cm using an EXM-1201-F (parallel light exposure device) manufactured by ORC. 2 After irradiating the entire surface with ultraviolet light for 4 seconds at an exposure dose of 1.0, the sample was left for 15 minutes. After that, the sample was sprayed with a 1.0 wt% aqueous solution of Na2CO3 at 30±1°C at a pressure of 1.5 kgf / cm 2 The film was developed for 1 minute using the jet developing conditions. After the development was completed, the laminate was cut into a size of 5 cm wide x 5 cm long to prepare a sample, which was then loaded onto a PFA wafer carrier of the same size and immersed in 1 L of a nickel aqueous solution plating solution to perform nickel plating. More specifically, for nickel plating, the cured film was immersed in a hydrochloric acid-based palladium catalyst ICP ACCERA H aqueous solution (a mixed solution of 90cc of 35% hydrochloric acid aqueous solution and 40cc of ICP ACCERA H in 870cc of distilled water) in accordance with the bath preparation conditions manufactured by MK Chem & Tech Co., Ltd. at 25°C for 1 minute, and then immersed in an electroless Ni-P chemical ICP NICORON GIB aqueous solution (a mixed solution of 100cc of ICP NICORON GIB-M and 50cc of ICP NICORON GIB-1 in 850cc of distilled water) for 10 minutes, 20 minutes, and 30 minutes, as shown in the immersion times in Table 2 below, at 80°C (the nickel plating solutions ICP ACCERA H, ICP NICORON GIB-M, and ICP NICORON GIB-1 were purchased from MK Chem & Tech Co., Ltd.). After nickel plating was completed, the adhesion of the dry film photoresist on the copper clad laminate was determined through an optical microscope image to evaluate plating resistance, and the results are shown in Table 2. The adhesion of the dry film photoresist means the percentage ratio of the surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the copper clad laminate after nickel plating to the surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the copper clad laminate before nickel plating, as shown in Equation 4 below.

[0067] [Formula 4] Adhesion (%) = (surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the copper-clad laminate after nickel plating / surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the copper-clad laminate before nickel plating) * 100 [Table 4] As can be seen from Table 4, the Examples maintained the adhesion to the substrate during nickel plating during ENIG plating compared to the Comparative Examples, and therefore, it was confirmed that the Examples had excellent plating resistance.

[0068] 6. Fine wire adhesion (unit: μm) The protective films of the dry film photoresists prepared in Examples 5 to 8 and Comparative Examples 3 and 4 were peeled off, and the photosensitive resin layer of the dry film photoresist was brought into contact with the copper layer surface of the copper-clad laminate having a thickness of 1.6 mm that had been subjected to a brush polishing treatment. The substrate preheat roll temperature was 120° C., the lamination roll temperature was 115° C., and the roll pressure was 4.0 kgf / cm. 2 The laminate was formed using a HAKUTO MACH 610i at a roll speed of 2.0 min / m. After removing the PET film that was the support for the dry film photoresist from the laminate, a photomask for circuit evaluation was used, and the laminate was exposed to 80 mJ / cm using an EXM-1201-F (parallel light exposure device) manufactured by ORC. 2 After irradiating the sample with ultraviolet light for 4 seconds at an exposure dose of 1.0, the sample was left for 15 minutes. After that, the sample was sprayed with a 1.0 wt% aqueous solution of Na2CO3 at 30±1°C under a pressure of 1.5 kgf / cm 2 The film was developed for 1 minute using the jet developing conditions. After the development was completed, the minimum line width of the photosensitive resin layer was measured using a ZEISS AXIOPHOT Microscope to evaluate the fine line adhesion. The smaller this value, the better the fine line adhesion. 7.1:1 resolution (unit: μm) The protective films of the dry film photoresists prepared in Examples 5 to 8 and Comparative Examples 3 and 4 were peeled off, and the photosensitive resin layer of the dry film photoresist was brought into contact with the copper layer surface of the copper-clad laminate having a thickness of 1.6 mm that had been subjected to a brush polishing treatment. The substrate preheat roll temperature was 120° C., the lamination roll temperature was 115° C., and the roll pressure was 4.0 kgf / cm. 2 The laminate was formed using a HAKUTO MACH 610i at a roll speed of 2.0 min / m. After removing the PET film, which is the support of the dry film photoresist, from the laminate, a photomask for circuit evaluation was used so that the width of the circuit line after development and the space between the circuit lines were 1:1. The photomask was then exposed to 80 mJ / cm using an EXM-1201-F (parallel light exposure device) manufactured by ORC. 2After irradiating the sample with ultraviolet light for 4 seconds at an exposure dose of 1.0, the sample was left for 15 minutes. After that, the sample was sprayed with a 1.0 wt% aqueous solution of Na2CO3 at 30±1°C under a pressure of 1.5 kgf / cm 2 The film was developed for 1 minute using the jet developing conditions. After the development was completed, the minimum distance between the photosensitive resin layers of the laminate was measured using a ZEISS AXIOPHOT Microscope to evaluate the 1:1 resolution. The smaller this value is, the better the 1:1 resolution is. [Table 5] As can be seen from Table 5 above, it was confirmed that the examples were superior in fine line adhesion and resolution compared to the comparative examples. [Explanation of symbols]

[0069] L Line width of upper line S Space between lines T photosensitive resin layer thickness d1: A point on the boundary between one side of the photosensitive resin layer line in contact with the bottom surface and the resist residue d2: The intersection point where the cross section of the resist residue along a plane formed by a perpendicular line from d1 to one side of the photosensitive resin layer line and a perpendicular line from d1 to the bottom surface meets the boundary line formed by the bottom surface and the resist residue. F Foot length

Claims

1. The present invention relates to an alkali developable binder resin including a repeating unit represented by the following chemical formula 1, a repeating unit represented by the following chemical formula 2, a repeating unit represented by the following chemical formula 3, and a repeating unit represented by the following chemical formula 4, a photopolymerization initiator, and a photopolymerizable compound: a second alkali developable binder resin including a repeating unit represented by the following Chemical Formula 14, a repeating unit represented by the following Chemical Formula 15, and a repeating unit represented by the following Chemical Formula 16: A photosensitive resin composition that satisfies the following (b): (b) when a film sample having a photosensitive resin layer containing the photosensitive resin composition laminated on a substrate is nickel-plated for 20 minutes or more using an aqueous solution containing nickel, the adhesion defined by the following Equation 1 is 90% or more, the photosensitive resin layer contains a dried or cured product of the photosensitive resin composition, The substrate is a copper-clad laminate having a copper layer having a thickness of 10 μm or more and 100 mm or less on a surface thereof, The nickel plating is performed by immersing a film sample having a photosensitive resin layer including the photosensitive resin composition laminated on the substrate in an aqueous solution containing nickel at a temperature of 50° C. or higher and 100° C. or lower for 20 minutes or longer; [Formula 1] Adhesion (%)=(surface area of ​​the photosensitive resin layer containing the photosensitive resin composition in contact with the substrate after nickel plating / surface area of ​​the photosensitive resin layer containing the photosensitive resin composition in contact with the substrate before nickel plating)*100 【Chemistry 1】 In the above Chemical Formula 1, R １ is hydrogen or alkyl having 1 to 10 carbon atoms, R ２ is an alkylene having 1 to 10 carbon atoms, Ar is an aryl having 6 to 20 carbon atoms; n is an integer from 1 to 20; 【Chemistry 2】 In the above Chemical Formula 2, R ３ is hydrogen or alkyl having 1 to 10 carbon atoms, 【Chemistry 3】 In the above Chemical Formula 3, R ４ is hydrogen or alkyl having 1 to 10 carbon atoms, R ５ is an alkyl group having 1 to 10 carbon atoms; 【Chemistry 4】 In the above Chemical Formula 4, Ar is an aryl having 6 to 20 carbon atoms; 【Chemistry 10】 In the above Chemical Formula 14, R 3 ' is an alkyl group having 1 to 10 carbon atoms; 【Chemistry 11】 In the above Chemical Formula 15, R 4 ″ is alkyl having 1 to 10 carbon atoms, R 5 ″ is alkyl having 1 to 10 carbon atoms, 【Chemistry 12】 In the above Chemical Formula 16, Ar is an aryl having 6 to 20 carbon atoms.

2. 10. The photosensitive resin composition of claim 1, further comprising an alkali developable binder resin prepared by polymerizing a monomer mixture of methacrylic acid, methyl methacrylate and styrene.

3. The photosensitive resin composition according to claim 1 , wherein the photopolymerizable compound comprises a difunctional (meth)acrylate compound, a trifunctional or higher polyfunctional (meth)acrylate compound, and a monofunctional (meth)acrylate compound.

4. The photosensitive resin composition according to claim 3, wherein the tri- or higher functional polyfunctional (meth)acrylate compound has a structure in which three or more alkylene oxide groups and three or more (meth)acrylate functional groups, each having 1 to 10 carbon atoms, are bonded to a central group having 1 to 20 carbon atoms.

5. The photosensitive resin composition according to claim 3, wherein the trifunctional or higher polyfunctional (meth)acrylate compound includes a compound represented by the following chemical formula 12: 【Chemistry 18】 In the above Chemical Formula 12, R １４ is hydrogen or alkyl having 1 to 10 carbon atoms, R １５ is an alkylene having 1 to 10 carbon atoms, R １６ contains a central group having 1 to 20 carbon atoms, p is a functional group, n12 is an integer from 1 to 20, p is the above R １６ is the number of functional groups substituted with , and is an integer of 3 to 10.

6. 4. The photosensitive resin composition according to claim 3, wherein the monofunctional (meth)acrylate compound comprises a (meth)acrylate containing an alkylene oxide group having 1 to 10 carbon atoms.

7. The photosensitive resin composition according to claim 3, wherein the monofunctional (meth)acrylate compound comprises a compound represented by the following chemical formula 11: 【Chemistry 19】 In the above Chemical Formula 11, R １１ is hydrogen or alkyl having 1 to 10 carbon atoms, R １２ is an alkylene having 1 to 10 carbon atoms, R １３ is an alkyl group having 1 to 10 carbon atoms; n11 is an integer from 1 to 20.

8. The photosensitive resin composition according to claim 3 , comprising 500 parts by weight or more and 1500 parts by weight or less of the difunctional (meth)acrylate compound relative to 100 parts by weight of the monofunctional (meth)acrylate compound.

9. The photosensitive resin composition according to claim 3 , comprising 500 parts by weight or more and 1000 parts by weight or less of the difunctional (meth)acrylate compound relative to 100 parts by weight of the trifunctional or higher polyfunctional (meth)acrylate compound.

10. 4. The photosensitive resin composition according to claim 3, comprising 110 parts by weight or more of the tri- or higher functional polyfunctional (meth)acrylate compound relative to 100 parts by weight of the monofunctional (meth)acrylate compound.

11. 4. The photosensitive resin composition according to claim 3, comprising 1 part by weight or more and 50 parts by weight or less of the monofunctional (meth)acrylate compound and the trifunctional or higher polyfunctional (meth)acrylate compound relative to 100 parts by weight of the bifunctional (meth)acrylate compound.

12. A dry film photoresist comprising a photosensitive resin layer comprising the photosensitive resin composition of claim 1.

13. The dry film photoresist of claim 12, which satisfies the following (b): (b) when a film sample having a photosensitive resin layer of the dry film photoresist laminated on a substrate is nickel-plated for 20 minutes or more in an aqueous solution containing nickel, the adhesion defined by the following Equation 2 is 90% or more; [Formula 2] Adhesion (%)=(surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the substrate after nickel plating / surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the substrate before nickel plating)*100

14. A polymer substrate; and a photosensitive resin layer formed on the polymer substrate, the photosensitive resin layer includes an alkali developable binder resin including a repeating unit represented by Chemical Formula 1 below, a repeating unit represented by Chemical Formula 2 below, a repeating unit represented by Chemical Formula 3 below, and a repeating unit represented by Chemical Formula 4 below, and a photopolymerizable compound, the photosensitive resin layer further comprises a second alkali developable binder resin including a repeating unit represented by the following Chemical Formula 14, a repeating unit represented by the following Chemical Formula 15, and a repeating unit represented by the following Chemical Formula 16: A photosensitive element that satisfies (b) below: (b) when a film sample having the photosensitive resin layer laminated on a substrate is nickel-plated for 20 minutes or more using an aqueous solution containing nickel, the adhesion defined by the following formula 3 is 90% or more, the photosensitive resin layer contains a dried or cured product of a photosensitive resin composition, The substrate is a copper-clad laminate having a copper layer having a thickness of 10 μm or more and 100 mm or less on a surface thereof, The nickel plating is performed by immersing a film sample having the photosensitive resin layer laminated on the substrate in an aqueous solution containing nickel at a temperature of 50° C. or higher and 100° C. or lower for 20 minutes or longer; [Formula 3] Adhesion (%)=(surface area of ​​the photosensitive resin layer of the photosensitive element in contact with the substrate after nickel plating / surface area of ​​the photosensitive resin layer of the photosensitive element in contact with the substrate before nickel plating)*100 【Chemistry 1】 In the above Chemical Formula 1, R １ is hydrogen or alkyl having 1 to 10 carbon atoms, R ２ is an alkylene having 1 to 10 carbon atoms, Ar is an aryl having 6 to 20 carbon atoms; n is an integer from 1 to 20; 【Chemistry 2】 In the above Chemical Formula 2, R ３ is hydrogen or alkyl having 1 to 10 carbon atoms, 【Chemistry 3】 In the above Chemical Formula 3, R ４ is hydrogen or alkyl having 1 to 10 carbon atoms, R ５ is an alkyl group having 1 to 10 carbon atoms; 【Chemistry 4】 In the above Chemical Formula 4, Ar is an aryl having 6 to 20 carbon atoms; 【Chemistry 10】 In the above Chemical Formula 14, R 3 ' is an alkyl group having 1 to 10 carbon atoms; 【Chemistry 11】 In the above Chemical Formula 15, R 4 ″ is alkyl having 1 to 10 carbon atoms, R 5 ″ is alkyl having 1 to 10 carbon atoms, 【Chemistry 12】 In the above Chemical Formula 16, Ar is an aryl having 6 to 20 carbon atoms.

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