Photosensitive element, dry film photoresist, resist pattern, circuit board, and display device using the same

Abstract

The present disclosure relates to a photosensitive element, a dry film photoresist, a resist pattern, a circuit board, and a display device using the same, the photosensitive element including: a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, wherein a thickness of a palladium plating layer is 0.01 µm or more, the palladium plating layer being obtained by immersing a film sample in which the photosensitive resin layer is laminated on a substrate in a palladium plating solution for 60 minutes, and then immersing a copper-clad laminate sample in the residual palladium plating solution for 5 minutes.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a photosensitive element, a dry film photoresist, a resist pattern, a circuit board, and a display device. BACKGROUND

[0002] A photosensitive resin composition is used in a dry film photoresist (DFR), a liquid photoresist (liquid photoresist ink), etc. for a printed circuit board (PCB) or a lead frame.

[0003] At present, a dry film photoresist is widely used not only in the manufacture of a printed circuit board (PCB) and a lead frame, but also in the manufacture of a barrier rib of a plasma display panel (PDP), an ITO electrode of other displays, a bus address electrode, and a black matrix.

[0004] Generally, this type of dry film photoresist is often used for lamination on a copper-clad laminate. In connection therewith, as an example of a manufacturing process of a printed circuit board (PCB), a pretreatment step is first performed in order to laminate a copper-clad laminate sample as an initial board material of the PCB. In an outer layer process, the pretreatment step is performed in the order of drilling, deburring, scrubbing, etc., and scrubbing or pickling is performed in an inner layer process. In the scrubbing step, a hard-bristle brush and a float stone process are mainly used, and in the pickling step, soft etching and 5 wt% sulfuric acid pickling can be performed.

[0005] In order to form a circuit on a copper-clad laminate that has undergone a pretreatment step, a dry film photoresist (hereinafter referred to as DFR) is generally laminated on a copper layer of the copper-clad laminate. In this step, a laminator is used to laminate a photoresist layer of the DFR on a copper surface while peeling off a protective film of the DFR. Generally, lamination is performed at a speed of 0.5 m / min to 3.5 m / min, a temperature of 100°C to 130°C, and a heating roll pressure of 10 psi to 90 psi.

[0006] A printed circuit board that has undergone a lamination step is left for 15 minutes or more to stabilize the circuit board, and then a photoresist of the DFR is exposed using a photomask on which a desired circuit pattern is formed. When the photomask is irradiated with ultraviolet rays in this process, the photoresist irradiated with ultraviolet rays begins to polymerize with the contained photoinitiator at the irradiation site. First, oxygen in the photoresist is consumed at an initial stage, and then active monomers are polymerized to cause a crosslinking reaction. Subsequently, the polymerization reaction continues while a large amount of monomers is consumed. On the other hand, an unexposed portion exists in a state in which no crosslinking reaction is performed.

[0007] Next, a developing step of removing the unexposed portion of the photoresist is performed. In the case of the alkali-developable DFR, an aqueous solution of 0.8 to 1.2 wt% of potassium carbonate and sodium carbonate is used as a developing solution. In this step, the unexposed portion of the photoresist is washed away by a saponification reaction between the developing solution and the carboxylic acid of the binder polymer in the developing solution, while the cured photoresist remains on the copper surface.

[0008] Then, depending on the inner layer and outer layer processes, a circuit is formed through different steps. In the inner layer process, a circuit is formed on the substrate through etching and stripping steps, while in the outer layer process, plating and tenting steps are performed, and then etching and solder stripping are performed, thereby forming a predetermined circuit. SUMMARY

[0009] TECHNICAL PROBLEM

[0010] An object of the present disclosure is to provide a photosensitive element that can achieve the effect of reducing contamination of a plating solution and enabling plating to be performed with a sufficient thickness.

[0011] Another object of the present disclosure is to provide a dry film photoresist, a resist pattern, a circuit board, and a display device using the above-described photosensitive element.

[0012] TECHNICAL SOLUTION

[0013] To achieve the above object, according to an aspect, there is provided a photosensitive element, including: a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, wherein a thickness of a palladium plating layer is 0.01 μm or more, the palladium plating layer being obtained by immersing a film sample in which the photosensitive resin layer is laminated on a substrate in a palladium plating solution for 60 minutes, and then immersing a copper-clad laminate sample in a residual palladium plating solution for 5 minutes.

[0014] According to another aspect, there is provided a dry film photoresist, including: a photosensitive resin composition including an alkali-developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the photopolymerizable compound includes at least one selected from a penta-type (meth)acrylate compound having five (meth)acryl groups and a multifunctional (meth)acrylate compound having seven or more (meth)acryl groups, and wherein a thickness of a palladium plating layer is 0.01 μm or more, the palladium plating layer being obtained by immersing a film sample in which the photosensitive resin layer is laminated on a substrate in a palladium plating solution for 60 minutes, and then immersing a copper-clad laminate sample in a residual palladium plating solution for 5 minutes.

[0015] According to another aspect, there is provided a dry film photoresist including: a photosensitive resin composition including an alkali-developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the alkali-developable binder resin includes four or more types of polymers different from each other, and wherein a thickness of a palladium plating layer obtained by immersing a film sample in which the photosensitive resin layer is laminated on a substrate in a palladium plating solution for 60 minutes, and then immersing a copper-clad laminate sample in the residual palladium plating solution for 5 minutes is 0.01 μm or more.

[0016] According to still another aspect, there is provided a resist pattern including a photosensitive resin pattern including the photosensitive resin composition included in the dry film photoresist.

[0017] According to still another aspect, there is provided a circuit board including the resist pattern or a metal pattern formed by the resist pattern.

[0018] According to still another aspect, there is provided a display device including the resist pattern or a metal pattern formed by the resist pattern.

[0019] Now, the photosensitive element, the dry film photoresist, the resist pattern, the circuit board, and the display device according to the specific embodiments of the disclosure will be described in more detail.

[0020] Unless otherwise specifically indicated in the specification, the technical terms used in the specification are only used to refer to the specific embodiments, and are not intended to limit the disclosure.

[0021] Unless the context clearly indicates otherwise, as used herein, the singular forms "a," "an," and "the" include plural referents.

[0022] The term "include" or "comprise" used in the specification indicates a specific feature, region, integer, step, operation, element, and / or component, but does not exclude the presence or addition of different specific features, regions, integers, steps, operations, elements, components, and / or groups.

[0023] In addition, the terms including ordinal numbers such as "first," "second," etc. are only used for the purpose of distinguishing one component from another component, and are not limited by the ordinal numbers. For example, without departing from the scope of the disclosure, a first component can be referred to as a second component, or similarly, a second component can be referred to as a first component.

[0024] In the disclosure, examples of substituents are described as follows, but are not limited thereto.

[0025] In the present disclosure, the term "substituted" means that a hydrogen atom in a substituent is bonded to another functional group, and there is no limitation on the position to be substituted, as long as the position is a position where a hydrogen atom is substituted, i.e., a position which can be substituted by a substituent, and when two or more are substituted, the two or more substituents can be the same as or different from each other.

[0026] In the present disclosure, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from deuterium; a halogen group; a cyano group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amide group; a primary amino group; a carboxyl group; a sulfonic acid group; a sulfonamide group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an alkoxy silyl alkyl group; an aryl phosphine group; or a heterocyclic group including at least one of N, O, and S atoms, or the term "substituted or unsubstituted" means unsubstituted or substituted with a substituent in which two or more of the above-described examples of substituents are linked. For example, the "substituent in which two or more of the above-described examples of substituents are linked" can be a biphenyl group. That is, the biphenyl group can also be an aryl group, and can be understood as a substituent in which two phenyl groups are linked.

[0027] In the present disclosure, the symbol or -* means a bond to another substituent, and while a direct bond means that there is no other atom in the moiety represented by L.

[0028] In the present disclosure, the (meth)acrylic group is intended to include both an acrylic group and a methacrylic group. For example, the (meth)acryloyl group can include both an acryloyl group and a methacryloyl group. In addition, the (meth)acrylate can include both an acrylate and a methacrylate.

[0029] In the present disclosure, an alkyl group is a monovalent functional group from an alkane, and can be linear or branched. The number of carbon atoms of a linear alkyl group is not particularly limited, but is preferably 1 to 20. Further, the number of carbon atoms of a branched alkyl group is 3 to 20. Specific examples of the alkyl group include: methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, t-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, t-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, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, iso-hexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptane-4-yl, and the like, but are not limited thereto. The alkyl group can be substituted or unsubstituted, and when it is substituted, examples of the substituent are the same as described above.

[0030] In the present disclosure, an aryl group is a monovalent functional group from an aromatic hydrocarbon, and is not particularly limited, but preferably has 6 to 20 carbon atoms, and can be a monocyclic aryl group or a polycyclic aryl group. Specific examples of the monocyclic aryl group can include phenyl, biphenyl, terphenyl, and the like, but are not limited thereto. Specific examples of the polycyclic aryl group can include naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, group, fluorenyl, and the like, but are not limited thereto. The aryl group can be substituted or unsubstituted, and when it is substituted, examples of the substituent are the same as described above.

[0031] Hereinafter, the present disclosure will be described in more detail.

[0032] 1. Photosensitive element

[0033] According to one embodiment of the present disclosure, a photosensitive element can be provided, including: a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, wherein a thickness of a palladium plating layer is 0.01 μm or more, the palladium plating layer being obtained by immersing a film sample in which the photosensitive resin layer is laminated on the substrate in a palladium plating solution for 60 minutes, and then immersing a copper-clad laminate sample in the residual palladium plating solution for 5 minutes.

[0034] Various plastic films can be used as the substrate film, and examples thereof can include at least one plastic film selected from the group consisting of an acrylic film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a poly norbornene (PNB) film, a cyclic olefin polymer (COP) film, and a polycarbonate (PC) film. The thickness of the substrate film is not particularly limited, and for example, it can be freely adjusted in the range of 0.01 μm to 1 mm.

[0035] A specific example of the polymer substrate can be a polyester film, wherein the anti-blocking layer is formed by an in-line coating method by uniaxially stretching an unstretched polyester film, coating a coating solution containing a binder resin and organic particles onto one surface thereof, and uniaxially stretching the remaining portion.

[0036] The polymer substrate is generally manufactured by an in-line coating method without adding an anti-blocking agent, which is generally added in consideration of runnability and winding characteristics during the manufacturing process, and has an organic particle layer using alternative particles that do not impair transparency.

[0037] Here, examples of the organic particles used while considering runnability and winding characteristics, which are not impaired in transparency, can include organic particles such as multilayer multi-component particles in which acrylic particles such as methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, n-butyl methyl methacrylate, acrylic acid, a methacrylic acid copolymer, or a terpolymer; olefin-based particles such as polyethylene, polystyrene, or polypropylene; an acrylic and olefin-based copolymer; or a homopolymer particle are formed, and then another type of monomer is coated on the layer.

[0038] Such organic particles should particularly have a refractive index different from that of the binder resin while being spherical. Here, "spherical" means that the ratio of the minor axis (a) and the major axis (b) in an ellipse is 0.5 < a / b < 2, and the relationship with the diagonal line (d) in a rectangle is defined as d < a2 + b2. Also, the relationship between the axis (f) having the longest distance between the vertices of a hexahedron and the c-axis other than the a-axis and the b-axis is defined as f2 < c2 + a2 + b2. The shape of the particle should be spherical, which is preferable in terms of runnability.

[0039] Further, it is characterized in that the difference in refractive index between the organic particle and the binder resin is 0.05 or less. When the difference in refractive index is greater than 0.05, the haze increases. This means that there is a large amount of scattered light, and when there is a large amount of such scattered light, the sidewall smoothing effect decreases. This also depends on the size and amount of the organic particles. Preferably, the average particle diameter of the organic particles is about 0.5 μm to 5 μm. When less than this range, the runnability and winding characteristics are deteriorated, and when greater than 5 μm, the haze increases, which is not preferable in consideration of the occurrence of a dripping problem. The content of the organic particles is preferably 1 wt% to 10 wt% based on the total amount of the binder resin.

[0040] When the content of the organic particles is less than 1% by weight based on the total amount of the binder resin, the anti-blocking effect is insufficient and is easily scratched, and the running performance and the winding characteristics are deteriorated, and when it exceeds 10% by weight, there are problems in that the haze increases and the transparency is deteriorated.

[0041] Meanwhile, in addition to the above organic particles, inorganic particles can be added. At this time, it is not preferable to add a commonly used inorganic anti-blocking agent, and it is preferable to add colloidal silica having a particle diameter of 100 nm or less. The content thereof is preferably 10 parts by weight or less based on 100 parts by weight of the binder resin. When the above particle diameter and content are satisfied, it is possible to prevent the occurrence of side wall defects or recesses such as pits caused by the anti-blocking layer when a pattern is formed using a dry film photoresist.

[0042] As the binder resin serving as a binder for applying such organic particles to the unstretched polyester film, a binder resin having excellent compatibility with the organic particles can be used. Examples of such a resin can include acrylic resins such as unsaturated polyester, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, n-butylmethyl methacrylate, acrylic acid, a methacrylic acid copolymer, or a terpolymer; polyurethane-based resins; epoxy-based resins; or melamine-based resins, etc., and an acrylic resin is preferable.

[0043] In preparing the application solution using the binder resin and the organic particles, the solvent that can be used is preferably water.

[0044] As described above, the unstretched polyester film obtained by melt extrusion of PET pellets is uniaxially stretched, and then the application solution containing the organic particles in the binder resin is applied to the uniaxially stretched film. The application can be performed on at least one side of the uniaxially stretched film, and the thickness thereof is preferably about 30 nm to 200 nm based on the thickness after final drying. If the application solution containing the organic particles is applied to the uniaxially stretched film to have a thickness greater than 30 nm, there is a problem in that the organic particles are easily dropped and are easily scratched, and white powder is generated. When applied to a thickness greater than 200 nm, since the viscosity of the application solution increases, in online application having a high application speed, application streaks are generated in the application direction.

[0045] The polymer substrate obtained by the online application method as described above, by applying using the organic particles instead of the conventional anti-blocking agent, is a substrate film that maintains the running performance and the winding characteristics due to the particle layer, and also has excellent transparency due to the organic particles having excellent light transmittance.

[0046] Since the lamination of the photosensitive resin layer is performed on the opposite surface of the layer containing the organic particles in the polymer substrate, the photosensitive resin layer is formed on the opposite surface of the layer containing the organic particles in this way. Therefore, the pit-shaped defect that occurs when the substrate film containing the anti-blocking agent is laminated as before does not occur. Since the particles such as silica are not only larger in size than the organic particles but also distributed throughout the substrate film, the influence of silica is negligible even in the region adjacent to the photosensitive resin layer.

[0047] On the other hand, in the polymer substrate used in the present disclosure, the organic particles have 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 affected. In addition, by using the organic particles having excellent light transmittance, the side wall defect can be reduced, and the other circuit performance is not impaired.

[0048] The photosensitive element can further include a protective film formed on the photosensitive resin layer. The protective film prevents damage to the photosensitive resin layer during operation, and serves as a protective cover to protect the photosensitive resin layer from foreign matter such as dust. The protective film 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 external influences. When a dry film photoresist is applied to post-processing, it needs to be easily separated, and needs appropriate peelability and adhesion so that it does not deform during storage and distribution.

[0049] Various plastic films can be used as the protective film, and examples thereof can include at least one plastic film selected from the group consisting of an acrylic film, a polyethylene (PE) film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a poly-norbornene (PNB) film, a cyclic olefin polymer (COP) film, and a polycarbonate (PC) film. The thickness of the protective film is not particularly limited, and for example, it can be freely adjusted in the range of 0.01 μm to 1 mm.

[0050] The photosensitive element is characterized in that the thickness of the palladium plating layer obtained by immersing a film sample in which the photosensitive resin layer is laminated on the substrate in a palladium plating solution for 60 minutes, and then immersing the copper-clad laminate sample in the residual palladium plating solution for 5 minutes, can be 0.01 μm or more, or 0.05 μm or more, or 0.1 μm or more, or 0.01 μm or more and 0.15 μm or less, or 0.05 μm or more and 0.15 μm or less, or 0.1 μm or more and 0.15 μm or less.

[0051] Further, the photosensitive element is characterized in that the thickness of a nickel-phosphorus plating layer obtained by immersing a film sample in which the photosensitive resin layer is laminated on a substrate in a nickel-phosphorus plating solution for 38 minutes and then immersing a copper-clad laminate sample in the residual nickel-phosphorus plating solution for 28 minutes can be 3.9 μm or more, or 3.95 μm or more, or 3.9 μm or more and 4.0 μm or less, or 3.95 μm or more and 4.0 μm or less, or the dry film photoresist is characterized in that the thickness of a gold plating layer obtained by immersing a film sample in which the photosensitive resin layer is laminated on a substrate in a gold plating solution for 98 minutes and then immersing a copper-clad laminate sample in the residual gold plating solution for 11 minutes can be 0.11 μm or more, or 0.11 μm or more and 0.13 μm or less, or 0.12 μm or more, or 0.12 μm or more and 0.13 μm or less.

[0052] The residual palladium plating solution is a palladium plating solution contaminated with a photosensitive resin layer component, and the thickness of a palladium plating layer obtained by immersing a copper-clad laminate sample in the contaminated residual palladium plating solution for 5 minutes is used to evaluate the contamination performance of the dry film photoresist on the plating solution when palladium is plated on a laminate on which a photosensitive resin layer is laminated. When the contamination of the plating solution is more severe, the thickness of the palladium plating layer obtained by immersing a copper-clad laminate sample in the palladium plating solution for 5 minutes becomes significantly lower. On the other hand, when the plating solution is less contaminated, the thickness of the palladium plating layer obtained by immersing a copper-clad laminate sample in the palladium plating solution for 5 minutes becomes significantly higher. Therefore, in actual electroless palladium plating processes, contaminants accumulate in a large amount of dry film photoresist, and the addition of palladium is only for continuous plating, which causes difficulties in other purification processes. Therefore, it is very important to evaluate the degree of contamination of the dry film photoresist on the palladium plating solution.

[0053] That is, in palladium plating, first, a first palladium plating is performed using a film on which a photosensitive resin layer is laminated. After the first electroplating is completed, a second palladium plating is performed on a new copper-clad laminate sample in the contaminated palladium plating solution, and the contamination performance of the dry film photoresist on the plating solution is evaluated from the thickness of the palladium plating layer at the time of the second electroplating.

[0054] Therefore, the thickness of the palladium plating layer obtained by immersing a film sample in which the photosensitive resin layer is laminated on a substrate in a palladium plating solution for 60 minutes and then immersing a copper-clad laminate sample in the residual palladium plating solution for 5 minutes is excessively reduced to less than 0.1 μm, which is a target value, and the degree of contamination of the plating solution can be evaluated accordingly. When the plating layer is plated to a thickness lower than the target value in evaluating the degree of contamination, the contamination of the electroless palladium plating solution is severe in actual processes, and thus it is difficult to repeatedly use a plating solution exceeding 0.5 MTO, which can be disadvantageous in terms of process efficiency and economy.

[0055] There are no particular limitations on the calculation of palladium coating thickness, and various known methods for measuring coating thickness can be applied without restriction. For example, it can be measured using an XRF coating thickness measuring instrument (Helmut Fischer XDV-μ).

[0056] The following describes a more specific example of a method for obtaining residual palladium plating solution by immersing a film sample in a palladium plating solution for 60 minutes, wherein the film sample having a photosensitive resin layer laminated on a substrate is immersed in the palladium plating solution.

[0057] First, the copper-clad laminate sample with the photosensitive resin layer laminated on top can also be immersed in a nickel-phosphorus plating solution for rinsing. While there are no particular restrictions on the specific conditions for immersing the copper-clad laminate sample with the photosensitive resin layer laminated on top in the nickel-phosphorus plating solution, for example, a sample with a cross-sectional area of ​​600 cm² can be immersed in the solution at temperatures above 65°C and below 95°C. 2 Above and 700cm 2 Below, or 640cm 2 Above and 660cm 2 Below, or 645cm 2 Above and 655cm 2 Below, or 650cm 2 The sample was immersed in 130 ml of NPR-4 (Uemura) plating solution, which is a nickel-phosphorus plating solution, for at least 20 minutes and less than 60 minutes for elution. The cross-sectional area refers to the area of ​​the cross section obtained by cutting the sample in a direction perpendicular to the direction of increasing sample thickness.

[0058] If necessary, the sample can also be immersed in an aqueous catalyst solution before being immersed in the nickel-phosphorus plating solution, and there are no particular restrictions on the specific conditions. For example, a copper-clad laminate sample in which a photosensitive resin layer is laminated on a substrate can be immersed for 30 to 90 seconds using CATANC-20 (MK Chem&Tech) as a palladium catalyst plating solution at a temperature above 10°C and below 40°C.

[0059] Next, the copper-clad laminate sample with a nickel-plated photosensitive resin layer laminated on it can be immersed in a palladium plating solution for elution. While there are no particular limitations on the specific conditions for immersing the copper-clad laminate sample with the photosensitive resin layer laminated on it in the palladium plating solution, for example, a sample with a cross-sectional area of ​​600 cm² can be immersed in the solution at a temperature above 30°C and below 70°C. 2 Above and 700cm 2 Below, or 640cm 2 Above and 660cm 2 Below, or 645cm 2 Above and 655cm 2 Below, or 650cm2 The sample was immersed in 130 ml of a TPD-21 (Uemura) plating solution as a palladium plating solution for 30 minutes or more and 90 minutes or less to perform elution.

[0060] Meanwhile, a copper-clad laminate sample on which a palladium-plated photosensitive resin layer was laminated can also be immersed in a gold plating solution to perform elution. Although there is no particular limitation on the specific conditions for immersing a copper-clad laminate sample on which a photosensitive resin layer was laminated in a gold plating solution, for example, a sample having a cross-sectional area of 600 cm 2 or more and 700 cm 2 or less, or 640 cm 2 or more and 660 cm 2 or less, or 645 cm 2 or more and 655 cm 2 or less, or 650 cm 2 may be immersed in 130 ml of a TMX-40 (Uemura) plating solution as a gold plating solution for 50 minutes or more and 150 minutes or less to perform elution.

[0061] Meanwhile, a more specific example of a method for measuring the thickness of a palladium-plated layer obtained by immersing a copper-clad laminate sample in a residual palladium plating solution for 5 minutes is described below.

[0062] First, a copper-clad laminate sample can be immersed in a residual nickel-phosphorus plating solution. Although there is no particular limitation on the specific conditions for immersing a copper-clad laminate sample in a residual nickel-phosphorus plating solution, for example, a sample having a cross-sectional area of 1 cm 2 or more and 10 cm 2 or less, or 4 cm 2 or more and 6 cm 2 or less, or 4.5 cm 2 or more and 5.5 cm 2 or less, or 5 cm 2 may be immersed in 130 ml of a residual NPR-4 (Uemura) plating solution and plated for 15 minutes or more and 45 minutes or less. The cross-sectional area refers to the area of a cross section obtained by cutting the sample in a direction perpendicular to the direction in which the thickness of the sample increases.

[0063] If necessary, the sample can also be immersed in an aqueous catalyst solution before being immersed in a nickel-phosphorus plating solution. Although there is no particular limitation on the specific conditions, for example, the sample can be immersed for 90 seconds at 10°C or more and 40°C or less by using CATA NC-20 (MK Chem & Tech) as a palladium catalyst.

[0064] When measuring the thickness of palladium plating, an exposure machine can be used at a speed of 20 mJ / cm. 2 Above 200mJ / cm 2 Below, or 50mJ / cm 2 Above and 100mJ / cm 2 The following exposure levels are applied using ultraviolet radiation. The exposure time can be more than 1 second and less than 10 minutes, or more than 1 second and less than 10 seconds.

[0065] When measuring the thickness of the palladium coating, development can be performed using an alkaline aqueous solution with a concentration of 0.5% to 1.5% by weight or 0.9% to 1.1% by weight. The pH of the alkaline aqueous solution can be in the range of 9 to 11, and the temperature can be adjusted according to the developability of the photosensitive resin layer. Specific examples of the alkaline aqueous solution include sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium hydroxide aqueous solution, etc.

[0066] The development can be performed by contacting an alkaline aqueous solution with the photosensitive resin layer. As an example of a specific contact method, a spray method or an immersion method can be used. The development time can be 30 seconds or more but less than 10 minutes, or 30 seconds or more but less than 2 minutes.

[0067] At this time, the photosensitive element is characterized in that the thickness of the nickel-phosphorus plating layer obtained by immersing a film sample in which a photosensitive resin layer is laminated on a substrate in a nickel-phosphorus plating solution for 38 minutes, and then immersing a copper-clad laminate sample in the residual nickel-phosphorus plating solution for 28 minutes, can be 3.9 μm or more, or 3.95 μm or more, or 3.9 μm or more and 4.0 μm or less, or 3.95 μm or more and 4.0 μm or less.

[0068] Next, the nickel-plated copper-clad laminate sample can also be immersed in a residual palladium plating solution for electroplating. While there are no particular restrictions on the specific conditions for immersing the nickel-phosphorus-plated copper-clad laminate sample in a residual palladium plating solution, for example, it is possible to immerse the sample with a cross-sectional area of ​​1 cm² in a solution at temperatures above 30°C and below 70°C. 2 Above and 10cm 2 Below or 4cm 2 Above and 6cm 2 Below, or 4.5cm 2 Above and 5.5cm 2 Below or 5cm 2 The sample was immersed in 130 ml of residual TPD-21 (Uemura) plating solution for more than 2 minutes and less than 10 minutes for electroplating.

[0069] Meanwhile, the palladium-plated copper-clad laminate sample can be immersed in the residual gold plating solution to be electroplated. Although the specific conditions for immersing the palladium-plated copper-clad laminate sample in the residual gold plating solution are not particularly limited, for example, a sample having a cross-sectional area of 1 cm 2 or more and 10 cm 2 or less can be immersed in 130 ml of the residual TWX-40 (Uemura) plating solution for 5 minutes or more and 20 minutes or less to be electroplated. 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2

[0070] At this time, the photosensitive element can have a feature in that the thickness of the gold plating layer obtained by immersing the film sample in which the photosensitive resin layer is laminated on the substrate in the gold plating solution for 98 minutes and then immersing the copper-clad laminate sample in the residual gold plating solution for 11 minutes can be 0.11 μm or more, or 0.11 μm or more and 0.13 μm or less, or 0.12 μm or more, or 0.12 μm or more and 0.13 μm or less.

[0071] Meanwhile, the film sample in which the photosensitive resin layer is laminated on the substrate can be a laminate in which the photosensitive resin layer is laminated on an arbitrary substrate. One example of the substrate can be a copper-clad laminate in which a copper layer having a thickness of 10 μm or more and 100 mm or less is provided on the surface.

[0072] The cross-sectional area of the film sample in which the photosensitive resin layer is laminated on the substrate can be 600 cm 2 or more and 700 cm 2 or less, or 640 cm 2 or more and 660 cm 2 or less, or 645 cm 2 or more and 655 cm 2 or less.

[0073] Further, the cross-sectional area of the copper-clad laminate sample for immersing the copper-clad laminate sample in the residual palladium plating solution for 5 minutes can be 1 cm 2 or more and 10 cm 2 or less, or 4 cm 2 or more and 6 cm 2 or less, or 4.5 cm 2 or more and 5.5 cm 2 or less.

[0074] The photosensitive resin layer can include an alkali-developable binder resin.

[0075] The photosensitive resin layer can include a dried product, or a cured product of the photosensitive resin composition. The dried product refers to a material obtained by a drying process of the photosensitive resin composition. The cured product refers to a material obtained by a curing step of the photosensitive resin composition. The thickness of the photosensitive resin layer is not particularly limited, but for example, it can be freely adjusted in the range of 0.01 μm to 1 mm.

[0076] The photosensitive resin layer comprises a photosensitive resin composition comprising an alkali-developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the photopolymerizable compound comprises at least one selected from a penta-type (meth)acrylate compound having five (meth)acryl groups and a multifunctional (meth)acrylate compound having seven or more (meth)acryl groups.

[0077] The present inventors have confirmed through experiments that the photosensitive resin composition comprising a penta-type (meth)acrylate compound having five (meth)acryl groups, a multifunctional (meth)acrylate compound having seven or more (meth)acryl groups, or a mixture of two or more thereof as a photopolymerizable compound, thereby enabling to achieve an effect of reducing contamination of a metal plating solution such as a palladium plating solution or a nickel-phosphorus plating solution, and enabling to perform electroplating at a sufficient thickness, and the present disclosure has been completed.

[0078] The alkali-developable binder resin can comprise a repeating unit represented by the following Chemical Formula E, a repeating unit represented by the following Chemical Formula F, a repeating unit represented by the following Chemical Formula G, and a repeating unit represented by the following Chemical Formula H.

[0079] [Chemical Formula E]

[0080]

[0081] wherein, in Chemical Formula E, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R2 is an alkylene group having 1 to 10 carbon atoms, Ar is an aryl group having 6 to 20 carbon atoms, and n is an integer of 1 to 20,

[0082] [Chemical Formula F]

[0083]

[0084] wherein, in Chemical Formula F, R3 is hydrogen or an alkyl group having 1 to 10 carbon atoms,

[0085] [Chemical Formula G]

[0086]

[0087] wherein, in Chemical Formula G, 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,

[0088] [Chemical Formula H]

[0089]

[0090] wherein, in Chemical Formula H, Ar is an aryl group having 6 to 20 carbon atoms.

[0091] Specifically, the alkali-developable adhesive resin can include a random copolymer of a repeating unit represented by Chemical Formula E, a repeating unit represented by Chemical Formula F, a repeating unit represented by Chemical Formula G, and a repeating unit represented by Chemical Formula H.

[0092] Since the repeating unit represented by Chemical Formula E is included in the alkali-developable adhesive resin, the degree of hydrophobicity of the alkali-developable adhesive resin is increased by the benzene structure included in the repeating unit represented by Chemical Formula E, which inhibits the generation of foam in the development process of a dry film photoresist using a photosensitive resin composition, thus exhibiting excellent development performance, and the substrate adhesion can be improved, thereby ensuring proper physical properties (resolution, fine line adhesion, etc.).

[0093] In Chemical Formula E, R1 can be any one of hydrogen or an alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group having 1 to 10 carbon atoms can include a methyl group.

[0094] In Chemical Formula E, R2 is an alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group having 1 to 10 carbon atoms can include an ethyl group.

[0095] In Chemical Formula E, Ar is an aryl group having 6 to 20 carbon atoms, and specific examples of the aryl group having 6 to 20 carbon atoms can be a phenyl group.

[0096] The repeating unit represented by Chemical Formula E can be a repeating unit from a monomer represented by the following Chemical Formula E-1.

[0097] [Chemical Formula E-1]

[0098]

[0099] wherein, in Chemical Formula E-1, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R2 is an alkyl group having 1 to 10 carbon atoms, Ar is an aryl group having 6 to 20 carbon atoms, and n is an integer of 1 to 20. In Chemical Formula E-1, the definitions of R1, R2, Ar, and n are the same as those described in Chemical Formula E.

[0100] Specific examples of the monomer represented by Chemical Formula E-1 can include phenoxy polyethyleneoxy propylene acrylate, and more specifically, 2-phenoxyethyl methacrylate (PHEMA).

[0101] The content of the repeating unit represented by Chemical Formula E can be 5 mol% or more and 40 mol% or less, or 5 mol% or more and 30 mol% or less, or 5 mol% or more and 25 mol% or less, or 10 mol% or more and 25 mol% or less, based on 100 mol% of the total repeating units contained in the alkali-developable adhesive resin.

[0102] In Chemical Formula F to Chemical Formula H, R3and R4are the same as or different from each other, and each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, R5is an alkyl group having 1 to 10 carbon atoms, and Ar is an aryl group having 6 to 20 carbon atoms.

[0103] In Chemical Formula F to Chemical Formula H, R3and R4are the same as or different from each other, and each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, R5is an alkyl group having 1 to 10 carbon atoms, and Ar is an aryl group having 6 to 20 carbon atoms.

[0104] R5is an alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group having 1 to 10 carbon atoms can include methyl.

[0105] Ar is an aryl group having 6 to 20 carbon atoms, and specific examples of the aryl group having 6 to 20 carbon atoms can include phenyl.

[0106] The repeating unit represented by Chemical Formula F can be a repeating unit from a monomer represented by the following Chemical Formula F-1.

[0107] [Chemical Formula F-1]

[0108]

[0109] In Chemical Formula F-1, R3is hydrogen or an alkyl group having 1 to 10 carbon atoms. In Chemical Formula F-1, the definition of R3is the same as that described in Chemical Formula F described above. Specific examples of the monomer represented by Chemical Formula F-1 can include methacrylic acid (MAA).

[0110] The repeating unit represented by Chemical Formula G can be a repeating unit from a monomer represented by the following Chemical Formula G-1.

[0111] [Chemical Formula G-1]

[0112]

[0113] wherein, in Chemical Formula G-1, 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. In Chemical Formula G-1, the definitions of R4 and R5 are the same as those described above with respect to Chemical Formula G. Specific examples of the monomer represented by Chemical Formula G-1 can include methyl methacrylate (MMA).

[0114] The repeating unit represented by Chemical Formula H can include a repeating unit from a monomer represented by the following Chemical Formula H-1.

[0115] [Chemical Formula H-1]

[0116]

[0117] wherein, in Chemical Formula H-1, Ar is an aryl group having 6 to 20 carbon atoms. In Chemical Formula H-1, the definition of Ar is the same as that described above with respect to Chemical Formula H. Specific examples of the monomer represented by Chemical Formula H-1 can include styrene (SM).

[0118] The alkali-developable adhesive resin can include 20 mole% or more and 60 mole% or less, or 20 mole% or more and 50 mole% or less, or 30 mole% or more and 40 mole% or less of the repeating unit represented by Chemical Formula F, based on 100% of the total repeating units included in the alkali-developable adhesive resin.

[0119] Further, the alkali-developable adhesive resin can include 1 mole% or more and 30 mole% or less, or 5 mole% or more and 30 mole% or less of the repeating unit represented by Chemical Formula G, and 30 mole% or more and 60 mole% or less, or 30 mole% or more and 50 mole% or less, or 30 mole% or more and 40 mole% or less of the repeating unit represented by Chemical Formula H, based on 100% of the total repeating units included in the alkali-developable adhesive resin.

[0120] More specifically, the mole ratio of the repeating unit represented by Chemical Formula G with respect to 100 moles of the repeating unit represented by Chemical Formula H can 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.

[0121] In this way, as the content of the repeating unit represented by Chemical Formula H having hydrophobicity increases, the degree of hydrophobicity of the alkali-developable adhesive resin also increases, thereby making it possible to inhibit the generation of foam during the development process of a dry film photoresist using the photosensitive resin composition.

[0122] In addition, the molar ratio of the repeating unit represented by Chemical Formula G with respect to 100 moles of the repeating unit represented by Chemical Formula E can be 16 moles or less, or 15.5 moles or less, or 15 moles or less, or 0.1 moles or more and 16 moles or less, or 0.1 moles or more and 5.5 moles or less, or 0.1 moles or more and 15 moles or less, or 10 moles or more and 16 moles or less, or 10 moles or more and 15.5 moles or less, or 10 moles or more and 15 moles or less.

[0123] The weight average molecular weight of the alkali-developable adhesive resin can be 30,000 g / mol or more and 150,000 g / mol or less, and the glass transition temperature can be 20°C or more and 150°C or less. Thus, the coating performance and followability of the dry film photoresist and the mechanical strength of the resist itself after circuit formation can be improved.

[0124] As used in this specification, the weight average molecular weight refers to the polystyrene conversion weight average molecular weight measured by gel permeation chromatography (GPC). In the process of measuring the polystyrene conversion weight average molecular weight by GPC, a detector and an analysis column such as a commonly used analysis instrument and a differential refractive index detector can be used, and commonly used temperature conditions, solvents, and flow rates can be used.

[0125] Specific examples of the measurement conditions are as follows: The alkali-developable adhesive resin is dissolved in tetrahydrofuran so that the concentration in THF is 1.0 (w / w) % (about 0.5 (w / w) % based on the solid content), filtered using a syringe filter having a pore size of 0.45 μm, and then injected into the GPC in an amount of 20 μl, using tetrahydrofuran (THF) as the mobile phase of the GPC, and the flow rate is 1.0 mL / min. The column configuration is connected in series with one Agilent PLgel 5 μm Guard (7.5 x 50 mm) and two Agilent PLgel 5 μm Mixed D (7.5 x 300 mm), and an Agilent 1260 Infinity II system, an RI detector are used as the detector, and the measurement is performed at 40°C.

[0126] Polystyrene standard samples (STD A, B, C, D) in which polystyrene having different molecular weights as described below are dissolved in tetrahydrofuran at a concentration of 0.1 (w / w) % are filtered through a syringe filter having a pore size of 0.45 μm, and then injected into the GPC, and the value of the weight average molecular weight (MW) of the alkali-developable adhesive resin is determined using a calibration curve.

[0127] STD A (Mp): 791,000 / 27,810 / 945

[0128] STD B (Mp): 282,000 / 10,700 / 580

[0129] STD C (Mp): 126,000 / 4,430 / 370

[0130] STD D (Mp): 51,200 / 1,920 / 162

[0131] The glass transition temperature of the reference and the adhesive polymer is compared by DSC (differential scanning calorimeter) (Perkin-Elmer, DSC-7). The measurement can be performed by keeping the temperature at 20°C for 15 minutes, and then increasing the temperature to 200°C at a rate of 1°C / min.

[0132] The acid value of the alkali-developable adhesive resin can be 120 mg KOH / g or more and 200 mg KOH / g or less, or 140 mg KOH / g or more and 160 mg KOH / g or less. The acid value is measured by the following process in which about 1 g of the alkali-developable adhesive resin is dissolved in 50 ml of a mixed solvent (20% MeOH, 80% acetone) to which two drops of 1% phenolphthalein indicator are added, and then titrated with 0.1 N-KOH to measure the acid value.

[0133] The content of the alkali-developable adhesive resin can be 20 wt% or more and 80 wt% or less, based on the solid content, with respect to the total weight of the photosensitive resin composition. When the content of the alkali-developable adhesive resin is within the above range, an effect of strengthening the adhesion of fine lines after circuit formation can be obtained. The solid content based on weight refers to the remaining components other than the solvent in the photosensitive resin composition.

[0134] The content of the alkali-developable adhesive resin can be 20 wt% or more and 80 wt% or less, based on the solid content, with respect to the total weight of the photosensitive resin composition. When the content of the alkali-developable adhesive resin is within the above range, an effect of strengthening the adhesion of fine lines after circuit formation can be obtained. The solid content based on weight refers to the remaining components other than the solvent in the photosensitive resin composition.

[0135] The content of the alkali-developable adhesive resin can be 40 wt% or more and 70 wt% or less, with respect to the total weight of the photosensitive resin composition. When the content of the alkali-developable adhesive resin is less than 40 wt% with respect to the entire photosensitive resin composition, there is a disadvantage that defects such as short circuits occur due to contamination during the development process, and when the content of the alkali-developable adhesive resin exceeds 70 wt%, there is a problem that the circuit performance such as adhesion and resolution is deteriorated.

[0136] The photopolymerization initiator included in the photosensitive resin composition is a material that initiates chain reaction of the photopolymerizable monomers by ultraviolet rays and other radiations, and plays an important role in curing the dry film photoresist.

[0137] The compound that can be used as the photopolymerization initiator can 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.

[0138] In addition, a compound selected from the group consisting of 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-[4-morpholinophenyl]-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propanone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl-1-propanone, 4-benzoyl-4'-methyl dimethyl sulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid butyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 4-dimethylaminobenzoic acid 2-isopentyl ester, 2,2-diethoxyacetophenone, benzyl ketone dimethyl acetal, benzyl ketone beta-methoxydiethyl acetal, 1-phenyl-1,2-propanediol oxime-o,o'-(2-carbonyl)ethoxy ether, methyl o-benzoylbenzoate, bis[4-dimethylaminophenyl)ketone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, isobutoxybenzoin, t-butoxybenzoin, p-dimethylaminophenylacetophenone, p-t-butyltrichlorophenylacetophenone, p-t-butyldichlorophenylacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberenone, α,α-dichloro-4-phenoxyacetophenone, and 4-dimethylaminobenzoic acid pentyl ester, but are not limited thereto.

[0139] The content of the alkali-developable binder resin can be 1% by weight or more and 10% by weight or less, based on the solid content with respect to the total weight of the photosensitive resin composition.

[0140] When the content of the photopolymerization initiator is within the above range, sufficient sensitivity can be obtained. The solid content as the basis of weight refers to the remaining components in the photosensitive resin composition excluding the solvent.

[0141] When the content of the photopolymerization initiator is less than 1% by weight, the light efficiency is low and a large amount of exposure must be applied, thus, there is a disadvantage that the production efficiency is extremely low. When the content of the photopolymerization initiator exceeds 10% by weight, there is a problem that the film becomes brittle and the contamination of the developer increases, resulting in defects such as short circuit.

[0142] The photopolymerizable compound of the present disclosure has resistance to a developer after ultraviolet exposure and is capable of forming a pattern.

[0143] The photopolymerizable compound can include at least one selected from a penta-type (meth)acrylate compound having five (meth)acryl groups and a multifunctional (meth)acrylate compound having seven or more (meth)acryl groups.

[0144] That is, the photopolymerizable compound can include one type of penta-type (meth)acrylate compound having five (meth)acryl groups, one type of multifunctional (meth)acrylate compound having seven or more (meth)acryl groups, or a mixture of two or more thereof.

[0145] When the photopolymerizable compound of one embodiment includes at least one selected from a penta-type (meth)acrylate compound having five (meth)acryl groups and a multifunctional (meth)acrylate compound having seven or more (meth)acryl groups, an effect of reducing the contamination of a metal plating solution such as a palladium plating solution or a nickel-phosphorus plating solution can be achieved, and plating is enabled to be performed at a sufficient thickness.

[0146] The weight ratio of the penta-type (meth)acrylate compound having five (meth)acryl groups to the multifunctional (meth)acrylate compound having seven or more (meth)acryl groups can be 99:1 to 1:99.

[0147] The penta-type (meth)acrylate compound having five (meth)acryl groups can have five (meth)acryl groups. The five (meth)acryl groups can each be the same as or different from each other. The penta-type (meth)acrylate compound can include all (meth)acrylate compounds having five (meth)acryl groups or derivatives thereof.

[0148] The pentatype (meth)acrylate compound can further include one hydroxyl group. Specifically, the pentatype (meth)acrylate compound can be a compound represented by the following Chemical Formula A.

[0149] [Chemical Formula A]

[0150]

[0151] In Chemical Formula A, five of T1 to T6 are the same as or different from each other, and each is independently a (meth)acryl group, and the remaining one is hydrogen. More specifically, in Chemical Formula 1, T1 to T5 can be acryl groups, and T6 can be hydrogen.

[0152] Specific examples of the compound represented by Chemical Formula A can include M500 (dipentaerythritol pentaacrylate, Mw 524, Miwon Specialty Chemical).

[0153] The multifunctional (meth)acrylate compound having seven or more (meth)acryl groups can have seven or more, or seven or more and 20 or less, or seven or more and 10 or less (meth)acryl groups. The seven or more (meth)acryl groups can each be the same as or different from each other. The multifunctional (meth)acrylate compound includes all (meth)acrylate compounds or derivatives thereof having seven or more, or seven or more and 20 or less, or seven or more and 10 or less (meth)acryl groups.

[0154] Specifically, the multifunctional (meth)acrylate compound can be a compound represented by the following Chemical Formula B.

[0155] [Chemical Formula B]

[0156]

[0157] In Chemical Formula B, T7 to T 12 are the same as or different from each other, and each is independently a (meth)acryl group, T 12 is hydrogen or a (meth)acryl group, and t is an integer of 2 to 10.

[0158] More specifically, in Chemical Formula B, T7 to T 11 are acryl groups, T 12 is hydrogen or a (meth)acryl group, and t is an integer of 2 to 3.

[0159] Specific examples of the compound represented by Chemical Formula B include: (1) a compound having seven (meth)acryl groups in Chemical Formula B, in which T7 to T 11 are acryl groups, T 12is a hydrogen, and t is an integer of 2; (2) a compound having eight (meth)acryloyl groups in Chemical Formula B, wherein T7to T 11 is a (meth)acryloyl group, T 12 is a (meth)acryloyl group, and t is an integer of 2; (3) a compound having nine (meth)acryloyl groups in Chemical Formula B, wherein T7to T 11 is a (meth)acryloyl group, T 12 is a hydrogen, and t is an integer of 3; and (4) a compound having ten (meth)acryloyl groups in Chemical Formula B, wherein T7to T 11 is a (meth)acryloyl group, T 12 is a hydrogen, and t is an integer of 3.

[0160] The multifunctional (meth)acrylate compound having seven or more (meth)acryloyl groups can be one specific example corresponding to the compound represented by Chemical Formula B, or a mixture of two or more thereof.

[0161] Specifically, the multifunctional (meth)acrylate compound having seven or more (meth)acryloyl groups can include a mixture of two types of compounds in which t in Chemical Formula B is 2 and t in Chemical Formula B is 3. At this time, the content of the compound in which t in Chemical Formula B is 3 can be 1 part by weight or more and 40 parts by weight or less, or 5 parts by weight or more and 30 parts by weight or less, or 7 parts by weight or more and 28 parts by weight or less, based on 100 parts by weight of the compound in which t in Chemical Formula B is 2.

[0162] The photopolymerizable compound can further include a six-type (meth)acrylate compound having six (meth)acryloyl groups. That is, in addition to at least one selected from the five-type (meth)acrylate compound having five (meth)acryloyl groups and the multifunctional (meth)acrylate compound having seven or more (meth)acryloyl groups, the photopolymerizable compound can further include the six-type (meth)acrylate compound having six (meth)acryloyl groups.

[0163] The six-type (meth)acrylate compound having six (meth)acryloyl groups can have six (meth)acryloyl groups. The six (meth)acryloyl groups can each be the same as or different from each other. The six-type (meth)acrylate compound can include all (meth)acrylate compounds having six (meth)acryloyl groups or derivatives thereof.

[0164] Specifically, the six-type (meth)acrylate compound can be a compound represented by the following Chemical Formula C.

[0165] [Chemical Formula C]

[0166]

[0167] wherein, in Chemical Formula C, T 12 to T 17 are the same as or different from each other, and each is independently a (meth)acryl group. More specifically, in Chemical Formula 3, T 12 to T 17 is an acryl group.

[0168] Meanwhile, the photopolymerizable compound can further include a di(meth)acrylate compound having two (meth)acryl groups. The di(meth)acrylate compound having two (meth)acryl groups can include an alkylene glycol di(meth)acrylate or a bisphenol di(meth)acrylate.

[0169] As the alkylene glycol di(meth)acrylate, a compound represented by the following Chemical Formula D can be used.

[0170] [Chemical Formula D]

[0171]

[0172] wherein, in Chemical Formula D, l+n is an integer of 2 or 3, and m is an integer of 12 to 18.

[0173] The compound represented by Chemical Formula D can improve the hydrophobicity of the photosensitive resin composition, significantly improve the resistance to a developing solution and a plating solution, and shorten the peeling time of a cured film.

[0174] The compound represented by Chemical Formula D can be 70% by weight or more and 90% by weight or less, or 75% by weight or more and 85% by weight or less, with respect to the total weight of the solid content of the photosensitive resin composition.

[0175] With respect to the total weight of the solid content of the photosensitive resin composition, if the content of the compound represented by Chemical Formula D is less than 70% by weight, the effect due to the addition of the compound represented by Chemical Formula D is insufficient, and if the content exceeds 90% by weight, there can be a problem in that the hydrophobicity increases and the developing time in the developing process after exposure rapidly increases.

[0176] As the bisphenol di(meth)acrylate, a bisphenol di(meth)acrylate including an oxirane can be used. The bisphenol di(meth)acrylate including an oxirane can include two types: a bisphenol di(meth)acrylate including 8 moles or less of an oxirane per molecule; and a bisphenol di(meth)acrylate including more than 8 moles and 16 moles or less of an oxirane per molecule.

[0177] Examples of the bisphenol-based di(meth)acrylate containing 8 moles or less of ethylene oxide can include Miramer M244 (BPA(EO)3DA, bisphenol A(EO)3 diacrylate), Miramer M240 (BPA(EO)4DA, bisphenol A(EO)4 diacrylate), Miramer M241 (bisphenol A((EO)4 dimethacrylate) manufactured by Miwon Specialty Chemical Co., Ltd.

[0178] Examples of the bisphenol-based di(meth)acrylate containing more than 8 moles and 16 moles or less of ethylene oxide can include 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) 10 dimethacrylate) manufactured by Miwon Specialty Chemical Co., Ltd.

[0179] More specifically, based on 100 parts by weight of the bisphenol-based di(meth)acrylate containing more than 8 moles and 16 moles or less of ethylene oxide per molecule, the content of the bisphenol-based di(meth)acrylate containing 8 moles or less of ethylene oxide per molecule can be 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.

[0180] The content of the photopolymerizable compound can be 10% by weight or more and 70% by weight or less based on the solid content with respect to the total weight of the photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, effects of enhancing light sensitivity, resolution, adhesion, etc. can be obtained. The solid content as the basis of weight refers to the remaining components other than the solvent in the photosensitive resin composition.

[0181] The photosensitive resin composition can contain 20% by weight or more and 80% by weight or less of the alkali-developable binder resin, 1% by weight or more and 10% by weight or less of the photopolymerization initiator, and 10% by weight or more and 70% by weight or less of the photopolymerizable compound based on the solid content.

[0182] The photosensitive resin composition can further include a solvent. The solvent is generally selected from the group consisting of methyl ethyl ketone (MEK), methanol, THF, toluene, and acetone, and is not particularly limited thereto, and the content thereof can also be adjusted depending on the contents of the photopolymerization initiator, the alkali-developable binder resin, and the photopolymerizable compound.

[0183] Further, the photosensitive resin composition can further include other additives as needed. The other additives are plasticizers, and can include dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate in the form of phthalic acid esters; triethylene glycol diacetate, tetraethylene glycol diacetate in the form of glycol esters; p-toluenesulfonamide, benzene sulfonamide, n-butyl benzene sulfonamide in the form of amides; triphenyl phosphate; and the like.

[0184] A leuco dye or a coloring material can also be added in order to improve the handling properties of the photosensitive resin composition. Examples of the leuco dye include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2-methylphenyl)methane, fluoran dye, and the like. Among them, when leuco crystal violet is used, the contrast is good, and thus is preferred. When the leuco dye is included, the content in the photosensitive resin composition can be 0.01% by weight or more and 1% by weight or less. 0.01% by weight or more is preferred from the viewpoint of exhibiting contrast, and 1% by weight or less is preferred from the viewpoint of maintaining storage stability.

[0185] Examples of the coloring material can include toluenesulfonic acid monohydrate, magenta, phthalocyanine green, auramine base, pararosaniline, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green, adamant green, and basic blue 20. When the coloring material is included, an amount of 0.001% by weight or more and 1% by weight or less can be added in the photosensitive resin composition. When the content is 0.001% by weight or more, there is an effect of improving the handling properties, and when the content is 1% by weight or less, there is an effect of maintaining storage stability.

[0186] In addition, the other additives can further include a thermal polymerization inhibitor, a dye, a color change agent, and an adhesion promoter.

[0187] Meanwhile, the photosensitive resin layer can include a photosensitive resin composition including an alkali-developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, in which the alkali-developable binder resin includes four or more types of polymers that are different from each other.

[0188] The inventors have confirmed through experiments that the photosensitive resin composition contains four or more types of polymers different from each other as the photopolymerizable compound, and thus is excellent in terms of peeling performance, and achieves the effects of reducing contamination of the plating solution and enabling plating at a sufficient thickness, and the present disclosure has been completed.

[0189] The alkali-developable adhesive resin can contain four or more types of polymers different from each other. The four or more types of polymers can have different configurations depending on the type of the repeating unit constituting each polymer.

[0190] Specifically, the alkali-developable adhesive resin can contain a first adhesive resin containing a repeating unit represented by the following Chemical Formula 1. That is, the alkali-developable adhesive resin can contain: a first adhesive resin containing a repeating unit represented by the following Chemical Formula 1; and three or more types of polymers different from the first adhesive resin.

[0191] [Chemical Formula 1]

[0192]

[0193] In Chemical Formula 1, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R2 is an alkylene group having 1 to 10 carbon atoms, Ar is an aryl group having 6 to 20 carbon atoms, and n is an integer of 1 to 20.

[0194] Since the repeating unit represented by Chemical Formula 1 is contained in the first adhesive resin, the degree of hydrophobicity of the first adhesive resin is increased by the benzene structure contained in the repeating unit represented by Chemical Formula 1, and thus it suppresses the generation of bubbles in the development process of the dry film photoresist using the photosensitive resin composition, thereby exhibiting excellent development performance, and can improve the substrate adhesion, thereby ensuring proper physical properties (resolution, fine line adhesion, etc.).

[0195] In Chemical Formula 1, R1 can be any one of hydrogen or an alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group having 1 to 10 carbon atoms can include a methyl group.

[0196] In Chemical Formula 1, R2 is an alkylene group having 1 to 10 carbon atoms, and specific examples of the alkylene group having 1 to 10 carbon atoms can include an ethyl group.

[0197] In Chemical Formula 1, Ar is an aryl group having 6 to 20 carbon atoms, and specific examples of the aryl group having 6 to 20 carbon atoms can be a phenyl group.

[0198] The repeating unit represented by Chemical Formula 1 can be a repeating unit from a monomer represented by the following Chemical Formula 1-1.

[0199] [Chemical Formula 1-1]

[0200]

[0201] wherein, in Chemical Formula 1-1, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R2 is an alkylene group having 1 to 10 carbon atoms, Ar is an aryl group having 6 to 20 carbon atoms, and n is an integer of 1 to 20. In Chemical Formula 1-1, the definitions of R1, R2, Ar, and n are the same as those described in Chemical Formula E.

[0202] Specific examples of the monomer represented by Chemical Formula 1-1 can include phenoxy polyethyleneoxy propenoate, and more specifically, 2-phenoxyethyl methacrylate (PHEMA).

[0203] Based on the total molar content of 100 mol% of the repeating units contained in the alkali-developable binder resin, the content of the repeating unit represented by Chemical Formula 1 can be 5 mol% or more and 40 mol% or less, or 5 mol% or more and 30 mol% or less, or 5 mol% or more and 25 mol% or less, or 10 mol% or more and 25 mol% or less.

[0204] In addition to the repeating unit represented by Chemical Formula 1, the first binder resin can further include 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:

[0205] [Chemical Formula 2]

[0206]

[0207] wherein, in Chemical Formula 2, R3 is hydrogen or an alkyl group having 1 to 10 carbon atoms,

[0208] [Chemical Formula 3]

[0209]

[0210] wherein, in Chemical 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,

[0211] [Chemical Formula 4]

[0212]

[0213] wherein, in Chemical Formula 4, Ar is an aryl group having 6 to 20 carbon atoms.

[0214] Specifically, the alkali-developable adhesive resin can 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.

[0215] In Chemical Formula 2 to Chemical Formula 4, R3and R4are the same as or different from each other, and each is independently hydrogen or an alkyl group having 1 to 10 carbon atoms, R5is an alkyl group having 1 to 10 carbon atoms, and Ar is an aryl group having 6 to 20 carbon atoms.

[0216] In Chemical Formula 2 to Chemical Formula 4, R3and R4are the same as or different from each other, and each can be independently any one of hydrogen or an alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group.

[0217] R5is an alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group.

[0218] Ar is an aryl group having 6 to 20 carbon atoms, and specific examples of the aryl group having 6 to 20 carbon atoms include a phenyl group.

[0219] The repeating unit represented by Chemical Formula 2 can be a repeating unit from a monomer represented by the following Chemical Formula 2-1.

[0220] [Chemical Formula 2-1]

[0221]

[0222] In Chemical Formula 2-1, R3is hydrogen or an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 2-1, the definition of R3is the same as that described in Chemical Formula 2 described above. Specific examples of the monomer represented by Chemical Formula 2-1 can include a methacrylic acid (MAA).

[0223] The repeating unit represented by Chemical Formula 3 can be a repeating unit from a monomer represented by the following Chemical Formula 3-1.

[0224] [Chemical Formula 3-1]

[0225]

[0226] In Chemical Formula 3-1, R4is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R5is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 3-1, the definitions of R4and R5are the same as those described in Chemical Formula 3 described above. Specific examples of the monomer represented by Chemical Formula 3-1 can include a methyl methacrylate (MMA).

[0227] The repeating unit represented by Chemical Formula 4 can include a repeating unit from a monomer represented by Chemical Formula 4-1 below.

[0228] [Chemical Formula 4-1]

[0229]

[0230] In Chemical Formula 4-1, Ar is an aryl group having 6 to 20 carbon atoms. In Chemical Formula 4-1, the definition of Ar is the same as the definition described above in Chemical Formula 4. Specific examples of the monomer represented by Chemical Formula 4-1 can include styrene (SM).

[0231] The first binder resin can include 20 mol% or more and 60 mol% or less, or 20 mol% or more and 50 mol% or less, or 30 mol% or more and 40 mol% or less of the repeating unit represented by Chemical Formula 2, based on 100 mol% of the total molar content of the repeating units included in the first binder resin.

[0232] Further, the first binder resin can include 1 mol% or more and 30 mol% or less, or 5 mol% or more and 30 mol% or less of the repeating unit represented by Chemical Formula 3, and 30 mol% or more and 60 mol% or less, or 30 mol% or more and 50 mol% or less, or 30 mol% or more and 40 mol% or less of the repeating unit represented by Chemical Formula 4, based on 100 mol% of the total molar content of the repeating units included in the first binder resin.

[0233] More specifically, the molar ratio of the repeating unit represented by Chemical Formula 3 with respect to 100 moles of the repeating unit represented by Chemical Formula 4 can be 10 mol or more and 99 mol or less, or 15 mol or more and 95 mol or less, or 20 mol or more and 95 mol or less.

[0234] Further, the molar ratio of the repeating unit represented by Chemical Formula 3 with respect to 100 moles of the repeating unit represented by Chemical Formula 1 can be 40 mol or less, or 35 mol or less, or 32 mol or less, or 0.1 mol or more and 40 mol or less, or 0.1 mol or more and 35 mol or less, or 0.1 mol or more and 32 mol or less, or 10 mol or more and 40 mol or less, or 10 mol or more and 35 mol or less, or 10 mol or more and 32 mol or less.

[0235] In this way, as the content of the repeating unit represented by Chemical Formula 4 having hydrophobicity increases, the degree of hydrophobicity of the first binder resin also increases, thereby being able to inhibit the generation of foam in the development process of a dry film photoresist using the photosensitive resin composition.

[0236] The weight average molecular weight of the first adhesive resin can be 30,000 g / mol or more and 150,000 g / mol or less, and the glass transition temperature can be 20°C or more and 150°C or less. Thus, the coating performance and followability of the dry film photoresist, and the mechanical strength of the resist itself after circuit formation can be improved.

[0237] As used in the present specification, the weight average molecular weight refers to the polystyrene-conversion weight average molecular weight measured by gel permeation chromatography (GPC). In the process of measuring the polystyrene-conversion weight average molecular weight by GPC, a detector and an analysis column such as a commonly used analytical instrument and a differential refractive index detector can be used, and commonly used temperature conditions, solvents, and flow rates can be used.

[0238] Specific examples of the measurement conditions are as follows: The alkali-developable adhesive resin is dissolved in tetrahydrofuran so that the concentration in THF is 1.0 (w / w) % (about 0.5 (w / w) % based on the solid content), filtered using a syringe filter having a pore size of 0.45 μm, and then injected into the GPC in an amount of 20 μl, using tetrahydrofuran (THF) as the mobile phase of the GPC, and the flow rate is 1.0 mL / min. The column configuration is one Agilent PLgel 5 μm Guard (7.5 x 50 mm) connected in series with two Agilent PLgel 5 μm Mixed D (7.5 x 300 mm), and an Agilent 1260 Infinity II system, an RI detector are used as the detector, and the measurement is performed at 40°C.

[0239] Polystyrene standard samples (STD A, B, C, D) having different molecular weights as described below are dissolved in tetrahydrofuran at a concentration of 0.1 (w / w) %, filtered through a syringe filter having a pore size of 0.45 μm, and then injected into the GPC, and the value of the weight average molecular weight (MW) of the alkali-developable adhesive resin is determined using a calibration curve.

[0240] STD A (Mp): 791,000 / 27,810 / 945

[0241] STD B (Mp): 282,000 / 10,700 / 580

[0242] STD C (Mp): 126,000 / 4,430 / 370

[0243] STD D (Mp): 51,200 / 1,920 / 162

[0244] The glass transition temperature of the reference and the adhesive polymer is compared by DSC (Differential Scanning Calorimeter) (Perkin-Elmer, DSC-7). The measurement can be performed by keeping the temperature at 20°C for 15 minutes, and then increasing the temperature to 200°C at a rate of 1°C / min.

[0245] The acid value of the first adhesive resin can be 120 mg KOH / g or more and 200 mg KOH / g or less, or 140 mg KOH / g or more and 160 mg KOH / g or less. The acid value is measured by the following process in which about 1 g of the alkali-developable adhesive resin is dissolved in 50 ml of a mixed solvent (20% MeOH, 80% acetone) to which two drops of 1% phenolphthalein indicator are added, and then titrated with 0.1 N-KOH to measure the acid value.

[0246] Meanwhile, the alkali-developable adhesive resin can include a second adhesive resin including a repeating unit represented by the following Chemical Formula 5. That is, the alkali-developable adhesive resin can include: a second adhesive resin including a repeating unit represented by the following Chemical Formula 5; and three or more types of polymers different from the second adhesive resin.

[0247] [Chemical Formula 5]

[0248]

[0249] In Chemical Formula 5, R6 is hydrogen, and R7 is an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group having 1 to 10 carbon atoms include a butyl group.

[0250] In addition to the repeating unit represented by Chemical Formula 5, the second adhesive resin can include a repeating unit represented by the following Chemical Formula 6, a repeating unit represented by the following Chemical Formula 7, a repeating unit represented by the following Chemical Formula 8, and a repeating unit represented by the following Chemical Formula 9:

[0251] [Chemical Formula 6]

[0252]

[0253] In Chemical Formula 6, R8 is hydrogen,

[0254] [Chemical Formula 7]

[0255]

[0256] In Chemical Formula 7, R9 is an alkyl group having 1 to 10 carbon atoms,

[0257] [Chemical Formula 8]

[0258]

[0259] wherein, in Chemical Formula 8, R 10 is an alkyl group having 1 to 10 carbon atoms, and R 11 is an alkyl group having 1 to 10 carbon atoms,

[0260] [Chemical Formula 9]

[0261]

[0262] wherein, in Chemical Formula 9, Ar is an aryl group having 6 to 20 carbon atoms.

[0263] In Chemical Formula 6 to Chemical Formula 9, specific examples of the alkyl group having 1 to 10 carbon atoms can include a methyl group.

[0264] Ar is an aryl group having 6 to 20 carbon atoms, and specific examples of the aryl group having 6 to 20 carbon atoms include a phenyl group.

[0265] The weight average molecular weight of the second binder resin can be 30,000 g / mol or more and 150,000 g / mol or less, and the glass transition temperature can be 20°C or more and 150°C or less. Thus, the coating properties and followability of the dry film photoresist, as well as the mechanical strength of the resist itself after circuit formation, can be improved. In addition, the acid value of the second binder resin can be 140 mg KOH / g or more and 160 mg KOH / g or less.

[0266] Specifically, the second binder resin can include a random copolymer of the repeating unit represented by Chemical Formula 5, the repeating unit represented by Chemical Formula 6, the repeating unit represented by Chemical Formula 7, the repeating unit represented by Chemical Formula 8, and the repeating unit represented by Chemical Formula 9.

[0267] More specifically, based on 100 mol% of the entire repeating units, the second binder resin can include 5 mol% or more and 20 mol% or less of the repeating unit represented by Chemical Formula 5, 5 mol% or more and 20 mol% or less of the repeating unit represented by Chemical Formula 6, 5 mol% or more and 20 mol% or less of the repeating unit represented by Chemical Formula 7, 40 mol% or more and 80 mol% or less of the repeating unit represented by Chemical Formula 8, and 5 mol% or more and 15 mol% or less of the repeating unit represented by Chemical Formula 9.

[0268] Meanwhile, the alkali-developable adhesive resin can include a third adhesive resin including a repeating unit represented by Chemical Formula 10, a repeating unit represented by Chemical Formula 11, and a repeating unit represented by Chemical Formula 12. That is, the alkali-developable adhesive resin can include: a third adhesive resin; and three or more types of polymers different from the third adhesive resin,

[0269] [Chemical Formula 10]

[0270]

[0271] wherein, in Chemical Formula 10, R9is an alkyl group having 1 to 10 carbon atoms,

[0272] [Chemical Formula 11]

[0273]

[0274] wherein, in Chemical Formula 11, R 10 is an alkyl group having 1 to 10 carbon atoms, and R 11 is an alkyl group having 1 to 10 carbon atoms,

[0275] [Chemical Formula 12]

[0276]

[0277] wherein, in Chemical Formula 12, Ar is an aryl group having 6 to 20 carbon atoms.

[0278] More specifically, based on 100 mol% of the entire repeating unit, the third adhesive resin can include 20 mol% or more and 40 mol% or less of the repeating unit represented by Chemical Formula 10, 50 mol% or more and 70 mol% or less of the repeating unit represented by Chemical Formula 11, and 5 mol% or more and 18 mol% or less of the repeating unit represented by Chemical Formula 12.

[0279] Further, the weight average molecular weight of the third adhesive resin can be 20,000 g / mol or more and 130,000 g / mol or less, and the glass transition temperature can be 30℃ or more and 160℃ or less. Accordingly, the coating properties and followability of the dry film photoresist, and the mechanical strength of the resist itself after circuit formation can be improved.

[0280] The acid value of the second adhesive resin can be 140 mg KOH / g or more and 160 mg KOH / g or less. Further, the acid value of the third adhesive resin can be 160 mg KOH / g or more and 200 mg KOH / g or less.

[0281] Meanwhile, the alkali-developable adhesive resin can include a fourth adhesive resin including a repeating unit represented by the following Chemical Formula 13. That is, the alkali-developable adhesive resin can include: the fourth adhesive resin; and three or more types of polymers different from the fourth adhesive resin,

[0282] [Chemical Formula 13]

[0283]

[0284] wherein, in Chemical Formula 13, R 12 is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R 13 is an alkylene group having 1 to 10 carbon atoms.

[0285] In Chemical Formula 13, R 12 may be any one of hydrogen or an alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group.

[0286] In Chemical Formula 13, R 13 is an alkylene group having 1 to 10 carbon atoms, and specific examples of the alkylene group having 1 to 10 carbon atoms include a methylene group.

[0287] Since the fourth adhesive resin includes the repeating unit represented by Chemical Formula 13, an effect of suppressing elution of the resist in a plating solution can be achieved due to excellent developing characteristics and thermal curing by dry heat.

[0288] In addition to the repeating unit represented by Chemical Formula 13, the fourth adhesive resin can include 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.

[0289] [Chemical Formula 14]

[0290]

[0291] wherein, in Chemical Formula 14, R 14 is hydrogen or an alkyl group having 1 to 10 carbon atoms,

[0292] [Chemical Formula 15]

[0293]

[0294] wherein, in Chemical Formula 15, R 15 is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R 16 is an alkyl group having 1 to 10 carbon atoms,

[0295] [Chemical Formula 16]

[0296]

[0297] wherein, in Chemical Formula 16, Ar is an aryl group having 6 to 20 carbon atoms.

[0298] Specifically, the alkali-developable binder resin can include a random copolymer of a repeating unit represented by Chemical Formula 13, a repeating unit represented by Chemical Formula 14, a repeating unit represented by Chemical Formula 15, and a repeating unit represented by Chemical Formula 16.

[0299] In Chemical Formula 14 to Chemical Formula 16, R 14 and R 15 are the same as or different from each other, and each is independently hydrogen or an alkyl group having 1 to 10 carbon atoms, R 16 is an alkyl group having 1 to 10 carbon atoms, and Ar is an aryl group having 6 to 20 carbon atoms.

[0300] In Chemical Formula 14 to Chemical Formula 16, R 14 and R 15 are the same as or different from each other, and each can be independently any one of hydrogen or an alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group having 1 to 10 carbon atoms can include a methyl group.

[0301] R 16 is an alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group.

[0302] Ar is an aryl group having 6 to 20 carbon atoms, and specific examples of the aryl group having 6 to 20 carbon atoms include a phenyl group.

[0303] The weight average molecular weight of the fourth binder resin can be 20,000 g / mol or more and 130,000 g / mol or less, and the glass transition temperature can be 30℃ or more and 160℃ or less. Accordingly, the coating properties and followability of the dry film photoresist, and the mechanical strength of the resist itself after circuit formation can be improved. In addition, the acid value of the fourth binder resin can be 140 mgKOH / g or more and 180 mgKOH / g or less.

[0304] More specifically, based on 100 mol% of the entire repeating units, the fourth binder resin can include 15 mol% or more and 25 mol% or less of the repeating unit represented by Chemical Formula 13, 30 mol% or more and 50 mol% or less of the repeating unit represented by Chemical Formula 14, 15 mol% or more and 25 mol% or less of the repeating unit represented by Chemical Formula 15, and 20 mol% or more and 30 mol% or less of the repeating unit represented by Chemical Formula 16.

[0305] Specifically, the alkali-developable binder resin can include a first binder resin; a second binder resin; a third binder resin; and a fourth binder resin. More specifically, based on 100 parts by weight of the alkali-developable binder resin, the photosensitive resin composition of one embodiment of the present disclosure can include 40 parts by weight or more and 80 parts by weight or less of the first binder resin, 0.1 parts by weight or more and 4 parts by weight or less of the second binder resin, 10 parts by weight or more and 20 parts by weight or less of the third binder resin, and 5 parts by weight or more and 45 parts by weight or less of the fourth binder resin.

[0306] Specifically, based on 100 parts by weight of the first binder resin, the content of the fourth binder resin can be 10 parts by weight or more and 90 parts by weight or less.

[0307] Further, based on 100 parts by weight of the second binder resin, the content of the fourth binder resin can be 500 parts by weight or more and 3000 parts by weight or less, or 600 parts by weight or more and 2700 parts by weight or less.

[0308] When the fourth binder resin is included in this way in a specific amount, it is possible to achieve the effect of suppressing elution of the resist in a plating solution due to excellent development characteristics and thermal curing by dry heat.

[0309] Further, based on 100 parts by weight of the second binder resin, the content of the third binder resin can be 500 parts by weight or more and 1000 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.

[0310] As described above, based on 100 parts by weight of the second binder resin, when the third binder resin is added in excess of 500 parts by weight, it is possible to achieve technical effects of imparting a hydrophobic function to the photosensitive resin, increasing resistance to a development solution, and improving circuit physical properties.

[0311] The content of the alkali-developable binder resin can be 20% by weight or more and 80% by weight or less, based on the total weight of the photosensitive resin composition, based on the solid content. When the content of the alkali-developable binder resin is within the above range, it is possible to achieve the effect of strengthening fine line adhesion after circuit formation. The solid content, which is the basis for weight, refers to the remaining components other than the solvent in the photosensitive resin composition.

[0312] The content of the alkali-developable binder resin can be 40% by weight or more and 70% by weight or less, relative to the total weight of the photosensitive resin composition. When the content of the alkali-developable binder resin is less than 40% by weight based on the entire photosensitive resin composition, there is a disadvantage in that defects such as short-circuiting due to contamination during development occur, and when the content of the alkali-developable binder resin exceeds 70% by weight, there is a problem in that the circuit performance such as adhesion and resolution is deteriorated.

[0313] The photopolymerization initiator included in the photosensitive resin composition is a material that initiates chain reaction of the photopolymerizable monomers by ultraviolet rays and other radiations, and plays an important role in curing the dry film photoresist.

[0314] The compound that can be used as the photopolymerization initiator can include anthraquinone derivatives such as 2-methylanthraquinone and 2-ethylanthraquinone; benzoin derivatives such as benzoin methyl ether, benzophenone, phenanthraquinone, and 4,4'-bis-(dimethylamino)benzophenone.

[0315] In addition, as the photopolymerization initiator, a compound selected from the group consisting of 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenyl-1-ethanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 2-benzyl-2-dimethylamino-1-[4-morpholinophenyl]-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propanone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl-1-propanone, 4-benzoyl-4'-methyl dimethyl sulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid butyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 4-dimethylaminobenzoic acid 2-isopentyl ester, 2,2-diethoxyacetophenone, benzyl ketone dimethyl acetal, benzyl ketone beta-methoxydiethyl acetal, 1-phenyl-1,2-propanedione-o,o'-(2-carbonyl)ethoxy ether, methyl o-benzoylbenzoate, bis[4-dimethylaminophenyl)ketone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, isobutoxybenzoin, t-butoxybenzoin, p-dimethylaminophenylacetophenone, p-t-butyltrichloro phenylacetophenone, p-t-butyldichloro phenylacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberenone, alpha,alpha-dichloro-4-phenoxyacetophenone, and 4-dimethylaminobenzoic acid pentyl ester, but are not limited thereto.

[0316] The content of the photopolymerization initiator is 1% by weight or more and 10% by weight or less, based on the solid content, with respect to the total weight of the photosensitive resin composition. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity can be obtained. The solid content as the basis of weight refers to the remaining components other than the solvent in the photosensitive resin composition.

[0317] When the content of the photopolymerization initiator is less than 1% by weight, the light efficiency is low and a large amount of exposure must be applied, thus, there is a disadvantage that the production efficiency is extremely low. When the content of the photopolymerization initiator exceeds 10% by weight, there is a problem that the film becomes brittle and the contamination of the developer increases, resulting in defects such as short circuit.

[0318] The photo-polymerizable compound is resistant to a developing solution after ultraviolet exposure and is capable of forming a pattern.

[0319] The photo-polymerizable compound can include a di-functional (meth)acrylate compound. The di-functional (meth)acrylate compound can include an alkylene glycol-based di-functional (meth)acrylate, or a bisphenol-based di-functional (meth)acrylate.

[0320] As the alkylene glycol-based di(meth)acrylate, a compound represented by Chemical Formula 17 below can be used.

[0321] [Chemical Formula 17]

[0322]

[0323] In Chemical Formula 17, l+n is an integer of 2 or 3, and m is an integer of 12 to 18.

[0324] The compound represented by Chemical Formula 17 can improve the hydrophobicity of the photosensitive resin composition, significantly increase the resistance to a developing solution and a plating solution, and shorten the peeling time of a cured film.

[0325] The compound represented by Chemical Formula 17 can be 10 wt% or more and 60 wt% or less, or 20 wt% or more and 40 wt% or less, with respect to the total weight of the solid content of the photosensitive resin composition.

[0326] If the content of the compound represented by Chemical Formula 17 is less than 10 wt%, the effect of adding the compound represented by Chemical Formula 17 is not sufficient, and if the content exceeds 60 wt%, there can be a problem in that the hydrophobicity increases and the developing time during the post-exposure developing process rapidly increases.

[0327] As the bisphenol-based di(meth)acrylate, a bisphenol-based di(meth)acrylate including an oxirane can be used. The bisphenol-based di(meth)acrylate including an oxirane can include two types: a bisphenol-based di(meth)acrylate including 8 moles or less of an oxirane per molecule; and a bisphenol-based di(meth)acrylate including more than 8 moles and 16 moles or less of an oxirane per molecule.

[0328] Examples of the bisphenol-based di(meth)acrylate containing 8 moles or less of ethylene oxide can include Miramer M244 (BPA(EO)3DA, bisphenol A(EO)3 diacrylate), Miramer M240 (BPA(EO)4DA, bisphenol A(EO)4 diacrylate), Miramer M241 (bisphenol A(EO)4 dimethacrylate) manufactured by Miwon Specialty Chemical Co., Ltd.

[0329] Examples of the bisphenol-based di(meth)acrylate containing more than 8 moles and 16 moles or less of ethylene oxide can include 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) 10 dimethacrylate) manufactured by Miwon Specialty Chemical Co., Ltd.

[0330] More specifically, based on 100 parts by weight of the bisphenol-based di(meth)acrylate containing more than 8 moles and 16 moles or less of ethylene oxide per molecule, the content of the bisphenol-based di(meth)acrylate containing 8 moles or less of ethylene oxide per molecule can be 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.

[0331] The content of the photopolymerizable compound can be 10% by weight or more and 70% by weight or less based on the solid content with respect to the total weight of the photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, effects of enhancing light sensitivity, resolution, adhesion, etc. can be obtained. The solid content as the basis of weight refers to the remaining components other than the solvent in the photosensitive resin composition.

[0332] The photosensitive resin composition can contain 20% by weight or more and 80% by weight or less of the alkali-developable binder resin, 1% by weight or more and 10% by weight or less of the photopolymerization initiator, and 10% by weight or more and 70% by weight or less of the photopolymerizable compound based on the solid content.

[0333] The photosensitive resin composition can further include a solvent. The solvent is generally selected from the group consisting of methyl ethyl ketone (MEK), methanol, THF, toluene, and acetone, without being particularly limited thereto, and the content thereof can also be adjusted depending on the content of the photopolymerization initiator, the alkali-developable binder resin, and the photopolymerizable compound.

[0334] In addition, the photosensitive resin composition can further include other additives as needed. The other additives are plasticizers, and can include dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate in the form of phthalic acid esters, triethylene glycol diacetate, tetraethylene glycol diacetate in the form of glycol esters, p-toluenesulfonamide, benzene sulfonamide, n-butyl benzene sulfonamide in the form of amides, triphenyl phosphate, and the like.

[0335] A leuco dye or a coloring material can also be added in order to improve the handling properties of the photosensitive resin composition. Examples of the leuco dye include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2-methylphenyl)methane, fluoran dye, and the like. Among them, when leuco crystal violet is used, the contrast is good, and thus is preferred. When the leuco dye is included, the content thereof in the photosensitive resin composition can be 0.01% by weight or more and 1% by weight or less. 0.01% by weight or more is preferred from the viewpoint of exhibiting contrast, and 1% by weight or less is preferred from the viewpoint of maintaining storage stability.

[0336] Examples of the coloring material can include toluenesulfonic acid monohydrate, fuchsine, phthalocyanine green, auramine base, pararosaniline, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite green, adamant green, and basic blue 20. When the coloring material is included, it can be added in an amount of 0.001% by weight or more and 1% by weight or less in the photosensitive resin composition. When the content is 0.001% by weight or more, there is an effect of improving the handling properties, and when the content is 1% by weight or less, there is an effect of maintaining storage stability.

[0337] In addition, the other additives can further include a thermal polymerization inhibitor, a dye, a color change agent, and an adhesion promoter.

[0338] 2. Dry film photoresist

[0339] According to another embodiment of the present disclosure, a dry film photoresist can be provided, including: a photosensitive resin composition including an alkali-developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the photopolymerizable compound includes at least one selected from a penta-type (meth)acrylate compound having five (meth)acryl groups and a multifunctional (meth)acrylate compound having seven or more (meth)acryl groups, and wherein the dry film photoresist has a feature that a thickness of a palladium plated layer obtained by immersing a film sample in which a photosensitive resin layer of the dry film photoresist is laminated on a substrate in a palladium plating solution for 60 minutes, and then immersing a copper-clad laminate sample in the residual palladium plating solution for 5 minutes is 0.01 μm or more.

[0340] According to another embodiment of the present disclosure, a dry film photoresist can be provided, including: a photosensitive resin composition including an alkali-developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the alkali-developable binder resin includes four or more types of polymers different from each other, and wherein the dry film photoresist has a feature that a thickness of a palladium plated layer obtained by immersing a film sample in which a photosensitive resin layer of the dry film photoresist is laminated on a substrate in a palladium plating solution for 60 minutes, and then immersing a copper-clad laminate sample in the residual palladium plating solution for 5 minutes is 0.01 μm or more.

[0341] The detailed contents regarding the photosensitive resin composition including the alkali-developable binder resin, the photopolymerization initiator, and the photopolymerizable compound, wherein the photopolymerizable compound includes at least one selected from a penta-type (meth)acrylate compound having five (meth)acryl groups and a multifunctional (meth)acrylate compound having seven or more (meth)acryl groups, include all the contents described in the above one embodiment.

[0342] The detailed contents regarding the photosensitive resin composition including the alkali-developable binder resin, the photopolymerization initiator, and the photopolymerizable compound, wherein the alkali-developable binder resin includes four or more types of polymers different from each other, include all the contents described in the above one embodiment.

[0343] Specifically, the photosensitive resin layer can include a dry product or a cured product of the photosensitive resin composition. The dry product refers to a material obtained through a drying process of the photosensitive resin composition. The cured product refers to a material obtained through a curing step of the photosensitive resin composition. The thickness of the photosensitive resin layer is not particularly limited, but for example, can be freely adjusted in the range of 0.01 μm to 1 mm.

[0344] The thickness of the dry film photoresist is not particularly limited, but for example, can be freely adjusted in the range of 0.01 μm to 1 mm. When the thickness of the dry film photoresist is increased or decreased by a certain value, the physical properties measured in the dry film photoresist can also vary by a certain value.

[0345] The dry film photoresist can further include a substrate film and a protective film. The substrate film serves as a support for the photosensitive resin layer during the manufacturing process of the dry film photoresist, and is easily handled during the exposure process of the photosensitive resin layer having adhesive strength.

[0346] Various plastic films can be used as the substrate film, and examples thereof can include at least one plastic film selected from the group consisting of an acrylic film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a poly norbornene (PNB) film, a cyclic olefin polymer (COP) film, and a polycarbonate (PC) film. The thickness of the substrate film is not particularly limited, and for example, can be freely adjusted in the range of 0.01 μm to 1 mm.

[0347] The protective film prevents damage to the resist during the process, and functions as a protective cover that protects 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 substrate film is not formed. The protective film is used to protect the photosensitive resin layer from external influences. When the dry film photoresist is applied to post-processing, easy separation is required, and proper peelability and adhesiveness are required so that it is not deformed during storage and distribution.

[0348] Various plastic films can be used as the protective film, and examples thereof can include at least one plastic film selected from the group consisting of an acrylic film, a polyethylene (PE) film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a poly norbornene (PNB) film, a cyclic olefin polymer (COP) film, and a polycarbonate (PC) film. The thickness of the protective film is not particularly limited, but for example, can be freely adjusted in the range of 0.01 μm to 1 mm.

[0349] Examples of the method of manufacturing the dry film photoresist are not particularly limited, and for example, the photosensitive resin composition of one embodiment is coated on a conventional substrate film such as polyethylene terephthalate using a conventional coating method, and then dried, and the upper surface of the dried photosensitive resin layer is laminated with a conventional protective film such as polyethylene to manufacture a dry film.

[0350] The method of coating the photosensitive resin composition of one embodiment is not particularly limited, and a method such as a coating bar can be used.

[0351] The step of drying the coated photosensitive resin composition can be performed by a heating means such as a hot air oven, a hot plate, a hot air circulating oven, and an infrared oven, and can be performed at a temperature of 50°C or higher and 120°C or lower.

[0352] Meanwhile, the dry film photoresist is characterized in that the thickness of a palladium plated layer obtained by immersing a sample of a film in which the photosensitive resin layer is laminated on a substrate in a palladium plating solution for 60 minutes and then immersing a copper-clad laminate sample in the residual palladium plating solution for 5 minutes can be 0.01 μm or more, or 0.05 μm or more, or 0.1 μm or more, or 0.01 μm or more and 0.15 μm or less, or 0.05 μm or more and 0.15 μm or less, or 0.1 μm or more and 0.15 μm or less.

[0353] The residual palladium plating solution is a palladium plating solution contaminated by the components of the photosensitive resin layer, and the thickness of a palladium plated layer obtained by immersing a copper-clad laminate sample in the contaminated residual palladium plating solution for 5 minutes is used to evaluate the contamination of the dry film photoresist on a laminate on which the photosensitive resin layer is laminated when palladium plating is performed. When the contamination of the plating solution is more severe, the thickness of the palladium plated layer obtained by immersing a copper-clad laminate sample in the palladium plating solution for 5 minutes becomes significantly lower. On the other hand, when the plating solution is less contaminated, the thickness of the palladium plated layer obtained by immersing a copper-clad laminate sample in the palladium plating solution for 5 minutes becomes significantly higher. Therefore, in actual electroless palladium plating processes, contaminants accumulate in a large amount of dry film photoresist, and the addition of palladium is only for continuous plating, which makes other purification processes difficult. Thus, it is very important to evaluate the degree of contamination of the dry film photoresist on the palladium plating solution.

[0354] In other words, in palladium plating, first, a first palladium plating is performed using a film on which a photosensitive resin layer is laminated. After the first electroplating is completed, a second palladium plating is performed on a new copper-clad laminate sample in the contaminated palladium plating solution, and the contamination of the dry film photoresist on the plating solution is evaluated from the thickness of the palladium plated layer at the second electroplating.

[0355] Therefore, by excessively lowering the thickness of the palladium plated layer obtained by immersing a sample of a film in which the photosensitive resin layer is laminated on a substrate in a palladium plating solution for 60 minutes and then immersing a copper-clad laminate sample in the residual palladium plating solution for 5 minutes to less than 0.01 μm, it is possible to evaluate the degree of contamination of the plating solution. When the plated layer is plated to a thickness lower than a target value in evaluating the degree of contamination, the contamination of the electroless palladium plating solution is severe in actual production processes, and thus it is difficult to reuse the plating solution over 0.5 MTO, which is disadvantageous in terms of process efficiency and economy.

[0356] The method for calculating the thickness of the palladium plating layer is not particularly limited, and various known methods for measuring the plating layer thickness can be applied without limitation. For example, the measurement can be performed by an XRF plating thickness meter (Helmut Fischer XDV-μ).

[0357] A more specific example of the method for obtaining the residual palladium plating solution after immersing the film sample in which the photosensitive resin layer is pressed on the substrate in the palladium plating solution for 60 minutes is described below.

[0358] First, the copper-clad laminate sample on which the photosensitive resin layer is laminated can be immersed in the nickel-phosphorus plating solution to perform elution. Although the specific conditions for immersing the copper-clad laminate sample on which the photosensitive resin layer is laminated in the nickel-phosphorus plating solution are not particularly limited, for example, a sample having a cross-sectional area of 600 cm 2 or more and 700 cm 2 or less can be immersed in 130 ml of NPR-4 (Uemura) plating solution as a nickel-phosphorus plating solution for 20 minutes or more and 60 minutes or less to perform elution. The cross-sectional area refers to the area of the cross section obtained by cutting the sample in a direction perpendicular to the direction of increase in the thickness of the sample. 2 2 or more and 660 cm 2 or less can be immersed in 130 ml of NPR-4 (Uemura) plating solution as a nickel-phosphorus plating solution for 20 minutes or more and 60 minutes or less to perform elution. The cross-sectional area refers to the area of the cross section obtained by cutting the sample in a direction perpendicular to the direction of increase in the thickness of the sample. 2 2 or more and 650 cm

[0359] If necessary, the sample can be immersed in an aqueous catalyst solution before being immersed in the nickel-phosphorus plating solution, and the specific conditions are not particularly limited. For example, a copper-clad laminate sample on which the photosensitive resin layer is laminated can be immersed in CATA NC-20 (MK Chem&Tech) as a palladium catalyst plating solution for 30 seconds to 90 seconds at a temperature of 10°C or more and 40°C or less.

[0360] Next, the copper-clad laminate sample on which the photosensitive resin layer is laminated with nickel plating can be immersed in the palladium plating solution to perform elution. Although the specific conditions for immersing the copper-clad laminate sample on which the photosensitive resin layer is laminated in the palladium plating solution are not particularly limited, for example, a sample having a cross-sectional area of 600 cm 2 or more and 700 cm 2 or less can be immersed in 130 ml of NPR-4 (Uemura) plating solution as a nickel-phosphorus plating solution for 20 minutes or more and 60 minutes or less to perform elution. The cross-sectional area refers to the area of the cross section obtained by cutting the sample in a direction perpendicular to the direction of increase in the thickness of the sample. 2 2 or more and 660 cm 2 or less can be immersed in 130 ml of NPR-4 (Uemura) plating solution as a nickel-phosphorus plating solution for 20 minutes or more and 60 minutes or less to perform elution. The cross-sectional area refers to the area of the cross section obtained by cutting the sample in a direction perpendicular to the direction of increase in the thickness of the sample. 2 or more and 650 cm​​​2 The sample was immersed in 130 ml of TPD-21 (Uemura) plating solution as a palladium plating solution for 30 minutes or more and 90 minutes or less to perform elution.

[0361] Meanwhile, the copper-clad laminate sample with the palladium-plated photosensitive resin layer laminated thereon can also be immersed in a gold plating solution to perform elution. Although the specific conditions for immersing the copper-clad laminate sample with the photosensitive resin layer laminated thereon in the gold plating solution are not particularly limited, for example, a copper-clad laminate sample having a cross-sectional area of 600 cm 2 or more and 700 cm 2 or less, or 640 cm 2 or more and 660 cm 2 or less, or 645 cm 2 or more and 655 cm 2 or less, or 650 cm 2 or more can be immersed in 130 ml of TMX-40 (Uemura) plating solution as a gold plating solution for 50 minutes or more and 150 minutes or less to perform elution.

[0362] Meanwhile, a more specific example of a method for measuring the thickness of the palladium-plated layer obtained by immersing the copper-clad laminate sample in the residual palladium plating solution for 5 minutes is described below.

[0363] First, the copper-clad laminate sample can be immersed in the residual nickel-phosphorus plating solution. Although the specific conditions for immersing the copper-clad laminate sample in the residual nickel-phosphorus plating solution are not particularly limited, for example, a copper-clad laminate sample having a cross-sectional area of 1 cm 2 or more and 10 cm 2 or less, or 4 cm 2 or more and 6 cm 2 or less, or 4.5 cm 2 or more and 5.5 cm 2 or less, or 5 cm 2 or more can be immersed in 130 ml of residual NPR-4 (Uemura) plating solution and plated for 15 minutes or more and 45 minutes or less. The cross-sectional area refers to the area of the cross section obtained by cutting the sample in a direction perpendicular to the direction in which the thickness of the sample increases.

[0364] If necessary, the sample can also be immersed in an aqueous catalyst solution before being immersed in the nickel-phosphorus plating solution. Although the specific conditions are not particularly limited, for example, the sample can be immersed for 90 seconds using CATANC-20 (MK Chem & Tech) as a palladium catalyst under conditions of 10°C or more and 40°C or less.

[0365] At this time, the thickness of the nickel-phosphorus plating layer obtained by immersing the film sample in which a photosensitive resin layer is laminated on the substrate in a nickel-phosphorus plating solution for 38 minutes, and then immersing the copper-clad laminate sample in the residual nickel-phosphorus plating solution for 28 minutes, can be 3.9 μm or more, or 3.95 μm or more, or 3.9 μm or more and 4.0 μm or less, or 3.95 μm or more and 4.0 μm or less.

[0366] Next, the nickel-plated copper-clad laminate sample can also be immersed in a residual palladium plating solution for electroplating. While there are no particular restrictions on the specific conditions for immersing the nickel-phosphorus-plated copper-clad laminate sample in a residual palladium plating solution, for example, it is possible to immerse the sample with a cross-sectional area of ​​1 cm² in a solution at temperatures above 30°C and below 70°C. 2 Above and 10cm 2 Below or 4cm 2 Above and 6cm 2 Below, or 4.5cm 2 Above and 5.5cm 2 Below or 5cm 2 The sample was immersed in 130 ml of residual TPD-21 (Uemura) plating solution for more than 2 minutes and less than 10 minutes.

[0367] Simultaneously, palladium-plated copper-clad laminate samples can be immersed in residual gold plating solution for electroplating. While there are no particular restrictions on the specific conditions for immersing palladium-plated copper-clad laminate samples in residual gold plating solution, for example, conditions above 65°C and below 95°C can be used for electroplating of samples with a cross-sectional area of ​​1 cm². 2 Above and 10cm 2 Below or 4cm 2 Above and 6cm 2 Below, or 4.5cm 2 Above and 5.5cm 2 Below or 5cm 2 The sample was immersed in 130 ml of residual TWX-40 (Uemura) plating solution for more than 5 minutes and less than 20 minutes for electroplating.

[0368] At this time, the dry film photoresist is characterized in that the thickness of the gold plating layer obtained by immersing a film sample in a gold plating solution in which a photosensitive resin layer of the dry film photoresist is laminated on a substrate for 98 minutes, and then immersing a copper-clad laminate sample in the residual gold plating solution for 11 minutes, can be 0.11 μm or more, or 0.11 μm or more and 0.13 μm or less, or 0.12 μm or more, or 0.12 μm or more and 0.13 μm or less.

[0369] That is, the dry film photoresist has a feature in that a gold plating layer obtained by immersing a film sample in which a photosensitive resin layer of a dry film photoresist is laminated on a substrate in a gold plating solution for 98 minutes and then immersing the copper-clad laminate sample in the residual gold plating solution for 11 minutes can have a thickness of 0.11 μm or more, or 0.11 μm or more and 0.13 μm or less, or 0.12 μm or more, or 0.12 μm or more and 0.13 μm or less.

[0370] Meanwhile, the film sample in which the photosensitive resin layer containing the photosensitive resin composition is laminated on the substrate can be a laminate in which the photosensitive resin layer is laminated on an arbitrary substrate. One example of the substrate can be a copper-clad laminate in which a copper layer having a thickness of 10 μm or more and 100 mm or less is provided on a surface.

[0371] The cross-sectional area of the film sample in which the photosensitive resin layer containing the photosensitive resin composition is laminated on the substrate can be 600 cm 2 or more and 700 cm 2 or less, or 640 cm 2 or more and 660 cm 2 or less, or 645 cm 2 or more and 655 cm 2 or less.

[0372] Further, the cross-sectional area of the copper-clad laminate sample for immersing the copper-clad laminate sample in the residual palladium plating solution for 5 minutes can be 1 cm 2 or more and 10 cm 2 or less, or 4 cm 2 or more and 6 cm 2 or less, or 4.5 cm 2 or more and 5.5 cm 2 or less.

[0373] When measuring the thickness of the palladium plating layer, the exposure device can be used to irradiate ultraviolet rays at an exposure dose of 20 mJ / cm 2 or more and 200 mJ / cm 2 or less, or 50 mJ / cm 2 or more and 100 mJ / cm 2 or less. The exposure time can be 1 second or more and 10 minutes or less, or 1 second or more and 10 seconds or less.

[0374] When the thickness of the palladium plating layer is measured, development can be performed by using an alkaline aqueous solution having a concentration of 0.5% by weight or more and 1.5% by weight or less, or 0.9% by weight or more and 1.1% by weight or less. The pH of the alkaline aqueous solution can be in the range of 9 or more and 11 or less, and the temperature can be adjusted depending on the developability of the photosensitive resin layer. Specific examples of the alkaline aqueous solution include a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, a sodium hydroxide aqueous solution, and the like.

[0375] The development can employ a method of bringing an alkaline aqueous solution into contact with the photosensitive resin layer. As one example of a specific contact method, a spraying method or an immersion method can be used. The development time can be 30 seconds or more and 10 minutes or less, or 30 seconds or more and 2 minutes or less.

[0376] The photosensitive resin layer can be in the form of a film without an opening, or in the form of a pattern having an opening.

[0377] Examples of a method of forming the photosensitive resin layer in a pattern shape include a method of laminating the photosensitive resin layer of the dry film resist of another embodiment on a substrate, and then performing exposure and development. In addition, a method of laminating the photosensitive resin layer of the photosensitive element according to another embodiment described later on a substrate, and then performing exposure and development can be mentioned.

[0378] When the dry film resist or the photosensitive element of another embodiment has a protective film on the photosensitive resin layer, a process of removing the protective film can also be performed before the process of laminating the photosensitive resin layer on a circuit board or a substrate for display device manufacturing.

[0379] In addition, when the dry film resist or the photosensitive element of another embodiment has a polymer substrate or a substrate film laminated on one side of the photosensitive resin layer, a process of removing the polymer substrate or the substrate film immediately after the exposure process can also be performed.

[0380] 3. Resist pattern

[0381] According to another embodiment of the present disclosure, a resist pattern can be provided, which includes a photosensitive resin pattern including the photosensitive resin composition included in the dry film resist of another embodiment. Details regarding the photosensitive resin composition included in the dry film resist include all of what is described in the above one embodiment.

[0382] The photosensitive resin pattern can be the photosensitive resin composition in the form of a pattern having an opening.

[0383] Examples of the method of forming a photosensitive resin pattern include a method of laminating the photosensitive resin layer of the dry film photoresist of another embodiment on a substrate, and then performing exposure and development. In addition, a method of laminating the photosensitive resin layer of the photosensitive element according to one embodiment on a substrate, and then performing exposure and development can be mentioned.

[0384] A copper-clad laminate; a glass substrate on which a transparent electrode such as ITO and IZO is sputtered or deposited; a similar film substrate; a glass substrate coated with a dielectric paste; a silicon wafer; a glass wafer on which amorphous silicon is deposited; a silicon wafer on which a metal film such as copper, tantalum, molybdenum, or the like is sputtered can be used as a substrate.

[0385] For the exposure process, it is preferable to use ultraviolet light, visible light rays, laser light, and particularly a laser direct exposure machine including a light source having a wavelength of 350 nm to 410 nm, specifically i-line (365 nm) or h-line (405 nm). In the case of using a laser direct exposure machine, when the exposure energy is 3 mJ / cm 2 to 15 mJ / cm 2 When a general lamp exposure machine is used under the following conditions, the exposure energy can be 20 mJ / cm 2 and work under the following conditions. Thus, it is useful for generating images of PCBs, lead frames, PDPs, and other display devices.

[0386] The development process can be performed by a dipping method, a shower method, a spray method, a brush coating method, or the like. An alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and an amine can be used as a developing solution.

[0387] When the dry film photoresist of another embodiment or the photosensitive element has a protective film on the photosensitive resin layer, a process of removing the protective film can be performed before the process of laminating the photosensitive resin layer on a circuit board or a substrate for display device manufacturing.

[0388] In addition, when the dry film photoresist of another embodiment or the photosensitive element of one embodiment has a polymer substrate or a substrate film laminated on one side of the photosensitive resin layer, a process of removing the polymer substrate or the substrate film immediately after the exposure process can also be performed.

[0389] 4. Circuit board, display device

[0390] According to still another embodiment of the present disclosure, a circuit board or a display device including the resist pattern of another embodiment or a metal pattern formed from the resist pattern of another embodiment can be provided. Details regarding the resist pattern include all of those described in the above another embodiment.

[0391] Specific details of the circuit board or display device are not particularly limited, and various conventional technical configurations can be applied without limitation.

[0392] The metal pattern can be formed from the above-described resist pattern. Specifically, the metal pattern can be formed by etching or plating through the openings included in the resist pattern. That is, the metal pattern can include the lower layer metal remaining after etching the lower layer metal of the resist pattern through the openings included in the resist pattern, or the metal plated in the openings included in the resist pattern.

[0393] Specifically, for example, by etching or plating the lower substrate exposed by the above-described resist pattern, a wire distribution map, a printed wiring board, a lead frame, an ITO electrode, a black matrix, a semiconductor bump, etc. can be manufactured. If necessary, after etching or plating, the patterned photosensitive resin layer can be peeled off from the substrate with an aqueous solution having a stronger alkalinity than the developing solution to be removed.

[0394] Accordingly, then, by using the dry film photoresist of the present disclosure, a conventional etching / plating process is performed to form a circuit having a fine line width, and by known processes, productivity can be maximized when creating images on PCBs having a fine line width, as well as lead frames, PDPs, other display devices, and semiconductor devices.

[0395] Advantageous Effects

[0396] According to the present disclosure, a photosensitive element that can achieve the effect of reducing contamination of a plating solution and enabling plating at a sufficient thickness, a dry film photoresist, a resist pattern, a circuit board, and a display device using the same can be provided. DETAILED DESCRIPTION

[0397] The present disclosure will be described in greater detail by the following examples. However, these examples are for illustrative purposes only, and are not intended to limit the scope of the present disclosure thereto.

[0398] <Preparation Example: Preparation of alkali-developable binder resin>

[0399] Preparation Example 1

[0400] A 4-necked jacketed reaction flask was equipped with a mechanical stirrer and a reflux device, and then the inside of the flask was purged with nitrogen. 90 g of methyl ethyl ketone (MEK) and 10 g of methanol (MeOH) were added to the flask purged with nitrogen, and then 0.9 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. 24 g of methacrylic acid (MAA), 6 g of methyl methacrylate (MMA), 30 g of styrene (SM), and 40 g of a monomer mixture of 2-phenoxyethyl methacrylate (PHEMA) were added as monomers, heated to 80°C, and then polymerized for 6 hours to prepare a base-developable adhesive resin (weight average molecular weight: 50,000 g / mol, solid content: 50.0 wt%, acid value: 155 mg KOH / g).

[0401] Specific examples of the measurement conditions of the weight average molecular weight are as follows. The base-developable adhesive resin was dissolved in tetrahydrofuran so that the concentration thereof in THF was 1.0 (w / w) % (about 0.5 (w / w) % based on the solid content), and filtered using a syringe filter having a pore size of 0.45 μm, and then an amount of 20 μl was injected into the GPC. Tetrahydrofuran (THF) was used as the mobile phase of the GPC, and flowed in at a flow rate of 1.0 mL / min. The chromatographic column was configured by connecting one Agilent PLgel 5 μm Guard (7.5 x 50 mm) and two Agilent PLgel 5 μm Mixed D (7.5 x 300 mm) in series, and the measurement was performed at 40°C using an Agilent 1260 Infinity II system, an RI detector.

[0402] The acid value was measured by sampling 1 g of the base-developable adhesive resin, dissolving it in 50 ml of a mixed solvent (20% MeOH, 80% acetone), adding two drops of 1% phenolphthalein indicator, and titrating with 0.1 N-KOH.

[0403] The weight percentage of the solid remaining after heating in an oven at 150°C for 120 minutes was measured as the solid content based on the weight of the base-developable adhesive resin prepared in the above Preparation Example.

[0404] Preparation Example 2

[0405] A 4-necked round-bottom flask was equipped with a mechanical stirrer and a reflux apparatus, and then the inside of the flask was purged with nitrogen. 80 g of methyl ethyl ketone (MEK) and 7.5 g of methanol (MeOH) were added to the flask purged with nitrogen, and then 0.45 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. A monomer mixture of 8 g of acrylic acid (AA) (0.11 mol, 10.91 mol% in 100 mol% of the total monomers), 15 g of methacrylic acid (MAA) (0.17 mol, 17.13 mol% in 100 mol% of the total monomers), 15 g of butyl acrylate (BA) (0.12 mol, 11.50 mol% in 100 mol% of the total monomers), 52 g of methyl methacrylate (MMA) (0.52 mol, 51.03 mol% in 100 mol% of the total monomers), and 10 g of styrene (SM) (0.10 mol, 9.43 mol% in 100 mol% of the total monomers) was added as a monomer, heated to 80°C, and then polymerized for 6 hours to prepare an alkali developable adhesive resin.

[0406] The alkali developable adhesive resin measured 71,538 g / mol in weight average molecular weight, 79°C in glass transition temperature, 51.4 wt% in solid content, and 156.3 mg KOH / g in acid value.

[0407] Preparation Example 3

[0408] A 4-necked round-bottom flask was equipped with a mechanical stirrer and a reflux apparatus, and then the inside of the flask was purged with nitrogen. 110 g of methyl ethyl ketone (MEK) and 10 g of methanol (MeOH) were added to the flask purged with nitrogen, and then 1 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. A monomer mixture of 30 g of methacrylic acid (MAA) (0.35 mol, 21.32 mol% in 100 mol% of the total monomers), 100 g of methyl methacrylate (MMA) (1.00 mol, 61.07 mol% in 100 mol% of the total monomers), and 30 g of styrene (SM) (0.29 mol, 17.61 mol% in 100 mol% of the total monomers) was added as a monomer, heated to 80°C, and then polymerized for 6 hours to prepare an alkali developable adhesive resin (weight average molecular weight: 49,852 g / mol, glass transition temperature: 125°C, solid content: 48.5 wt%, acid value: 163.17 mg KOH / g).

[0409] Preparation Example 4

[0410] A 4-necked round bottom flask was equipped with a mechanical stirrer and a reflux apparatus, and then the inside of the flask was purged with nitrogen. 90 g of methyl ethyl ketone (MEK) and 10 g of methanol (MeOH) were added to the flask purged with nitrogen, and then 0.85 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. A monomer mixture of 25 g of methacrylic acid (MAA) (0.29 mol, 30.86 mol% in 100 mol% of the total monomers), 20 g of methyl methacrylate (MMA) (0.20 mol, 21.22 mol% in 100 mol% of the total monomers), 25 g of styrene (SM) (0.24 mol, 25.50 mol% in 100 mol% of the total monomers), and 30 g of glycidyl methacrylate (GMA) (0.21 mol, 22.42 mol% in 100 mol% of the total monomers) was added as a monomer thereto, heated to 80°C, and then polymerized for 6 hours to prepare a alkali developable binder resin.

[0411] The alkali developable binder resin had a weight average molecular weight of 55,201 g / mol, a glass transition temperature of 112°C, a solid content of 50.2 wt%, and an acid value of 162.0 mg KOH / g.

[0412] [Examples and Comparative Examples: Preparation of photosensitive resin composition and dry film photoresist]

[0413] A photopolymerization initiator was dissolved in methyl ethyl ketone (MEK) as a solvent according to the composition shown in Table 1 below, and then a photopolymerizable compound and an alkali developable binder resin were added and mixed for about 1 hour using a mechanical stirrer to prepare a photosensitive resin composition.

[0414] The resulting photosensitive resin composition was coated on a 19 μm PET film using a coating bar to form a photosensitive resin composition layer, and then dried using a hot air oven. At this time, the drying temperature was 80°C, the drying time was 5 minutes, and the thickness of the dried photosensitive resin composition layer was 40 μm.

[0415] A protective film (polyethylene) was laminated on the dried photosensitive resin composition layer to prepare a dry film photoresist.

[0416] [Table 1]

[0417]

[0418]

[0419] [Table 2]

[0420]

[0421]

[0422] <Experimental Example>

[0423] The physical properties of the dry film photoresists prepared in the examples and comparative examples were measured using the following methods, and the results are shown in Tables 3 and 4 below.

[0424] 1. Pollution properties of chemical palladium plating solution

[0425] A protective film was peeled off from the dry film photoresist prepared in the examples and comparative examples, and the photosensitive resin layer of the dry film photoresist was double-sided laminated using HAKUTO MACH610i, bringing it into contact with the copper layer surface of a 1.6 mm thick copper-clad laminate. The substrate preheating roller temperature was 120°C, the laminator roller temperature was 115°C, and the roller pressure was 4.0 kgf / cm². 2 The laminator is formed by brushing and grinding under the condition of a roller speed of 2.0 min / m.

[0426] The supporting PET film for the dry film photoresist is peeled off from the laminate, and then a photomask is used at 80 mJ / cm. 2 The exposure was determined by irradiating the entire surface with ultraviolet light using an ORCEXM-1201-F (parallel exposure machine) for 4 seconds, followed by a 15-minute resting period. Subsequently, the surface was sprayed at a pressure of 1.5 kgf / cm². 2 Under spray-type developing conditions, the laminar flow was carried out at 30±1℃ with a 1.0 wt% Na2CO3 aqueous solution for 1 minute. The developed laminar flow was then baked in an oven at 140℃ for 30 minutes.

[0427] After the baked laminate has cooled sufficiently, a 650cm² lamination is prepared. 2 The samples were divided into several sections. The samples were sequentially immersed in 130 ml of CATA NC-20 (MK Chem&Tech) palladium catalyst at 25 °C for 1 min 30 s, rinsed in distilled water for 1 min, immersed in 130 ml of NPR-4 (Uemura) nickel-phosphorus plating solution at 80 ± 2 °C for 38 min, rinsed in distilled water for 1 min, immersed in 130 ml of TPD-21 (Uemura) palladium plating solution at 55 ± 2 °C for 60 min, rinsed in distilled water for 1 min, and immersed in 130 ml of TWX-40 (Uemura) gold plating solution at 80 ± 2 °C for 98 min, and rinsed in distilled water for 1 min.

[0428] Then, in the plating solution in which the dry film photoresist component is washed off by impregnation with the laminate, the 5cm brushed plate is... 2The copper-clad laminate having a cross-sectional area of 130 ml and a thickness of 1.6 mm was sequentially immersed in 130 ml of CATANC-20 (MK Chem & Tech) palladium catalyst at 25°C for 1 minute 30 seconds, rinsed in distilled water for 1 minute, immersed in 130 ml of NPR-4 (Uemura) nickel-phosphorus plating solution at 80±2°C for 28 minutes, rinsed in distilled water for 1 minute, immersed in 130 ml of TPD-21 (Uemura) palladium plating solution at 55±2°C for 5 minutes, rinsed in distilled water for 1 minute, immersed in 130 ml of TWX-40 (Uemura) gold plating solution at 80±2°C for 11 minutes, and rinsed in distilled water for 1 minute.

[0429] The plating layer thickness of the nickel-phosphorus-plated, palladium-plated, and gold-plated copper-clad laminate was measured in order using a Helmut Fischer XDV-μ, and the plating solution contamination performance was evaluated by the degree of plating layer thickness.

[0430] 2. Fine line adhesion (unit: μm)

[0431] The protective film was peeled off from the dry film photoresist prepared in the examples and comparative examples, and the photosensitive resin layer of the dry film photoresist was laminated in contact with the copper layer surface of the copper-clad laminate having a thickness of 1.6 mm using a HAKUTO MACH 610i under the conditions of a substrate preheating roll temperature of 120°C, a laminator roll temperature of 115°C, a roll pressure of 4.0 kgf / cm 2 and a roll speed of 2.0 min / m, thereby forming a laminate.

[0432] The support PET film for the dry film photoresist was peeled off from the laminate, and then the entire surface was exposed to ultraviolet radiation for 4 seconds using a photomask at an exposure amount of 80 mJ / cm 2 using an ORC EXM-1201-F (parallel exposure machine), and then allowed to stand for 15 minutes. Subsequently, development was performed using a 1.0 wt% Na2CO3 aqueous solution under spray-type development conditions at a spray pressure of 1.5 kgf / cm 2 at 30±1°C for 1 minute.

[0433] The minimum line width of the photosensitive resin layer was measured using a ZEISS AXIOPHOT microscope in the laminate that had been developed, and evaluated as fine line adhesion. The smaller the numerical value, the better the fine line adhesion.

[0434] 3. 1:1 resolution (unit: μm)

[0435] A protective film was peeled off from the dry film photoresist prepared in the examples and comparative examples, and a photosensitive resin layer of the dry film photoresist was laminated using HAKUTO MACH610i, bringing it into contact with the copper layer surface of a 1.6 mm thick copper-clad laminate. The substrate preheating roller temperature was 120°C, the laminator roller temperature was 115°C, and the roller pressure was 4.0 kgf / cm². 2 The laminator is formed by brushing and grinding under the condition of a roller speed of 2.0 min / m.

[0436] The supporting PET film for the dry film photoresist was peeled off from the laminate, and then, using an ORCEXM-1201-F (parallel exposure machine), the photomask used for circuit evaluation was passed through at 80 mJ / cm². 2 The exposure was achieved by irradiating the circuit with ultraviolet light for 4 seconds, allowing the width of the circuit wires and the spacing between them to be 1:1, followed by a 15-minute resting period. Subsequently, the circuit was sprayed at a pressure of 1.5 kgf / cm². 2 Under spray-type developing conditions, development was performed for 1 minute at 30±1℃ using a 1.0 wt% Na2CO3 aqueous solution.

[0437] In the developed laminate, the minimum spacing between the photosensitive resin layers was measured using a ZEISS AXIOPHOT microscope and evaluated as a 1:1 resolution. It can be assessed that the smaller the value, the better the 1:1 resolution.

[0438] 4. Peeling rate (unit: seconds)

[0439] A protective film was peeled off from the dry film photoresist prepared in the examples and comparative examples, and a photosensitive resin layer of the dry film photoresist was laminated using HAKUTO MACH610i, bringing it into contact with the copper layer surface of a 1.6 mm thick copper-clad laminate. The substrate preheating roller temperature was 120°C, the laminator roller temperature was 115°C, and the roller pressure was 4.0 kgf / cm². 2 The laminate is formed by brushing and grinding under the condition of a roller speed of 2.0 min / m.

[0440] The supporting PET film for the dry film photoresist is peeled off from the laminate, and then the photomask used for circuit evaluation is irradiated with ultraviolet light using an ORCEXM-1201-F (parallel exposure machine) until it reaches 40 mJ / cm². 2 The exposure was then adjusted, and the mixture was allowed to stand for 15 minutes. Subsequently, the spray pressure was increased to 1.5 kgf / cm². 2 Under spray-type developing conditions, development was performed at 30±1℃ using a 1.0 wt% Na2CO3 aqueous solution for a time twice the minimum developing time.

[0441] Then, the photosensitive resin layer was peeled off from the copper-clad laminate using a 3% aqueous sodium hydroxide solution (temperature 50°C). At this time, the time required for the photosensitive resin layer to fall off from the copper-clad laminate was measured.

[0442] [Table 3]

[0443]

[0444] As shown in Table 3, it was confirmed that in Examples 1 to 3, the measured thickness of the palladium plating layer was 0.1 μm or more and 0.138 μm or less, and thus the degree of plating with palladium was sufficiently improved compared to Comparative Example 1 in which the thickness of the plating layer was 0.008 μm. Further, it was confirmed that in Examples 1 to 3, the measured thickness of the nickel-phosphorus plating layer was 3.905 μm or more and 3.976 μm or less, and thus the degree of plating was sufficiently improved even when nickel-phosphorus was used compared to Comparative Example 1 in which the thickness of the plating layer was 3.718 μm.

[0445] From the above results, it was confirmed that the dry film photoresist prepared in Examples 1 to 3 had low contamination properties with respect to the plating solution, and thus a sufficient degree of plating properties could be ensured even when the plating solution was repeatedly used.

[0446] [Table 4]

[0447]

[0448] As shown in Table 4, it was confirmed that in Examples 4 to 5, the measured thickness of the palladium plating layer was 0.113 μm or more and 0.121 μm or less, and thus the degree of plating with palladium was sufficiently improved compared to Comparative Example 2 in which the thickness of the plating layer was 0.002 μm. Further, it was confirmed that in Examples 4 to 5, the measured thickness of the nickel-phosphorus plating layer was 3.916 μm or more and 3.926 μm or less, and thus the degree of plating was sufficiently improved even when nickel-phosphorus was used compared to Comparative Example 2 in which the thickness of the plating layer was 3.863 μm.

[0449] Further, it was confirmed that in Examples 4 to 5, the measured thickness of the gold plating layer was 0.112 μm or more and 0.122 μm or less, and thus the degree of plating was sufficiently improved even when gold was used compared to Comparative Example 2 in which the thickness of the plating layer was 0.100 μm.

[0450] From the above results, it was confirmed that the dry film photoresist prepared in Examples 4 to 5 had low contamination properties with respect to the plating solution, and thus a sufficient degree of plating properties could be ensured even when the plating solution was repeatedly used.

[0451] In addition, the dry film photoresist prepared in Examples 4 to 5 exhibited a short peeling time of 66 seconds or more and 81 seconds or less, thereby achieving excellent peeling performance.

Claims

1. A photosensitive element comprising: a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, wherein the photosensitive resin layer contains a photosensitive resin composition containing an alkali-developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the photopolymerizable compound contains a difunctional (meth)acrylate compound and at least one selected from a penta-type (meth)acrylate compound having five (meth)acryloyl groups and a multifunctional (meth)acrylate compound having seven or more (meth)acryloyl groups, and wherein the content of the photopolymerizable compound is 10% by weight or more and 70% by weight or less, based on the solid content, with respect to the total weight of the photosensitive resin composition, wherein the thickness of the palladium plating layer is obtained by immersing a film sample in which the photosensitive resin layer is laminated on a copper-clad laminate in a nickel-phosphorus plating solution for 38 minutes, in a palladium plating solution for 60 minutes, and in a gold plating solution for 98 minutes, and then immersing a new sample of the copper-clad laminate in the residual nickel-phosphorus plating solution for 28 minutes, in the residual palladium plating solution for 5 minutes, and in the residual gold plating solution for 11 minutes, wherein the thickness of the palladium plating layer is evaluated as 0.01 μm or more when the new sample of the copper-clad laminate is immersed in the residual palladium plating solution for 5 minutes.

2. The photosensitive element according to claim 1, wherein: the photosensitive element has a feature further in that the thickness of the nickel-phosphorus plating layer is obtained by immersing a film sample in which the photosensitive resin layer is laminated on a copper-clad laminate in a nickel-phosphorus plating solution for 38 minutes, in a palladium plating solution for 60 minutes, and in a gold plating solution for 98 minutes, and then immersing a new sample of the copper-clad laminate in the residual nickel-phosphorus plating solution for 28 minutes, in the residual palladium plating solution for 5 minutes, and in the residual gold plating solution for 11 minutes, wherein the thickness of the nickel-phosphorus plating layer is evaluated as 3.9 μm or more when the new sample of the copper-clad laminate is immersed in the residual nickel-phosphorus plating solution for 28 minutes.

3. The photosensitive element according to claim 1, wherein: the penta-type (meth)acrylate compound further contains one hydroxyl group.

4. The photosensitive element according to claim 1, wherein: the penta-type (meth)acrylate compound is a compound represented by the following Chemical Formula A: [Chemical Formula A] wherein, in Chemical Formula A, five of T1 to T6 are the same as or different from each other and are each independently a (meth)acryloyl group, and the remaining one is hydrogen.

5. The photosensitive element according to claim 1, wherein: the multifunctional (meth)acrylate compound is a compound represented by the following Chemical Formula B: [Chemical Formula B] wherein, in Chemical Formula B, T7to T 11 each independently is (meth)acryloyl, T 12 is hydrogen or (meth)acryloyl, t is an integer of 2 to 10.

6. A photosensitive element comprising: a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, The thickness of the palladium plating layer is obtained by immersing a film sample in which the photosensitive resin layer is laminated on a copper-clad laminate in a nickel-phosphorus plating solution for 38 minutes, in a palladium plating solution for 60 minutes, and in a gold plating solution for 98 minutes. Then, a new copper-clad laminate sample is immersed in the residual nickel-phosphorus plating solution for 28 minutes, in the residual palladium plating solution for 5 minutes, and in the residual gold plating solution for 11 minutes. In one instance, when a new copper-clad laminate sample was immersed in residual palladium plating solution for 5 minutes, the thickness of the palladium plating layer was assessed to be greater than 0.01 μm. in: The photosensitive resin layer comprises a photosensitive resin composition, which includes an alkaline-developable adhesive resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the alkaline-developable adhesive resin comprises four or more different types of polymers. The alkaline-developable adhesive resin comprises a first adhesive resin containing repeating units represented by the following chemical formula 1. [Chemical Formula 1] In chemical formula 1, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms. R2 is an alkylene group having 1 to 10 carbon atoms. Ar is an aryl group having 6 to 20 carbon atoms. n is an integer from 1 to 20. The alkaline-developable adhesive resin comprises a second adhesive resin containing repeating units represented by the following chemical formula 5: [Chemical Formula 5] In chemical formula 5, R6 is hydrogen. R7 is an alkyl group having 1 to 10 carbon atoms. The alkaline-developable adhesive resin comprises a third adhesive resin, which includes repeating units represented by chemical formula 10, repeating units represented by chemical formula 11, and repeating units represented by chemical formula 12. [Chemical Formula 10] In chemical formula 10, R9 is an alkyl group having 1 to 10 carbon atoms. [Chemical Formula 11] In chemical formula 11, R 10 is an alkyl group having 1 to 10 carbon atoms, R 11 is an alkyl group having 1 to 10 carbon atoms, [Chemical Formula 12] In chemical formula 12, Ar is an aryl group having 6 to 20 carbon atoms. The alkaline-developable adhesive resin comprises a fourth adhesive resin containing repeating units represented by the following chemical formula 13: [Chemical Formula 13] In chemical formula 13, R 12 is hydrogen or alkyl having 1 to 10 carbon atoms, R 13 alkylene having 1 to 10 carbon atoms.

7. The photosensitive element according to claim 6, wherein: In addition to the repeating unit represented by Chemical Formula 1, the first adhesive resin also comprises repeating units represented by Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4: [Chemical Formula 2] In chemical formula 2, R3 is hydrogen or an alkyl group having 1 to 10 carbon atoms. [Chemical Formula 3] In chemical formula 3, R4 is hydrogen or an alkyl group having 1 to 10 carbon atoms. R5 is an alkyl group having 1 to 10 carbon atoms. [Chemical Formula 4] In chemical formula 4, Ar is an aryl group having 6 to 20 carbon atoms.

8. The photosensitive element according to claim 6, wherein: In addition to the repeating unit represented by chemical formula 5, the second adhesive resin further comprises repeating units represented by chemical formula 6, chemical formula 7, chemical formula 8, and chemical formula 9: [Chemical Formula 6] In chemical formula 6, R8 is hydrogen. [Chemical Formula 7] In chemical formula 7, R9 is an alkyl group having 1 to 10 carbon atoms. [Chemical Formula 8] In chemical formula 8, R 10 is an alkyl group having 1 to 10 carbon atoms, R 11 is an alkyl group having 1 to 10 carbon atoms, [Chemical Formula 9] In chemical formula 9, Ar is an aryl group having 6 to 20 carbon atoms.

9. The photosensitive element according to claim 6, wherein: In addition to the repeating unit represented by chemical formula 13, the fourth adhesive resin further comprises repeating units represented by chemical formula 14, repeating units represented by chemical formula 15, and repeating units represented by chemical formula 16: [Chemical Formula 14] In chemical formula 14, R 14 is hydrogen or alkyl having 1 to 10 carbon atoms, [Chemical Formula 15] In chemical formula 15, R 15 is hydrogen or alkyl having 1 to 10 carbon atoms, R 16 alkyl having 1 to 10 carbon atoms, [Chemical Formula 16] In chemical formula 16, Ar is an aryl group having 6 to 20 carbon atoms.

10. A dry film photoresist, comprising: A photosensitive resin composition comprising an alkaline developable adhesive resin, a photopolymerizable initiator, and a photopolymerizable compound, wherein the photopolymerizable compound comprises a bifunctional (meth)acrylate compound and at least one selected from type 5 (meth)acrylate compounds having five (meth)acryloyl groups and polyfunctional (meth)acrylate compounds having seven or more (meth)acryloyl groups. Wherein, relative to the total weight of the photosensitive resin composition, based on solid content, the content of the photopolymerizable compound is 10% by weight or more and 70% by weight or less, and The dry film photoresist is characterized in that the thickness of the palladium plating layer is obtained by immersing a film sample in a nickel-phosphorus plating solution for 38 minutes, a palladium plating solution for 60 minutes, and a gold plating solution for 98 minutes, wherein the film sample in which the dry film photoresist is laminated on a copper-clad laminate is immersed; then, a new copper-clad laminate sample is immersed in a residual nickel-phosphorus plating solution for 28 minutes, a residual palladium plating solution for 5 minutes, and a residual gold plating solution for 11 minutes. Among them, the thickness of the palladium plating layer was evaluated to be greater than 0.01 μm when the new copper-clad laminate sample was immersed in the residual palladium plating solution for 5 minutes.

11. A dry film photoresist, comprising: A photosensitive resin composition comprising an alkaline-developable adhesive resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the alkaline-developable adhesive resin comprises four or more different types of polymers. The dry film photoresist is characterized in that the thickness of the palladium plating layer is obtained by immersing a film sample in a nickel-phosphorus plating solution for 38 minutes, in a palladium plating solution for 60 minutes, and in a gold plating solution for 98 minutes, wherein a new copper-clad laminate sample is immersed in a residual nickel-phosphorus plating solution for 28 minutes, in a residual palladium plating solution for 5 minutes, and in a residual gold plating solution for 11 minutes. Among them, when the new copper-clad laminate sample was immersed in the residual palladium plating solution for 5 minutes, the thickness of the palladium plating layer was evaluated to be greater than 0.01 μm. The alkaline-developable adhesive resin comprises a first adhesive resin containing repeating units represented by the following chemical formula 1. [Chemical Formula 1] In chemical formula 1, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms. R2 is an alkylene group having 1 to 10 carbon atoms. Ar is an aryl group having 6 to 20 carbon atoms. n is an integer from 1 to 20. The alkaline-developable adhesive resin comprises a second adhesive resin containing repeating units represented by the following chemical formula 5: [Chemical Formula 5] In chemical formula 5, R6 is hydrogen. R7 is an alkyl group having 1 to 10 carbon atoms. The alkaline-developable adhesive resin comprises a third adhesive resin, which includes repeating units represented by chemical formula 10, repeating units represented by chemical formula 11, and repeating units represented by chemical formula 12. [Chemical Formula 10] In chemical formula 10, R9 is an alkyl group having 1 to 10 carbon atoms. [Chemical Formula 11] In chemical formula 11, R 10 is an alkyl group having 1 to 10 carbon atoms, R 11 is an alkyl group having 1 to 10 carbon atoms, [Chemical Formula 12] In chemical formula 12, Ar is an aryl group having 6 to 20 carbon atoms. The alkaline-developable adhesive resin comprises a fourth adhesive resin containing repeating units represented by the following chemical formula 13: [Chemical Formula 13] In chemical formula 13, R 12 is hydrogen or alkyl having 1 to 10 carbon atoms, R 13 alkylene having 1 to 10 carbon atoms.

12. A resist pattern comprising: A photosensitive resin pattern comprising the photosensitive resin composition contained in the dry film photoresist of claim 10 or 11.

13. A circuit board comprising: The resist pattern of claim 12, or a metal pattern formed from the resist pattern of claim 12.

14. A display device comprising: The resist pattern of claim 12, or a metal pattern formed from the resist pattern of claim 12.

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