TW202235453A - Photosensitive element, dry film photoresist, resist pattern, circuit board, and display device using the same - Google Patents

Abstract

The present disclosure relates to a photosensitive element comprising: a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, wherein a thickness of a palladium plating layer, which is 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 a residual palladium plating solution for 5 minutes, is 0.01 μm or more, and a dry film photoresist, a resist pattern, a circuit board, and a display device using the same.

Description

Photosensitive elements, dry film resists, resist patterns, circuit boards, display devices using them

The disclosure relates to a photosensitive element, a dry film photoresist, an impedance pattern, a circuit board and a display device.

The photosensitive resin composition is used for dry film photoresist (dry film photoresist, DFR) and liquid photoresist (liquid photoresist ink) for printed circuit board (printed circuit board, PCB) or lead frame.

At present, dry film photoresist is not only widely used in the manufacture of printed circuit boards (PCBs) and lead frames, but also used in the manufacture of rib barriers (rib barriers) for plasma display panels (PDPs) and indium tin oxide for other displays. (indium tin oxide, ITO) electrode, bus address electrode (Bus Address electrode) and black matrix.

Generally, this type of dry film photoresist is often used in applications where it is laminated on a copper clad laminate. In this regard, as an example of a manufacturing process of a printed circuit board (PCB), in order to laminate a sample of a copper-clad laminate as an original board material of the PCB, a preprocessing step is first performed. In the outer layer process, pretreatment steps are performed in the order of drilling, deburring, scrubbing, etc., and in the inner layer process, scrubbing or pickling is performed. In the scrubbing step, bristle brushes and pumice stone processes are mainly used, while in the pickling step, soft etching and 5% by weight sulfuric acid pickling can be performed.

In order to form circuits on the copper clad laminate that has undergone a preprocessing step, dry film photoresist (DFR) (hereinafter referred to as DFR) is usually laminated on the copper layer of the copper clad laminate. In this step, the photoresist layer of the DFR is laminated on the copper surface while the protective film of the DFR is peeled off using a laminator. Typically performed at speeds from 0.5 meters per minute (m/min) to 3.5 m/min, temperatures from 100°C to 130°C, and heated roller pressures from 10 pounds per square inch (psi) to 90 psi cascading.

The printed circuit board that has passed through the lamination step is left to stand for 15 minutes or more to stabilize the board, and then exposed to a photoresist of DFR 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 starts to polymerize with the contained photoinitiator at the irradiation site. First, oxygen in the photoresist is consumed at an initial stage, and then reactive monomers are polymerized to cause a crosslinking reaction. Subsequently, the polymerization reaction continues while consuming a large amount of monomer. On the other hand, the unexposed portion exists in a state where the crosslinking reaction has not yet proceeded.

Next, a development step is performed to remove the unexposed portions of the photoresist. In the case of alkaline developable DFR, an aqueous solution of 0.8% to 1.2% by weight of potassium carbonate and sodium carbonate is used as the developing solution. In this step, the unexposed portion of the photoresist is washed off by a saponification reaction between the developing solution and the carboxylic acid of the binder polymer in the developing solution, and the cured photoresist remains on the copper surface.

Then, according to the inner layer and outer layer process, the circuit is formed through different steps. In the inner layer process, circuits are formed on the substrate by etching and stripping steps, and in the outer layer process, plating and tenting steps are performed, and then etching and solder stripping are performed, thereby forming predetermined circuits.

[technical problem]

An object of the present disclosure is to provide a photosensitive member capable of reducing contamination of a plating solution and allowing plating to be performed with a sufficient thickness.

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 photosensitive element. [Technical solution]

In order to achieve the above object, according to one aspect, a photosensitive element is provided, the photosensitive element includes: a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, wherein the thickness of the palladium plating layer is 0.01 micron or greater 0.01 μm, the palladium plating layer was obtained by immersing a film sample in which the photosensitive resin layer was laminated on the substrate in a palladium plating solution for 60 minutes and then immersing a copper clad laminate sample in the remaining palladium plating solution for 5 obtained in minutes.

According to another aspect, a dry film photoresist is provided, the dry film photoresist includes: a photosensitive resin composition, including an alkaline developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the photopolymerizable The photopolymerizable compound comprises five types of (meth)acrylate compounds having five (meth)acryl groups and polyfunctional (meth)acrylic acid compounds having seven or more (meth)acryl groups. At least one of the group consisting of ester-based compounds, and wherein the film sample in which the photosensitive resin layer of the dry film photoresist is laminated on the substrate is immersed in a palladium plating solution for 60 minutes and then the copper-clad laminate The palladium plating layer obtained by immersing the sample in the remaining palladium plating solution for 5 minutes has a thickness of 0.01 micrometer or more.

According to another aspect, a dry film photoresist is provided, the dry film photoresist includes: a photosensitive resin composition, including an alkaline developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the alkali A non-developable adhesive resin comprising four or more polymers different from each other, and wherein a film sample in which a photosensitive resin layer of the dry film resist is laminated on a substrate is immersed in a palladium plating solution for 60 minutes and The thickness of the palladium plating layer obtained by immersing the copper-clad laminate sample in the remaining palladium plating solution for 5 minutes is 0.01 micron or more.

According to still another aspect, there is provided a resist pattern, the resist pattern includes a photosensitive resin pattern containing the photosensitive resin composition contained in the dry film photoresist.

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

According to another aspect, there is provided a display device including the impedance pattern or a metal pattern formed by the impedance pattern.

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

Unless otherwise specified throughout the specification, technical terms used herein are for referring to specific embodiments only and are not intended to limit the present disclosure.

As used herein, the singular forms "a/an" and "the" also include plural references unless the context clearly dictates otherwise.

As used herein, the term "including" or "comprising" specifies specific features, regions, integers, steps, actions, elements and/or components, but does not exclude different specific features, regions, integers, Existence or addition of steps, actions, elements, components and/or groups.

In addition, terms including ordinal numbers such as "first (first)" and "second (second)" are only used for the purpose of distinguishing each component and are not limited to the ordinal numbers. For example, a first component could be termed a second component, or similarly, a second component could be termed a first component, without departing from the scope of the present disclosure.

In the present disclosure, examples of substituents are set forth below, but are not limited thereto.

In this disclosure, the term "substituted" means that other functional groups are bonded instead of the hydrogen atoms in the compound, and the position to be substituted is not limited as long as the position is the position where the hydrogen atom is substituted ( That is, the position where the substituent can be substituted), and when two or more are substituted, the two or more substituents may be the same or different from each other.

In this disclosure, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; halo; cyano ; Nitro; Hydroxy; Carbonyl; Ester; Imide; Amide; Primary Amino; Carboxyl; Oxygen; Arylsulfoxyl; Alkylsulfonyloxy; Arylsulfonyloxy; Silyl; Boronyl; Alkyl; Cycloalkyl; Alkenyl; Aryl; Aralkyl; Aralkenyl; Alkylaryl; alkoxysilylalkyl; arylphosphino; or heterocyclyl, containing at least one of N, O and S atoms, or meaning unsubstituted or through the substituents exemplified above Substitution with substituents linked to two or more substituents. For example, the "substituent linked to two or more substituents" may be biphenyl. That is, a biphenyl group can also be an aryl group, and can be construed as a substituent linked to two phenyl groups.

或

意指與另一取代基連結的鍵，且直接鍵結意指在表示為L的部分中不存在其他原子的情形。 In this disclosure, notation

or

means a bond to another substituent, and a direct bond means the case where no other atom exists in the moiety denoted L.

In the present disclosure, (meth)acrylic is intended to include both acrylic and methacrylic. For example, (meth)acryl may include both acryl and methacryl. In addition, (meth)acrylate may include both acrylate and methacrylate.

In the present disclosure, an alkyl group is a monovalent functional group derived from an alkane, and may be straight or branched. The number of carbon atoms of the linear alkyl group is not particularly limited, but is preferably 1-20. In addition, the number of carbon atoms of the branched alkyl group is 3 to 20. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, second-butyl, 1-methylbutyl , 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, third pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl Base-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, third octyl, 1 -Methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1-dimethylpropyl , isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptan-4-yl and the like, but not limited thereto. The alkyl group may be substituted or unsubstituted, and when it is substituted, examples of the substituent are the same as those described above.

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

Hereinafter, the present disclosure will be explained in more detail. 1. Photosensitive element

According to an embodiment of the present disclosure, there is provided a photosensitive element, the photosensitive element includes: a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, wherein the thickness of the palladium plating layer is 0.01 micron or greater than 0.01 micron micron, the palladium plating layer was obtained by immersing the film sample in which the photosensitive resin layer was laminated on the substrate in the palladium plating solution for 60 minutes and then immersing the copper clad laminate sample in the remaining palladium plating solution for 5 minutes.

Various plastic films can be used as the substrate film, and examples thereof may include a film selected from acrylic film, polyethylene terephthalate (PET) film, triacetylcellulose (TAC) film, polyrephthalate At least one plastic film selected from the group consisting of a polynorbornene (PNB) film, a cycloolefin 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 within a range of 0.01 μm to 1 mm.

A specific example of the polymer substrate may be a polyester film in which, by uniaxially stretching an unstretched polyester film, a coating solution containing a binder resin and organic particles is applied thereto. An in-line coating method on one surface, and uniaxially stretching the rest forms an anti-blocking layer.

Polymer substrates are generally manufactured by in-line coating methods rather than adding anti-blocking agents (which are generally added for runnability and winding characteristics during manufacturing), and have the advantage of using without compromising transparency. The organic particle layer of alternative particles.

Here, examples of organic particles used as particles that do not impair transparency while taking feed-out property and winding characteristics into consideration may include, for example, organic particles in which, for example, methyl methacrylate, ethyl methacrylate, methyl methacrylate, etc. are formed. Acrylic particles such as isobutyl acrylate, n-butyl methacrylate, n-butyl methyl methacrylate, acrylic acid, methacrylic acid copolymers or terpolymers; olefinic particles such as polyethylene, polystyrene or poly propylene); acrylic and olefinic copolymers; or multi-layer multi-component particles of homopolymer particles and then coating another type of monomer on top of said layer.

Such organic particles should specifically 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) to the major axis (b) in the ellipse is 0.5 <a/b <2, and the relationship with the diagonal (d) in the rectangle is given by d2≤a2+ b2 definition. And, the relationship between the axis (f) having the longest distance between vertices in the hexahedron and the c-axis other than the a-axis and the b-axis is defined by f2≦c2+a2+b2. The shape of the particles should be spherical, which is better in terms of feeding.

And, it is characterized in that the difference in refractive index between the organic particles and the binder resin is 0.05 or less. When the refractive index difference is greater than 0.05, the haze increases. This means that there is a lot of scattered light, and when there is a lot of this scattered light, the sidewall smoothing effect is reduced. This also depends on the size and amount of organic particles. It is preferred that the organic particles have an average particle size of about 0.5 microns to 5 microns. When it is smaller than this value, feedability and winding characteristics are deteriorated, and when it is larger than 5 micrometers, haze increases, which is not preferable in view of occurrence of drop problem. Based on the total amount of the binder resin, the content of the organic particles is preferably 1% by weight to 10% by weight.

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 easily scratched (scratch), and the feedability and winding characteristics are deteriorated, and when it exceeds 10% by weight When , there may be a problem that the haze increases and the transparency property deteriorates.

Meanwhile, in addition to the above organic particles, inorganic particles may also be added. At this time, it is not preferable to add a common inorganic anti-blocking agent, and it is preferable to add colloidal silica having a particle diameter of 100 nm or less. Based on 100 parts by weight of the binder resin, the content thereof is preferably 10 parts by weight or less than 10 parts by weight. When the particle size and content as described above are satisfied, the occurrence of sidewall defects or grooves (such as pits) caused by the anti-blocking layer when forming a pattern using a dry film resist can be prevented.

As a binder resin serving as a binder for coating such organic particles onto an unstretched polyester film, a binder resin having excellent compatibility with organic particles can be used. Examples of such resins may include: acrylic resins such as unsaturated polyesters, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, n-butyl methyl methacrylate , acrylic, methacrylic acid copolymers or terpolymers; urethane-based resins; epoxy-based resins; or melamine-based resins and the like, and acrylic-based resins are preferred.

A solvent that can be used to prepare a coating solution using a binder resin and organic particles is preferably water.

As described above, the unstretched polyester film obtained by melt-extruding PET pellets is uniaxially stretched, and then the coating solution containing organic particles in the binder resin is applied to the uniaxially stretched film superior. The coating may be performed on at least one side of the uniaxially stretched film, and the thickness thereof is preferably about 30 nm to 200 nm in terms of thickness after final drying. If a coating solution containing organic particles is applied to a thickness of more than 30 nm on a uniaxially stretched film, there is a problem that the organic particles are easily dropped and scratched, and white powder is generated. When coating to be thicker than 200 nm, coating streaks may be generated in the coating direction in in-line coating with a high coating speed due to an increase in the viscosity of the coating solution.

The polymer substrate obtained by coating with organic particles different from general anti-blocking agents by the online coating method as described above maintains feedability and winding characteristics due to the particle layer and because the organic particles have excellent Substrate film with light transmission and excellent transparency.

Since the lamination of the photosensitive resin layer is performed on the opposite surface of the organic particle-containing layer in the polymer substrate, the photosensitive resin layer is formed on the opposite surface of the organic particle-containing layer in this manner. Therefore, when the substrate film including the anti-blocking agent is laminated as before, pit-like defects do not occur. Since particles such as silicon dioxide are not only larger in size than organic particles, but are also distributed throughout the substrate film, the effect of silicon dioxide is negligible even in regions adjacent to the photosensitive resin layer.

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 effects of the organic particles are not affected. In addition, by using organic particles with excellent light transmittance, sidewall defects can be reduced without compromising other circuit properties.

The photosensitive element may further include a protective film formed on the photosensitive resin layer. The protective film prevents damage to the photosensitive resin layer during handling, and functions as a protective cover that protects the photosensitive resin layer from foreign matter such as dust. A protective film is laminated on the backside of the photosensitive resin layer on which the polymer substrate is not formed. The protective film is used to protect the photosensitive resin layer from external influences. When the dry film photoresist is applied for post-processing, it needs to be easily detached, and it needs proper releasability and adhesion so that it deforms during storage and distribution.

Various plastic films can be used as the protective film, and examples thereof may include films selected from acrylic films, polyethylene (PE) films, polyethylene terephthalate (PET) films, triacetylcellulose (TAC) At least one plastic film in the group consisting of polynorbornene (PNB) film, cycloolefin polymer (COP) film and polycarbonate (PC) film. The thickness of the protective film is not particularly limited, and, for example, it can be freely adjusted within a range of 0.01 μm to 1 mm.

The thickness of the photosensitive element with palladium plating layer can be 0.01 micron or more than 0.01 micron, or 0.05 micron or more than 0.05 micron, or 0.1 micron or more than 0.1 micron, or 0.01 micron or more than 0.01 micron and 0.15 micron or less than 0.15 micron, or 0.05 Micron or less than 0.05 micron, or 0.15 micron or less than 0.15 micron, or 0.1 micron or greater than 0.1 micron and 0.15 micron or less than 0.15 micron, the palladium plating layer is obtained by laminating a photosensitive resin layer on a substrate. The samples were obtained by immersing the samples in the palladium plating solution for 60 minutes and then immersing the copper clad laminate samples in the residual palladium plating solution for 5 minutes.

In addition, the thickness of the photosensitive element with nickel-phosphorus plating layer can be 3.9 microns or greater than 3.9 microns, or 3.95 microns or greater than 3.95 microns, or 3.9 microns or greater than 3.9 microns and 4.0 microns or less than 4.0 microns, or 3.95 microns or greater than 3.95 microns Micron and 4.0 micron or less than 4.0 micron features, the nickel-phosphorus plating layer is obtained by immersing the film sample in which the photosensitive resin layer is laminated on the substrate in the nickel-phosphorus plating solution for 38 minutes and then the copper-clad laminate sample Obtained by immersion in residual nickel-phosphorous plating solution for 28 minutes, or alternatively, dry film photoresist having a gold plating layer thickness of 0.11 micron or greater, or 0.11 micron or greater and 0.13 micron or Features less than 0.13 microns, or 0.12 microns or greater, or 0.12 microns or greater, and 0.13 microns or less, the gold-plated layer obtained by immersing a film sample in which a photosensitive resin layer is laminated on a substrate into the gold-plated solution for 98 minutes and then immerse the copper clad laminate samples in the residual gold plating solution for 11 minutes.

The residual palladium plating solution is the palladium plating solution contaminated with the components of the photosensitive resin layer, and the thickness of the palladium plating layer obtained by immersing the copper clad laminate sample in the contaminated residual palladium plating solution for 5 minutes was used for evaluation The property that the plating solution is contaminated by the dry film photoresist when palladium is plated on a laminate on which a photosensitive resin layer is laminated. The thickness of the palladium-plated layer obtained by immersing the copper-clad laminate samples in the palladium-plating solution for 5 minutes became significantly lower as the contamination of the plating solution became more serious. On the other hand, the thickness of the palladium plating layer obtained by immersing the copper clad laminate sample in the contaminated palladium plating solution for 5 minutes became significantly higher as the plating solution was less contaminated. Therefore, during the actual electroless palladium plating process, contaminants accumulate in bulk dry film photoresists, and palladium is only added for continuous plating, which makes other cleaning processes difficult. Therefore, it is extremely important to assess the degree of contamination of the palladium plating solution by the dry film photoresist.

That is, in palladium plating, first, first palladium plating using a film on which a photosensitive resin layer is laminated is performed. After the first plating has been completed, a second palladium plating is performed on a new copper clad laminate sample in a contaminated palladium plating solution and the plating solution is evaluated for the thickness of the palladium layer on the second plating The nature of contamination by dry film resist.

Therefore, the thickness of the palladium plating layer obtained by immersing the film sample in which the photosensitive resin layer was laminated on the substrate in the palladium plating solution for 60 minutes and then immersing the copper-clad laminate sample in the remaining palladium plating solution for 5 minutes was excessively reduced. As small as less than 0.1 micron as the target value, and according to which the pollution degree of the plating solution can be evaluated. In evaluating the pollution degree, when the plating layer is plated to a thickness lower than the target value, the pollution of the electroless palladium plating solution is serious in the actual process, and therefore, it is difficult to reuse more than 0.5 metal cycle (metal turn over, MTO) plating solution, which may be disadvantageous in terms of process efficiency and economy.

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

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

First, the copper-clad laminate sample on which the photosensitive resin layer is laminated may also be immersed in a nickel-phosphorous 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, it may be at a temperature of 65° C. or greater than 65° C. and 95° C. or less than 95° C. Under certain conditions, the cross-sectional area is 600 square centimeters or more than 600 square centimeters and 700 square centimeters or less than 700 square centimeters, or 640 square centimeters or more than 640 square centimeters and 660 square centimeters or less than 660 square centimeters, or 645 square centimeters or Samples larger than 645 cm2 and 655 cm2 or less than 655 cm2, or 650 cm2 were immersed in 130 ml of NPR-4 (Uemura) plating solution (as a nickel-phosphorus containing plating solution) for 20 minutes or More than 20 minutes and 60 minutes or less than 60 minutes to perform elution. The cross-sectional area refers to the area of a cross-section obtained by cutting a sample in a direction perpendicular to the direction in which the thickness of the sample increases.

If necessary, the sample may also be immersed in the aqueous catalyst solution before being immersed in the nickel-phosphorus plating solution, and the specific conditions are not particularly limited. For example, by using CATA NC-20 (MK Chem & Tech) as a palladium plating-catalyst solution under the conditions of 10°C or more and 40°C or less The copper-clad laminate sample in which the photosensitive water layer is laminated on the substrate is immersed for 30 seconds to 90 seconds.

Next, the copper-clad laminate sample on which the nickel-plated photosensitive resin layer is laminated may be immersed in a 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, it may be carried out under the conditions of 30° C. or more and 70° C. or less than 70° C. , with a cross-sectional area of 600 square centimeters or more and 700 square centimeters or less than 700 square centimeters, or 640 square centimeters or more than 640 square centimeters and 660 square centimeters or less than 660 square centimeters, or 645 square centimeters or more than 645 A sample of 655 cm2 or less, or a sample of 650 cm2 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 than 90 minutes to perform elution.

Meanwhile, the copper-clad laminate sample on which the palladium-plated photosensitive resin layer is laminated may also be immersed in the gold-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 gold plating solution are not particularly limited, for example, under the conditions of 65° C. or greater than 65° C. and 95° C. or less than 95° C., The cross-sectional area is 600 cm2 or more and 700 cm2 or less than 700 cm2, or 640 cm2 or more than 640 cm2 and 660 cm2 or less than 660 cm2, or 645 cm2 or more than 645 cm2 cm and 655 cm2 or less, or 650 cm2 samples immersed in 130 ml of TMX-40 (Uemura (Uemura)) plating solution (as a gold plating solution) for 50 minutes or more and 150 minutes or less than 150 minutes to perform the elution.

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

First, a 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, under the conditions of 65°C or higher and 95°C or lower, the cross-sectional The area is 1 square centimeter or greater and 10 square centimeters or less than 10 square centimeters, or 4 square centimeters or greater than 4 square centimeters and 6 square centimeters or less than 6 square centimeters, or 4.5 square centimeters or greater than 4.5 square centimeters and 5.5 A copper-clad laminate sample of 5.5 cm2 or less, or 5 cm2, was immersed in 130 ml of residual NPR-4 (Uemura) plating solution and plated for 15 minutes or more and 45 minutes or less 45 minutes. The cross-sectional area refers to the area of a cross-section obtained by cutting a sample in a direction perpendicular to the direction in which the thickness of the sample increases.

If necessary, the sample can also be immersed in the aqueous catalyst solution before immersing in the nickel-phosphorus plating solution. Although specific conditions are not particularly limited, for example, it can be obtained by using CATA NC-20 (MK Chemical and Technology Co., Ltd.) as a palladium catalyst under the conditions of 10° C. or more and 40° C. or less than 40° C. The samples were immersed for 90 seconds.

When measuring the thickness of the palladium coating, it can be measured by using an exposure machine at 20 millijoules/cm2 (mJ/ ^cm2 ) or greater than 20 millijoules/cm2 and 200 millijoules/cm2 or less than 200 millijoules/cm2 Exposure is performed by irradiating ultraviolet light at an exposure dose of 50 mJ/cm2 or more and 100 mJ/cm2 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.

When measuring the thickness of the palladium plating layer, by using a concentration of 0.5% by weight or greater than 0.5% by weight and 1.5% by weight or less than 1.5% by weight, or 0.9% by weight or greater than 0.9% by weight and 1.1% by weight or less than 1.1 The development is carried out with an aqueous alkaline solution of % by weight. The pH of the alkaline aqueous solution may be in the range of 9 or more and 11 or less, and the temperature may be adjusted in accordance with the developability of the photosensitive resin layer. Specific examples of aqueous alkaline solutions include aqueous sodium carbonate, aqueous potassium carbonate, aqueous sodium hydroxide, and the like.

For image development, a method of bringing an alkaline aqueous solution into contact with a photosensitive resin layer can be used. As an example of a specific contact method, a spray spraying method or a dipping method can be used. The developing time may be 30 seconds or more and 10 minutes or less, or 30 seconds or more and 2 minutes or less.

At this time, the thickness of the photosensitive element having the nickel-phosphorus plating layer may be 3.9 microns or greater than 3.9 microns, or 3.95 microns or greater than 3.95 microns, or 3.9 microns or greater than 3.9 microns and 4.0 microns or less than 4.0 microns, or 3.95 microns or greater Features of 3.95 microns and 4.0 microns or less, the nickel-phosphorus plating layer is obtained by immersing the film sample in which the photosensitive resin layer is laminated on the substrate in the nickel-phosphorus plating solution for 38 minutes and then the copper clad laminate The samples were obtained by immersing in the residual nickel-phosphorous solution for 28 minutes.

Next, the nickel-plated copper-clad laminate sample can also be dipped into the remaining palladium plating solution to perform plating. Although the specific conditions for immersing the nickel-phosphorus-plated copper-clad laminate sample in the residual palladium plating solution are not particularly limited, for example, it can be carried out under the conditions of 30°C or more and 70°C or less. , the cross-sectional area is 1 square centimeter or more than 1 square centimeter and 10 square centimeters or less than 10 square centimeters, or 4 square centimeters or more than 4 square centimeters and 6 square centimeters or less than 6 square centimeters, or 4.5 square centimeters or more than 4.5 A sample of 5.5 cm2 or less than 5.5 cm2 or 5 cm2 is immersed in 130 ml of residual TPD-21 (Uemura) plating solution for 2 minutes or more and 10 minutes or less than 10 minutes, to perform plating.

At the same time, the palladium-plated copper-clad laminate sample can be dipped into the residual gold plating solution to perform plating. Although the specific conditions for immersing the palladium-plated copper-clad laminate sample in the remaining gold-plating solution are not particularly limited, for example, the transverse The cross-sectional area is 1 square centimeter or more and 10 square centimeters or less than 10 square centimeters, or 4 square centimeters or more and 6 square centimeters or less than 6 square centimeters, or 4.5 square centimeters or more than 4.5 square centimeters and A sample of 5.5 cm2 or less, or a sample of 5 cm2 was immersed in 130 ml of residual TWX-40 (Uemura) plating solution for 5 minutes or more and 20 minutes or less to perform plating cover.

At this time, the thickness of the gold-plated layer of the photosensitive element may be 0.11 microns or greater than 0.11 microns, or 0.11 microns or greater than 0.11 microns and 0.13 microns or less than 0.13 microns, or 0.12 microns or greater than 0.12 microns, or 0.12 microns or greater than 0.12 microns and Features of 0.13 microns or less, the gold plating layer was obtained by immersing a film sample in which a photosensitive resin layer was laminated on a substrate in a gold plating solution for 98 minutes and then immersing a copper clad laminate sample in a remaining gold plating solution for 11 minutes and obtained.

Meanwhile, the film sample in which a photosensitive resin layer is laminated on a substrate may be a laminate in which a photosensitive resin layer is laminated on any substrate. An example of the substrate may 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.

Film samples in which a photosensitive resin layer is laminated on a substrate may have a cross-sectional area of 600 cm2 or more and 700 cm2 or less, or 640 cm2 or more and 660 cm2 or less 660 square centimeters, or 645 square centimeters or greater than 645 square centimeters and 655 square centimeters or less than 655 square centimeters.

In addition, the cross-sectional area of the copper-clad laminate sample used to immerse the copper-clad laminate sample in the residual palladium plating solution for 5 minutes may be 1 cm2 or more and 10 cm2 or less, or 4 square centimeters or more than 4 square centimeters and 6 square centimeters or less than 6 square centimeters, or 4.5 square centimeters or more than 4.5 square centimeters and 5.5 square centimeters or less than 5.5 square centimeters.

The photosensitive resin layer may contain an alkaline developable binder resin.

The photosensitive resin layer may include a dried product or a cured product of the photosensitive resin composition. The dried product refers to a material obtained through a drying step of the photosensitive resin composition. The cured product refers to the material obtained through the 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 within a range of 0.01 micron to 1 mm.

The photosensitive resin layer contains a photosensitive resin composition, and the photosensitive resin composition includes an alkaline developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the photopolymerizable compound is selected from the group consisting of five (a At least one of the group consisting of five types of (meth)acrylate compounds having seven or more (meth)acryl groups and polyfunctional (meth)acrylate compounds having seven or more (meth)acryl groups By.

The inventors have confirmed by experiments that the photosensitive resin composition contains five types of (meth)acrylic ester compounds with five (meth)acryl groups, seven or more (meth)acryl groups The polyfunctional (meth) acrylate compound of group, or the mixture of two or more thereof can be used as photopolymerizable compound, thereby can achieve the pollution of metal plating solutions such as palladium plating solution or nickel-phosphorus plating solution etc. , and allow plating to be performed with sufficient thickness, and completes the present disclosure.

其中，在化學式E中，R ₁為氫或具有1至10個碳原子的烷基，R ₂為具有1至10個碳原子的伸烷基，Ar為具有6至20個碳原子的芳基，且n為1至20的整數， [化學式F]

其中，在化學式F中，R ₃為氫或具有1至10個碳原子的烷基， [化學式G]

其中，在化學式G中，R ₄為氫或具有1至10個碳原子的烷基，並且R ₅為具有1至10個碳原子的烷基，並且 [化學式H]

其中，在化學式H中，Ar為具有6至20個碳原子的芳基。 The alkali-developable binder resin may include 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. [chemical formula E]

Wherein, in the chemical formula E, R is hydrogen or an alkyl group having ₁ to 10 carbon atoms, R 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 from 1 to 20, [chemical formula F]

Wherein, in chemical formula F, R ₃ is hydrogen or an alkyl group having 1 to 10 carbon atoms, [chemical formula G]

Wherein, in chemical formula G, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₅ is an alkyl group having 1 to 10 carbon atoms, and [chemical formula H]

Wherein, in the chemical formula H, Ar is an aryl group having 6 to 20 carbon atoms.

Specifically, the alkali-developable binder resin may include a random copolymer having a repeating unit represented by Formula E, a repeating unit represented by Formula F, a repeating unit represented by Formula G, and a repeating unit represented by Formula H .

Since the repeating unit represented by the chemical formula E is included in the alkaline developable binder resin to thereby increase the degree of hydrophobicity of the alkaline developable binder resin through the benzene structure contained in the repeating unit represented by the chemical formula E, it Suppresses foam generation in the development process of dry film resists using photosensitive resin compositions, and thus exhibits excellent development properties, and can improve substrate adhesion and thus ensure appropriate physical properties (resolution, fine line adhesion, etc.) .

In Chemical Formula E, R ₁ may be any 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 may include a methyl group.

In Chemical Formula E, R ₂ is an alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group having 1 to 10 carbon atoms may include ethyl.

In Chemical Formula E, Ar is an aryl group having 6 to 20 carbon atoms, and a specific example of the aryl group having 6 to 20 carbon atoms may be a phenyl group.

其中，在化學式E-1中，R ₁為氫或具有1至10個碳原子的烷基，R ₂為具有1至10個碳原子的烷基，Ar為具有6至20個碳原子的芳基，且n為1至20的整數。在化學式E-1中，R ₁、R ₂、Ar及n的定義與針對化學式E所述者相同。 The repeating unit represented by Chemical Formula E may be a repeating unit derived from a monomer represented by the following Chemical Formula E-1. [Chemical Formula E-1]

Wherein, in the chemical formula E-1, R ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₂ is an alkyl group having 1 to 10 carbon atoms, Ar is an aromatic group having 6 to 20 carbon atoms base, and n is an integer from 1 to 20. In Chemical Formula E-1, the definitions of R ₁ , R ₂ , Ar and n are the same as those described for Chemical Formula E.

Specific examples of the monomer represented by Chemical Formula E-1 may include phenoxypolyethyleneoxyacrylate, more specifically, 2-phenoxyethyl methacrylate (PHEMA).

Based on 100 mol% of all repeating units contained in the alkaline developable binder resin, the content of the repeating unit represented by the chemical formula E may be 5 mol% or more and 40 mol% or less mol%, or 5 mol% or greater than 5 mol% and 30 mol% or less than 30 mol%, or 5 mol% or greater than 5 mol% and 25 mol% or less than 25 mol%, or 10 mol% or greater than 10 mol% and 25 mol% or less than 25 mol%.

In chemical formula F to chemical formula H, R ₃ and R ₄ are the same or different from each other, and are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₅ is an alkyl group having 1 to 10 carbon atoms, And Ar is an aryl group having 6 to 20 carbon atoms.

_In Chemical Formula F to Chemical Formula H, _R3 and R4 are the same or different from each other, and may each independently be any of hydrogen or an alkyl group having 1 to 10 carbon atoms, and having 1 to 10 carbon atoms Specific examples of the alkyl group may include methyl.

R ₅ is an alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group having 1 to 10 carbon atoms may include a methyl group.

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

其中，在化學式F-1中，R ₃為氫或具有1至10個碳原子的烷基。在化學式F-1中，R ₃的定義與以上針對化學式F所述者相同。由化學式F-1表示的單體的具體實例可包括甲基丙烯酸（methacrylic acid，MAA）。 The repeating unit represented by Chemical Formula F may be a repeating unit derived from a monomer represented by the following Chemical Formula F-1. [Chemical Formula F-1]

Wherein, in Chemical Formula F-1, R ₃ is hydrogen or an alkyl group having 1 to 10 carbon atoms. In Chemical Formula F-1, the definition of _R3 is the same as that described above for Chemical Formula F. Specific examples of the monomer represented by Chemical Formula F-1 may include methacrylic acid (MAA).

其中，在化學式G-1中，R ₄為氫或具有1至10個碳原子的烷基，並且R ₅為具有1至10個碳原子的烷基。在化學式G-1中，R ₄及R ₅的定義與以上針對化學式G所述者相同。由化學式G-1表示的單體的具體實例可包括甲基丙烯酸甲酯（methylmethacrylate，MMA）。 The repeating unit represented by Chemical Formula G may be a repeating unit derived from a monomer represented by the following Chemical Formula G-1. [chemical formula G-1]

Wherein, in the chemical formula G-1, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₅ is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula G-1, the definitions of R ₄ and R ₅ are the same as those described above for Chemical Formula G. Specific examples of the monomer represented by Chemical Formula G-1 may include methylmethacrylate (MMA).

其中，在化學式H-1中，Ar為具有6至20個碳原子的芳基。在化學式H-1中，Ar的定義與以上針對化學式H所述者相同。由化學式H-1表示的單體的具體實例可包括苯乙烯（SM）。 The repeating unit represented by Chemical Formula H may include a repeating unit derived from a monomer represented by the following Chemical Formula H-1. [Chemical formula H-1]

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 for Chemical Formula H. Specific examples of the monomer represented by Chemical Formula H-1 may include styrene (SM).

The alkaline developable binder resin may contain 20 mol % or more and 60 mol % or less based on 100 mol % of all repeating units contained in the alkaline developable binder resin , or 20 mol% or greater than 20 mol% and 50 mol% or less than 50 mol%, or 30 mol% or greater than 30 mol% and 40 mol% or less than 40 mol% by chemical formula F Represents the repeating unit.

In addition, the alkaline developable binder resin may contain 1 mol % or more and 30 mol % or less based on 100 mol % of all repeating units contained in the alkaline developable binder resin mol%, or 5 mol% or greater than 5 mol% and 30 mol% or less than 30 mol% of the repeating unit represented by chemical formula G, and 30 mol% or greater than 30 mol% and 60 mol% Or less than 60 mol%, or 30 mol% or greater than 30 mol%, and 50 mol% or less than 50 mol%, or 30 mol% or greater than 30 mol%, and 40 mol% or less than 40 mol% % of the repeating unit represented by the chemical formula H.

More specifically, the molar ratio of the repeating unit represented by the chemical formula G relative to 100 moles of the repeating unit represented by the chemical formula H may be 10 moles or more and 99 moles or less, or 15 mol or more and 95 mol or less, or 20 mol or more and 95 mol or less.

In this way, as the content of the hydrophobic repeating unit represented by the chemical formula H increases, the degree of hydrophobicity of the alkaline developable binder resin also increases, thereby suppressing the dry film photoresist using the photosensitive resin composition. Foaming occurs during the developing process.

In addition, relative to 100 moles of the repeating unit represented by the chemical formula E, the molar ratio of the repeating unit represented by the chemical formula G may be 16 moles or less, or 15.5 moles or less, or 15 moles Ear or less than 15 moles, or 0.1 moles or more than 0.1 moles and 16 moles or less than 16 moles, or 0.1 moles or more than 0.1 moles and 5.5 moles or less than 5.5 moles, or 0.1 moles or More than 0.1 mole and 15 moles or less than 15 moles, or 10 moles or more and 16 moles or less than 16 moles, or 10 moles or more than 10 moles and 15.5 moles or less than 15.5 moles ear, or 10 moles or greater than 10 moles and 15 moles or less than 15 moles.

The alkaline developable binder resin may have a weight average molecular weight of 30,000 g/mole or more and 150,000 g/mole or less and 20°C or more and 150°C or A glass transition temperature of less than 150°C. Thereby, the coating properties and followability of the dry film photoresist, as well as the mechanical strength of the impedance itself after the circuit is formed, can be improved.

The weight average molecular weight used herein refers to the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). In the process of measuring the polystyrene-equivalent weight-average molecular weight measured by GPC, a detector and an analysis column, such as well-known analytical equipment and a differential refractive index detector, can be used, and the usual The temperature conditions, solvents and flow rates of the application.

A specific example of the measurement conditions is as follows: The alkaline developable binder resin is dissolved in tetrahydrofuran so that its concentration in THF is 1.0 (w/w) % (about 0.5 (w/w) in terms of solid content) %), which was filtered using a syringe filter with a pore size of 0.45 μm, and then injected into the GPC in an amount of 20 μl, using tetrahydrofuran (tetrahydrofuran, THF) as the mobile phase of the GPC, and the flow rate was 1.0 ml/min ( mL/min). The column consists of an Agilent Plagal 5 micron guard column (Guard) (7.5 mm × 50 mm) and two Agilent Plagal 5 micron mixed D columns (7.5 mm × 300 mm) connected in series constituted, and measurements were performed at 40° C. by using an Agilent 1260 Infinity II system with an RI detector as a detector.

Polystyrene standards (STD A, B, C, D) were filtered through syringe filters with a pore size of 0.45 μm and then injected into the GPC, and the calibration curve was used to determine the concentration of the alkaline developable binder resin. Values of weight average molecular weight (Mw) In the polystyrene standard sample, polystyrene having various molecular weights as described below was dissolved in tetrahydrofuran at a concentration of 0.1 (w/w)%. STD A (Mp): 791,000 / 27,810 / 945 STD B (Mp): 282,000 / 10,700 / 580 STD C (Mp): 126,000 / 4,430 / 370 STD D (Mp): 51,200 / 1,920 / 162

The glass transition temperatures of the reference polymer and the binder polymer were compared by means of a Differential Scanning Calorimeter (DSC) (Perkin-Elmer, DSC-7). The measurement can be performed by keeping the temperature at 20°C for 15 minutes and then raising the temperature to 200°C at a rate of 1°C/minute.

The acid value of the alkaline developable binder resin may be 120 mg KOH/g or more and 200 mg KOH/g or less, or 140 mg KOH/g or more gram and 160 mg KOH/gram or less than 160 mg KOH/gram. Acid value was measured by the following procedure: In said procedure, about 1 gram of alkaline developable binder resin was sampled and dissolved in 50 ml of mixed solvent (MeOH 20 %, acetone 80%), and then titrated with 0.1N-KOH to measure the acid value.

Based on the solid content, the content of the alkaline developable binder resin is 20% by weight or more and 80% by weight or less than 80% by weight relative to the total weight of the photosensitive resin composition. When the content of the alkali-developable binder resin is within the above-mentioned range, an effect of enhancing adhesion of fine wires after circuit formation can be obtained. The solid content as a weight basis refers to the remaining components in the photosensitive resin composition other than the solvent.

Based on the solid content, the content of the alkaline developable binder resin is 20% by weight or more and 80% by weight or less than 80% by weight relative to the total weight of the photosensitive resin composition. When the content of the alkali-developable binder resin is within the above-mentioned range, an effect of enhancing adhesion of fine wires after circuit formation can be obtained. The solid content as a weight basis refers to the remaining components in the photosensitive resin composition other than the solvent.

Relative to the total weight of the photosensitive resin composition, the content of the alkaline developable binder resin may be 40% by weight or greater than 40% by weight and 70% by weight or less than 70% by weight. When the content of the alkali-developable binder resin is less than 40% by weight relative to the total photosensitive resin composition, there is a disadvantage of causing defects such as short circuits due to contamination in development, and when the content of the alkali-developable binder resin exceeds When it is 70% by weight, there is a problem that circuit properties such as adhesion and resolution deteriorate.

The photopolymerization initiator contained in the photosensitive resin composition is a material that initiates a chain reaction of photopolymerizable monomers by ultraviolet (ultraviolet, UV) and other radiation, and plays an important role in curing dry film photoresists.

Compounds that can be used as photopolymerization initiators may 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.

In addition, selected from 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy Base-1,2-diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl- 2-Dimethylamino-1-[4-morpholinophenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-tri Tolyldiphenylphosphine oxide, 1-[4-(2-hydroxymethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, 2,4-diethyl Thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4 -Propoxythioxanthone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy -2-methylpropan-1-one, 4-benzoyl-4'-methyl dimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate , Ethyl 4-Dimethylaminobenzoate, Butyl 4-Dimethylaminobenzoate, 2-Ethylhexyl 4-Dimethylaminobenzoate, 4-Dimethylaminobenzoic Acid 2-Isoamyl ester, 2,2-diethoxyacetophenone, benzyl ketone dimethyl acetal, benzyl ketone β-methoxydiethyl acetal, 1-phenyl-1,2- Propylenedioxime-o,o'-(2-carbonyl)ethoxyether, methyl phthalylbenzoate, bis[4-dimethylaminophenyl]ketone, 4,4'-bis( Diethylamino) benzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, Isobutoxybenzoin, tertiary butoxybenzoin, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2- Methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, α,α-dichloro-4-phenoxyacetophenone and pentyl-4-dimethylaminobenzoate Compounds in esters can be used as photopolymerization initiators, but are not limited thereto.

Based on the solid content, the content of the photopolymerization initiator is 1% by weight or more and 10% by weight or less than 10% by weight relative 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 a weight basis refers to the remaining components in the photosensitive resin composition other than the solvent.

When the content of the photopolymerization initiator is less than 1% by weight, light efficiency is low, and a large amount of light exposure must be applied, and thus, there is a disadvantage that production efficiency is greatly reduced. When the content of the photopolymerization initiator exceeds 10% by weight, there are problems of fragility of the film and increased contamination of the developing solution, resulting in defects such as short circuits.

The photopolymerizable compounds of the present disclosure are resistant to developing solutions after UV exposure and are capable of forming patterns.

The photopolymerizable compound may include five types of (meth)acrylate compounds having five (meth)acryl groups and polyfunctional (meth)acryl compounds having seven or more (meth)acryl groups. ) at least one of the group consisting of acrylate-based compounds.

That is, the photopolymerizable compound may include one type of five-type (meth)acrylate-based compound having five (meth)acryl groups, one type of five-type (meth)acryl group having seven or more (meth)acryl groups A multifunctional (meth)acrylate compound, or a mixture of two or more thereof.

Since the photopolymerizable compound of one embodiment includes five types of (meth)acrylate compounds having five (meth)acryl groups and poly(meth)acryl groups having seven or more (meth)acryl groups At least one of the group consisting of functional (meth)acrylate-based compounds, thereby reducing contamination of metal plating solutions such as palladium plating solutions or nickel-phosphorus plating solutions and allowing plating to be performed with a sufficient thickness can be achieved. Effect.

The weight ratio of the five-type (meth)acrylate compound with five (meth)acryl groups and the multifunctional (meth)acrylate compound with seven or more (meth)acryl groups Available from 99:1 to 1:99.

The pentatype (meth)acrylate compound having five (meth)acryl groups may have five (meth)acryl groups. Each of the five (meth)acryl groups may be the same as or different from each other. The five-type (meth)acrylate compound may include all (meth)acrylate compounds having five (meth)acryl groups or derivatives thereof.

其中，在化學式A中，T ₁至T ₆中的五者彼此相同或不同，並且各自獨立地為(甲基)丙烯醯基，並且剩餘的一者為氫。更具體而言，在化學式1中，T ₁至T ₅可為丙烯醯基，且T ₆可為氫。 The five-type (meth)acrylate compound may further include a hydroxyl group. Specifically, the five-type (meth)acrylate-based compound may be a compound represented by Chemical Formula A below. [chemical formula A]

Wherein, in Chemical Formula _A , five of T1 to _T6 are the same or different from each other, and each independently is a (meth)acryloyl group, and the remaining one is hydrogen. More specifically, in Chemical Formula 1, T ₁ to T ₅ may be acryl groups, and T ₆ may be hydrogen.

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

The polyfunctional (meth)acrylate compound having seven or more (meth)acryloyl groups may have seven or more, or seven or more and 20 or less, or 7 or more and 10 or less (meth)acryloyl groups. Each of the seven or more (meth)acryloyl groups may be the same as or different from each other. Multifunctional (meth)acrylate compounds include 7 or greater than 7, or 7 or greater than 7 and 20 or less than 20, or 7 or greater than 7 and 10 or less than 10 (forma All (meth)acrylate compounds of acryl group or derivatives thereof.

其中，在化學式B中，T ₇至T ₁₂彼此相同或不同，並且各自獨立地為(甲基)丙烯醯基，T ₁₂為氫或(甲基)丙烯醯基，並且t為2至10的整數。 Specifically, the polyfunctional (meth)acrylate compound may be a compound represented by the following Chemical Formula B. [chemical formula B]

Wherein, in the chemical formula B, _T7 to _T12 are the same or different from each other, and are each independently a (meth)acryl group, _T12 is hydrogen or a (meth)acryl group, and t is 2 to 10 integer.

More specifically, in Chemical Formula B, T ₇ to T ₁₁ are acryl groups, T ₁₂ is hydrogen or (meth)acryl groups, and t is an integer of 2 to 3.

Specific examples of the compound represented by the chemical formula B include: (1) in the chemical formula B, a compound having _seven (meth)acryloyl groups, wherein T7 to _T11 are acryloyl groups, _T12 is hydrogen, and t is an integer of 2, (2) in chemical formula B, a compound having eight (meth)acryl groups, wherein T ₇ to T ₁₁ are acryl groups, T ₁₂ is an acryl group, and t is an integer of 2 , (3) in chemical formula B, a compound having nine (meth)acryloyl groups, wherein T ₇ to T ₁₁ are acryloyl groups, T ₁₂ is hydrogen, and t is an integer of 3, and (4) in In chemical formula B, a compound having ten (meth)acryl groups, wherein T ₇ to T ₁₁ are acryl groups, T ₁₂ is hydrogen, and t is an integer of 3.

The polyfunctional (meth)acrylate compound having seven or more (meth)acryl groups may correspond to one specific example of the compound represented by Chemical Formula B, or a mixture of two or more thereof.

Specifically, the polyfunctional (meth)acrylate compound having 7 or more (meth)acryl groups may include a mixture of the following two types of compounds: compounds wherein t is 2 in Chemical Formula B , and compounds wherein t is 3 in Formula B. At this time, based on 100 parts by weight of the compound whose t is 2 in the chemical formula B, the content of the compound whose t is 3 in the chemical formula B may be 1 part by weight or more and 40 parts by weight or less than 40 parts by weight, or 5 parts by weight or more than 5 parts by weight and 30 parts by weight or less than 30 parts by weight, or 7 parts by weight or more than 7 parts by weight and 28 parts by weight or less than 28 parts by weight.

The photopolymerizable compound may further include a hexa(meth)acrylate compound having six (meth)acryl groups. That is, except those selected from five types of (meth)acrylic ester compounds having five (meth)acryl groups and polyfunctional (meth)acrylic acid compounds having seven or more (meth)acryl groups In addition to at least one of the group of ester compounds, the photopolymerizable compound may further include a hexa(meth)acrylate compound having six (meth)acryl groups.

The hexa-type (meth)acrylate compound having six (meth)acryl groups may have six (meth)acryl groups. Each of the six (meth)acryl groups may be the same as or different from each other. The hexa-type (meth)acrylate compound may include all (meth)acrylate compounds having six (meth)acryl groups or derivatives thereof.

其中，在化學式C中，T ₁₂至T ₁₇彼此相同或不同，並且各自獨立地為(甲基)丙烯醯基。更具體而言，在化學式3中，T ₁₂至T ₁₇為丙烯醯基。 Specifically, the hexa-type (meth)acrylate-based compound may be a compound represented by Chemical Formula C below. [chemical formula C]

Wherein, in the chemical formula C, _T12 to _T17 are the same or different from each other, and are each independently a (meth)acryloyl group. More specifically, in Chemical Formula 3, T ₁₂ to T ₁₇ are acryl groups.

Meanwhile, the photopolymerizable compound may further include a di(meth)acrylate compound having two (meth)acryl groups. The di(meth)acrylate-based compound having two (meth)acryl groups may include alkylene glycol-based di(meth)acrylate or bisphenol-based di(meth)acrylate.

其中，在化學式D中，l+n為2或3的整數，且m為12至18的整數。 As the alkylene glycol-based di(meth)acrylate, a compound represented by the following chemical formula D may be used. [chemical formula D]

Wherein, in the chemical formula D, l+n is an integer of 2 or 3, and m is an integer of 12 to 18.

The compound represented by the chemical formula D can improve the hydrophobicity of the photosensitive resin composition, significantly increase the resistance to the developing solution and the plating solution, and shorten the peeling time of the cured film.

With respect to the total weight of the solid content of the photosensitive resin composition, the compound represented by the chemical formula D may be 70% by weight or more than 70% by weight and 90% by weight or less than 90% by weight, or 75% by weight or more than 75% by weight and 85% by weight. % by weight or less than 85% by weight.

If the content of the compound represented by the chemical formula D is less than 70% by weight relative to the total weight of the solid content of the photosensitive resin composition, the effect due to the addition of the compound represented by the chemical formula D is insufficient, and if the content exceeds 90% by weight %, there may be a problem that the hydrophobicity increases and the developing time in the developing process increases rapidly after exposure.

As bisphenol type di(meth)acrylate, the bisphenol type di(meth)acrylate containing ethylene oxide can be used. Bisphenol-based di(meth)acrylates containing ethylene oxide may include two types of bisphenol-based di(meth)acrylates: bisphenol-based di(meth)acrylates containing 8 moles or less of ethylene oxide per molecule It is a di(meth)acrylate, and a bisphenol-based di(meth)acrylate containing more than 8 moles and 16 moles or less than 16 moles of ethylene oxide per molecule.

Examples of bisphenol-based di(meth)acrylates containing 8 moles or less of ethylene oxide may include Miramer manufactured by Miwon Specialty Chemical Co., Ltd. ) M244 (BPA(EO) ₃ DA, Bisphenol A (EO) ₃ Diacrylate), Miramer M240 (BPA(EO) ₄ DA, Bisphenol A (EO) ₄ Diacrylate), Miramer M241 (Bisphenol A (EO) ₄ dimethacrylate).

Examples of bisphenol-based di(meth)acrylates containing more than 8 moles and 16 moles or less than 16 moles of ethylene oxide may 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) .

More specifically, based on 100 parts by weight of bisphenol-based di(meth)acrylates containing more than 8 moles and 16 moles or less than 16 moles of ethylene oxide per molecule, 8 moles or less than 8 moles per molecule The content of bisphenol di(meth)acrylate of mole oxirane can be 100 parts by weight or less, 50 parts by weight or less than 50 parts by weight, 1 part by weight or more and 100 parts by weight Or less than 100 parts by weight, or 1 part by weight or more than 1 part by weight and 50 parts by weight or less than 50 parts by weight.

Based on the solid content, the content of the photopolymerizable compound may be 10% by weight or more and 70% by weight or less than 70% by weight relative to the total weight of the photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, effects such as enhancing photosensitivity, resolution, and adhesive force can be obtained. The solid content as a weight basis refers to the remaining components in the photosensitive resin composition other than the solvent.

Based on the solid content, the photosensitive resin composition may include 20% by weight or more and 80% by weight or less than 80% by weight of an alkaline developable binder resin, 1% by weight or more than 1% by weight and 10% by weight or less 10% by weight of a photopolymerization initiator, and 10% by weight or more and 70% by weight or less of a photopolymerizable compound.

The photosensitive resin composition may further include a solvent. The solvent is usually selected from methyl ethyl ketone (methyl ethyl ketone, MEK), methanol, THF, toluene, and acetone, and is not particularly limited thereto, and its content can also be determined according to the photopolymerization initiator, alkalinity, The content of developing binder resin and photopolymerizable compound can be adjusted.

In addition, the photosensitive resin composition may further contain other additives as needed. Other additives are plasticizers and may include: dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diene phthalate in the form of phthalates Propyl esters; triethylene glycol diacetate, tetraethylene glycol diacetate in the form of ethylene glycol esters; p-toluenesulfonamide, benzenesulfonamide, n-butyl in the form of acid amide Base benzene sulfonamide; triphenyl phosphate, etc.

In order to improve the handling property of the photosensitive resin composition, leuco dyes or coloring materials may also be added. Examples of the leuco dye include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2-methylphenyl)methane, fluorane dye, and the like. Among them, when leuco crystal violet is used, the contrast is good, so this is preferable. When a leuco dye is contained, its content in the photosensitive resin composition may be 0.01% by weight or greater than 0.01% by weight and 1% by weight or less than 1% by weight. From the viewpoint of expressing contrast, 0.01% by weight or more is preferable, and from the viewpoint of maintaining storage stability, 1% by weight or less is preferable.

Examples of coloring materials may include toluenesulfonic acid monohydrate, magenta, phthalocyanine green, auramine base, paramagentin, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, diamond green ( Diamond green), basic blue 20, etc. When a coloring material is contained, its addition amount in the photosensitive resin composition may be 0.001% by weight or more than 0.001% by weight and 1% by weight or less than 1% by weight. When the content is 0.001% by weight or more, it has the effect of improving handling properties, and when the content is 1% by weight or less, it has the effect of maintaining storage stability.

In addition, other additives may further include thermal polymerization inhibitors, dyes, decolorizers, and adhesion promoters.

Meanwhile, the photosensitive resin layer may contain a photosensitive resin composition comprising an alkaline developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the alkaline developable binder resin includes four or more More than four polymers that are different from each other.

The present inventors have confirmed by experiments that the photosensitive resin composition contains four or more than four different polymers as photopolymerizable compounds, thereby having excellent peeling (peeling) properties, and achieving reduction of contamination of the plating solution and This effect allows the plating to be performed with sufficient thickness and completes the present disclosure.

The alkaline developable binder resin may include four or more polymers different from each other. The four or more types of polymers may have different configurations depending on the types of repeating units constituting each polymer.

其中，在化學式1中，R ₁為氫或具有1至10個碳原子的烷基，R ₂為具有1至10個碳原子的伸烷基，Ar為具有6至20個碳原子的芳基，且n為1至20的整數。 Specifically, the alkali-developable binder resin may include a first binder resin containing a repeating unit represented by Chemical Formula 1 below. That is, the alkali-developable binder resin may include a first binder resin including a repeating unit represented by the following Chemical Formula 1; and three or more types of polymers different therefrom. [chemical formula 1]

Wherein, in Chemical Formula ₁ , R is hydrogen or an alkyl group having 1 to 10 carbon atoms, R 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 from 1 to 20.

Since the repeating unit represented by Chemical Formula 1 is contained in the first binder resin to thereby increase the degree of hydrophobicity of the first binder resin through the benzene structure contained in the repeating unit represented by Chemical Formula 1, it suppresses the use of photosensitizers. The dry film resist of the resin composition generates foam during the development process, and thus exhibits excellent development properties, and can improve substrate adhesion and thus ensure appropriate physical properties (resolution, fine line adhesion, etc.).

In Chemical Formula 1, R ₁ 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 may include a methyl group.

In Chemical Formula 1, R ₂ is an alkylene group having 1 to 10 carbon atoms, and specific examples of the alkylene group having 1 to 10 carbon atoms may include ethylene.

In Chemical Formula 1, Ar is an aryl group having 6 to 20 carbon atoms, and a specific example of the aryl group having 6 to 20 carbon atoms may be a phenyl group.

其中，在化學式1-1中，R ₁為氫或具有1至10個碳原子的烷基，R ₂為具有1至10個碳原子的伸烷基，Ar為具有6至20個碳原子的芳基，且n為1至20的整數。在化學式1-1中，R ₁、R ₂、Ar及n的定義與以上針對化學式1所述者相同。 The repeating unit represented by Chemical Formula 1 may be a repeating unit derived from a monomer represented by the following Chemical Formula 1-1. [chemical formula 1-1]

Wherein, in Chemical Formula 1-1, R ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₂ is an alkylene group having 1 to 10 carbon atoms, Ar is an alkylene group having 6 to 20 carbon atoms Aryl, and n is an integer from 1 to 20. In Chemical Formula 1-1, the definitions of R ₁ , R ₂ , Ar, and n are the same as those described above for Chemical Formula 1.

Specific examples of the monomer represented by Chemical Formula 1-1 may include phenoxypolyethyleneoxyacrylate, more specifically, 2-phenoxyethyl methacrylate (PHEMA).

The content of the repeating unit represented by Chemical Formula 1 may be 5 mol% or more and 40 mol% based on 100 mol% of the total molar content of the repeating unit contained in the alkaline developable binder resin Or less than 40 mol%, or 5 mol% or greater than 5 mol%, and 30 mol% or less than 30 mol%, or 5 mol% or greater than 5 mol%, and 25 mol% or less than 25 mol% ear %, or 10 mole % or more than 10 mole % and 25 mole % or less than 25 mole %.

其中，在化學式2中，R ₃為氫或具有1至10個碳原子的烷基， [化學式3]

其中，在化學式3中，R ₄為氫或具有1至10個碳原子的烷基，並且R ₅為具有1至10個碳原子的烷基，並且 [化學式4]

其中，在化學式4中，Ar為具有6至20個碳原子的芳基。 In addition to the repeating unit represented by Chemical Formula 1, the first binder resin may 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: [Chemical Formula 2]

Wherein, in Chemical Formula 2, R ₃ is hydrogen or an alkyl group having 1 to 10 carbon atoms, [Chemical Formula 3]

wherein, in Chemical Formula 3, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₅ is an alkyl group having 1 to 10 carbon atoms, and [Chemical Formula 4]

Wherein, in Chemical Formula 4, Ar is an aryl group having 6 to 20 carbon atoms.

Specifically, the alkali-developable binder resin may include a random copolymer of the repeating unit represented by Chemical Formula 1, the repeating unit represented by Chemical Formula 2, the repeating unit represented by Chemical Formula 3, and the repeating unit represented by Chemical Formula 4.

In Chemical Formula 2 to Chemical Formula 4, R ₃ and R ₄ are the same or different from each other, and are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₅ is an alkyl group having 1 to 10 carbon atoms, And Ar is an aryl group having 6 to 20 carbon atoms.

In Chemical Formula 2 to Chemical Formula 4, R ₃ and R ₄ are the same or different from each other, and may each independently be any of hydrogen or an alkyl group having 1 to 10 carbon atoms, and having 1 to 10 carbon atoms Specific examples of the alkyl group include methyl.

R ₅ is an alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group having 1 to 10 carbon atoms include methyl.

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 phenyl.

其中，在化學式2-1中，R ₃為氫或具有1至10個碳原子的烷基。在化學式2-1中，R ₃的定義與以上針對化學式2所述者相同。由化學式2-1表示的單體的具體實例可包括甲基丙烯酸（MAA）。 The repeating unit represented by Chemical Formula 2 may be a repeating unit derived from a monomer represented by the following Chemical Formula 2-1. [chemical formula 2-1]

Wherein, in Chemical Formula 2-1, R ₃ is hydrogen or an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 2-1, the definition of R ₃ is the same as that described above for Chemical Formula 2. Specific examples of the monomer represented by Chemical Formula 2-1 may include methacrylic acid (MAA).

其中，在化學式3-1中，R ₄為氫或具有1至10個碳原子的烷基，並且R ₅為具有1至10個碳原子的烷基。在化學式3-1中，R ₄及R ₅的定義與以上針對化學式3所述者相同。由化學式3-1表示的單體的具體實例可包括甲基丙烯酸甲酯（MMA）。 The repeating unit represented by Chemical Formula 3 may be a repeating unit derived from a monomer represented by the following Chemical Formula 3-1. [chemical formula 3-1]

Wherein, in Chemical Formula 3-1, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₅ is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 3-1, the definitions of R ₄ and R ₅ are the same as those described above for Chemical Formula 3. Specific examples of the monomer represented by Chemical Formula 3-1 may include methyl methacrylate (MMA).

其中，在化學式4-1中，Ar為具有6至20個碳原子的芳基。在化學式4-1中，Ar的定義與以上針對化學式4所述者相同。由化學式4-1表示的單體的具體實例可包括苯乙烯（SM）。 The repeating unit represented by Chemical Formula 4 may include a repeating unit derived from a monomer represented by Chemical Formula 4-1 below. [chemical formula 4-1]

Wherein, 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 that described above for Chemical Formula 4. Specific examples of the monomer represented by Chemical Formula 4-1 may include styrene (SM).

The first binder resin may contain 20 mol % or more and 60 mol % or less based on 100 mol % of the total molar content of repeating units contained in the first binder resin , or 20 mol% or greater than 20 mol% and 50 mol% or less than 50 mol%, or 30 mol% or greater than 30 mol% and 40 mol% or less than 40 mol% by chemical formula 2 Represents the repeating unit.

In addition, the first binder resin may contain 1 mol % or more and 30 mol % or less based on 100 mol % of the total molar content of repeating units contained in the first binder resin. mol%, or 5 mol% or greater than 5 mol% and 30 mol% or less than 30 mol% of the repeating unit represented by chemical formula 3, and 30 mol% or greater than 30 mol% and 60 mol% Or less than 60 mol%, or 30 mol% or greater than 30 mol%, and 50 mol% or less than 50 mol%, or 30 mol% or greater than 30 mol%, and 40 mol% or less than 40 mol% % of the repeating unit represented by Chemical Formula 4.

More specifically, the molar ratio of the repeating unit represented by Chemical Formula 3 relative to 100 Moles of the repeating unit represented by Chemical Formula 4 may be 10 moles or more and 99 moles or less, or 15 mol or more and 95 mol or less, or 20 mol or more and 95 mol or less.

In addition, the molar ratio of the repeating unit represented by Chemical Formula 3 may be 40 mol or less, or 35 mol or less, or 32 mol relative to 100 mol of the repeating unit represented by Chemical Formula 1 Ear or less than 32 moles, or 0.1 moles or more than 0.1 moles and 40 moles or less than 40 moles, or 0.1 moles or more and 35 moles or less than 35 moles, or 0.1 moles or More than 0.1 mole and 32 moles or less than 32 moles, or 10 moles or more than 10 moles and 40 moles or less than 40 moles, or 10 moles or more than 10 moles and 35 moles or less than 35 moles ear, or 10 moles or greater than 10 moles and 32 moles or less than 32 moles.

In this way, as the content of the hydrophobic repeating unit represented by Chemical Formula 4 increases, the degree of hydrophobicity of the first binder resin also increases, thereby suppressing the development of the dry film photoresist using the photosensitive resin composition. Foaming occurs during the process.

The first binder resin may have a weight average molecular weight of 30,000 g/mol or more and 150,000 g/mol or less, and 20°C or more and 150°C or less °C glass transition temperature. Thereby, the coating properties and followability of the dry film photoresist, as well as the mechanical strength of the impedance itself after the circuit is formed, can be improved.

The weight average molecular weight used herein refers to a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC). In the process of measuring the polystyrene-equivalent weight-average molecular weight measured by GPC, a detector and an analysis column, such as well-known analytical equipment and a differential refractive index detector, can be used, and the usual The temperature conditions, solvents and flow rates of the application.

A specific example of the measurement conditions is as follows: The alkaline developable binder resin is dissolved in tetrahydrofuran so that its concentration in THF is 1.0 (w/w) % (about 0.5 (w/w) in terms of solid content) %), which was filtered using a syringe filter with a pore size of 0.45 μm, and then injected into GPC in an amount of 20 μl, using tetrahydrofuran (THF) as the mobile phase of GPC, and the flow rate was 1.0 ml/min. The column consists of an Agilent Plagal 5 micron guard column (Guard) (7.5 mm × 50 mm) and two Agilent Plagal 5 micron mixed D columns (7.5 mm × 300 mm) connected in series constituted, and measurements were performed at 40° C. by using an Agilent 1260 Infinity II system with an RI detector as a detector.

Polystyrene standards (STD A, B, C, D) were filtered through syringe filters with a pore size of 0.45 μm and then injected into the GPC, and the calibration curve was used to determine the concentration of the alkaline developable binder resin. Values of weight average molecular weight (Mw) In the polystyrene standard sample, polystyrene having various molecular weights as described below was dissolved in tetrahydrofuran at a concentration of 0.1 (w/w)%. STD A (Mp): 791,000 / 27,810 / 945 STD B (Mp): 282,000 / 10,700 / 580 STD C (Mp): 126,000 / 4,430 / 370 STD D (Mp): 51,200 / 1,920 / 162

The glass transition temperatures of the reference polymer and the binder polymer were compared by means of differential scanning calorimetry (DSC) (Perkin-Elmer, DSC-7). The measurement can be performed by keeping the temperature at 20°C for 15 minutes and then raising the temperature to 200°C at a rate of 1°C/minute.

The acid value of the first binder resin may be 120 mg KOH/g or greater and 200 mg KOH/g or less than 200 mg KOH/g, or 140 mg KOH/g or greater and 160 mg KOH/g or less than 160 mg KOH/g. Acid value was measured by the following procedure: In said procedure, about 1 gram of alkaline developable binder resin was sampled and dissolved in 50 ml of mixed solvent (MeOH 20 %, acetone 80%), and then titrated with 0.1N-KOH to measure the acid value.

其中，在化學式5中，R ₆為氫，且R ₇為具有1至10個碳原子的烷基。具有1至10個碳原子的烷基的具體實例包括丁基。 Meanwhile, the alkali-developable binder resin may include a second binder resin containing a repeating unit represented by Chemical Formula 5 below. That is, the alkali-developable binder resin may include a second binder resin including a repeating unit represented by the following Chemical Formula 5; and three or more types of polymers different therefrom. [chemical formula 5]

Wherein, in Chemical Formula 5, R ₆ is hydrogen, and R ₇ 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.

其中，在化學式6中，R ₈為氫， [化學式7]

其中，在化學式7中，R ₉為具有1至10個碳原子的烷基， [化學式8]

其中，在化學式8中，R ₁₀為具有1至10個碳原子的烷基，並且R ₁₁為具有1至10個碳原子的烷基， [化學式9]

其中，在化學式9中，Ar為具有6至20個碳原子的芳基。 In addition to the repeating unit represented by Chemical Formula 5, the second binder resin may further 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 Represents the repeating unit. [chemical formula 6]

Wherein, in chemical formula 6, R ₈ is hydrogen, [chemical formula 7]

Wherein, in Chemical Formula ₇ , R is an alkyl group having 1 to 10 carbon atoms, [Chemical Formula 8]

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, [Chemical Formula 9]

Wherein, in Chemical Formula 9, Ar is an aryl group having 6 to 20 carbon atoms.

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

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 phenyl.

The second binder resin may have a weight average molecular weight of 30,000 g/mole or more and 150,000 g/mole or less, and 20°C or more and 150°C or less °C glass transition temperature. Thereby, the coating properties and followability of the dry film photoresist, as well as the mechanical strength of the impedance itself after the circuit is formed, can be improved. In addition, the second binder resin may have an acid value of 140 mgKOH/g or more and 160 mgKOH/g or less.

Specifically, the second binder resin may include a repeating unit represented by Chemical Formula 5, a repeating unit represented by Chemical Formula 6, a repeating unit represented by Chemical Formula 7, a repeating unit represented by Chemical Formula 8, and a repeating unit represented by Chemical Formula 9 random copolymers.

More specifically, the second binder resin may contain 5 mol% or more and 20 mol% or less of the repeating unit represented by Chemical Formula 5 based on 100 mol% of all repeating units. Unit, 5 mol % or greater than 5 mol % and 20 mol % or less than 20 mol % of the repeating unit represented by chemical formula 6, 5 mol % or greater than 5 mol % and 20 mol % or less than 20 Mole % of the repeating unit represented by Chemical Formula 7, 40 Mole % or greater than 40 Mole % and 80 Mole % or less than 80 Mole % of the repeating unit represented by Chemical Formula 8, and 5 Mole % or greater than 5 mol% and 15 mol% or less than 15 mol% of the repeating unit represented by Chemical Formula 9.

其中，在化學式10中，R ₉為具有1至10個碳原子的烷基， [化學式11]

其中，在化學式11中，R ₁₀為具有1至10個碳原子的烷基，並且R ₁₁為具有1至10個碳原子的烷基，並且 [化學式12]

其中，在化學式12中，Ar為具有6至20個碳原子的芳基。 Meanwhile, the alkali-developable binder resin may include a third binder resin containing a repeating unit represented by the following Chemical Formula 10, a repeating unit represented by the following Chemical Formula 11, and a repeating unit represented by the following Chemical Formula 12. unit. That is, the alkali-developable binder resin may include a third binder resin; and three or more types of polymers different therefrom, [Chemical Formula 10]

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

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, and [Chemical Formula 12]

Wherein, in Chemical Formula 12, Ar is an aryl group having 6 to 20 carbon atoms.

More specifically, the third binder resin may contain 20 mol% or more and 40 mol% or less of the repeating unit represented by Chemical Formula 10 based on 100 mol% of all repeating units. unit, 50 mol% or greater than 50 mol% and 70 mol% or less than 70 mol% of the repeating unit represented by chemical formula 11, and 5 mol% or greater than 5 mol% and 18 mol% or less 18 mol% of the repeating unit represented by Chemical Formula 12.

In addition, the third binder resin may have a weight average molecular weight of 20,000 g/mol or more and 130,000 g/mol or less, and 30° C. or more and 160° C. or Glass transition temperature of less than 160°C. Thereby, the coating properties and followability of the dry film photoresist, as well as the mechanical strength of the impedance itself after the circuit is formed, can be improved.

The second binder resin may have an acid value of 140 mgKOH/g or greater and 160 mgKOH/g or less. In addition, the third binder resin may have an acid value of 160 mgKOH/g or more and 200 mgKOH/g or less.

其中，在化學式13中，R ₁₂為氫或具有1至10個碳原子的烷基，且R ₁₃為具有1至10個碳原子的伸烷基。 Meanwhile, the alkali-developable binder resin may include a fourth binder resin including a repeating unit represented by Chemical Formula 13 below. That is, the alkali-developable binder resin may include the fourth binder resin; and three or more types of polymers different therefrom, [Chemical Formula 13]

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.

In Chemical Formula 13, R ₁₂ may be any 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.

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 methylene.

Since the fourth binder resin contains the repeating unit represented by Chemical Formula 13, an effect of suppressing elution of resistance in a plating solution may be achieved due to excellent developing characteristics and thermal curing by drying heat.

其中，在化學式14中，R ₁₄為氫或具有1至10個碳原子的烷基， [化學式15]

其中，在化學式15中，R ₁₅為氫或具有1至10個碳原子的烷基，並且R ₁₆為具有1至10個碳原子的烷基， [化學式16]

其中，在化學式16中，Ar為具有6至20個碳原子的芳基。 In addition to the repeating unit represented by Chemical Formula 13, the fourth binder resin may further 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. [chemical formula 14]

Wherein, in Chemical Formula 14, R ₁₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, [Chemical Formula 15]

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, [Chemical Formula 16]

Wherein, in Chemical Formula 16, Ar is an aryl group having 6 to 20 carbon atoms.

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

In Chemical Formula 14 to Chemical Formula 16, R ₁₄ and R ₁₅ are the same or different from each other, and are each 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.

In Chemical Formula 14 to Chemical Formula 16, R ₁₄ and R ₁₅ are the same or different from each other, and may each independently be any of hydrogen or an alkyl group having 1 to 10 carbon atoms, and having 1 to 10 carbon atoms Specific examples of the alkyl group include methyl.

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 methyl.

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 phenyl.

The fourth binder resin may have a weight average molecular weight of 20,000 g/mol or more and 130,000 g/mol or less, and 30°C or more and 160°C or less °C glass transition temperature. Thereby, the coating properties and followability of the dry film photoresist, as well as the mechanical strength of the impedance itself after the circuit is formed, can be improved. In addition, the fourth binder resin may have an acid value of 140 mgKOH/g or more and 180 mgKOH/g or less.

More specifically, the fourth binder resin may contain 15 mol% or more and 25 mol% or less of the repeating unit represented by Chemical Formula 13 based on 100 mol% of all repeating units. Unit, 30 mol% or greater than 30 mol% and 50 mol% or less than 50 mol% of the repeating unit represented by chemical formula 14, 15 mol% or greater than 15 mol% and 25 mol% or less than 25 mol% 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.

Specifically, the alkali-developable binder resin may include a first binder resin; a second binder resin; a third binder resin; and a fourth binder resin. More specifically, based on 100% by weight of the alkaline developable binder resin, the photosensitive resin composition according to an embodiment of the present disclosure may contain 40% by weight or more and 80% by weight or less than 80% by weight of the second A binder resin, 0.1 wt% or more and 4 wt% or less of the second binder resin, 10 wt% or more and 20 wt% or less of the third adhesive Binder resin and 5% by weight or greater than 5% by weight and 45% by weight or less than 45% by weight of the fourth binder resin.

Specifically, based on 100 parts by weight of the first binder resin, the content of the fourth binder resin may be 10 parts by weight or more and 90 parts by weight or less than 90 parts by weight.

In addition, based on 100 parts by weight of the second binder resin, the content of the fourth binder resin may be 500 parts by weight or more and 3000 parts by weight or less than 3000 parts by weight, or 600 parts by weight or more than 600 parts by weight and 2700 parts by weight or less than 2700 parts by weight.

Since the specific amount of the fourth binder resin is contained in this manner, an effect of suppressing elution of resistance in a plating solution can be achieved due to excellent developing characteristics and thermal curing by dry heat.

In addition, based on 100 parts by weight of the second binder resin, the content of the third binder resin may be 500 parts by weight or more, 1000 parts by weight or less, 600 parts by weight or more, and 800 parts by weight. Parts by weight or less than 800 parts by weight, and 700 parts by weight or more than 700 parts by weight and 800 parts by weight or less than 800 parts by weight.

Since the third binder resin is added in an amount exceeding 500 parts by weight or greater than 500 parts by weight based on 100 parts by weight of the second binder resin as described above, it is possible to impart a hydrophobic function to the photosensitive resin, increase the resistance to the developing solution Acceptability and technical effects of improving the physical properties of circuits.

Based on the solid content, the content of the alkaline developable binder resin is 20% by weight or more and 80% by weight or less than 80% by weight relative to the total weight of the photosensitive resin composition. When the content of the alkali-developable binder resin is within the above range, the effect of enhancing the adhesion of fine wires after circuit formation can be obtained. The solid content as a weight basis refers to the remaining components in the photosensitive resin composition other than the solvent.

Relative to the total weight of the photosensitive resin composition, the content of the alkaline developable binder resin may be 40% by weight or greater than 40% by weight and 70% by weight or less than 70% by weight. Based on the total photosensitive resin composition, when the content of the alkali-developable binder resin is less than 40% by weight, there is a disadvantage of causing defects such as short circuits due to contamination in development, and when the content of the alkali-developable binder resin When it exceeds 70 weight%, there exists a problem that circuit properties, such as adhesive force and resolution, deteriorate.

The photopolymerization initiator contained in the photosensitive resin composition is a material that initiates a chain reaction of photopolymerizable monomers by UV and other radiation, and plays an important role in curing dry film photoresists.

Compounds that can be used as photopolymerization initiators may 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.

In addition, selected from 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy Base-1,2-diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl- 2-Dimethylamino-1-[4-morpholinophenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-tri Tolyldiphenylphosphine oxide, 1-[4-(2-hydroxymethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, 2,4-diethyl Thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4 -Propoxythioxanthone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy -2-methylpropan-1-one, 4-benzoyl-4'-methyl dimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate , Ethyl 4-Dimethylaminobenzoate, Butyl 4-Dimethylaminobenzoate, 2-Ethylhexyl 4-Dimethylaminobenzoate, 4-Dimethylaminobenzoic Acid 2-Isoamyl ester, 2,2-diethoxyacetophenone, benzyl ketone dimethyl acetal, benzyl ketone β-methoxydiethyl acetal, 1-phenyl-1,2- Propylenedioxime-o,o'-(2-carbonyl)ethoxyether, methyl phthalylbenzoate, bis[4-dimethylaminophenyl]ketone, 4,4'-bis( Diethylamino) benzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, Isobutoxybenzoin, tertiary butoxybenzoin, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2- Methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, α,α-dichloro-4-phenoxyacetophenone and amyl 4-dimethylaminobenzoate The compound can be used as a photopolymerization initiator, but is not limited thereto.

Based on the solid content, the content of the photopolymerization initiator is 1% by weight or more and 10% by weight or less than 10% by weight relative 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 a weight basis refers to the remaining components in the photosensitive resin composition other than the solvent.

When the content of the photopolymerization initiator is less than 1% by weight, light efficiency is low, and a large amount of light exposure must be applied, and thus, there is a disadvantage that production efficiency is greatly reduced. When the content of the photopolymerization initiator exceeds 10% by weight, there are problems of fragility of the film and increased contamination of the developing solution, resulting in defects such as short circuits.

The photopolymerizable compound is resistant to developing solutions after UV exposure and is capable of forming patterns.

The photopolymerizable compound may include a bifunctional (meth)acrylate compound. The bifunctional (meth)acrylate compound may include alkylene glycol-based di(meth)acrylate or bisphenol-based di(meth)acrylate.

其中，在化學式17中，l+n為2或3的整數，且m為12至18的整數。 As the alkylene glycol-based di(meth)acrylate, a compound represented by the following Chemical Formula 17 may be used. [chemical formula 17]

Wherein, in Chemical Formula 17, l+n is an integer of 2 or 3, and m is an integer of 12 to 18.

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

Relative to the total weight of the solid content of the photosensitive resin composition, the compound represented by Chemical Formula 17 may be 10% by weight or more and 60% by weight or less than 60% by weight, or 20% by weight or more than 20% by weight and 40% by weight. % by weight or less than 40% by weight.

If the content of the compound represented by Chemical Formula 17 is less than 10% by weight relative to the total weight of the solid content of the photosensitive resin composition, the effect due to the addition of the compound represented by Chemical Formula 17 is insufficient, and if the content exceeds 60% by weight %, there may be a problem that the hydrophobicity increases and the developing time in the developing process increases rapidly after exposure.

As bisphenol type di(meth)acrylate, the bisphenol type di(meth)acrylate containing ethylene oxide can be used. Bisphenol-based di(meth)acrylates containing ethylene oxide may include two types of bisphenol-based di(meth)acrylates: bisphenol-based di(meth)acrylates containing 8 moles or less of ethylene oxide per molecule It is a di(meth)acrylate, and a bisphenol-based di(meth)acrylate containing more than 8 moles and 16 moles or less than 16 moles of ethylene oxide per molecule.

Examples of bisphenol-based di(meth)acrylates containing 8 moles or less of ethylene oxide may include Miramer M244 (BPA(EO) ₃ DA, Bisphenol A (EO) ₃ Diacrylate), Miramer M240 (BPA(EO) ₄ DA, Bisphenol A (EO) ₄ Diacrylate), Miramer M241 (Bisphenol A (EO) ₄ Dimethacrylate) .

Examples of bisphenol-based di(meth)acrylates containing more than 8 moles and 16 moles or less than 16 moles of ethylene oxide may 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) .

More specifically, based on 100 parts by weight of bisphenol-based di(meth)acrylates containing more than 8 moles and 16 moles or less than 16 moles of ethylene oxide per molecule, 8 moles or less than 8 moles per molecule The content of bisphenol di(meth)acrylate of mole oxirane can be 100 parts by weight or less, 50 parts by weight or less than 50 parts by weight, 1 part by weight or more and 100 parts by weight Or less than 100 parts by weight, or 1 part by weight or more than 1 part by weight and 50 parts by weight or less than 50 parts by weight.

Based on the solid content, the content of the photopolymerizable compound may be 10% by weight or more and 70% by weight or less than 70% by weight relative to the total weight of the photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, effects such as enhancing photosensitivity, resolution, and adhesive force can be obtained. The solid content as a weight basis refers to the remaining components in the photosensitive resin composition other than the solvent.

Based on the solid content, the photosensitive resin composition may include 20% by weight or more and 80% by weight or less than 80% by weight of an alkaline developable binder resin, 1% by weight or more than 1% by weight and 10% by weight or less 10% by weight of a photopolymerization initiator, and 10% by weight or more and 70% by weight or less of a photopolymerizable compound.

The photosensitive resin composition may further include a solvent. The solvent is usually selected from methyl ethyl ketone (MEK), methanol, THF, toluene, and acetone, and is not particularly limited thereto, and its content can also be determined according to photopolymerization initiator, alkaline developable binder resin, and the content of photopolymerizable compounds to adjust.

In addition, the photosensitive resin composition may further contain other additives as needed. Other additives are plasticizers and may include: dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diene phthalate in the form of phthalates Propyl esters; triethylene glycol diacetate, tetraethylene glycol diacetate in the form of ethylene glycol esters; p-toluenesulfonamide, benzenesulfonamide, n-butylbenzenesulfonamide in the form of amides Amine; triphenyl phosphate, etc.

In order to improve the handling properties of the photosensitive resin composition, leuco dyes or coloring materials can also be added. Examples of the leuco dye include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2-methylphenyl)methane, fluorane dye, and the like. Among them, when leuco crystal violet is used, the contrast is good, so this is preferable. When a leuco dye is contained, its content in the photosensitive resin composition may be 0.01% by weight or greater than 0.01% by weight and 1% by weight or less than 1% by weight. From the viewpoint of expressing contrast, 0.01% by weight or more is preferable, and from the viewpoint of maintaining storage stability, 1% by weight or less is preferable.

Examples of coloring materials may include toluenesulfonic acid monohydrate, magenta, phthalocyanine green, auramine base, paramagentin, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, diamond green, Basic Blue 20 etc. When a coloring material is contained, its addition amount in the photosensitive resin composition may be 0.001% by weight or more than 0.001% by weight and 1% by weight or less than 1% by weight. When the content is 0.001% by weight or more, it has the effect of improving handling properties, and when the content is 1% by weight or less, it has the effect of maintaining storage stability.

In addition, other additives may further include thermal polymerization inhibitors, dyes, decolorizers, and adhesion promoters. 2. Dry film photoresist

According to another embodiment of the present disclosure, a dry film photoresist may be provided, the dry film photoresist includes: a photosensitive resin composition, including an alkaline developable binder resin, a photopolymerization initiator and a photopolymerizable compound, Wherein the photopolymerizable compound comprises five types of (meth)acrylate compounds selected from five (meth)acryl groups and multifunctional (meth)acryl compounds having seven or more (meth)acryl groups. ) at least one of the group consisting of acrylate-based compounds, and wherein the dry film photoresist is characterized in that the thickness of the palladium-plated layer is 0.01 micrometer or more than 0.01 micrometer. A film sample in which a resistive photosensitive resin layer was laminated on a substrate was immersed in a palladium plating solution for 60 minutes and then a copper-clad laminate sample was immersed in the remaining palladium plating solution for 5 minutes.

According to another embodiment of the present disclosure, a dry film photoresist may be provided, the dry film photoresist includes: a photosensitive resin composition, including an alkaline developable binder resin, a photopolymerization initiator and a photopolymerizable compound, wherein the alkaline developable binder resin comprises four or more polymers different from each other, and wherein the dry film photoresist is characterized by a palladium plating layer having a thickness of 0.01 micrometer or more, the palladium plating layer was obtained by immersing a film sample in which a photosensitive resin layer of a dry film photoresist was 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.

Details about the photosensitive resin composition comprising an alkaline developable binder resin, a photopolymerization initiator, and a photopolymerizable compound include all those described above for an embodiment, wherein the photopolymerizable compound comprises a group selected from the group consisting of five In the group consisting of five types of (meth)acrylate compounds with (meth)acryl groups and polyfunctional (meth)acrylate compounds with seven or more (meth)acryl groups at least one.

Details regarding the photosensitive resin composition comprising an alkaline developable binder resin, a photopolymerization initiator, and a photopolymerizable compound include all of the above for an embodiment wherein the alkaline developable binder resin comprises four or more than four different polymers from each other.

Specifically, the photosensitive resin layer may include a dried product or a cured product of the photosensitive resin composition. The dried product refers to a material obtained through a drying step of the photosensitive resin composition. The cured product refers to the material obtained through the 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 within a range of 0.01 micron to 1 mm.

The thickness of the dry film photoresist is not particularly limited, but for example, it can be freely adjusted within a range of 0.01 μm to 1 mm. When the thickness of the dry film resist increases or decreases by a specific value, the physical properties measured in the dry film resist may also change by a specific value.

The dry film photoresist may further include a substrate film and a protective film. The substrate film serves as a support for the photosensitive resin layer during manufacture of the dry film photoresist and facilitates handling during exposure of the photosensitive resin layer with adhesive strength.

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

The protective film prevents damage to the impedance during handling, and functions as a protective cover that protects the photosensitive resin layer from foreign substances such as dust, and is laminated on the backside of the photosensitive resin layer on which no substrate film is formed superior. The protective film is used to protect the photosensitive resin layer from external influences. When the dry film photoresist is applied for post-processing, it needs to be easily detached, and it needs proper releasability and adhesion so that it deforms during storage and distribution.

Various plastic films can be used as the protective film, and examples thereof may include films selected from acrylic films, polyethylene (PE) films, polyethylene terephthalate (PET) films, triacetylcellulose (TAC) At least one plastic film in the group consisting of polynorbornene (PNB) film, cycloolefin polymer (COP) film and polycarbonate (PC) film. The thickness of the protective film is not particularly limited, and, for example, it can be freely adjusted within a range of 0.01 μm to 1 mm.

Examples of methods of manufacturing dry film resists are not particularly limited, and for example, the photosensitive resin composition of one embodiment is applied to 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 was laminated with a conventional protective film such as polyethylene to produce a dry film.

A method of coating the photosensitive resin composition of one embodiment is not particularly limited, and a method such as a coating bar may be used.

The step of drying the coated photosensitive resin composition can be performed by a heating device such as a hot air oven, a hot plate, a hot air circulation oven, and an infrared oven, and can be performed at 50°C or more and 120°C or less performed at a temperature.

At the same time, the thickness of the dry film photoresist with palladium plating layer can be 0.01 micron or greater than 0.01 micron, or 0.05 micron or greater than 0.05 micron, or 0.1 micron or greater than 0.1 micron, or 0.01 micron or greater than 0.01 micron and 0.15 micron or less than 0.15 Micron, or 0.05 micron or greater than 0.05 micron and 0.15 micron or less than 0.15 micron, or 0.1 micron or greater than 0.1 micron and 0.15 micron or less than 0.15 micron, the palladium plating layer is obtained by photosensitive dry film photoresist A film sample of a resin layer laminated on a substrate was obtained by immersing a palladium plating solution for 60 minutes and then immersing a copper clad laminate sample in the remaining palladium plating solution for 5 minutes.

The residual palladium plating solution is the palladium plating solution contaminated with the components of the photosensitive resin layer, and the thickness of the palladium plating layer obtained by immersing the copper clad laminate sample in the contaminated residual palladium plating solution for 5 minutes was used for evaluation Contamination of the dry film photoresist to the plating solution when palladium plating is performed on a laminate on which a photosensitive resin layer is laminated. The thickness of the palladium-plated layer obtained by immersing the copper-clad laminate samples in the palladium-plating solution for 5 minutes became significantly lower as the contamination of the plating solution became more serious. On the other hand, the thickness of the palladium plating layer obtained by immersing the copper clad laminate sample in the contaminated palladium plating solution for 5 minutes became significantly higher as the plating solution was less contaminated. Therefore, during the actual electroless palladium plating process, contaminants accumulate in bulk dry film photoresists, and palladium is only added for continuous plating, which makes other cleaning processes difficult. Therefore, it is extremely important to assess the degree of contamination of the palladium plating solution by the dry film photoresist.

That is, in palladium plating, first, first palladium plating using a film on which a photosensitive resin layer is laminated is performed. After the first plating has been completed, a second palladium plating is performed on a new copper clad laminate sample in a contaminated palladium plating solution and the plating solution is evaluated for the thickness of the palladium layer on the second plating The nature of contamination by dry film resist.

Therefore, the thickness of the palladium plating layer obtained by immersing the film sample in which the photosensitive resin layer was laminated on the substrate in the palladium plating solution for 60 minutes and then immersing the copper-clad laminate sample in the remaining palladium plating solution for 5 minutes was excessively reduced. As small as less than 0.01 micron, this allows the degree of contamination of the plating solution to be assessed. When evaluating the degree of pollution, when the plating layer is plated to a thickness lower than the target value, the pollution of the electroless palladium plating solution is serious in the actual process, and therefore, it is difficult to reuse the plating solution exceeding 0.5MTO. Process efficiency and economics aspects may be disadvantageous.

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

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

First, a copper-clad laminate sample on which a photosensitive resin layer is laminated may be immersed in a nickel-phosphorous 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, it may be at a temperature of 65° C. or greater than 65° C. and 95° C. or less than 95° C. Under certain conditions, the cross-sectional area is 600 square centimeters or more than 600 square centimeters and 700 square centimeters or less than 700 square centimeters, or 640 square centimeters or more than 640 square centimeters and 660 square centimeters or less than 660 square centimeters, or 645 square centimeters or Samples larger than 645 cm2 and 655 cm2 or less than 655 cm2, or 650 cm2 were immersed in 130 ml of NPR-4 (Uemura) plating solution (as a nickel-phosphorus containing plating solution) for 20 minutes or More than 20 minutes and 60 minutes or less than 60 minutes to perform elution. The cross-sectional area refers to the area of a cross-section obtained by cutting a sample in a direction perpendicular to the direction in which the thickness of the sample increases.

If necessary, the sample may be immersed in the aqueous catalyst solution before being immersed in the nickel-phosphorus plating solution, and the specific conditions are not particularly limited. For example, the photosensitive aqueous layer can be laminated by using CATA NC-20 (MK Chemical and Technology Co., Ltd.) as a palladium plating-catalyst solution under the conditions of 10°C or more and 40°C or less The copper clad laminate samples on the substrate were immersed for 30 seconds to 90 seconds.

Next, the copper-clad laminate sample on which the nickel-plated photosensitive resin layer is laminated may be immersed in a 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, it may be carried out under the conditions of 30° C. or more and 70° C. or less than 70° C. , with a cross-sectional area of 600 square centimeters or more and 700 square centimeters or less than 700 square centimeters, or 640 square centimeters or more than 640 square centimeters and 660 square centimeters or less than 660 square centimeters, or 645 square centimeters or more than 645 A sample of 655 cm2 or less, or a sample of 650 cm2 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 than 90 minutes to perform elution.

Meanwhile, the copper-clad laminate sample on which the palladium-plated photosensitive resin layer is laminated may also be immersed in the gold-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 gold plating solution are not particularly limited, for example, under the conditions of 65° C. or greater than 65° C. and 95° C. or less than 95° C., The cross-sectional area is 600 cm2 or more and 700 cm2 or less than 700 cm2, or 640 cm2 or more than 640 cm2 and 660 cm2 or less than 660 cm2, or 645 cm2 or more than 645 cm2 cm and 655 cm2 or less, or 650 cm2 samples immersed in 130 ml of TMX-40 (Uemura (Uemura)) plating solution (as a gold plating solution) for 50 minutes or more and 150 minutes or less than 150 minutes to perform the elution.

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

First, a 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, under the conditions of 65°C or higher and 95°C or lower, the cross-sectional The area is 1 square centimeter or greater and 10 square centimeters or less than 10 square centimeters, or 4 square centimeters or greater than 4 square centimeters and 6 square centimeters or less than 6 square centimeters, or 4.5 square centimeters or greater than 4.5 square centimeters and 5.5 A copper-clad laminate sample of 5.5 cm2 or less, or 5 cm2, was immersed in 130 ml of residual NPR-4 (Uemura) plating solution and plated for 15 minutes or more and 45 minutes or less 45 minutes. The cross-sectional area refers to the area of a cross-section obtained by cutting a sample in a direction perpendicular to the direction in which the thickness of the sample increases.

If necessary, the sample can also be immersed in the aqueous catalyst solution before immersing in the nickel-phosphorus plating solution. Although specific conditions are not particularly limited, for example, it can be obtained by using CATA NC-20 (MK Chemical and Technology Co., Ltd.) as a palladium catalyst under the conditions of 10° C. or more and 40° C. or less than 40° C. The samples were immersed for 90 seconds.

At this time, the thickness of the nickel-phosphorus plating layer may be 3.9 microns or greater than 3.9 microns, or 3.95 microns or greater than 3.95 microns, or 3.9 microns or greater than 3.9 microns and 4.0 microns or less than 4.0 microns, or 3.95 microns or greater than 3.95 microns and 4.0 microns or less, the nickel-phosphorus plating layer is obtained by immersing the film sample in which the photosensitive resin layer is laminated on the substrate in the nickel-phosphorus plating solution for 38 minutes and then immersing the copper-clad laminate sample in the remaining plating obtained in nickel-phosphorus solution for 28 minutes.

Next, the nickel-plated copper-clad laminate sample can also be dipped into the remaining palladium plating solution to perform plating. Although the specific conditions for immersing the nickel-phosphorus-plated copper-clad laminate sample in the residual palladium plating solution are not particularly limited, for example, it can be carried out under the conditions of 30°C or more and 70°C or less. , the cross-sectional area is 1 square centimeter or more than 1 square centimeter and 10 square centimeters or less than 10 square centimeters, or 4 square centimeters or more than 4 square centimeters and 6 square centimeters or less than 6 square centimeters, or 4.5 square centimeters or more than 4.5 A sample of 5.5 cm2 or less than 5.5 cm2 or 5 cm2 is immersed in 130 ml of residual TPD-21 (Uemura) plating solution for 2 minutes or more and 10 minutes or less than 10 minutes, to perform plating.

At the same time, the palladium-plated copper-clad laminate sample can be dipped into the residual gold plating solution to perform plating. Although the specific conditions for immersing the palladium-plated copper-clad laminate sample in the remaining gold-plating solution are not particularly limited, for example, the transverse The cross-sectional area is 1 square centimeter or more and 10 square centimeters or less than 10 square centimeters, or 4 square centimeters or more and 6 square centimeters or less than 6 square centimeters, or 4.5 square centimeters or more than 4.5 square centimeters and A sample of 5.5 cm2 or less, or a sample of 5 cm2 was immersed in 130 ml of residual TWX-40 (Uemura) plating solution for 5 minutes or more and 20 minutes or less to perform plating cover.

At this time, the thickness of the gold-plated layer of the dry film photoresist can be 0.11 microns or greater than 0.11 microns, or 0.11 microns or greater than 0.11 microns and 0.13 microns or less than 0.13 microns, or 0.12 microns or greater than 0.12 microns, or 0.12 microns or greater than 0.12 microns. Micron and 0.13 micron or less than 0.13 micron features, the gold-plated layer is obtained by immersing the film sample in which the photosensitive resin layer of the dry film photoresist is laminated on the substrate in the gold-plating solution for 98 minutes and then immersing the copper-clad laminate sample in The remaining gold plating solution was obtained for 11 min.

That is, the thickness of the dry film photoresist with the gold plating layer can be 0.11 microns or greater than 0.11 microns, or 0.11 microns or greater than 0.11 microns and 0.13 microns or less than 0.13 microns, or 0.12 microns or greater than 0.12 microns, or 0.12 microns or greater than 0.12 Micron and 0.13 micron or less than 0.13 micron features, the gold-plated layer is obtained by immersing the film sample in which the photosensitive resin layer of the dry film photoresist is laminated on the substrate in the gold-plating solution for 98 minutes and then immersing the copper-clad laminate sample in The remaining gold plating solution was obtained for 11 min.

Meanwhile, the film sample in which a photosensitive resin layer containing a photosensitive resin composition is laminated on a substrate may be a laminate in which a photosensitive resin layer is laminated on any substrate. An example of the substrate may 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.

A film sample in which a photosensitive resin layer containing a photosensitive resin composition is laminated on a substrate may have a cross-sectional area of 600 cm2 or more and 700 cm2 or less, or 640 cm2 or more And 660 square centimeters or less than 660 square centimeters, or 645 square centimeters or more than 645 square centimeters and 655 square centimeters or less than 655 square centimeters.

In addition, the cross-sectional area of the copper-clad laminate sample used to immerse the copper-clad laminate sample in the residual palladium plating solution for 5 minutes may be 1 cm2 or more and 10 cm2 or less, or 4 square centimeters or more than 4 square centimeters and 6 square centimeters or less than 6 square centimeters, or 4.5 square centimeters or more than 4.5 square centimeters and 5.5 square centimeters or less than 5.5 square centimeters.

When measuring the thickness of the palladium coating, it can be measured by using an exposure device at 20 millijoules/cm2 or greater than 20 millijoules/cm2 and 200 millijoules/cm2 or less than 200 millijoules/cm2, or 50 millijoules/cm2 Exposure is performed by irradiating ultraviolet light at an exposure dose of 50 mJ/cm2 or more and 100 mJ/cm2 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.

When measuring the thickness of the palladium plating layer, by using a concentration of 0.5% by weight or greater than 0.5% by weight and 1.5% by weight or less than 1.5% by weight, or 0.9% by weight or greater than 0.9% by weight and 1.1% by weight or less than 1.1 The development is carried out with an aqueous alkaline solution of % by weight. The pH of the alkaline aqueous solution may be in the range of 9 or more and 11 or less, and the temperature may be adjusted in accordance with the developability of the photosensitive resin layer. Specific examples of aqueous alkaline solutions include aqueous sodium carbonate, aqueous potassium carbonate, aqueous sodium hydroxide, and the like.

For image development, a method of bringing an alkaline aqueous solution into contact with a photosensitive resin layer can be used. As an example of a specific contact method, a spray method or a dipping method can be used. The developing time may be 30 seconds or more and 10 minutes or less, or 30 seconds or more and 2 minutes or less.

The photosensitive resin layer may be in the form of a film without openings or in the form of a pattern with openings.

Examples of a method of forming a patterned photosensitive resin layer include a method of laminating a photosensitive resin layer of a dry film resist of another embodiment on a substrate and then performing exposure and development. In addition, there may be mentioned a method of laminating a photosensitive resin layer of a photosensitive element according to another embodiment described later on a substrate and then performing exposure and development.

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

In addition, when the dry film photoresist or photosensitive element of another embodiment has a polymer substrate or substrate film laminated on one side of the photosensitive resin layer, removing the polymer substrate or substrate film immediately after the exposure process may be further performed. process. 3. Impedance pattern

According to another embodiment of the present disclosure, there may be provided a resist pattern including a photosensitive resin pattern containing the photosensitive resin composition included in the dry film photoresist of another embodiment. Details about the photosensitive resin composition contained in the dry film photoresist include all the contents described above for one embodiment.

The photosensitive resin pattern may be a photosensitive resin composition in the form of a pattern having openings.

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

As the substrate, a copper-clad laminate, a glass substrate on which a transparent electrode such as ITO and indium zinc oxide (IZO) is sputtered or deposited, a similar film substrate, a glass coated with a dielectric paste Substrates, silicon wafers, glass wafers deposited with amorphous silicon, silicon wafers sputtered with metal films such as copper, tantalum, and molybdenum.

For the exposure process, it is preferable to use UV, visible light, laser, and especially to use a laser direct (Laser Direct) exposure machine containing a light source with a wavelength of 350 nm to 410 nm, especially using i-line ( 365 nm) or h-line (405 nm). In the case of using a laser direct exposure machine, when an ordinary lamp exposure machine is used under the condition that the exposure energy is 3 mJ/cm2 to 15 mJ/cm2 or less, it may be used in the exposure Work under the condition that the energy is 20 mJ/cm2 or less than 20 mJ/cm2. Therefore, it can be used to produce images for PCBs, lead frames, PDPs, and other display devices.

The development process can be performed by dipping, spraying, spraying, brushing and the like. As a developing solution, alkaline aqueous solutions, such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and an amine, can be used, for example.

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

In addition, when the dry film resist of the other embodiment or the photosensitive element of the one embodiment has a polymer substrate or a substrate film laminated on one side of the photosensitive resin layer, it may further be performed immediately after the exposure process. The process of removing a polymeric substrate or substrate film. 4. Circuit board, display device

According to still another embodiment of the present disclosure, there may be provided a circuit board or a display device including the impedance pattern of the other embodiment or a metal pattern formed by the impedance pattern of the other embodiment . The details about the impedance pattern include all those described above in the other embodiment.

The specific details of the circuit board or the display device are not particularly limited, and various conventionally known technical configurations can be applied without limitation.

The metal pattern may be formed of the above-mentioned resistance pattern. Specifically, the metal pattern may be formed by performing etching or plating through openings included in the resist pattern. That is, the metal pattern may include the lower metal remaining after the lower metal of the resist pattern is etched through the opening included in the resist pattern, or the metal plated in the opening included in the resist pattern.

Specifically, for example, conductive patterns, printed wiring boards, lead frames, ITO electrodes, black mats, semiconductor bumps, etc. can be produced by etching or plating the lower substrate exposed by the above-mentioned impedance pattern. . 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.

Thereby, by using the dry film photoresist of the present disclosure to perform a conventional etching/plating process to form a circuit with a thin line width, and to form a circuit with a thin line width by a known process on the PCB and the leads with a thin line width Productivity can be maximized when generating images on frames, PDPs, other display devices, and semiconductor devices. [beneficial effect]

According to the present disclosure, it is possible to provide a photosensitive element which can reduce contamination of a plating solution and allow plating to be performed with a sufficient thickness, as well as a dry film photoresist, a resist pattern, a circuit board, and a display device using the same. Effect.

The present disclosure will be described in more detail by the examples shown below. However, such examples are for illustrative purposes only and are not intended to limit the scope of the invention thereto. < Preparation Example: Preparation of Alkaline Developable Binder Resin > Preparation Example 1

A 4-neck jacketed reaction flask was equipped with a mechanical stirrer and 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 into the flask purged with nitrogen, and then 0.9 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. 24 grams of methacrylic acid (MAA), 6 grams of methyl methacrylate (MMA), 30 grams of styrene (SM) and 40 grams of 2-phenoxyethyl methacrylate (2-phenoxyethyl methacrylate, PHEMA) A monomer mixture was added thereto as a monomer, which was heated to 80° C., and then polymerized for 6 hours to prepare an alkaline developable binder resin (weight-average molecular weight: 50,000 g/mol, solid content: 50.0% by weight, Acid value: 155 mg KOH/g).

Specific examples of weight average molecular weight measurement conditions are as follows. Dissolve the alkaline developable binder resin in tetrahydrofuran so that the concentration in THF is 1.0 (w/w) % (approximately 0.5 (w/w) % in terms of solids content) and use a 0.45 It was filtered through a micron syringe filter and injected into the GPC at 20 microliters. Tetrahydrofuran (THF) was used as the mobile phase of GPC, and was allowed to flow at a flow rate of 1.0 ml/min. The column consists of an Agilent PLgel 5 micron guard column (Guard) (7.5 mm × 50 mm) and two Agilent PLgel 5 micron mixed D columns (7.5 mm × 300 mm) connected in series constituted, and measurements were performed at 40°C using an Agilent 1260 Infinity II system, RI detector.

The acid value was measured by sampling 1 g of alkaline developable binder resin, dissolving it in 50 ml of mixed solvent (MeOH 20%, acetone 80%), adding two drops of 1% phenolphthalein indicator , and titrated with 0.1N-KOH.

Based on the weight of the alkaline developable binder resin prepared in the above preparations, the solids content was measured as the weight percent of solids remaining after heating in an oven at 150° C. for 120 minutes. Preparation example 2

A four-neck round bottom flask was equipped with a mechanical stirrer and a reflux device, and then the inside of the flask was purged with nitrogen. 80 grams of methyl ethyl ketone (MEK) and 7.5 grams of methanol (MeOH) were added to the flask purged with nitrogen, and then 0.45 grams of azobisisobutyronitrile (AIBN) was added and completely dissolved. 8 grams of acrylic acid (AA) (0.11 mol, accounting for 10.91 mol% of 100 mol% of all monomers), 15 grams of methacrylic acid (MAA) (0.17 mol, accounting for 17.13 mol% of 100 mol% of all monomers) mol%), 15 grams of butyl acrylate (BA) (0.12 mol, accounting for 11.50 mol% of all monomers in 100 mol%), 52 grams of methyl methacrylate (MMA) (0.52 mol, accounting for 100 51.03 mol% of all monomers) and 10 grams of styrene (SM) (0.10 mol, accounting for 9.43 mol% of 100 mol% of all monomers) are added as monomers, This was heated to 80° C., and then polymerized for 6 hours to prepare an alkaline developable binder resin.

After measurement, the weight average molecular weight of the alkaline developable binder resin is 71,538 g/mol, the glass transition temperature is 79° C., the solid content is 51.4 wt%, and the acid value is 156.3 mg KOH/g. Preparation example 3

A four-neck round bottom flask was equipped with a mechanical stirrer and a reflux device, and then the inside of the flask was purged with nitrogen. 110 grams of methyl ethyl ketone (MEK) and 10 grams of methanol (MeOH) were added to the flask purged with nitrogen, and then 1 gram of azobisisobutyronitrile (AIBN) was added and completely dissolved. Add 30 grams of methacrylic acid (MAA) (0.35 mol, accounting for 21.32 mol% of 100 mol% of all monomers), 100 grams of methyl methacrylate (MMA) (1.00 mol, accounting for 100 mol% of all 61.07 mol% of the monomer) and 30 grams of styrene (SM) (0.29 mol, accounting for 17.61 mol% of 100 mol% of all monomers) monomer mixture was added as a monomer, and it was heated to 80 ℃, and then polymerized for 6 hours to prepare an alkaline developable binder resin (weight-average molecular weight: 49,852 g/mol, glass transition temperature: 125°C, solid content: 48.5% by weight, and acid value: 163.17 mg KOH /gram). Preparation Example 4

A four-neck round bottom flask was equipped with a mechanical stirrer and a reflux device, and then the inside of the flask was purged with nitrogen. 90 grams of methyl ethyl ketone (MEK) and 10 grams of methanol (MeOH) were added to the flask purged with nitrogen, and then 0.85 grams of azobisisobutyronitrile (AIBN) was added and completely dissolved. Add 25 grams of methacrylic acid (MAA) (0.29 mol, accounting for 30.86 mol% of 100 mol% of all monomers), 20 grams of methyl methacrylate (MMA) (0.20 mol, accounting for 100 mol% of all 21.22 mol% of monomer), 25 grams of styrene (SM) (0.24 mol, accounting for 25.50 mol% of 100 mol% of all monomers) and 30 grams of glycidyl methacrylate (GMA) (0.21 mol ear, 22.42 mol% of 100 mol% of all monomers) was added thereto as a monomer, which was heated to 80° C., and then polymerized for 6 hours to prepare an alkaline developable binder resin.

After measurement, the alkaline developable binder resin has a weight average molecular weight of 55,201 g/mole, a glass transition temperature of 112° C., a solid content of 50.2 wt %, and an acid value of 162.0 mg KOH/g. < Example and Comparative Example: Preparation of Photosensitive Resin Composition and Dry Film Photoresist >

According to the composition shown in Table 1 below, the photopolymerization initiator was dissolved in methyl ethyl ketone (MEK) as a solvent, and then a photopolymerizable compound and an alkaline developable binder resin were added, and mechanically The mixer was mixed for about 1 hour to prepare a photosensitive resin composition.

The obtained photosensitive resin composition was coated on a 19 micron PET film using a coating bar to form a photosensitive resin composition layer, which was 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 photosensitive resin composition layer after drying was 40 μm.

（4）Viscoat#802：三季戊四醇丙烯酸酯（Mw 805，大阪友紀（Osaka Yuki））

J為氫或丙烯醯基， j為10%~20%的j=1的化合物、55%~65%的j=2的化合物及5%~15%的j=3的化合物的混合物 （5）EAB：4,4'-(雙二乙胺基)二苯甲酮（奧德里奇化學公司） （6）BCIM：2,2'-雙-(2-氯苯基-4,5,4',5'-四苯基雙咪唑（奧德里奇化學公司） （7）N,N-BDA：N,N-苄基二甲基醯胺 [表2] 組分 產品名稱（或組分名稱） 含量（基於100 wt.%的感光樹脂組成物的各wt.%） 實例4 實例5 比較例2 鹼性可顯影黏合劑樹脂 製備例1 50.0 （基於100 wt.%的黏合劑樹脂為76.92 wt.%） 30.0 （基於100 wt.%的黏合劑樹脂為46.15 wt.%） - 製備例2 1.0 （基於100 wt.%的黏合劑樹脂為1.54 wt.%） 1.0 （基於100 wt.%的黏合劑樹脂為1.54 wt.%） 7.6 製備例3 7.5（基於100 wt.%的黏合劑樹脂為11.54 wt.%） 7.5 （基於100 wt.%的黏合劑樹脂為11.54 wt.%） 57.4 製備例4 6.5 （基於100 wt.%的黏合劑樹脂為10.00 wt.%） 26.5 （基於100 wt.%的黏合劑樹脂為40.77 wt.%） -    總計 65.0 65.0 65.0 可光聚合化合物 M241 5.0 5.0 5.0 M2101 20.0 20.0 20.0 總計 25.0 25.0 25.0 光聚合起始劑 EAB 0.05 0.05 0.05 BCIM 1.30 1.30 1.30 總計 1.35 1.35 1.35 添加劑 甲苯磺酸一水合物（奧德里奇化學公司） 0.044 0.044 0.044 N,N-BDA 0.066 0.066 0.066 無色結晶紫（保土谷公司，日本） 0.170 0.170 0.170 鑽石綠GH（保土谷公司，日本） 0.015 0.015 0.015 總計 0.295 0.295 0.295 溶劑 MEK（甲基乙基酮） 8.355 8.355 8.355 （1）M241：雙酚A (EO) ₄二甲基丙烯酸酯（美源特種化工有限公司） （2）M2101：雙酚A (EO) ₁₀二甲基丙烯酸酯（美源特種化工有限公司） （3）EAB：4,4'-(雙二乙胺基)二苯甲酮（奧德里奇化學公司） （4）BCIM：2,2'-雙-(2-氯苯基-4,5,4',5'-四苯基雙咪唑（奧德里奇化學公司） （5）N,N-BDA：N,N-苄基二甲基醯胺 ＜ 實驗例 ＞ A protective film (polyethylene) is laminated on the dried photosensitive resin composition layer to prepare a dry film photoresist. [Table 1] components Product name (or component name) Content (wt.%) Example 1 Example 2 Example 3 Comparative example 1 Alkaline developable binder resin Preparation Example 1 65.0 65.0 65.0 65.0 photopolymerizable compound M241 4.0 4.0 4.0 5.0 M2101 16.0 16.0 16.0 20.0 M500 5.0 0 2.5 0 Viscoat #802 0 5.0 2.5 0 Photopolymerization initiator EAB 0.05 0.05 0.05 0.05 BCIM 1.30 1.30 1.30 1.30 additive Toluenesulfonic acid monohydrate (Aldrich Chemical) 0.044 0.044 0.044 0.044 N,N-BDA 0.066 0.066 0.066 0.066 Colorless crystal violet (Hodogaya Co., Japan) 0.170 0.170 0.170 0.170 Diamond Green GH (Hodogaya Company, Japan) 0.015 0.015 0.015 0.015 solvent MEK (methyl ethyl ketone) 8.355 8.355 8.355 8.355 (1) M241: Bisphenol A (EO) ₄ Dimethacrylate (Meiyuan Specialty Chemicals Co., Ltd.) (2) M2101: Bisphenol A (EO) ₁₀ Dimethacrylate (Meiyuan Specialty Chemicals Co., Ltd.) (3) M500: dipentaerythritol pentaacrylate (Mw 524, Meiyuan Specialty Chemical Co., Ltd.)

(4) Viscoat#802: tripentaerythritol acrylate (Mw 805, Osaka Yuki)

J is hydrogen or acryl, and j is a mixture of 10%~20% of compounds with j=1, 55%~65% of compounds with j=2 and 5%~15% of compounds with j=3 (5) EAB: 4,4'-(bisdiethylamino)benzophenone (Aldrich Chemical Company) (6) BCIM: 2,2'-bis-(2-chlorophenyl-4,5,4',5'-tetraphenylbisimidazole (Aldrich Chemical Co.) (7) N,N-BDA: N,N-benzyldimethylamide [Table 2] components Product name (or component name) Content (based on 100 wt.% of each wt.% of the photosensitive resin composition) Example 4 Example 5 Comparative example 2 Alkaline developable binder resin Preparation Example 1 50.0 (76.92 wt.% based on 100 wt.% binder resin) 30.0 (46.15 wt.% based on 100 wt.% binder resin) - Preparation example 2 1.0 (1.54 wt.% based on 100 wt.% binder resin) 1.0 (1.54 wt.% based on 100 wt.% binder resin) 7.6 Preparation example 3 7.5 (11.54 wt.% based on 100 wt.% binder resin) 7.5 (11.54 wt.% based on 100 wt.% binder resin) 57.4 Preparation Example 4 6.5 (10.00 wt.% based on 100 wt.% binder resin) 26.5 (40.77 wt.% based on 100 wt.% binder resin) - total 65.0 65.0 65.0 photopolymerizable compound M241 5.0 5.0 5.0 M2101 20.0 20.0 20.0 total 25.0 25.0 25.0 Photopolymerization initiator EAB 0.05 0.05 0.05 BCIM 1.30 1.30 1.30 total 1.35 1.35 1.35 additive Toluenesulfonic acid monohydrate (Aldrich Chemical Company) 0.044 0.044 0.044 N,N-BDA 0.066 0.066 0.066 Colorless crystal violet (Hodogaya Co., Ltd., Japan) 0.170 0.170 0.170 Diamond Green GH (Hodogaya Company, Japan) 0.015 0.015 0.015 total 0.295 0.295 0.295 solvent MEK (methyl ethyl ketone) 8.355 8.355 8.355 (1) M241: Bisphenol A (EO) ₄ Dimethacrylate (Meiyuan Specialty Chemicals Co., Ltd.) (2) M2101: Bisphenol A (EO) ₁₀ Dimethacrylate (Meiyuan Specialty Chemicals Co., Ltd.) (3) EAB: 4,4'-(bisdiethylamino)benzophenone (Aldrich Chemical Company) (4) BCIM: 2,2'-bis-(2-chlorophenyl-4,5 ,4',5'-tetraphenylbisimidazole (Aldrich Chemical Company) (5) N,N-BDA: N,N-benzyldimethylamide ＜ Experimental example ＞

The physical properties of the dry film photoresists prepared in Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 3 and Table 4 below. 1. Pollution properties of electroless palladium plating solution

The protective film was peeled off from the dry film photoresist prepared in Examples and Comparative Examples, and the photosensitive resin layer of the dry film photoresist was laminated on both sides using HAKUTO MACH 610i so that it was bonded to the 1.6 mm thick copper-clad laminate. The surface of the copper layer is in contact with the brushing treatment 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/cm2, and a roll speed of 2.0 min/m, thereby A laminate is formed.

The supporting PET film for dry film photoresist was peeled off from the laminate, and then irradiated with ultraviolet rays at an exposure dose of 80 mJ/cm2 by ORC EXM-1201-F (parallel light exposure machine) using a photomask A full surface exposure was done for 4 seconds and then allowed to stand for 15 minutes. Subsequently, development was performed with a 1.0% by weight Na ₂ CO ₃ aqueous solution at 30±1° C. for one minute under jet-type developing conditions at a jet pressure of 1.5 kgf/cm 2 . The developed laminate was baked in an oven at 140°C for 30 minutes.

After the baked laminate had cooled sufficiently, samples with a cross-sectional area of 650 cm2 were prepared. Sequentially immerse the sample in 130 ml of CATA NC-20 (MK Chemical and Technology Company) palladium catalyst at 25°C for 1 minute and 30 seconds, rinse in distilled water for 1 minute, and immerse in 130 ml of NPR- 4 (Uemura) nickel-phosphorous solution for 38 minutes, rinsed in distilled water for 1 minute, immersed in 130 ml of TPD-21 (Uemura) palladium plating solution at 55±2°C for 60 minutes, in Rinse in distilled water for 1 minute, immerse in 130 ml of TWX-40 (Uemura) gold plating solution at 80±2°C for 98 minutes, and rinse in distilled water for 1 minute.

Then, in the plating solution in which the dry film photoresist component was eluted by immersing the laminated board, the copper-clad laminated board sample having a cross-sectional area of 5 cm square and a thickness of 1.6 mm subjected to the brushing treatment was treated according to Sequence immersion in 130 ml of CATA NC-20 (MK Chemical and Technology Co.) palladium catalyst at 25 °C for 1 min 30 sec, rinse in distilled water for 1 min, and immerse in 130 ml of NPR-4 (Uemura) at 80 ± 2 °C (Uemura)) nickel-phosphorus plating solution for 28 minutes, rinsed in distilled water for 1 minute, immersed in 130 ml TPD-21 (Uemura (Uemura)) palladium plating solution at 55±2°C for 5 minutes, rinsed in distilled water for 1 min, immersed in 130 ml TWX-40 (Uemura) gold plating solution at 80±2°C for 11 min, and rinsed in distilled water for 1 min.

Helmut Fischer XDV-μ was used to measure the plating thickness of nickel-phosphorous, palladium and gold-plated copper-clad laminates in sequence, and the contamination properties of the plating solution were evaluated by the degree of plating thickness . 2. Thin line adhesion (unit: micron)

The protective film was peeled off from the dry film resists prepared in Examples and Comparative Examples, and the photosensitive resin layer of the dry film resist was laminated using HAKUTO MACH 610i so that it was in contact with the copper layer of the 1.6 mm thick copper clad laminate. Surface contact, subjected to brushing treatment under the following conditions: substrate preheating roll temperature of 120°C, laminator roll temperature of 115°C, roll pressure of 4.0 kgf/cm2 and roll speed of 2.0 min/m, thereby forming Laminate.

The supporting PET film for dry film photoresist was peeled off from the laminate, and then irradiated with ultraviolet rays at an exposure dose of 80 mJ/cm2 by ORC EXM-1201-F (parallel light exposure machine) using a photomask A full surface exposure was done for 4 seconds and then allowed to stand for 15 minutes. Subsequently, development was performed with a 1.0% by weight Na ₂ CO ₃ aqueous solution at 30±1° C. for one minute under jet-type developing conditions at a jet pressure of 1.5 kgf/cm 2 .

In the laminated board that has been developed, the minimum line width of the photosensitive resin layer was measured with a Zeiss (ZEISS) AXIOPHOT microscope, and evaluated as fine line adhesion. It can be estimated that the smaller this value is, the better the fine line adhesion is. 3. 1:1 resolution ( unit: micron)

The protective film was peeled off from the dry film resists prepared in Examples and Comparative Examples, and the photosensitive resin layer of the dry film resist was laminated using HAKUTO MACH 610i so that it was in contact with the copper layer of the 1.6 mm thick copper clad laminate. Surface contact, subjected to brushing treatment under the following conditions: substrate preheating roll temperature of 120°C, laminator roll temperature of 115°C, roll pressure of 4.0 kgf/cm2 and roll speed of 2.0 min/m, thereby forming Laminate.

The supporting PET film for dry film photoresist was peeled off from the laminate, and then exposed at 80 mJ/cm2 through a photomask for circuit evaluation using ORC EXM-1201-F (parallel light exposure machine) The dose was irradiated with ultraviolet light for 4 seconds so that the width of the circuit line and the space interval between the circuit lines could become 1:1, and then it was allowed to stand for 15 minutes. Subsequently, development was performed with a 1.0% by weight Na ₂ CO ₃ aqueous solution at 30±1° C. for one minute under jet-type developing conditions at a jet pressure of 1.5 kgf/cm 2 .

In the developed laminate, the minimum value of the interval between the photosensitive resin layers was measured with a Zeiss (ZEISS) AXIOPHOT microscope and evaluated as 1:1 resolution. It can be estimated that the smaller the value, the better the 1:1 resolution value. 4. Peeling rate (unit: second)

The protective film was peeled off from the dry film resists prepared in Examples and Comparative Examples, and the photosensitive resin layer of the dry film resist was laminated using HAKUTO MACH 610i so that it was in contact with the copper layer of the 1.6 mm thick copper clad laminate. Surface contact, subjected to brushing treatment under the following conditions: substrate preheating roll temperature of 120°C, laminator roll temperature of 115°C, roll pressure of 4.0 kgf/cm2 and roll speed of 2.0 min/m, thereby forming Laminate.

The supporting PET film for dry film photoresist was peeled off from the laminate, and then irradiated with ultraviolet rays through a photomask for circuit evaluation using ORC EXM-1201-F (parallel light exposure machine) until reaching 40 mm Exposure dose in Joules/cm2 and then allowed to stand for 15 minutes. Subsequently, development was performed at 30±1° C. for a time twice the minimum development time with a 1.0 wt % Na ₂ CO ₃ aqueous solution under jet-type developing conditions with a jet pressure of 1.5 kgf/cm 2 .

Then, the photosensitive resin layer was peeled from the copper-clad laminated board using 3% sodium hydroxide aqueous solution (temperature: 50 degreeC). At this time, the time required for the photosensitive resin layer to come off from the copper-clad laminate was measured. [table 3] category Pollution Properties of Electroless Palladium Plating Solutions Fine line adhesion (μm) 1:1 resolution (μm) Peel rate (seconds) Nickel-Phosphorus Thickness (μm) Palladium plating thickness (μm) Gold plating thickness (μm) Example 1 3.926 0.138 0.112 14 12 200 Example 2 3.976 0.101 0.105 14 12 180 Example 3 3.905 0.100 0.121 14 12 190 Comparative example 1 3.718 0.008 0.111 14 12 150

As shown in Table 3, it can be confirmed that, in Examples 1 to 3, the thickness of palladium plating was measured to be 0.1 micron or more and 0.138 micron or less, and therefore compared to the case where the plating thickness was 0.008 micron In Comparative Example 1, the plating level was sufficiently improved with palladium. In addition, it was confirmed that in Examples 1 to 3, the nickel-phosphorous plating thickness was measured to be 3.905 micrometers or more and 3.976 micrometers or less, and thus compared with the comparative example in which the plating thickness was 3.718 micrometers 1. Even with nickel-phosphorus, the plating level will be substantially improved.

Thereby, it was confirmed that the dry film resists prepared in Examples 1 to 3 were low in the contamination property of the plating solution, and thus a sufficient level of plating property could be ensured even when the plating solution was repeatedly used . [Table 4] category Pollution Properties of Electroless Palladium Plating Solutions Fine line adhesion (μm) 1:1 resolution (μm) Peel rate (seconds) Nickel-Phosphorus Thickness (μm) Palladium plating thickness (μm) Gold plating thickness (μm) Example 4 3.916 0.121 0.112 14 12 81 Example 5 3.926 0.113 0.122 18 16 66 Comparative example 2 3.863 0.002 0.100 18 16 102

As shown in Table 4, it can be confirmed that in Examples 4 to 5, the thickness of palladium plating was measured to be 0.113 micrometers or more and 0.121 micrometers or less than 0.121 micrometers, and therefore compared with those in which the plating thickness was 0.002 micrometers In Comparative Example 2, the plating level was sufficiently improved with palladium. In addition, it was confirmed that in Examples 4 to 5, the nickel-phosphorous plating thickness was measured to be 3.916 micrometers or more and 3.926 micrometers or less, and thus compared with the comparative example in which the plating thickness was 3.863 micrometers 2. Even with nickel-phosphorus, the plating level will be substantially improved.

In addition, it was confirmed that in Examples 4 to 5, the thickness of gold plating was measured to be 0.112 μm or more and 0.122 μm or less, and therefore compared to Comparative Example 2 in which the plating thickness was 0.100 μm, even The use of gold also substantially increases the level of plating.

From the above results, it was confirmed that the dry film resists prepared in Examples 4 to 5 were low in contamination properties to the plating solution, and thus a sufficient level of plating could be ensured even when the plating solution was reused. covering nature.

In addition, the dry film resists prepared in Examples 4 to 5 exhibited short peeling times of 66 seconds or more and 81 seconds or less, thereby implementing excellent peeling properties.

none

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Claims (20)

A photosensitive element, comprising: polymeric substrates; and a photosensitive resin layer formed on the polymer substrate, wherein the thickness of the palladium-plated layer is 0.01 micron or greater, and the palladium-plated layer is 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 coating copper Laminate samples were obtained by immersing in residual palladium plating solution for 5 minutes. The photosensitive element as claimed in item 1, wherein: The photosensitive resin layer contains an alkaline developable binder resin. The photosensitive element as claimed in item 1, wherein: The photosensitive element is characterized in that the thickness of the nickel-phosphorus plating layer obtained by immersing a film sample in which the photosensitive resin layer is laminated on the substrate is 3.9 micrometers or more. Nickel-phosphorus solution for 38 minutes and then immerse the copper clad laminate samples in the residual nickel-phosphorus solution for 28 minutes. The photosensitive element as claimed in item 1, wherein: The photosensitive resin layer contains a photosensitive resin composition, the photosensitive resin composition includes an alkaline developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the photopolymerizable compound includes five In the group consisting of five types of (meth)acrylate compounds with (meth)acryl groups and polyfunctional (meth)acrylate compounds with seven or more (meth)acryl groups at least one. The photosensitive element as described in claim item 4, wherein: The five-type (meth)acrylate compound further includes a hydroxyl group. The photosensitive element according to claim 4, wherein: the five-type (meth)acrylate compound is a compound represented by the following chemical formula A: [chemical formula A]

Wherein, in the chemical formula _A , five of T1 to _T6 are the same or different from each other, and are each independently a (meth)acryloyl group, and the remaining one is hydrogen. The photosensitive element according to claim 4, wherein: the polyfunctional (meth)acrylate compound is a compound represented by the following chemical formula B: [chemical formula B]

Wherein, in the chemical formula B, _T7 to _T12 are the same or different from each other, and are each independently a (meth)acryl group, _T12 is hydrogen or a (meth)acryl group, and t is 2 to 10 integer. The photosensitive element as claimed in item 1, wherein: The photosensitive resin layer contains a photosensitive resin composition, the photosensitive resin composition includes an alkaline developable binder resin, a photopolymerization initiator and a photopolymerizable compound, wherein the alkaline developable binder resin includes four or more than four different polymers from each other. The photosensitive member according to claim 8, wherein: the alkali-developable binder resin includes a first binder resin containing the following repeating unit represented by Chemical Formula 1: [Chemical Formula 1]

Wherein, in Chemical Formula 1, R ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₂ 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 from 1 to 20. The photosensitive element according to claim 9, wherein: in addition to the repeating unit represented by Chemical Formula 1, the first binder resin further includes a repeating unit represented by Chemical Formula 2 below, a repeating unit represented by Chemical Formula 3 below unit and the following repeating unit represented by Chemical Formula 4: [Chemical Formula 2]

Wherein, in Chemical Formula 2, R ₃ is hydrogen or an alkyl group having 1 to 10 carbon atoms, [Chemical Formula 3]

wherein, in Chemical Formula 3, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₅ is an alkyl group having 1 to 10 carbon atoms, and [Chemical Formula 4]

Wherein, in Chemical Formula 4, Ar is an aryl group having 6 to 20 carbon atoms. The photosensitive member according to claim 8, wherein: the alkali-developable binder resin includes a second binder resin containing the following repeating unit represented by Chemical Formula 5: [Chemical Formula 5]

Wherein, in Chemical Formula 5, R ₆ is hydrogen, and R ₇ is an alkyl group having 1 to 10 carbon atoms. The photosensitive element according to claim 11, wherein: in addition to the repeating unit represented by Chemical Formula 5, the second binder resin further includes a repeating unit represented by Chemical Formula 6 below, a repeating unit represented by Chemical Formula 7 below unit, the following repeating unit represented by Chemical Formula 8, and the following repeating unit represented by Chemical Formula 9: [Chemical Formula 6]

Wherein, in chemical formula 6, R ₈ is hydrogen, [chemical formula 7]

Wherein, in Chemical Formula 7, R ₉ is an alkyl group having 1 to 10 carbon atoms, [Chemical Formula 8]

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, [Chemical Formula 9]

Wherein, in Chemical Formula 9, Ar is an aryl group having 6 to 20 carbon atoms. The photosensitive member according to claim 8, wherein: the alkali-developable binder resin includes a third binder resin, and the third binder resin contains a repeating unit represented by the following chemical formula 10, and the following is represented by the chemical formula 11 and the following repeating units represented by Chemical Formula 12: [Chemical Formula 10]

Wherein, in Chemical Formula 10, R ₉ is an alkyl group having 1 to 10 carbon atoms, [Chemical Formula 11]

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, and [Chemical Formula 12]

Wherein, in Chemical Formula 12, Ar is an aryl group having 6 to 20 carbon atoms. The photosensitive member according to claim 8, wherein: the alkali-developable binder resin includes a fourth binder resin containing the following repeating unit represented by Chemical Formula 13: [Chemical Formula 13]

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. The photosensitive element according to claim 14, wherein: in addition to the repeating unit represented by the chemical formula 13, the fourth binder resin further includes the repeating unit represented by the following chemical formula 14, the repeating unit represented by the following chemical formula 15 unit and the following repeating unit represented by Chemical Formula 16: [Chemical Formula 14]

Wherein, in Chemical Formula 14, R ₁₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, [Chemical Formula 15]

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, [Chemical Formula 16]

Wherein, in Chemical Formula 16, Ar is an aryl group having 6 to 20 carbon atoms. A dry film photoresist comprising: A photosensitive resin composition comprising an alkaline developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the photopolymerizable compound comprises five (meth)acryl groups selected from the group consisting of five (meth)acryl groups. At least one of the group consisting of acrylate-based compounds and polyfunctional (meth)acrylate-based compounds having seven or more (meth)acryl groups, and Wherein the dry film photoresist has the feature that the thickness of the palladium plating layer is 0.01 micrometer or more than 0.01 micrometer, and the palladium plating layer is a film sample obtained by laminating the photosensitive resin layer of the dry film photoresist on the substrate obtained by immersing in the palladium plating solution for 60 minutes and then immersing the copper clad laminate samples in the remaining palladium plating solution for 5 minutes. A dry film photoresist comprising: A photosensitive resin composition comprising an alkaline developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the alkaline developable binder resin comprises four or more polymers different from each other, and Wherein the dry film photoresist has the feature that the thickness of the palladium plating layer is 0.01 micrometer or more than 0.01 micrometer, and the palladium plating layer is a film sample obtained by laminating the photosensitive resin layer of the dry film photoresist on the substrate obtained by immersing in the palladium plating solution for 60 minutes and then immersing the copper clad laminate samples in the remaining palladium plating solution for 5 minutes. A resist pattern comprising a photosensitive resin pattern containing the photosensitive resin composition contained in the dry film photoresist according to claim 16 or 17. A circuit board, comprising the impedance pattern described in claim 18, or a metal pattern formed by the impedance pattern described in claim 18. A display device comprising the impedance pattern as claimed in claim 18, or a metal pattern formed by the impedance pattern as claimed in claim 18.