WO2022145764A1

WO2022145764A1 - Photosensitive element, dry film photoresist, resist pattern, circuit board and display device

Info

Publication number: WO2022145764A1
Application number: PCT/KR2021/018101
Authority: WO
Inventors: 김용현
Original assignee: 코오롱인더스트리 주식회사
Priority date: 2020-12-29
Filing date: 2021-12-02
Publication date: 2022-07-07
Also published as: TW202235453A

Abstract

The present invention relates to a photosensitive element, a dry film photoresist, a resist pattern, a circuit board and a display device, the photosensitive element comprising a polymer substrate and a photosensitive resin layer formed on the polymer substrate, wherein, with respect to a residual palladium plating solution after a film sample having the photosensitive resin layer stacked on the substrate is immersed in a palladium plating solution for 60 minutes, the thickness of the palladium-plated layer obtained by immersing a copper-clad laminate sample into the residual palladium plating solution for five minutes is 0.01 ㎛ or more.

Description

Photosensitive elements, dry film photoresists, resist patterns, circuit boards, and display devices

FIELD OF THE INVENTION The present invention relates to photosensitive elements, dry film photoresists, resist patterns, circuit boards, and display devices.

The photosensitive resin composition is used in the form of dry film photoresist (DFR), liquid photoresist (Liquid Photoresist Ink), etc. used in printed circuit boards (PCB) or lead frames. .

Currently, not only manufacturing printed circuit boards (PCB) or lead frames, but also manufacturing rib barriers for plasma display panels (PDP), ITO electrodes for other displays, bus address electrodes, and black matrices. Dry film photoresist is also widely used for the like.

Such, in general, dry film photoresist is widely used for lamination on copper clad laminates. In this regard, as an example of a manufacturing process of a printed circuit board (PCB), a pretreatment process is first performed in order to laminate a copper-clad laminate sample, which is an original plate material of the PCB. The pretreatment process is in the order of drilling, deburing, and front face in the outer layer process, and undergoes face or pickling in the inner layer process. In the face process, bristle brush and jet pumice are mainly used. For pickling, soft etching and 5wt% sulfuric acid pickling can be used.

In order to form a circuit on the copper-clad laminate that has undergone the pretreatment process, dry film photoresist (hereinafter referred to as DFR) is generally laminated on the copper layer of the copper-clad laminate. In this process, a photoresist layer of DFR is laminated on the copper surface while peeling off the protective film of DFR using a laminator. In general, lamination speed 0.5~3.5m/min, temperature 100~130℃, roller pressure heating roll pressure 10~90psi.

The printed circuit board, which has undergone the lamination process, is left for at least 15 minutes to stabilize the board, and then is exposed to the photoresist of the DFR using a photomask having a desired circuit pattern formed thereon. In this process, when the photomask is irradiated with ultraviolet rays, polymerization of the photoresist irradiated with ultraviolet rays is initiated by the photoinitiator contained in the irradiated area. First, oxygen in the photoresist is consumed, then the activated monomer is polymerized to cause a crosslinking reaction, and then a large amount of the monomer is consumed and the polymerization reaction proceeds. On the other hand, the unexposed portion exists in a state in which the crosslinking reaction has not progressed.

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

Then, a circuit is formed through different processes according to the inner layer and outer layer processes. In the inner layer process, a circuit is formed on the substrate through corrosion and peeling processes, and in the outer layer process, plating and tenting processes are performed, followed by etching and solder stripping, and a predetermined circuit is formed.

An object of the present invention is to provide a photosensitive element capable of implementing the effect of enabling plating of a sufficient thickness by reducing contamination of a plating solution.

Another object of the present invention is to provide a dry film photoresist, a resist pattern, a circuit board, and a display device using the photosensitive element.

In order to solve the above problems, in the present specification, a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, wherein the film sample in which the photosensitive resin layer is laminated on the substrate is immersed in the palladium plating solution for 60 minutes and then the residual palladium plating solution is immersed in the copper-clad laminate sample for 5 minutes The obtained palladium plating layer thickness is 0.01 micrometer or more, The photosensitive element is provided.

In the present specification, it also includes an alkali developable binder resin, a photoinitiator, and a photopolymerizable compound, wherein the photopolymerizable compound is a penta-type (meth)acrylate-based compound having five (meth)acryloyl groups and seven or more A photosensitive resin layer containing a photosensitive resin composition comprising at least one selected from the group consisting of polyfunctional (meth)acrylate-based compounds having a (meth)acryloyl group, wherein the dry film photoresist is formed on a substrate The palladium plating layer obtained by immersing the copper-clad laminate sample for 5 minutes with respect to the residual palladium plating solution after immersing the film sample in which the photosensitive resin layer of the dry film photoresist is laminated in the palladium plating solution for 60 minutes is 0.01 μm or more, the dry film A photoresist is provided.

In the present specification, also including an alkali developable binder resin, a photoinitiator, and a photopolymerizable compound, wherein the alkali developable binder resin is a photosensitive resin layer containing a photosensitive resin composition comprising four or more different polymers from each other. and the dry film photoresist is obtained by immersing a copper-clad laminate sample for 5 minutes with respect to the residual palladium plating solution after immersing the film sample in which the photosensitive resin layer of the dry film photoresist is laminated on the substrate in the palladium plating solution for 60 minutes A dry film photoresist having a palladium plating layer thickness of 0.01 μm or greater is provided.

In the present specification, a resist pattern is also provided, including a photosensitive resin pattern containing the photosensitive resin composition included in the dry film photoresist.

The present specification also provides a circuit board and a display device including the resistor pattern or a metal pattern formed by the resistor pattern.

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

Unless explicitly stated herein, terminology is for the purpose of referring to specific embodiments only, and is not intended to limit the present invention.

As used herein, the singular forms also include the plural forms unless the phrases clearly indicate the opposite.

As used herein, the meaning of 'comprising' specifies a particular characteristic, region, integer, step, operation, element and/or component, and other specific characteristic, region, integer, step, operation, element, component, and/or group. It does not exclude the existence or addition of

And, in the present specification, terms including ordinal numbers such as 'first' and 'second' are used for the purpose of distinguishing one component from other components, and are not limited by the ordinal number. For example, within the scope of the present invention, a first element may be referred to as a second element, and similarly, a second element may be referred to as a first element.

In the present specification, examples of the substituent are described below, but is not limited thereto.

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

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amide group; primary amino group; carboxyl group; sulfonic acid group; sulfonamide group; a phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; alkoxysilylalkyl group; an arylphosphine group; Or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more, or substituted or unsubstituted, two or more of the above-exemplified substituents are linked. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.

In this specification,

, or

denotes a bond connected to another substituent, and a direct bond denotes a case in which a separate atom does not exist in the portion represented by L .

In the present specification, (meth) acryl is meant to include both acryl and methacryl. For example, the (meth)acryloyl group may include both an acryloyl group and a methacryloyl group. In addition, (meth)acrylate may include both acrylate and methacrylate.

In the present specification, the alkyl group is a monovalent functional group derived from an alkane, and may be straight-chain or branched, and the number of carbon atoms in the straight-chain alkyl group is not particularly limited, but is preferably 1 to 20. In addition, the number of carbon atoms of the branched chain 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, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl- propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptan-4-yl, and the like. The alkyl group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.

In the present specification, the aryl group is a monovalent functional group derived from arene, 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. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto. The aryl group may be substituted or unsubstituted, and when substituted, examples of the substituent are the same as described above.

Hereinafter, the present invention will be described in more detail.

1. 감광성 엘리먼트1. Photosensitive element

According to one embodiment of the invention, a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, wherein the film sample in which the photosensitive resin layer is laminated on the substrate is immersed in the palladium plating solution for 60 minutes and then the residual palladium plating solution is immersed in the copper-clad laminate sample for 5 minutes A photosensitive element having an obtained palladium plating layer thickness of 0.01 mu m or more can be provided.

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

As a specific example of the polymer substrate, an anti-blocking layer is formed by an in-line coating method in which an unstretched polyester film is uniaxially stretched, a crude liquid containing a binder resin and organic particles is applied on one surface of the polymer substrate and the remaining uniaxial stretching is performed. film can be mentioned.

In the polymer substrate, an in-line coating method was selected instead of adding an anti-blocking agent, which has been usually added in consideration of running properties and winding characteristics during manufacturing, and an organic particle layer using substitute particles that do not impair transparency. did it

Here, examples of organic particles used as particles that do not impair transparency while considering running properties and winding characteristics include methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, and normal butyl methyl methacrylate. Acrylic particles, such as a copolymer or terpolymer of acrylic acid or methacrylic acid; olefinic particles such as polyethylene, polystyrene, and polypropylene; acrylic and olefinic copolymers; Alternatively, organic particles such as multi-layered multi-component particles in which homopolymer particles are formed and then a different type of monomer is coated on the layer may be used.

These organic particles should be specifically spherical and have a difference in refractive index with the binder resin. Here, the 'spherical' is defined as that the ratio of the minor axis (a) to the major axis (b) is 0.5 < a/b < 2 in the ellipse, and the relation with the diagonal line d in the rectangle is d2≤a2+b2. And in the cube, the relationship between the axis f with the longest distance between vertices and the c axis other than the a and b axes is defined as f2≤c2+a2+b2. The shape of the particles should be spherical, which is preferable in terms of running properties.

And, it is characterized in that the difference in refractive index between the organic particles and the binder resin is 0.05 or less. If the difference in refractive index is greater than 0.05, Haze is increased. This means that there is a lot of scattered light, and when there is a lot of such scattered light, the smoothing effect of the sidewall is lowered. It also depends on the size and quantity of organic particles. It is preferable that the organic particles have an average particle diameter of about 0.5 μm to 5 μm, and when it is smaller than this, running characteristics and winding characteristics are deteriorated, and when it is larger than 5 μm, haze is increased, and is undesirable in consideration of the occurrence of a drop-off problem. The content of the organic particles is preferably 1 to 10% by weight based on the total amount with the binder resin.

If the content of organic particles is less than 1% by weight based on the total amount with the binder resin, the anti-blocking effect is insufficient and it is weak to scratches, and the winding characteristics and running characteristics are deteriorated. There may be a problem with this getting worse.

On the other hand, inorganic particles may be added in addition to the organic particles as described above. In this case, it is not preferable to add an inorganic anti-blocking agent that has been commonly used, and colloidal silica having a particle size of 100 nm or less is preferably added. The content is preferably included in an amount of 10 parts by weight or less based on 100 parts by weight of the binder resin. When the particle size and content as described above are satisfied, sidewall defects or crater-like grooves caused by the anti-blocking layer in pattern formation using dry film photoresist may not be generated.

As a binder resin that acts as an adhesive for applying such organic particles to an unstretched polyester film, one having good compatibility with organic particles may be used. Examples of such resins include unsaturated polyester, methyl methacrylate, acrylic resins such as ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, normal butyl methyl methacrylate, acrylic acid, a copolymer or terpolymer of methacrylic acid; urethane-based resin; epoxy resin; Or a melamine-type resin etc. are mentioned, Preferably it is an acrylic resin.

The solvent that can be used in preparing the binder resin and organic particles is preferably water.

In this way, a crude liquid containing organic particles in a binder resin is uniaxially stretched on an unstretched polyester film obtained by melt-extrusion of PET pellets, and then is applied on the uniaxially stretched film. The application may be performed on at least one surface of the uniaxially oriented film, and the thickness thereof is preferably about 30 nm to 200 nm based on the thickness after final drying. If the crude liquid containing organic particles is applied thinner than 30 nm on the uniaxially stretched film, the organic particles are easily removed and are vulnerable to scratches, and there is a problem that white powder is generated. For this reason, in-line coating with a fast coating speed, coating streaks occur in the coating direction.

As described above, by the in-line coating method, the polymer substrate obtained by applying organic particles instead of a general anti-blocking agent has excellent transparency due to organic particles having excellent light transmittance while maintaining winding characteristics and running characteristics due to the particle layer. It is a base film.

Lamination of the photosensitive resin layer is performed on the opposite side of the layer containing organic particles in the polymer substrate. There is no crater-shaped flaw that appears as the base film is laminated. Since the particles such as silica are larger in size than organic particles and their distribution is throughout the base film, the effect of silica appears in the portion adjacent to the photosensitive resin layer, although insignificant.

On the other hand, in the polymer substrate used in the present invention, the size of the organic particles is 0.5㎛ to 5㎛, the organic particle layer is not adjacent to the photosensitive resin layer, there is no physical influence of the organic particles. In addition, by using organic particles having excellent light transmittance, defects of the sidewall can be reduced and other circuit properties are not impaired.

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 serves as a protective cover to protect the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface of the photosensitive resin layer on which the polymer substrate is not formed. The protective film serves to protect the photosensitive resin layer from the outside, and when the photosensitive element is applied in a post-process, it is easily detached, and it requires proper release property and adhesiveness so as not to be released when stored and distributed.

As the protective film, various plastic films can be used, for example, an acrylic film, a polyethylene (PE) film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a polynorbornene (PNB) film, a cyclo It may include at least one plastic film selected from the group consisting of an olefin polymer (COP) film, and a polycarbonate (PC) film. The thickness of the protective film is not particularly limited, but can be freely adjusted within, for example, 0.01 μm to 1 mm.

The photosensitive element has a palladium plating layer thickness of 0.01 µm or more, or 0.05 μm or more, or 0.1 μm or more, or 0.01 μm or more and 0.15 μm or less, or 0.05 μm or more and 0.15 μm or less, or 0.1 μm or more and 0.15 μm or less.

In addition, the photosensitive element is a nickel-phosphorus plating solution obtained by immersing a copper-clad laminate sample for 28 minutes with respect to the residual nickel-phosphorus plating solution after immersing the film sample in which the photosensitive resin layer is laminated on the substrate for 38 minutes. The plating layer thickness is 3.9 μm or more, or 3.95 μm or more, or 3.9 μm or more and 4.0 μm or less, or 3.95 μm or more and 4.0 μm or less, or the dry film photoresist is a film sample in which the photosensitive resin layer is laminated on a substrate. With respect to the residual gold plating solution after immersion in the plating solution for 98 minutes, the thickness of the gold plating layer obtained by immersing the copper-clad laminate sample for 11 minutes is 0.11 μm or more, or 0.11 μm or more and 0.13 μm or less, or 0.12 μm or more, or 0.12 μm or more, or 0.13 μm or more may be below.

The residual palladium plating solution is a palladium plating solution contaminated with the photosensitive resin layer component, and the palladium plating layer thickness obtained by immersing a copper-clad laminate sample in the contaminated residual palladium plating solution for 5 minutes is the thickness of the photosensitive resin layer laminated body. This is to evaluate the contamination of the plating solution by the dry film photoresist during palladium plating. As the contamination of the plating solution increases, the thickness of the palladium plating layer obtained by immersing the copper-clad laminate sample in the palladium plating solution for 5 minutes becomes significantly lower. On the other hand, as the plating solution is less contaminated, the thickness of the palladium plating layer obtained by immersing the copper-clad laminate sample in the contaminated palladium plating solution for 5 minutes becomes significantly higher. In the actual electroless palladium process, contamination accumulates in a large amount of dry film photoresist, and palladium is added for continuous plating, and other refining processes are difficult. Therefore, it is very important to evaluate the palladium plating solution contamination level of dry film photoresist.

That is, in the palladium plating, first palladium plating using the film on which the photosensitive resin layer is laminated is performed, and after the first plating is completed, a second palladium plating is performed on a new copper-clad laminate sample in the contaminated palladium plating solution. , The contamination of the plating solution by the dry film photoresist was evaluated with respect to the thickness of the palladium plating layer during the second plating.

Therefore, with respect to the residual palladium plating solution after immersing the film sample in which the photosensitive resin layer is laminated on the substrate for 60 minutes, the palladium plating layer thickness obtained by immersing the copper-clad laminate sample for 5 minutes is less than the target value of 0.1 μm. Through the excessive reduction, it is possible to evaluate the degree of contamination of the plating solution. If the plating layer is plated with a thickness lower than the target value in the evaluation of the contamination level, the contamination of the electroless palladium plating solution in the actual process is severe and it is difficult to repeatedly use the plating solution more than 0.5 MTO, which may adversely affect process efficiency and economic feasibility.

The method for obtaining the palladium plating layer thickness is not particularly limited, and various known plating layer thickness measurement methods can be applied without limitation, for example, it can be measured through an XRF plating thickness meter (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 the photosensitive resin layer is laminated on the substrate in a palladium plating solution for 60 minutes will be described as follows.

First, the copper-clad laminate sample on which the photosensitive resin layer is laminated may be immersed in a nickel-phosphorus plating solution to perform elution. Specific conditions for immersing the copper-clad laminate sample on which the photosensitive resin layer is laminated in a nickel-phosphorus plating solution are not particularly limited, but for example, a nickel-phosphorus-containing plating solution is added to 130 ml of NPR-4 (Uemura) plating solution at 65 ° C. Under the conditions of 95 ° C or higher, for 20 minutes or more and 60 minutes or less, the cross-sectional area of 600 cm2 or more and 700 cm2 or less, or 640 cm2 or more 660 cm2 or less, or 645 cm2 or more 655 cm2 or less, or 650 cm2 can The cross-sectional area means the area of the cross-section obtained by cutting the sample in a direction perpendicular to the thickness increasing direction of the sample.

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

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. 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, but for example, 30 ml of a TPD-21 (Uemura) plating solution with a palladium plating solution at 30°C or more and 70°C. It can be eluted by immersing the sample having a cross-sectional area of 600 cm 2 or more and 700 cm 2 or less, or 640 cm 2 or more 660 cm 2 or less, or 645 cm 2 or more 655 cm 2 or less, or 650 cm 2 for a minute or more and 90 minutes or less.

Meanwhile, the copper-clad laminate sample on which the palladium-plated photosensitive resin layer is laminated may be immersed in a gold plating solution and eluted. 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, but for example, in 130 ml of TWX-40 (Uemura) plating solution as a gold plating solution, under the conditions of 65 ℃ or more and 95 ℃ or less. For 50 minutes or more and 150 minutes or less, the sample having a cross-sectional area of 600 cm 2 or more and 700 cm 2 or less, or 640 cm 2 or more 660 cm 2 or less, or 645 cm 2 or more 655 cm 2 or less, or 650 cm 2 It can be immersed and eluted.

On the other hand, with respect to the residual palladium plating solution, a more specific example of the method of measuring the thickness of the palladium plating layer obtained by immersing the copper-clad laminate sample for 5 minutes will be described as follows.

First, the copper-clad laminate sample may be immersed in the residual nickel-phosphorus plating solution. The specific conditions for immersing the copper-clad laminate sample in the residual nickel-phosphorus plating solution are not particularly limited, but for example, in 130 ml of the residual NPR-4 (Uemura) plating solution at 65 ℃ or more and 95 ℃ or less for 15 minutes or more 45 A copper-clad laminate sample having a cross-sectional area of 1 cm2 or more and 10 cm2 or less, or 4 cm2 or more and 6 cm2 or less, or 4.5 cm2 or more and 5.5 cm2 or less, or 5 cm2 can be immersed for a minute or less. The cross-sectional area means the area of the cross-section obtained by cutting the sample in a direction perpendicular to the thickness increasing direction of the sample.

If necessary, the sample may be immersed in an aqueous catalyst solution prior to immersion in the nickel-phosphorus plating solution, and specific conditions are not particularly limited, but, for example, using CATA NC-20 (MK Chem&Tech) as a palladium catalyst The sample may be immersed for 90 seconds under conditions of 10 °C or higher and 40 °C or lower.

When measuring the thickness of the palladium plating layer, the exposure conditions are 20mJ/cm ² or more and 200mJ/cm ² or less, or 50mJ/cm ² or more and 100mJ/cm ² or less by using an exposure machine. UV rays may be irradiated. The exposure time may 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, an aqueous alkali solution having a concentration of 0.5 wt% or more and 1.5 wt% or less, or 0.9 wt% or more and 1.1 wt% or less may be used. The pH of the aqueous alkali solution may be in the range of 9 or more and 11 or less, and the temperature may be adjusted according to the developability of the photosensitive resin layer. Specific examples of the aqueous alkali solution include sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium hydroxide aqueous solution, and the like.

For the development, a method of bringing the aqueous alkali solution into contact with the photosensitive resin layer may be used, and specific examples of the contact method may include spraying or immersion. The developing time may be 30 seconds or more and 10 minutes or less, or 30 seconds or more and 2 minutes or less.

In this case, the photosensitive element was obtained by immersing the copper-clad laminate sample for 28 minutes with respect to the residual nickel-phosphorus plating solution after immersing the film sample in which the photosensitive resin layer was laminated on the substrate for 38 minutes in the nickel-phosphorus plating solution. The plating layer thickness may be 3.9 μm or more, or 3.95 μm or more, or 3.9 μm or more and 4.0 μm or less, or 3.95 μm or more and 4.0 μm or less.

Next, the nickel-plated copper-clad laminate sample may be plated by immersion in the residual palladium plating solution. The specific conditions for immersing the nickel-phosphorus plated copper clad laminate sample in the residual palladium plating solution are not particularly limited, but for example, in 130 ml of the residual TPD-21 (Uemura) plating solution, 2 The sample having a cross-sectional area of 1 cm2 or more and 10 cm2 or less, or 4 cm2 or more and 6 cm2 or less, or 4.5 cm2 or more and 5.5 cm2 or less, or 5 cm2 may be immersed and plated for at least 10 minutes.

Meanwhile, the palladium-plated copper-clad laminate sample may be immersed in a residual gold plating solution to perform plating. Specific conditions for immersing the palladium-plated copper-clad laminate sample in the residual gold plating solution are not particularly limited, but for example, 130 ml of residual TWX-40 (Uemura) plating solution at 65°C or higher and 95°C or lower for 5 minutes The sample having a cross-sectional area of 1 cm 2 or more and 10 cm 2 or less, or 4 cm 2 or more 6 cm 2 or less, or 4.5 cm 2 or more and 5.5 cm 2 or less, or 5 cm 2 can be immersed and eluted for 20 minutes or more.

In this case, the photosensitive element is 0.11 μm or more, or 0.11 μm obtained by immersing the copper-clad laminate sample for 11 minutes in the gold plating solution remaining after the film sample in which the photosensitive resin layer is laminated on the substrate is immersed in the gold plating solution for 98 minutes. It may be 0.13 μm or more, or 0.12 μm or more, or 0.12 μm or more and 0.13 μm or less.

Meanwhile, the film sample in which the photosensitive resin layer is laminated on the substrate may be a laminate in which the photosensitive resin layer is laminated on any substrate, and an example of the substrate is copper having a thickness of 10 μm or more and 100 mm or less. and a copper clad laminate in which the layer is located on the surface.

The cross-sectional area of the film sample in which the photosensitive resin layer is laminated on the substrate may be 600 cm2 or more and 700 cm2 or less, or 640 cm2 or more and 660 cm2 or less, or 645 cm2 or more and 655 cm2 or less.

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

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

The photosensitive resin layer may include a dried product or a cured product of the photosensitive resin composition. The said dried material means the substance obtained through the drying process of the photosensitive resin composition. The cured product means a substance obtained through a curing step of the photosensitive resin composition. The thickness of the photosensitive resin layer is not particularly limited, but can be freely adjusted within the range of, for example, 0.01 μm to 1 mm.

The photosensitive resin layer includes an alkali developable binder resin, a photoinitiator, and a photopolymerizable compound, wherein the photopolymerizable compound is a penta-type (meth)acrylate-based compound having five (meth)acryloyl groups and seven or more A photosensitive resin composition comprising at least one selected from the group consisting of polyfunctional (meth)acrylate-based compounds having a (meth)acryloyl group may be included.

The present inventors claim that the photosensitive resin composition is a photopolymerizable compound, a penta-type (meth) acrylate-based compound having five (meth) acryloyl groups, and a polyfunctional (meth) acrylate having seven or more (meth) acryloyl groups. By including a compound or a mixture of two or more thereof, it is confirmed through experiments that the effect of enabling plating of sufficient thickness by reducing contamination of metal plating solutions such as palladium plating solution or nickel-phosphorus plating solution can be realized completed.

The alkali developable binder resin may include a repeating unit represented by the following formula (E), a repeating unit represented by the following formula (F), a repeating unit represented by the following formula (G), and a repeating unit represented by the following formula (H).

[Formula E]

In Formula E, R ₁ is hydrogen or alkyl having 1 to 10 carbon atoms, R ₂ is alkyl having 1 to 10 carbon atoms, Ar is aryl having 6 to 20 carbon atoms, n is an integer from 1 to 20,

[Formula F]

In Formula F, R ₃ is hydrogen or alkyl having 1 to 10 carbon atoms,

[Formula G]

In Formula G, R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms, R ₅ is alkyl having 1 to 10 carbon atoms,

[Formula H]

In the above formula (H), Ar is aryl having 6 to 20 carbon atoms.

Specifically, the alkali developable binder resin is a random copolymer of the repeating unit represented by the formula E, the repeating unit represented by the formula F, the repeating unit represented by the formula G, and the repeating unit represented by the formula H may include

By including the repeating unit represented by the formula E in the alkali developable binder resin to increase the hydrophobicity of the alkali developable binder resin through the benzene structure included in the repeating unit represented by the formula E, the photosensitivity In the developing process of dry film photoresist using the resin composition, it suppresses the generation of foam and exhibits excellent developability, and improves substrate adhesion to ensure proper physical properties (resolution, fine wire adhesion, etc.).

In Formula E, R ₁ may be any one of hydrogen or alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms include methyl.

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

In Formula E, Ar is an aryl having 6 to 20 carbon atoms, and specific examples of the aryl having 6 to 20 carbon atoms include phenyl.

The repeating unit represented by Formula E may be a repeating unit derived from a monomer represented by Formula E-1.

[Formula E-1]

In Formula E-1, R ₁ is hydrogen or alkyl having 1 to 10 carbon atoms, R ₂ is alkyl having 1 to 10 carbon atoms, Ar is aryl having 6 to 20 carbon atoms, and n is an integer from 1 to 20 . In Formula E-1, R ₁ , R ₂ , Ar, and n are the same as those described above in Formula E.

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

The repeating unit represented by Formula E is 5 mol% or more and 40 mol% or less, or 5 mol% or more and 30 mol% or less, or 5 based on 100 mol% of the total repeating unit molar content contained in the alkali developable binder resin. It may be contained in mol% or more and 25 mol% or less, or 10 mol% or more and 25 mol% or less.

In Formulas F to 14, R ₃ and R ₄ are the same as or different from each other, and each independently represents hydrogen or alkyl having 1 to 10 carbon atoms, R ₅ is alkyl having 1 to 10 carbon atoms, and Ar is 6 to 20 carbon atoms. is the aryl of

In Formulas F to 14, R ₃ and R ₄ are the same as or different from each other, and each independently may be any one of hydrogen or alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms include methyl can be heard

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

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

The repeating unit represented by the formula F may be a repeating unit derived from a monomer represented by the following formula F-1.

[Formula F-1]

In Formula F-1, R ₃ is hydrogen or alkyl having 1 to 10 carbon atoms. In Formula F-1, the contents of R ₃ are the same as those described above in Formula F. Specific examples of the monomer represented by Formula F-1 may include methacrylic acid (MAA).

The repeating unit represented by the formula G may be a repeating unit derived from a monomer represented by the following formula G-1.

[Formula G-1]

In Formula G-1, R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms, and R ₅ is alkyl having 1 to 10 carbon atoms. In Formula G-1, R ₄ and R ₅ are the same as described above in Formula G. A specific example of the monomer represented by Formula G-1 may be methylmethacrylate (MMA).

The repeating unit represented by the formula (H) may be a repeating unit derived from a monomer represented by the following formula (H-1).

[Formula H-1]

In Formula H-1, Ar is aryl having 6 to 20 carbon atoms. In Formula H-1, the content of Ar is the same as described above in Formula H. Specific examples of the monomer represented by Formula H-1 may include styrene (Styrene, SM).

The alkali developable binder resin is 20 mol% or more and 60 mol% or more, or 20 mol% or more of the repeating unit represented by Formula F, based on 100 mol% of the total repeating unit molar content contained in the alkali developable binder resin. 50 mol% or less, or 30 mol% or more and 40 mol% or less.

In addition, the alkali developable binder resin is based on 100 mol% of the total repeating unit molar content contained in the alkali developable binder resin, 1 mol% or more and 30 mol% or less of the repeating unit represented by Formula G, or 5 mol % or more and 30 mol% or less, and 30 mol% or more and 60 mol% or less of the repeating unit represented by Formula H, or 30 mol% or more and 50 mol% or less, or 30 mol% or more and 40 mol% or less.

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

As such, as the content of the repeating unit represented by the hydrophobic formula H increases, the degree of hydrophobicity of the alkali developable binder resin also increases, thereby preventing the generation of bubbles in the developing process of the dry film photoresist using the photosensitive resin composition. can be suppressed

In addition, the molar ratio of the repeating unit represented by the formula (G) to 100 moles of the repeating unit represented by the formula (E) is 16 moles or less, or 15.5 moles or less, or 15 moles or less, or 0.1 moles or more and 16 moles or less, or 0.1 mol or more and 15.5 mol or less, or 0.1 mol or more and 15 mol or less, or 10 mol or more and 16 mol or less, or 10 mol or more and 15.5 mol or less, or 10 mol or more and 15 mol or less.

The alkali developable binder resin may have a weight average molecular weight of 30,000 g/mol or more and 150,000 g/mol or less, and a glass transition temperature of 20°C or more and 150°C or less. Accordingly, coatability, traceability, and mechanical strength of the resist itself after circuit formation of the dry film photoresist may be improved.

In this specification, the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the polystyrene equivalent weight average molecular weight measured by the GPC method, a commonly known analyzer, a detector such as a differential refraction detector, and a column for analysis may be used, and the temperature at which it is normally applied Conditions, solvents, and flow rates can be applied.

As a specific example of the measurement conditions, the alkali developable binder resin is dissolved in tetrahydrofuran so as to have a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on solid content) to have a 0.45㎛ pore size Syringe After filtration using a filter, 20 μl was injected into GPC, tetrahydrofuran (THF) was used as the mobile phase of GPC, and was introduced at a flow rate of 1.0 mL/min, and the column was Agilent PLgel 5㎛ Guard (7.5 x 50 mm) and Agilent PLgel 5㎛ Mixed D (7.5 x 300 mm) were connected in series, and the Agilent 1260 Infinity Ⅱ system, RI Detector was used as a detector to measure at 40 ℃.

For this, polystyrene standard samples (STD A, B, C, D) obtained by dissolving polystyrene having various molecular weights as follows at a concentration of 0.1 (w/w)% in tetrahydrofuran were filtered with a 0.45㎛ pore size Syringe Filter and then GPC The value of the weight average molecular weight (Mw) of the alkali developable binder resin was obtained using a calibration curve formed by injecting into the .

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

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

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

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

The glass transition temperature was compared with the reference and the binder polymer in a Differential Scanning Calorimeter (DSC) (Perkin-Elmer, DSC-7). The temperature setting can be measured by maintaining the temperature at 20°C for 15 minutes, and then increasing the temperature to 200°C at a heating rate of 1°C/min.

The alkali developable binder resin may have an acid value of 120 mgKOH/g or more and 200 mgKOH/g or less, or 140 mgKOH/g or more and 160 mgKOH/g or less. For the acid value, about 1 g of the alkali developable binder resin was sampled, dissolved in 50 ml of a mixed solvent (MeOH 20%, Acetone 80%), two drops of 1%-phenolphthalein indicator were added, and then titrated with 0.1N-KOH to measure the acid value.

The alkali developable binder resin is included in an amount of 20 wt% or more and 80 wt% or less, based on the total weight of the photosensitive resin composition on a solid basis. When the content of the alkali developable binder resin is within the above range, it is possible to obtain an effect of strengthening the fine wire adhesion after circuit formation. The solid content, which is the basis of the weight, refers to the remaining components excluding the solvent in the photosensitive resin composition.

The content of the alkali developable binder resin may be 40 wt% or more and 70 wt% or less based on the total weight of the photosensitive resin composition. If the content of the alkali developable binder resin is less than 40% by weight with respect to the total photosensitive resin composition, there is a disadvantage of causing defects such as short circuit due to contamination of the developing end, and when it exceeds 70% by weight, adhesion and resolution, etc. There is a problem in that the circuit properties are poor.

The photopolymerization initiator included 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 the dry film photoresist.

Examples of the compound usable as the photopolymerization initiator include anthraquinone derivatives such as 2-methyl anthraquinone and 2-ethyl anthraquinone; and benzoin derivatives such as benzoin methyl ether, benzophenone, phenanthrene quinone, and 4,4'-bis-(dimethylamino)benzophenone.

In addition, 2,2'-bis(2-chlorophenyl)-4,4'-5,5'-tetraphenylbisimidazole, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2- Diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-[4-morph Polynophenyl] butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-[4-(2- Hydroxymethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethyl thioxanthone, 3, 3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1 -(4-Dodecylphenyl)-2hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4- Dimethylaminobenzoate, Butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzylketone dimethylacetal, benzyl Ketone β-methoxy diethylacetal, 1-phenyl-1,2-propyldioxime-o,o'-(2-carbonyl)ethoxyether, methyl o-benzoylbenzoate, bis[4-dimethylaminophenyl ) ketone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-part Toxybenzoin, isobutoxybenzoin, tert-butoxybenzoin, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthi A compound selected from oxanthone, 2-isopropylthioxanthone, dibenzosuberone, α, α-dichloro-4-phenoxyacetophenone, and pentyl 4-dimethylaminobenzoate may be used as the photopolymerization initiator, but is limited thereto it is not

The photopolymerization initiator is included in an amount of 1 wt% or more and 10 wt% or less, based on the total weight of the photosensitive resin composition based on the solid content. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity may be obtained. The solid content, which is the basis of the weight, refers to the remaining components excluding the solvent in the photosensitive resin composition.

When the content of the photopolymerization initiator is less than 1% by weight, there is a disadvantage that the production efficiency is extremely reduced because the light efficiency is low and a large amount of exposure is required, and when it exceeds 10% by weight, the film is brittle. This increases and there is a problem of causing defects such as short circuit.

The photopolymerizable compound has resistance to a developer after UV exposure to enable pattern formation.

The photopolymerizable compound is selected from the group consisting of a penta-type (meth) acrylate-based compound having 5 (meth) acryloyl groups and a polyfunctional (meth) acrylate-based compound having 7 or more (meth) acryloyl groups It may include one or more types.

That is, the photopolymerizable compound is a penta-type (meth) acrylate-based compound having 5 (meth) acryloyl groups, and a polyfunctional (meth) acrylate-based compound 1 having 7 or more (meth) acryloyl groups. species, or a mixture of two or more thereof.

The photosensitive resin composition of the embodiment is a penta-type (meth) acrylate-based compound having five (meth) acryloyl groups and a polyfunctional (meth) acrylate-based compound having seven or more (meth) acryloyl groups. By including at least one selected from the group consisting of, it is possible to realize an effect of enabling plating of a sufficient thickness by reducing contamination of a metal plating solution such as a palladium plating solution or a nickel-phosphorus plating solution.

The weight ratio of the penta-type (meth)acrylate-based compound having five (meth)acryloyl groups and the polyfunctional (meth)acrylate-based compound having seven or more (meth)acryloyl groups is 99:1 to 1 It could be :99.

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

The penta-type (meth)acrylate-based compound may further include one hydroxyl group. Specifically, the penta-type (meth)acrylate-based compound may be a compound represented by the following formula (A).

[Formula A]

In Formula A, 5 of T ₁ to T ₆ are the same as or different from each other and each independently represent a (meth)acryloyl group, and the other one is hydrogen. More specifically, in Formula 1, T ₁ to T ₅ may be an acryloyl group, and T ₆ may be hydrogen.

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

The polyfunctional (meth)acrylate-based compound having 7 or more (meth)acryloyl groups has 7 or more, or 7 or more and 20 or less, or 7 or more and 10 or less (meth)acryloyl groups. can Each of the seven or more (meth)acryloyl groups may be the same as or different from each other. The polyfunctional (meth)acrylate-based compound includes all (meth)acrylate compounds or derivatives thereof having 7 or more, or 7 or more and 20 or less, or 7 or more and 10 or less (meth)acryloyl groups. may include

Specifically, the polyfunctional (meth) acrylate-based compound may be a compound represented by the following Chemical Formula B.

[Formula B]

In Formula B, T ₇ to T ₁₂ are the same as or different from each other and each independently represent a (meth)acryloyl group, T ₁₂ is hydrogen or a (meth)acryloyl group, and t is an integer of 2 to 10.

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

Specific examples of the compound represented by Formula B include (1) In Formula B, T ₇ to T ₁₁ are an acryloyl group, T ₁₂ is hydrogen, and t is an integer of 2 7 (meth)acryloyl groups (2) In the above formula (B), T ₇ to T ₁₁ are an acryloyl group, T ₁₂ is an acryloyl group, and t is an integer of 2, a compound having 8 (meth)acryloyl groups, (3) In Formula B, T ₇ to T ₁₁ are an acryloyl group, T ₁₂ is hydrogen, and t is a compound having 9 (meth)acryloyl groups that are an integer of 3, (4) In Formula B, T ₇ to T ₁₁ is an acryloyl group, T ₁₂ is hydrogen, and t is an integer of 3, and the compound which has 10 (meth)acryloyl groups is mentioned.

The polyfunctional (meth)acrylate-based compound having 7 or more (meth)acryloyl groups may be one specific example corresponding to the compound represented by Formula B, or a mixture of two or more thereof.

In particular, the polyfunctional (meth)acrylate-based compound having 7 or more (meth)acryloyl groups includes a mixture of two types of a compound in which t is 2 in Formula B and a compound in which t is 3 in Formula B. In this case, with respect to 100 parts by weight of the compound in which t is 2 in Formula B, the content of the compound in which t is 3 in Formula B is 1 part by weight or more and 40 parts by weight or less, or 5 parts by weight or more and 30 parts by weight or less, Or 7 parts by weight or more and 28 parts by weight or less.

The photopolymerizable compound may further include a hexa-type (meth)acrylate-based compound having six (meth)acryloyl groups. That is, the photopolymerizable compound is a penta-type (meth) acrylate-based compound having 5 (meth) acryloyl groups and a polyfunctional (meth) acrylate-based compound having 7 or more (meth) acryloyl groups. In addition to at least one selected from the above, a hexa-type (meth)acrylate-based compound having six (meth)acryloyl groups may be further included.

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

Specifically, the hexa-type (meth) acrylate-based compound may be a compound represented by the following formula (C).

[Formula C]

In Formula C, T ₁₂ to T ₁₇ are the same as or different from each other and each independently represent a (meth)acryloyl group. More specifically, in Formula 3, T ₁₂ to T ₁₇ are acryloyl groups.

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

As the alkylene glycol-based di(meth)acrylate, a compound represented by the following formula (D) may be used.

[Formula D]

In Formula D, l+n is an integer of 2 or 3, and m is an integer of 12 to 18.

The compound represented by Formula D may improve the hydrophobicity of the photosensitive resin composition to significantly increase resistance to a developer and a plating solution, and shorten the peeling time of the cured film.

The amount of the compound represented by Formula D may be 70 wt% or more and 90 wt% or less, or 75 wt% or more and 85 wt% or less, based on the total solid weight of the photosensitive resin composition.

If the content of the compound represented by Formula D is less than 70% by weight based on the total solid weight of the photosensitive resin composition, the effect of the addition of the compound represented by Formula 15 is insufficient, and when it exceeds 90% by weight, hydrophobicity This increase may cause a problem in that the development time in the development process after exposure is rapidly increased.

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

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

Examples of the bisphenol-based di(meth)acrylate containing more than 8 moles and not more than 16 moles of ethylene oxide include Miramer M2100 (BPA(EO) ₁₀ DA, Bisphenol A (EO) ₁₀ manufactured by Miwon Specialty Chemical Co., Ltd.) Diacrylate), Miramer M2200 (BPA(EO) ₂₀ DA, Bisphenol A (EO) ₂₀ Diacrylate), Miramer M2101 (Bisphenol A (EO) ₁₀ Dimethacrylate), etc. can be used.

More specifically, with respect to 100 parts by weight of the bisphenol-based di(meth)acrylate containing more than 8 moles and not more than 16 moles of ethylene oxide per molecule, bisphenol-based di(meth)acryl containing 8 moles or less of ethylene oxide per molecule The rate may be included in an amount of 100 parts by weight or less, 50 parts by weight or less, 1 part by weight or more and 100 parts by weight or less, or 1 part by weight or more and 50 parts by weight or less.

The content of the photopolymerizable compound may be included in an amount of 10% by weight or more and 70% by weight or less, based on the total weight of the photosensitive resin composition based on the solid content. When the content of the photopolymerizable compound is within the above range, it is possible to obtain an effect of enhancing photosensitivity, resolution, adhesion, and the like. The solid content, which is the basis of the weight, refers to the remaining components excluding the solvent in the photosensitive resin composition.

The photosensitive resin composition may contain 20 wt% or more and 80 wt% or less of an alkali developable binder resin, 1 wt% or more and 10 wt% or less of a photopolymerization initiator, and 10 wt% or more and 70 wt% or less of a photopolymerizable compound based on the solid content have.

The photosensitive resin composition may further include a solvent. The solvent is generally selected from among methyl ethyl ketone (MEK), methanol, THF, toluene, and acetone, and the solvent is not particularly limited, and the content is also of the photopolymerization initiator, alkali developable binder resin and photopolymerizable compound. It may be contained by adjusting according to the content.

In addition, the photosensitive resin composition may further include other additives as necessary. Examples of the other additives include dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diallyl phthalate in the form of phthalic acid esters as plasticizers; triethylene glycol diacetate, tetraethylene glycol diacetate in the form of glycol esters; p-toluene sulfonamide, benzenesulfonamide, n-butylbenzenesulfonamide in acid amide form; triphenyl phosphate and the like can be used.

In order to improve the handleability of the said photosensitive resin composition, you may put a leuco dye or a coloring substance. Examples of the leuco dye include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, and fluoran dye. Especially, when leuco crystal violet is used, the contrast is favorable and it is preferable. In the case of containing the leuco dye, the content may be 0.01% by weight or more and 1% by weight or less in the photosensitive resin composition. From a viewpoint of expression of contrast, 0.01 weight% or more is preferable, and 1 weight% or less is preferable from a viewpoint of maintaining storage stability.

As the coloring material, for example, toluenesulfonic acid monohydrate, fuchsine, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green, Diamond Green, Basic Blue 20, etc. can be heard In the case of containing the coloring material, the added amount may be 0.001% by weight or more and 1% by weight or less in the photosensitive resin composition. At a content of 0.001% by weight or more, there is an effect of improving handling, and at a content of 1% by weight or less, there is an effect of maintaining storage stability.

In addition, other additives may further include a thermal polymerization inhibitor, a dye, a discoloring agent, an adhesion promoter, and the like.

Meanwhile, the photosensitive resin layer includes an alkali developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, and the alkali developable binder resin may contain a photosensitive resin composition including four or more polymers different from each other.

The present inventors experimented that the photosensitive resin composition contains at least four different polymers as an alkali developable binder resin, so that it has excellent peeling properties, and can achieve an effect to enable plating of sufficient thickness by reducing contamination of the plating solution. Through confirmation, the invention was completed.

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

Specifically, the alkali developable binder resin may include a first binder resin including a repeating unit represented by the following formula (1). 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 3 or more types of polymers different therefrom.

[Formula 1]

In Formula 1, R ₁ is hydrogen or alkyl having 1 to 10 carbon atoms, R ₂ is alkylene having 1 to 10 carbon atoms, Ar is aryl having 6 to 20 carbon atoms, and n is an integer from 1 to 20.

By including the repeating unit represented by Formula 1 in the first binder resin to increase the hydrophobicity of the first binder resin through the benzene structure included in the repeating unit represented by Formula 1, the photosensitive resin composition In the developing process of dry film photoresist using

In Formula 1, R ₁ may be any one of hydrogen or alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms include methyl.

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

In Formula 1, Ar is an aryl having 6 to 20 carbon atoms, and specific examples of the aryl having 6 to 20 carbon atoms include phenyl.

The repeating unit represented by Formula 1 may be a repeating unit derived from a monomer represented by Formula 1-1.

[Formula 1-1]

In Formula 1-1, R ₁ is hydrogen or alkyl having 1 to 10 carbon atoms, R ₂ is alkylene having 1 to 10 carbon atoms, Ar is aryl having 6 to 20 carbon atoms, and n is an integer from 1 to 20 to be. In Formula 1-1, R ₁ , R ₂ , Ar, and n are the same as described above in Formula 1 above.

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

The repeating unit represented by Formula 1 is 5 mol% or more and 40 mol% or less, or 5 mol% or more and 30 mol% or less, or 5 mol% based on 100 mol% of the total repeating unit molar content contained in the first binder resin. % or more and 25 mol% or less, or 10 mol% or more and 25 mol% or less.

The first binder resin may further include, in addition to the repeating unit represented by Chemical Formula 1, a repeating unit represented by the following Chemical Formula 2, a repeating unit represented by the following Chemical Formula 3, and a repeating unit represented by the following Chemical Formula 4.

[Formula 2]

In Formula 2, R ₃ is hydrogen or alkyl having 1 to 10 carbon atoms,

[Formula 3]

In Formula 3, R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms, R ₅ is alkyl having 1 to 10 carbon atoms,

[Formula 4]

In Formula 4, Ar is aryl having 6 to 20 carbon atoms.

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

In Formulas 2 to 4, R ₃ and R ₄ are the same as or different from each other, and each independently represents hydrogen or alkyl having 1 to 10 carbon atoms, R ₅ is alkyl having 1 to 10 carbon atoms, and Ar is 6 to 20 carbon atoms. is the aryl of

In Formulas 2 to 4, R ₃ and R ₄ are the same as or different from each other, and each independently may be any one of hydrogen or alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms include methyl can be heard

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

The repeating unit represented by Formula 2 may be a repeating unit derived from a monomer represented by Formula 2-1 below.

[Formula 2-1]

In Formula 2-1, R ₃ is hydrogen or alkyl having 1 to 10 carbon atoms. In Formula 2-1, the contents of R ₃ are the same as those described above in Formula 2 above. Specific examples of the monomer represented by Formula 2-1 may include methacrylic acid (MAA).

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.

[Formula 3-1]

In Formula 3-1, R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms, and R ₅ is alkyl having 1 to 10 carbon atoms. In Formula 3-1, R ₄ and R ₅ are the same as described above in Formula 3 above. A specific example of the monomer represented by Formula 3-1 may be methylmethacrylate (MMA).

The repeating unit represented by Chemical Formula 4 may be a repeating unit derived from a monomer represented by the following Chemical Formula 4-1.

[Formula 4-1]

In Formula 4-1, Ar is aryl having 6 to 20 carbon atoms. In Formula 4-1, the contents of Ar are the same as those described above in Formula 4 above. A specific example of the monomer represented by Formula 4-1 may include styrene (Styrene, SM).

The first binder resin is 20 mol% or more and 60 mol% or less, or 20 mol% or more and 50 mol% of the repeating unit represented by Formula 2, based on 100 mol% of the total repeating unit molar content contained in the first binder resin. % or less, or 30 mol% or more and 40 mol% or less.

In addition, the first binder resin is 1 mol% or more and 30 mol% or less, or 5 mol% or more of the repeating unit represented by Formula 3 based on 100 mol% of the total repeating unit molar content contained in the first binder resin. 30 mol% or less, and 30 mol% or more and 60 mol% or less, or 30 mol% or more and 50 mol% or less, or 30 mol% or more and 40 mol% or less of the repeating unit represented by Formula 4 may be included.

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

In addition, the molar ratio of the repeating unit represented by Formula 3 to 100 moles of the repeating unit represented by Formula 1 is 40 mol or less, or 35 mol or less, or 32 mol or less, or 0.1 mol or more and 40 mol or less, or 0.1 moles or more and 35 moles or less, or 0.1 moles or more and 32 moles or less, or 10 moles or more and 40 moles or less, or 10 moles or more and 35 moles or less, or 10 moles or more and 32 moles or less.

As such, as the content of the repeating unit represented by Chemical Formula 4, which is hydrophobic, increases, the degree of hydrophobicity of the first binder resin also increases, thereby suppressing the generation of bubbles in the developing process of the dry film photoresist using the photosensitive resin composition. can do.

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 a glass transition temperature of 20°C or more and 150°C or less. Accordingly, coatability, traceability, and mechanical strength of the resist itself after circuit formation of the dry film photoresist may be improved.

In this specification, the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a commonly known analyzer and a detector such as a differential refraction detector and a column for analysis may be used, and a temperature that is normally applied Conditions, solvents, and flow rates can be applied.

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 first binder resin may have an acid value of 120 mgKOH/g or more and 200 mgKOH/g or less, or 140 mgKOH/g or more and 160 mgKOH/g or less. For the acid value, about 1 g of the first binder resin was sampled, dissolved in 50 ml of a mixed solvent (MeOH 20%, Acetone 80%), two drops of 1%-phenolphthalein indicator were added, and then titrated with 0.1N-KOH to measure the acid value.

Meanwhile, the alkali developable binder resin may include a second binder resin including a repeating unit represented by the following Chemical Formula 5. 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 3 or more types of polymers different therefrom.

[Formula 5]

In Formula 5, R ₆ is hydrogen, and R ₇ is alkyl having 1 to 10 carbon atoms. Specific examples of the alkyl having 1 to 10 carbon atoms include butyl.

The second binder resin is, in addition to the repeating unit represented by Chemical Formula 5, 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 It may further include a repeating unit.

[Formula 6]

In Formula 6, R ₈ is hydrogen,

[Formula 7]

In Formula 7, R ₉ is an alkyl having 1 to 10 carbon atoms,

[Formula 8]

In Formula 8, R ₁₀ is an alkyl having 1 to 10 carbon atoms, R ₁₁ is an alkyl having 1 to 10 carbon atoms,

[Formula 9]

In Formula 9, Ar is aryl having 6 to 20 carbon atoms.

In Formulas 6 to 9, specific examples of the alkyl having 1 to 10 carbon atoms may include methyl.

The second binder resin may have a weight average molecular weight of 30,000 g/mol or more and 150,000 g/mol or less, and a glass transition temperature of 20°C or more and 150°C or less. Accordingly, coatability, traceability, and mechanical strength of the resist itself after circuit formation of the dry film photoresist may 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 be 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 It may include a random copolymer of repeating units.

More specifically, the second binder resin is 5 mol% or more and 20 mol% or less of the repeating unit represented by Chemical Formula 5, 5 mol% or more of the repeating unit represented by Chemical Formula 6, based on 100 mol% of the total repeating unit 20 mol% or less, 5 mol% or more and 20 mol% or less of the repeating unit represented by Chemical Formula 7, 40 mol% or more and 80 mol% or less of the repeating unit represented by Chemical Formula 8, and 5 mol% or more of the repeating unit represented by Chemical Formula 9 15 mol% or less.

Meanwhile, the alkali developable binder resin may include a third binder resin including 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. That is, the alkali developable binder resin may include the third binder resin; and 3 or more types of polymers different therefrom.

[Formula 10]

In Formula 10, R ₉ is an alkyl having 1 to 10 carbon atoms,

[Formula 11]

In Formula 11, R ₁₀ is an alkyl having 1 to 10 carbon atoms, R ₁₁ is an alkyl having 1 to 10 carbon atoms,

[Formula 12]

In Formula 12, Ar is aryl having 6 to 20 carbon atoms.

More specifically, the third binder resin is 20 mol% or more and 40 mol% or less of the repeating unit represented by Chemical Formula 10, 50 mol% or more of the repeating unit represented by Chemical Formula 11, based on 100 mol% of the total repeating unit 70 It may contain 5 mol% or more and 18 mol% or less of the repeating unit represented by the formula (12) in mol% or less.

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 a glass transition temperature of 30° C. or more and 160° C. or less. Accordingly, coatability, traceability, and mechanical strength of the resist itself after circuit formation of the dry film photoresist may be improved.

The second binder resin may have an acid value of 140 mgKOH/g or more 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.

Meanwhile, the alkali developable binder resin may include a fourth binder resin including a repeating unit represented by the following Chemical Formula 13. That is, the alkali developable binder resin may include the fourth binder resin; and 3 or more types of polymers different therefrom.

[Formula 13]

In Formula 13, R ₁₂ is hydrogen or alkyl having 1 to 10 carbon atoms, and R ₁₃ is alkylene having 1 to 10 carbon atoms.

In Formula 13, R ₁₂ may be any one of hydrogen or alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms include methyl.

In Formula 13, R ₁₃ is alkylene having 1 to 10 carbon atoms, and specific examples of the alkylene having 1 to 10 carbon atoms include methylene.

Since the fourth binder resin contains the repeating unit represented by Chemical Formula 13, it is possible to implement an effect of suppressing the dissolution of resist in the plating solution due to excellent developing characteristics and thermal curing by drying heat.

The fourth binder resin may further include, in addition to the repeating unit represented by Chemical Formula 13, 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.

[Formula 14]

In Formula 14, R ₁₄ is hydrogen or alkyl having 1 to 10 carbon atoms,

[Formula 15]

In Formula 15, R ₁₅ is hydrogen or alkyl having 1 to 10 carbon atoms, R ₁₆ is alkyl having 1 to 10 carbon atoms,

[Formula 16]

In Formula 16, Ar is aryl having 6 to 20 carbon atoms.

Specifically, the alkali developable binder resin is a random copolymer of the repeating unit represented by the formula 13, the repeating unit represented by the formula 14, the repeating unit represented by the formula 15, and the repeating unit represented by the formula 16 may include

In Formulas 14 to 16, R ₁₄ and R ₁₅ are the same as or different from each other, and each independently represents hydrogen or alkyl having 1 to 10 carbon atoms, R ₁₆ is alkyl having 1 to 10 carbon atoms, Ar is 6 to 20 carbon atoms. is the aryl of

In Formulas 14 to 16, R ₁₄ and R ₁₅ are the same as or different from each other, and each independently may be any one of hydrogen or alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms include methyl can be heard

R ₁₆ is alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms include methyl.

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 a glass transition temperature of 30° C. or more and 160° C. or less. Accordingly, coatability, traceability, and mechanical strength of the resist itself after circuit formation of the dry film photoresist may 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 is 15 mol% or more and 25 mol% or less of the repeating unit represented by Chemical Formula 13, and 30 mol% or more of the repeating unit represented by Chemical Formula 14, based on 100 mol% of the total repeating units. mol% or less, 15 mol% or more and 25 mol% or less of the repeating unit represented by Chemical Formula 15, and 20 mol% or more and 30 mol% or less of the repeating unit represented by Chemical Formula 16 may be contained.

Specifically, the alkali developable binder resin may include the above-described first binder resin; a second binder resin; third binder resin; and a fourth binder resin. More specifically, the photosensitive resin composition of one embodiment of the present invention is based on 100% by weight of the alkali developable binder resin, 40% by weight or more of the first binder resin 80% by weight, 0.1% by weight or more of the second binder resin 4% by weight, The third binder resin may be contained in an amount of 10 wt% or more and 20 wt% or more, and 5 wt% or more and 45 wt% or more of the fourth binder resin.

In particular, 10 parts by weight or more and 90 parts by weight or less of the fourth binder resin may be included with respect to 100 parts by weight of the first binder resin.

In addition, 500 parts by weight or more and 3000 parts by weight or less, and 600 parts by weight or more and 2700 parts by weight or less of the fourth binder resin may be included with respect to 100 parts by weight of the second binder resin.

As such, by containing the fourth binder resin in a specific amount, it is possible to realize the effect of suppressing the elution of resist in the plating solution due to excellent development characteristics and thermal curing by drying heat.

In addition, 500 parts by weight or more and 1000 parts by weight or less, 600 parts by weight or more and 800 parts by weight or less, 700 parts by weight or more and 800 parts by weight or less of the third binder resin may be included with respect to 100 parts by weight of the second binder resin.

As described above, when the third binder resin is added in an excess of 500 parts by weight or more with respect to 100 parts by weight of the second binder resin, a hydrophobic function is given to the photosensitive resin to increase resistance to the developer and improve circuit properties is realized. can be

The above photopolymerizable compound has resistance to a developer after UV exposure to enable pattern formation.

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

As the alkylene glycol-based di(meth)acrylate, a compound represented by the following Chemical Formula 17 may be used.

[Formula 17]

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

The compound represented by Formula 17 may improve the hydrophobicity of the photosensitive resin composition to remarkably increase resistance to a developer and a plating solution, and shorten the peeling time of the cured film.

The amount of the compound represented by Formula 17 may be 10 wt% or more and 60 wt% or less, or 20 wt% or more and 40 wt% or less, based on the total solid weight of the photosensitive resin composition.

If the content of the compound represented by Formula 17 is less than 10% by weight based on the total solid weight of the photosensitive resin composition, the effect of the addition of the compound represented by Formula 17 is insufficient, and when it exceeds 60% by weight, hydrophobicity This increase may cause a problem in that the development time in the development process after exposure is rapidly increased.

The photosensitive resin composition may further include a solvent. The solvent is generally selected from among methyl ethyl ketone (MEK), methanol, THF, toluene, and acetone, and the solvent is not particularly limited, and the content is also of the photopolymerization initiator, alkali developable binder resin and photopolymerizable compound. It may be contained by adjusting the content according to the content.

2. 드라이 필름 포토레지스트2. Dry Film Photoresist

According to another embodiment of the invention, it includes an alkali developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the photopolymerizable compound is a penta-type (meth)acrylate-based compound having five (meth)acryloyl groups, and A photosensitive resin layer containing a photosensitive resin composition comprising at least one selected from the group consisting of polyfunctional (meth)acrylate-based compounds having 7 or more (meth)acryloyl groups, the dry film photoresist The palladium plating layer thickness obtained by immersing the copper-clad laminate sample for 5 minutes with respect to the residual palladium plating solution after immersing the film sample in which the photosensitive resin layer of the dry film photoresist is laminated on the substrate for 60 minutes in the palladium plating solution is 0.01 μm or more , dry film photoresist may be provided.

According to another embodiment of the invention, a photosensitive resin composition containing a photosensitive resin composition comprising an alkali developable binder resin, a photoinitiator, and a photopolymerizable compound, wherein the alkali developable binder resin includes at least four different polymers from each other The dry film photoresist includes a resin layer, and the residual palladium plating solution after immersing the film sample in which the photosensitive resin layer of the dry film photoresist is laminated on the substrate for 60 minutes in the palladium plating solution, copper-clad laminate sample for 5 minutes A palladium plating layer thickness of 0.01 μm or more obtained by immersing a dry film photoresist may be provided.

and the alkali developable binder resin, a photoinitiator, and a photopolymerizable compound, wherein the photopolymerizable compound is a penta-type (meth)acrylate-based compound having five (meth)acryloyl groups and seven or more (meth)acryl groups The content of the photosensitive resin composition, including at least one selected from the group consisting of polyfunctional (meth)acrylate-based compounds having a loyl group, includes all of the content described above in the one embodiment.

The content of the photosensitive resin composition comprising the alkali developable binder resin, the photopolymerization initiator, and the photopolymerizable compound, wherein the alkali developable binder resin includes at least four different polymers, the content described above in the one embodiment includes all

Specifically, the photosensitive resin layer may include a dried product or a cured product of the photosensitive resin composition. The said dried material means the substance obtained through the drying process of the said photosensitive resin composition. The cured product means a substance obtained through a curing step of the photosensitive resin composition. The thickness of the photosensitive resin layer is not particularly limited, but can be freely adjusted within the range of, for example, 0.01 μm to 1 mm.

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

The dry film photoresist may further include a base film and a protective film. The base film serves as a support for the photosensitive resin layer during manufacturing of the dry film photoresist, and facilitates handling during exposure of the photosensitive resin layer having adhesive force.

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

The protective film prevents damage to the resist during handling and serves as a protective cover for protecting the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface of the photosensitive resin layer on which the base film is not formed. The protective film serves to protect the photosensitive resin layer from the outside, and when the dry film photoresist is applied in a post-process, it is easily detached, and it requires proper releasability and adhesiveness so as not to be released during storage and distribution.

An example of the method for preparing the dry film photoresist is not particularly limited, for example, the photosensitive resin composition of one embodiment is coated using a conventional coating method on a conventional base film such as polyethylene terephthalate, and then dried A dry film may be prepared by laminating the dried photosensitive resin layer using a conventional protective film such as polyethylene on the upper surface.

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

Drying the coated photosensitive resin composition may be performed by a heating means such as a hot air oven, a hot plate, a hot air circulation furnace, an infrared furnace, and may be performed at a temperature of 50 °C or more and 120 °C or less.

On the other hand, the dry film photoresist is obtained by immersing a copper-clad laminate sample for 5 minutes in the residual palladium plating solution after immersing the film sample in which the photosensitive resin layer of the dry film photoresist is laminated on the substrate in the palladium plating solution for 60 minutes. The palladium plating layer thickness may be 0.01 μm or more, or 0.05 μm or more, or 0.1 μm or more, or 0.01 μm or more and 0.15 μm or less, or 0.05 μm or more and 0.15 μm or less, or 0.1 μm or more and 0.15 μm or less.

The residual palladium plating solution is a palladium plating solution contaminated with the photosensitive resin layer component of the dry film photoresist, and the palladium plating layer thickness obtained by immersing a copper-clad laminate sample in the contaminated residual palladium plating solution for 5 minutes is the thickness of the dry film photoresist. This is to evaluate the contamination of the plating solution by the dry film photoresist during palladium plating on the laminated body. The more severe the contamination of the plating solution, the lower the thickness of the palladium plating layer obtained by immersing the copper-clad laminate sample in the palladium plating solution for 5 minutes. do. On the other hand, as the plating solution is less contaminated, the thickness of the palladium plating layer obtained by immersing the copper-clad laminate sample in the contaminated palladium plating solution for 5 minutes becomes significantly higher. In the actual electroless palladium process, contamination accumulates in a large amount of dry film photoresist, and palladium is added for continuous plating, and other refining processes are difficult. Therefore, it is very important to evaluate the palladium plating solution contamination level of dry film photoresist.

That is, in the palladium plating, first palladium plating using a film on which the photosensitive resin layer of the dry film photoresist is laminated is performed. The second plating was performed, and the contamination of the plating solution by the dry film photoresist was evaluated with respect to the thickness of the palladium plating layer during the second plating.

Therefore, the thickness of the palladium plating layer obtained by immersing the copper-clad laminate sample for 5 minutes with respect to the residual palladium plating solution after immersing the film sample in which the photosensitive resin layer of the dry film photoresist is laminated on the substrate for 60 minutes in the palladium plating solution is 0.01 μm Through being excessively reduced to less than, it is possible to evaluate the degree of contamination of the plating solution. If the plating layer is plated with a thickness lower than the target value in the evaluation of the contamination level, the contamination of the electroless palladium plating solution in the actual process is severe and it is difficult to repeatedly use the plating solution more than 0.5 MTO, which may adversely affect process efficiency and economic feasibility.

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

First, the copper-clad laminate sample on which the photosensitive resin layer of the dry film photoresist is laminated may be immersed in a nickel-phosphorus plating solution to perform elution. Specific conditions for immersing the copper-clad laminate sample on which the photosensitive resin layer of the dry film photoresist is laminated in the nickel-phosphorus plating solution are not particularly limited, but for example, NPR-4 (Uemura) as a plating solution containing nickel-phosphorus The sample having a cross-sectional area of 600 cm2 or more and 700 cm2 or less, or 640 cm2 or more 660 cm2 or less, or 645 cm2 or more and 655 cm2 or less, or 650 cm2 in 130 ml of plating solution under the conditions of 65 ℃ or more and 95 ℃ or less for 20 minutes or more and 60 minutes or less It can be eluted by immersion. The cross-sectional area means the area of the cross-section obtained by cutting the sample in a direction perpendicular to the thickness increasing direction of the sample.

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

Next, the copper-clad laminate sample on which the photosensitive resin layer of the nickel-plated dry film photoresist is laminated may be immersed in a palladium plating solution to perform elution. The specific conditions for immersing the copper-clad laminate sample on which the photosensitive resin layer of the dry film photoresist is laminated in the palladium plating solution are not particularly limited, but, for example, in 130 ml of TPD-21 (Uemura) plating solution with palladium plating solution, 30 ° C. or higher 70 The sample having a cross-sectional area of 600 cm2 or more and 700 cm2 or less, or 640 cm2 or more 660 cm2 or less, or 645 cm2 or more 655 cm2 or less, or 650 cm2 can be immersed and eluted under the condition of ℃ for 30 minutes or more and 90 minutes or less.

Meanwhile, the copper-clad laminate sample in which the photosensitive resin layer of the palladium-plated dry film photoresist is laminated may be immersed in a gold plating solution and eluted. The specific conditions for immersing the copper-clad laminate sample on which the photosensitive resin layer of the dry film photoresist is laminated in the gold plating solution are not particularly limited, but, for example, in the gold plating solution, 130 ml of TWX-40 (Uemura) plating solution at 65 ° C. or higher 95 For 50 minutes or more and 150 minutes or less at ° C. or less, the sample having a cross-sectional area of 600 cm or more and 700 cm or less, or 640 cm or more and 660 cm or less, or 645 cm or more and 655 cm or less, or 650 cm .

If necessary, the sample may be immersed in the aqueous catalyst solution prior to immersion in the nickel-phosphorus plating solution, and specific conditions are not particularly limited. For example, CATA NC-20 (MK Chem&Tech) is used as a palladium catalyst. Thus, the sample can be immersed for 90 seconds under conditions of 10 ℃ or more and 40 ℃ or less.

At this time, the dry film photoresist is a film sample in which the photosensitive resin layer of the dry film photoresist is laminated on a substrate, and the residual nickel-phosphorus plating solution after immersing it in the nickel-phosphorus plating solution for 38 minutes, the copper-clad laminate sample for 28 minutes The thickness of the nickel-phosphorus plating layer obtained by dipping may be 3.9 µm or more, or 3.95 µm or more, or 3.9 µm or more and 4.0 µm or less, or 3.9 µm or more and 3.94 µm or less.

That is, in the dry film photoresist, the residual nickel-phosphorus plating solution after immersing the film sample in which the photosensitive resin layer of the dry film photoresist is laminated on the substrate for 38 minutes in the nickel-phosphorus plating solution, for 28 minutes, the copper-clad laminate sample The nickel-phosphorus plating layer obtained by dipping may have a thickness of 3.9 μm or more, or 3.95 μm or more, or 3.9 μm or more and 4.0 μm or less, or 3.95 μm or more and 4.0 μm or less.

In this case, the dry film photoresist was obtained by immersing the copper-clad laminate sample for 11 minutes in the gold plating solution remaining after immersing the film sample in which the photosensitive resin layer of the dry film photoresist was laminated on the substrate in the gold plating solution for 98 minutes. The thickness of the gold plating layer may be 0.11 μm or more, or 0.11 μm or more and 0.13 μm or less, or 0.12 μm or more, or 0.12 μm or more and 0.13 μm or less.

That is, the dry film photoresist was obtained by immersing the copper-clad laminate sample for 11 minutes in the gold plating solution remaining after immersing the film sample in which the photosensitive resin layer of the dry film photoresist was laminated on the substrate in the gold plating solution for 98 minutes. The thickness of the gold plating layer may be 0.11 μm or more, or 0.11 μm or more and 0.13 μm or less, or 0.12 μm or more, or 0.12 μm or more and 0.13 μm or less.

On the other hand, the film sample in which the photosensitive resin layer containing the photosensitive resin composition is laminated on the substrate may be a laminate in which the photosensitive resin layer containing the photosensitive resin composition is laminated on any substrate. is a copper-clad laminate in which a copper layer having a thickness of 10 μm or more and 100 mm or less is located on the surface.

The cross-sectional area of the film sample in which the photosensitive resin layer containing the photosensitive resin composition is laminated on the substrate may be 600 cm2 or more and 700 cm2 or less, or 640 cm2 or more and 660 cm2 or less, or 645 cm2 or more and 655 cm2 or less.

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

As an example of a method of forming the pattern-shaped photosensitive resin layer, a method of laminating the photosensitive resin layer of the dry film photoresist of the other embodiment on a substrate, followed by exposure and development. In addition, after laminating the photosensitive resin layer of the photosensitive element of another embodiment to be described later on a substrate, there is a method of performing exposure and development.

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

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

3. 레지스터 패턴3. Register pattern

According to another embodiment of the invention, a resist pattern comprising a photosensitive resin pattern containing the photosensitive resin composition included in the dry film photoresist of the other embodiment may be provided. The content of the photosensitive resin composition included in the dry film photoresist includes all of the content described above in the embodiment.

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

An example of the method of forming the photosensitive resin pattern may include a method of laminating the photosensitive resin layer of the dry film photoresist of the other embodiment on a substrate, followed by exposure and development. In addition, after laminating the photosensitive resin layer of the photosensitive element of the embodiment on a substrate, there is a method of performing exposure and development.

As the substrate, a copper clad laminate, a glass substrate sputtered or deposited with transparent electrodes such as ITO and IZO, the same film substrate, a glass substrate coated with dielectric paste, a silicon wafer, a glass wafer deposited with amorphous silicon, copper, tantalum, molybdenum, etc. A silicon wafer on which a metal thin film is sputtered can be used.

For the exposure process, it is preferable to use a laser direct exposure machine including a light source such as UV, visible light, laser, particularly light having a wavelength of 350 to 410 nm, particularly i-line (365 nm) or h-line (405 nm). When using a laser direct exposure machine, it is possible to work under the condition of 3 to 15 mJ/cm2 or less of exposure energy, and when using a general lamp exposure machine, it is possible to work under the condition of 20mJ/cm2 or less, so PCB, lead frame, PDP, and other It is useful for producing images of display devices and the like.

The developing process can be carried out by a dipping method, a shower method, a spraying method, a brush method, etc., and as a developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines can be used. .

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

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

4. 회로 기판, 디스플레이 장치4. Circuit board, display device

According to another embodiment of the present invention, there may be provided a circuit board or a display device including the resist pattern of the other embodiment or a metal pattern formed by the resistor pattern of the other embodiment. The contents of the register pattern include all the contents described above in the other embodiments.

Specific details regarding the circuit board or the display device are not particularly limited, and various conventionally known technical configurations are applicable without limitation.

The metal pattern may be formed by the above-described resist pattern. Specifically, the metal pattern may be formed by etching or plating through the opening included in the resist pattern. That is, the metal pattern may include a lower metal remaining after etching of the lower metal of the resist pattern through the opening included in the resistor pattern, or a metal plated in the opening included in the resistor pattern.

Specifically, for example, by etching or plating the lower substrate exposed by the resist pattern described above, a conductor pattern, a printed wiring board, a lead frame, an ITO electrode, a black mattress, a semiconductor bump, etc. can be manufactured. If necessary, after the etching or plating, the resist pattern may be removed by peeling it from the substrate with an aqueous solution having a stronger alkalinity than a developer.

Accordingly, using the dry film photoresist of the present invention, a circuit having a fine line width is formed through a conventional etching/plating process, and a PCB having a fine line width through a known process, in addition to a lead frame, PDP, and other displays Productivity can be maximized in generating images on devices, semiconductor devices, and the like.

According to the present invention, it is possible to provide a photosensitive element, a dry film photoresist, a resist pattern, a circuit board, and a display device capable of realizing an effect of enabling plating of a sufficient thickness by reducing contamination of a plating solution.

The invention is described in more detail in the following examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

<제조예: 알칼리 현상성 바인더 수지의 제조><Production Example: Preparation of alkali developable binder resin>

Preparation Example 1

A mechanical stirrer and a reflux device were mounted on the jacket set of the 4-necked reaction flask, and then the inside of the flask was purged with nitrogen. In the flask purged with nitrogen, 90 g of methyl ethyl ketone (Methyl Ethyl Ketone, MEK) and 10 g of methanol (Methanol, MeOH) were added, and then 0.9 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. . Here, as a monomer, methacrylic acid (MAA) 24 g, methyl methacrylate (MMA) 6 g, styrene (Styrene, SM) 30 g, and 2-phenoxyethyl methacrylate (2-phenoxyethyl methacrylate, PHEMA) ) 40 g of the monomer mixture was added, the temperature was raised to 80 ° C, and polymerization was performed for 6 hours to prepare an alkali developable binder resin (weight average molecular weight: 50,000 g/mol, solid content 50.0 wt%, acid value 155 mgKOH/g). .

As a specific example of the weight average molecular weight measurement condition, the alkali developable binder resin is dissolved in tetrahydrofuran so as to have a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on the solid content) to 0.45㎛ Pore After filtration using a Syringe Filter of the size, 20 μl was injected into GPC, tetrahydrofuran (THF) was used as the mobile phase of GPC, and it was introduced at a flow rate of 1.0 mL/min, and the column was Agilent PLgel 5 μm Guard One (7.5 x 50 mm) and two Agilent PLgel 5㎛ Mixed D (7.5 x 300 mm) were connected in series, and the Agilent 1260 Infinity Ⅱ system, RI Detector was used as a detector to measure at 40°C.

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

The solid content was determined by measuring the weight percent ratio of the solid content remaining after heating at 150° C. for 120 minutes in an oven based on the weight of the alkali developable binder resin prepared in Preparation Example described above.

Preparation Example 2

A mechanical stirrer and a reflux device were installed in a four-necked round-bottom flask, and then the inside of the flask was purged with nitrogen. In the flask purged with nitrogen, 80 g of methyl ethyl ketone (Methyl Ethyl Ketone, MEK) and 7.5 g of methanol (Methanol, MeOH) were added, and then 0.45 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. made it Acrylic acid (AA) as a monomer 8g (0.11 mol, 10.91 mol% of 100 mol% of all monomers), methacrylic acid (MAA) 15g (0.17 mol, 17.13 mol% of 100 mol% of all monomers) ), Butyl acrylate (BA) 15g (0.12 mol, 11.50 mol% of 100 mol% of total monomer), Methyl methacrylate (MMA) 52g (0.52 mol, 51.03 mol of 100 mol% of total monomer) %), and styrene (Styrene, SM) 10g (0.10 mol, 9.43 mol% out of 100 mol% of the total monomer) of a monomer mixture was added, and the temperature was raised to 80 ° C. and then polymerized for 6 hours to prepare an alkali developable binder resin. did

The alkali developable binder resin was measured to have a weight average molecular weight of 71,538 g/mol, a glass transition temperature of 79° C., a solid content of 51.4% by weight, and an acid value of 156.3 mgKOH/g.

Preparation 3

A mechanical stirrer and a reflux device were installed in a four-necked round-bottom flask, and then the inside of the flask was purged with nitrogen. In the flask purged with nitrogen, 110 g of methyl ethyl ketone (Methyl Ethyl Ketone, MEK) and 10 g of methanol (Methanol, MeOH) were added, and then 1 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. Here, 30 g of methacrylic acid (MAA) as a monomer (0.35 mol, 21.32 mol% of 100 mol% of the total monomer), 100 g of methyl methacrylate (MMA) (1.00 mol, 100 mol of the total monomer) % of 61.07 mol%), and styrene (Styrene, SM) 30 g (0.29 mol, 17.61 mol% out of 100 mol% of total monomers) of a monomer mixture were added, the temperature was raised to 80 ° C, and polymerization was performed for 6 hours to develop alkali A resinous binder resin (weight average molecular weight of 49,852 g/mol, glass transition temperature of 125 °C, solid content of 48.5 wt%, acid value of 163.17 mgKOH/g) was prepared.

Preparation 4

A mechanical stirrer and a reflux device were installed in a four-necked round-bottom flask, and then the inside of the flask was purged with nitrogen. In the flask purged with nitrogen, 90 g of methyl ethyl ketone (Methyl Ethyl Ketone, MEK) and 10 g of methanol (Methanol, MeOH) were added, and then 0.85 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. . Here, 25 g of methacrylic acid (MAA) as a monomer (0.29 mol, 30.86 mol% of 100 mol% of the total monomer), 20 g (0.20 mol of the total monomer 100 mol% of methyl methacrylate, MMA) 21.22 mol %), Styrene (SM) 25 g (0.24 mol, 25.50 mol % of 100 mol % total monomer), and 30 g (0.21 mol GMA) glycidyl methacrylate (0.21 mol, 100 mol % total monomer) 22.42 mol%) of the monomer mixture was added, and the temperature was raised to 80° C. and then polymerized for 6 hours to prepare an alkali developable binder resin.

The alkali developable binder resin was measured to have a weight average molecular weight of 55,201 g/mol, a glass transition temperature of 112° C., a solid content of 50.2% by weight, and an acid value of 162.0 mgKOH/g.

<실시예 및 비교예 : 감광성 수지 조성물 및 드라이 필름 포토레지스트 제조><Examples and Comparative Examples: Preparation of photosensitive resin composition and dry film photoresist>

According to the composition shown in Tables 1 and 2 below, the photopolymerization initiators are dissolved in methyl ethyl ketone (MEK) as a solvent, and then the photopolymerizable compound and the alkali developable binder resin are added and mixed using a mechanical stirrer for about 1 hour. to prepare a photosensitive resin composition.

The obtained photosensitive resin composition is coated on a PET film of 19 μm using a coating bar to form a photosensitive resin layer, and dried using a hot air oven, wherein the drying temperature is 80° C., and the drying time is 5 min, and the thickness of the photosensitive resin layer after drying was 40 μm.

A dry film photoresist was prepared by lamination using a protective film (polyethylene) on the dried photosensitive resin layer.

성 분ingredient	상품명(또는 성분명)Trade name (or ingredient name)	함량(중량%)content (wt%)
성 분ingredient	상품명(또는 성분명)Trade name (or ingredient name)	실시예1Example 1	실시예2Example 2	실시예3Example 3	비교예1Comparative Example 1
알칼리 현상성 바인더 수지Alkali developable binder resin	제조예1Preparation Example 1	65.065.0	65.065.0	65.065.0	65.065.0
광중합성 화합물photopolymerizable compound	M241M241	4.04.0	4.04.0	4.04.0	5.05.0
	M2101M2101	16.016.0	16.016.0	16.016.0	20.020.0
	M500M500	5.05.0	00	2.52.5	00
	Viscoat#802Viscoat#802	00	5.05.0	2.52.5	00
광중합 개시제photopolymerization initiator	EABEAB	0.050.05	0.050.05	0.050.05	0.050.05
광중합 개시제photopolymerization initiator	BCIMBCIM	1.301.30	1.301.30	1.301.30	1.301.30
첨가제additive	톨루엔술폰산1수화물 (Aldrich Chemical)Toluenesulfonic acid monohydrate (Aldrich Chemical)	0.0440.044	0.0440.044	0.0440.044	0.0440.044
	N,N-BDAN,N-BDA	0.0660.066	0.0660.066	0.0660.066	0.0660.066
	루이코 크리스탈 바이올렛(일본 Hodogaya Co.)Ruiko Crystal Violet (Hodogaya Co., Japan)	0.1700.170	0.1700.170	0.1700.170	0.1700.170
	다이아몬드 그린 GH(일본 Hodogaya Co.)Diamond Green GH (Japan Hodogaya Co.)	0.0150.015	0.0150.015	0.0150.015	0.0150.015
용 제solvent	MEK(Methyl Ethyl Ketone)MEK (Methyl Ethyl Ketone)	8.3558.355	8.3558.355	8.3558.355	8.3558.355
(1) M241 : Bisphenol A (EO)₄ dimethacrylate (미원스페셜티케미칼) (2) M2101 : Bisphenol A (EO)₁₀ dimethacrylate(미원스페셜티케미칼) (3) M500 : Dipentaerythritol pentaacrylate(Mw 524, 미원스페셜티케미칼) (4) Viscoat#802 : Tripentaerythritol Acrylate(Mw 805, Osaka Yuki) J은 수소 또는 아크릴로일기이고, j은 1인 화합물 10~20%, j=2인 화합물 55~65%, j=3인 화합물 5~15%의 혼합물 (5) EAB : 4,4'-(Bisdiethylamino)benzophenone(Aldrich Chemical) (6) BCIM : 2,2'-Bis-(2-chlorophenyl-4,5,4',5'-tetraphenylbisimidazole(Aldrich Chemical) (7) N,N-BDA : N,N-benzyldimethylamide(1) M241: Bisphenol A (EO) ₄ dimethacrylate (Miwon Specialty Chemical) (2) M2101: Bisphenol A (EO) ₁₀ dimethacrylate (Miwon Specialty Chemical) (3) M500: Dipentaerythritol pentaacrylate (Mw 524, Miwon Specialty Chemical) (4) Viscoat#802 : Tripentaerythritol Acrylate (Mw 805, Osaka Yuki) J is hydrogen or an acryloyl group, A mixture of 10-20% of the compound with j being 1, 55-65% of the compound with j=2, and 5-15% of the compound with j=3 (5) EAB: 4,4'-(Bisdiethylamino)benzophenone (Aldrich Chemical) (6) BCIM: 2,2'-Bis-(2-chlorophenyl-4,5,4',5'-tetraphenylbisimidazole (Aldrich Chemical) (7) N,N-BDA: N,N-benzyldimethylamide

성 분ingredient	상품명(또는 성분명)Trade name (or ingredient name)	함량(감광성 수지 조성물 100 중량% 기준 각 중량%)Content (each weight % based on 100 weight % of the photosensitive resin composition)
성 분ingredient	상품명(또는 성분명)Trade name (or ingredient name)	실시예4Example 4	실시예5Example 5	비교예2Comparative Example 2
알칼리 현상성 바인더 수지Alkali developable binder resin	제조예1Preparation Example 1	50.0 (바인더 수지 100 중량% 기준 76.92 중량%)50.0 (76.92 wt% based on 100 wt% of binder resin)	30.0 (바인더 수지 100 중량% 기준 46.15 중량%)30.0 (46.15 wt% based on 100 wt% of binder resin)	--
	제조예2Preparation Example 2	1.0 (바인더 수지 100 중량% 기준 1.54 중량%)1.0 (1.54% by weight based on 100% by weight of binder resin)	1.0 (바인더 수지 100 중량% 기준 1.54 중량%)1.0 (1.54% by weight based on 100% by weight of binder resin)	7.67.6
	제조예3Preparation 3	7.5(바인더 수지 100 중량% 기준 11.54 중량%)7.5 (11.54 wt% based on 100 wt% of binder resin)	7.5(바인더 수지 100 중량% 기준 11.54 중량%)7.5 (11.54 wt% based on 100 wt% of binder resin)	57.457.4
	제조예4Preparation 4	6.5(바인더 수지 100 중량% 기준 10.00 중량%)6.5 (10.00 wt% based on 100 wt% of binder resin)	26.5 (바인더 수지 100 중량% 기준 40.77 중량%)26.5 (40.77 wt% based on 100 wt% of binder resin)	--
	합계Sum	65.065.0	65.065.0	65.065.0
광중합성 화합물photopolymerizable compound	M241M241	5.05.0	5.05.0	5.05.0
	M2101M2101	20.020.0	20.020.0	20.020.0
	합계Sum	25.025.0	25.025.0	25.025.0
광중합 개시제photopolymerization initiator	EABEAB	0.050.05	0.050.05	0.050.05
	BCIMBCIM	1.301.30	1.301.30	1.301.30
	합계Sum	1.351.35	1.351.35	1.351.35
첨가제additive	톨루엔술폰산1수화물 (Aldrich Chemical)Toluenesulfonic acid monohydrate (Aldrich Chemical)	0.0440.044	0.0440.044	0.0440.044
	N,N-BDAN,N-BDA	0.0660.066	0.0660.066	0.0660.066
	루이코 크리스탈 바이올렛(일본 Hodogaya Co.)Ruiko Crystal Violet (Hodogaya Co., Japan)	0.1700.170	0.1700.170	0.1700.170
	다이아몬드 그린 GH(일본 Hodogaya Co.)Diamond Green GH (Japan Hodogaya Co.)	0.0150.015	0.0150.015	0.0150.015
	합계Sum	0.2950.295	0.2950.295	0.2950.295
용 제solvent	MEK(Methyl Ethyl Ketone)MEK (Methyl Ethyl Ketone)	8.3558.355	8.3558.355	8.3558.355
(1) M241 : Bisphenol A (EO)₄ dimethacrylate (미원스페셜티케미칼) (2) M2101 : Bisphenol A (EO)₁₀ dimethacrylate(미원스페셜티케미칼) (3) EAB : 4,4'-(Bisdiethylamino)benzophenone(Aldrich Chemical) (4) BCIM : 2,2'-Bis-(2-chlorophenyl-4,5,4',5'-tetraphenylbisimidazole(Aldrich Chemical) (5) N,N-BDA : N,N-benzyldimethylamide(1) M241: Bisphenol A (EO) ₄ dimethacrylate (Miwon Specialty Chemical) (2) M2101: Bisphenol A (EO) ₁₀ dimethacrylate (Miwon Specialty Chemical) (3) EAB: 4,4'-(Bisdiethylamino)benzophenone (Aldrich Chemical) (4) BCIM: 2,2'-Bis-(2-chlorophenyl-4,5,4',5'-tetraphenylbisimidazole (Aldrich Chemical) (5) N,N-BDA: N,N-benzyldimethylamide

<실험예><Experimental example>

For the dry film photoresists prepared in Examples and Comparative Examples, physical properties were measured in the following manner, and the results are shown in Tables 3 and 4.

1. 무전해 팔라듐 도금액 오염성1. Contamination of electroless palladium plating solution

Peel off the protective film of the dry film photoresist prepared in Examples and Comparative Examples, and preheat the substrate so that the photosensitive resin layer of the dry film photoresist comes into contact with the surface of the copper layer of the 1.6 mm thick copper-clad laminate that has been brush-polished. A laminate was formed by lamination on both sides using a HAKUTO MACH 610i under the conditions of a roll temperature of 120° C. and a laminator roll temperature of 115° C., a roll pressure of 4.0 kgf/cm 2 , and a roll speed of 2.0 min/m.

After peeling off the support PET film of the dry film photoresist from the laminate, using a photomask for front exposure, both sides of UV light for 4 seconds at an exposure amount of 80 mJ/cm 2 through ORC EXM-1201-F (parallel light exposure machine) After irradiation, it was left for 15 minutes. After that, development was carried out for 1 minute with a spray pressure of 1.5 kgf/cm 2 with a 1.0 wt% aqueous solution of Na ₂ CO ₃ at 30±1° C. under spray-type development conditions. The developed laminate was baked in an oven at 140°C for 30 minutes.

After the baked laminate was sufficiently cooled, a sample having a cross-sectional area of 650 cm2 was prepared, and the sample was sequentially immersed in 130 ml CATA NC-20 (MK Chem&Tech) palladium catalyst at 25 ° C. for 1 minute 30 seconds, rinsed in distilled water for 1 minute, 80 ±2 ℃ 130ml NPR-4 (Uemura) immersion in nickel-phosphorus plating solution for 38 minutes, rinse in distilled water for 1 minute, 55±2 ℃ 130ml immersion in TPD-21 (Uemura) palladium plating solution for 60 minutes, rinse in distilled water for 1 minute, 80 ±2 ℃ 130ml TWX-40 (Uemura) immersed in gold plating solution for 98 minutes, rinsed in distilled water for 1 minute.

After that, with respect to the plating solution in which the dry film photoresist component was eluted by immersion of the laminate, in the order of a copper-clad laminate sample with a brush-polished cross-sectional area of 5 cm2 and a thickness of 1.6 mm, CATA NC-20 (MK Chem&Tech) ) Immersion in palladium catalyst for 1 min 30 sec, rinse in distilled water for 1 min, immerse in 80±2 ℃ 130ml NPR-4 (Uemura) nickel-phosphorus plating solution for 28 min, rinse in distilled water for 1 min, 55±2 ℃ 130ml TPD-21 (Uemura) Immersion in palladium plating solution for 5 minutes, rinsing in distilled water for 1 minute, immersion in 130ml TWX-40 (Uemura) gold plating solution at 80±2 ℃ for 11 minutes, and rinsing in distilled water for 1 minute.

The plating thickness was measured with Helmut Fischer XDV-μ on the copper-clad laminates plated with nickel-phosphorus, palladium, and gold in order, and the plating solution contamination was evaluated through the degree of plating thickness.

2. 세선 밀착력(단위: ㎛)2. Fine wire adhesion (unit: ㎛)

Peel off the protective film of the dry film photoresist prepared in Examples and Comparative Examples, and preheat the substrate so that the photosensitive resin layer of the dry film photoresist comes into contact with the surface of the copper layer of the 1.6 mm thick copper-clad laminate that has been brush-polished. Roll temperature 120℃, laminator roll temperature 115℃, roll pressure 4.0kgf/cm2Then, a laminate was formed by lamination using a HAKUTO MACH 610i under the condition of a roll speed of 2.0 min/m.

After peeling off the support PET film of the dry film photoresist from the laminate, using a photomask for circuit evaluation, UV rays at an exposure amount of 80 mJ/cm ² through ORC EXM-1201-F (parallel light exposure machine) for 4 seconds After irradiation, it was left for 15 minutes. After that, development was carried out for 1 minute with a spray pressure of 1.5 kgf/cm 2 with a 1.0 wt% aqueous solution of Na ₂ CO ₃ at 30±1 ℃ under the spray-type development conditions.

In the developed laminate, the minimum line width of the photosensitive resin layer was measured with a ZEISS AXIOPHOT Microscope, and the fine wire adhesion was evaluated. It can be evaluated that the fine wire adhesion is excellent, so that this value is small.

3. 1:1 해상도(단위: ㎛)3. 1:1 resolution (unit: μm)

After peeling off the support PET film of the dry film photoresist from the laminate, a photomask for circuit evaluation is used so that the distance between the circuit line width and the circuit line space is 1:1 after development. Thus, UV light was irradiated for 4 seconds at an exposure amount of 80 mJ/cm ² through ORC EXM-1201-F (parallel light exposure machine), and then left for 15 minutes. After that, development was carried out for 1 minute with a spray pressure of 1.5 kgf/cm 2 with a 1.0 wt% aqueous solution of Na ₂ CO ₃ at 30±1 ℃ under the spray-type development conditions.

In the developed laminate, the minimum value of the gap between the photosensitive resin layers was measured with a ZEISS AXIOPHOT Microscope and evaluated at 1:1 resolution. As this value is smaller, it can be evaluated that the 1:1 resolution value is excellent.

4. 박리속도(단위 : 초)4. Peeling speed (unit: seconds)

After peeling off the PET film, which is the support for the dry film photoresist, from the laminate, using ORC's EXM-1201 (parallel light exposure machine) using a photomask for circuit evaluation until the exposure amount of 40 mJ/cm ² is reached. After irradiation with ultraviolet light, it was left for 15 minutes. After that, development was carried out for twice the minimum development time under the spray pressure of 1.5 kgf/cm 2 with a 1.0 wt% aqueous solution of Na ₂ CO ₃ at 30±1 ℃.

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

구분division	무전해 팔라듐 도금액 오염성Contamination of electroless palladium plating solution			세선밀착력(㎛)Fine wire adhesion (㎛)	1:1 해상도(㎛)1:1 resolution (㎛)	박리시간(초)Peeling time (sec)
구분division	니켈-인 도금두께 (㎛)nickel-phosphorus plating thickness (μm)	팔라듐 도금두께 (㎛)palladium plating thickness (μm)	금 도금두께 (㎛)gold plating thickness (μm)	세선밀착력(㎛)Fine wire adhesion (㎛)	1:1 해상도(㎛)1:1 resolution (㎛)	박리시간(초)Peeling time (sec)
실시예 1Example 1	3.9263.926	0.1380.138	0.1120.112	1414	1212	200200
실시예 2Example 2	3.9763.976	0.1010.101	0.1050.105	1414	1212	180180
실시예 3Example 3	3.9053.905	0.1000.100	0.1210.121	1414	1212	190190
비교예 1Comparative Example 1	3.7183.718	0.0080.008	0.1110.111	1414	1212	150150

As shown in Table 3, in Examples 1 to 3, the palladium plating thickness was measured to be 0.1 μm or more and 0.138 μm or less, and it was confirmed that sufficient plating was increased in palladium compared to Comparative Example 1 having a plating thickness of 0.008 μm. In addition, in Examples 1 to 3, the nickel-phosphorus plating thickness was measured to be 3.905 μm or more and 3.976 μm or less, and it was confirmed that sufficient plating was increased even with nickel-phosphorus compared to Comparative Example 1 having a plating thickness of 3.718 μm. Through this, it was confirmed that the dry film photoresist prepared in Examples 1 to 3 had low contamination with the plating solution, and thus a sufficient level of plating property could be secured even when the plating solution was reused.

구분division	무전해 도금액 오염성Contamination of electroless plating solution			세선밀착력(㎛)Fine wire adhesion (㎛)	1:1 해상도(㎛)1:1 resolution (㎛)	박리시간(초)Peeling time (sec)
구분division	니켈-인 도금두께 (㎛)nickel-phosphorus plating thickness (μm)	팔라듐 도금두께 (㎛)palladium plating thickness (μm)	금 도금두께 (㎛)gold plating thickness (μm)	세선밀착력(㎛)Fine wire adhesion (㎛)	1:1 해상도(㎛)1:1 resolution (㎛)	박리시간(초)Peeling time (sec)
실시예 4Example 4	3.9163.916	0.1210.121	0.1120.112	1414	1212	8181
실시예 5Example 5	3.9263.926	0.1130.113	0.1220.122	1818	1616	6666
비교예 2Comparative Example 2	3.8633.863	0.0020.002	0.1000.100	1818	1616	102102

As shown in Table 4, in Examples 4 to 5, the palladium plating thickness was measured to be 0.113 µm or more and 0.121 µm or less, and it was confirmed that sufficient plating was increased in palladium compared to Comparative Example 2 having a plating thickness of 0.002 µm. In addition, in Examples 4 to 5, the nickel-phosphorus plating thickness was measured to be 3.916 µm or more and 3.926 µm or less, and it was confirmed that sufficient plating was increased even in nickel-phosphorus compared to Comparative Example 2 having a plating thickness of 3.863 µm. In addition, in Examples 4 to 5, the gold plating thickness was measured to be 0.112 µm or more and 0.122 µm or less, and it was confirmed that sufficient plating was increased even in gold compared to Comparative Example 2 having a plating thickness of 0.100 µm.

Through this, it was confirmed that the dry film photoresist prepared in Examples 4 to 5 had low contamination with the plating solution, and thus a sufficient level of plating property could be secured even when the plating solution was reused.

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

Claims

polymer substrate; and a photosensitive resin layer formed on the polymer substrate,

The palladium plating layer thickness obtained by immersing the copper clad laminate sample for 5 minutes with respect to the residual palladium plating solution after immersing the film sample in which the photosensitive resin layer is laminated on the substrate for 60 minutes in the palladium plating solution is 0.01 μm or more, the photosensitive element.
According to claim 1,

The photosensitive resin layer contains an alkali developable binder resin, the photosensitive element.
According to claim 1,

The photosensitive element is the thickness of the nickel-phosphorus plating layer obtained by immersing the copper-clad laminate sample for 28 minutes with respect to the residual nickel-phosphorus plating solution after immersing the film sample in which the photosensitive resin layer is laminated on the substrate for 38 minutes in the nickel-phosphorus plating solution A photosensitive element having a value of 3.9 µm or more.
According to claim 1,

The photosensitive resin layer includes an alkali developable binder resin, a photoinitiator, and a photopolymerizable compound, wherein the photopolymerizable compound is a penta-type (meth)acrylate-based compound having five (meth)acryloyl groups and seven or more A photosensitive element containing a photosensitive resin composition comprising at least one selected from the group consisting of polyfunctional (meth)acrylate-based compounds having a (meth)acryloyl group.
5. The method of claim 4,

The penta-type (meth) acrylate-based compound is a photosensitive element further comprising one hydroxyl group.
5. The method of claim 4,

The penta-type (meth) acrylate-based compound is a photosensitive element, which is a compound represented by the following formula (A):

[Formula A]

In the formula A,

Five of T 1 to T 6 are the same as or different from each other and each independently is a (meth)acryloyl group, and the other one is hydrogen.
5. The method of claim 4,

The polyfunctional (meth) acrylate-based compound is a photosensitive element, which is a compound represented by the following Chemical Formula B:

[Formula B]

In the formula B,

T 7 to T 12 are the same as or different from each other and each independently a (meth) acryloyl group, T 12 is hydrogen or a (meth) acryloyl group,

t is an integer from 2 to 10;
According to claim 1,

The photosensitive resin layer includes an alkali developable binder resin, a photoinitiator, and a photopolymerizable compound, wherein the alkali developable binder resin contains a photosensitive resin composition comprising four or more different polymers from each other, a photosensitive element.
9. The method of claim 8,

The alkali developable binder resin,

A photosensitive element comprising a first binder resin including a repeating unit represented by the following formula (1):

[Formula 1]

In Formula 1,

R 1 is hydrogen or alkyl having 1 to 10 carbon atoms,

R 2 is alkylene having 1 to 10 carbon atoms,

Ar is aryl having 6 to 20 carbon atoms,

n is an integer from 1 to 20;
10. The method of claim 9,

The first binder resin, in addition to the repeating unit represented by the formula (1),

A photosensitive element further comprising a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3), and a repeating unit represented by the following formula (4):

[Formula 2]

In the above formula (2),

R 3 is hydrogen or alkyl having 1 to 10 carbon atoms,

[Formula 3]

In Formula 3,

R 4 is hydrogen or alkyl having 1 to 10 carbon atoms,

R 5 is alkyl having 1 to 10 carbon atoms,

[Formula 4]

In the above formula (4),

Ar is aryl having 6 to 20 carbon atoms.
9. The method of claim 8,

The alkali developable binder resin,

A photosensitive element comprising a second binder resin including a repeating unit represented by the following Chemical Formula 5:

[Formula 5]

In Formula 5,

R 6 is hydrogen,

R 7 is alkyl having 1 to 10 carbon atoms.
12. The method of claim 11,

The second binder resin, in addition to the repeating unit represented by Formula 5,

A photosensitive element further comprising a repeating unit represented by the following formula (6), a repeating unit represented by the following formula (7), a repeating unit represented by the following formula (8), and a repeating unit represented by the following formula (9):

[Formula 6]

In Formula 6,

R 8 is hydrogen,

[Formula 7]

In Formula 7,

R 9 is alkyl having 1 to 10 carbon atoms,

[Formula 8]

In Formula 8,

R 10 is alkyl having 1 to 10 carbon atoms, R 11 is alkyl having 1 to 10 carbon atoms,

[Formula 9]

In Formula 9,

Ar is aryl having 6 to 20 carbon atoms.
9. The method of claim 8,

The alkali developable binder resin,

A photosensitive element comprising a third binder resin including 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:

[Formula 10]

In the formula (10),

R 9 is alkyl having 1 to 10 carbon atoms,

[Formula 11]

In the above formula (11),

R 10 is alkyl having 1 to 10 carbon atoms, R 11 is alkyl having 1 to 10 carbon atoms,

[Formula 12]

In the above formula (12),

Ar is aryl having 6 to 20 carbon atoms.
9. The method of claim 8,

The alkali developable binder resin,

A photosensitive element comprising a fourth binder resin including a repeating unit represented by the following Chemical Formula 13:

[Formula 13]

In the above formula (13),

R 12 is hydrogen or alkyl having 1 to 10 carbon atoms,

R 13 is alkylene having 1 to 10 carbon atoms.
15. The method of claim 14,

The fourth binder resin is, in addition to the repeating unit represented by the formula (13),

A photosensitive element further comprising 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:

[Formula 14]

In the above formula (14),

R 14 is hydrogen or alkyl having 1 to 10 carbon atoms,

[Formula 15]

In the above formula (15),

R 15 is hydrogen or alkyl having 1 to 10 carbon atoms,

R 16 is alkyl having 1 to 10 carbon atoms,

[Formula 16]

In the above formula (16),

Ar is aryl having 6 to 20 carbon atoms.
An alkali developable binder resin, a photoinitiator, and a photopolymerizable compound, wherein the photopolymerizable compound is a penta-type (meth)acrylate-based compound having 5 (meth)acryloyl groups and 7 or more (meth)acryloyl groups A photosensitive resin layer containing a photosensitive resin composition comprising at least one selected from the group consisting of polyfunctional (meth)acrylate-based compounds having a diary,

The dry film photoresist is a palladium plating layer obtained by immersing a copper-clad laminate sample for 5 minutes in the residual palladium plating solution after immersing the film sample in which the photosensitive resin layer of the dry film photoresist is laminated on the substrate for 60 minutes in the palladium plating solution A dry film photoresist having a thickness of 0.01 μm or greater.
An alkali developable binder resin, a photoinitiator, and a photopolymerizable compound, wherein the alkali developable binder resin comprises a photosensitive resin layer containing a photosensitive resin composition comprising at least four different polymers,

The dry film photoresist is a palladium plating layer obtained by immersing a copper-clad laminate sample for 5 minutes in the residual palladium plating solution after immersing the film sample in which the photosensitive resin layer of the dry film photoresist is laminated on the substrate for 60 minutes in the palladium plating solution A dry film photoresist having a thickness of 0.01 μm or greater.
A resist pattern comprising a photosensitive resin pattern containing the photosensitive resin composition contained in the dry film photoresist of any one of claims 16 or 17.
A circuit board comprising the resist pattern of claim 18 , or a metal pattern formed by the resist pattern of claim 18 .
A display device comprising the resist pattern of claim 18, or a metal pattern formed by the resist pattern of claim 18.