TWI767481B - Photosensitive resin composition, and dry film photoresist, photosensitive element, circuit board, and display device using the same - Google Patents

Abstract

The present disclosure relates to a photosensitive resin composition including: an alkaline developable binder resin which includes a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 2, a repeating unit represented by Chemical Formula 3, and a repeating unit represented by Chemical Formula 4, and a dry film photoresist, a photosensitive element, a circuit board, and a display device using the same.

Description

Photosensitive resin composition and dry film photoresist, photosensitive Components, circuit boards and display devices

The present disclosure relates to a photosensitive resin composition and a dry film photoresist, a photosensitive element, a circuit board and a display device using the same.

The photosensitive resin composition is used in the form of dry film photoresist (DFR), liquid photoresist ink, or the like and used for printed circuit boards (PCBs) or lead frames.

Currently, dry film photoresist is widely used not only in the manufacture of printed circuit boards (PCBs) and lead frames, but also in the manufacture of rib barriers for plasma display panels (PDPs), ITO electrodes for other displays, and bus bars. Address electrodes, black matrices, and the like.

In general, dry film photoresists of this type are commonly used in applications where they are laminated to copper clad laminates. In relation to this, as an example of a manufacturing process of a printed circuit board (PCB), a pre-processing process is first performed to laminate a copper clad laminate, which is the original plate material of the PCB. The pretreatment process is performed in the order of drilling, deburring, surface conditioning and the like in the outer layer process, and the surface conditioning or the like is performed in the inner layer process Dip. In surface conditioning, a bristle brush process and a jet pumice process are mainly used and the dip may undergo soft etching and 5 wt% sulfuric acid dip.

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

The printed circuit board that has undergone the lamination process is allowed to stand for 15 minutes or more to stabilize the board, and then the photoresist of the DFR is exposed through a reticle on which the desired circuit pattern is formed. When the photomask is irradiated with UV light in this process, the photoresist irradiated with UV light starts to polymerize by the photoinitiator contained in the irradiated portion. First, the oxygen in the photoresist is consumed, and then the activated monomer is polymerized to cause a crosslinking reaction. Thereafter, the polymerization reaction proceeds while consuming a large amount of monomers. Meanwhile, the unexposed portion exists in a state in which the cross-linking reaction has not yet proceeded.

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

Then, depending on the inner layer process and the outer layer process, circuits are formed through different processes. However, in the inner layer process, a circuit is formed on the board through an etching process and a lift-off process, and in the outer layer process, a plating process and a tenting process are performed, followed by etching and solder stripping to form a predetermined circuit.

Meanwhile, in the process of electroplating, when the electroplating resistance of the dry film is insufficient, there is a problem that air bubbles are generated due to high pH or the cured photoresist is detached or lost. In particular, it is common for cured photoresist to detach or wear out due to air bubbles generated during nickel plating of the ENIG electroplating process.

Accordingly, there is an increasing demand for dry films with improved plating resistance.

An object of the present disclosure is to provide a photosensitive resin composition capable of reducing cavities and realizing high-resolution patterns during pattern plating.

Another object of the present disclosure is to provide a photosensitive resin composition that can achieve an excellent 1:1 resolution of 25 microns or less while achieving improved plating resistance.

Another object of the present disclosure is to provide a dry film photoresist, a photosensitive element, a circuit board and a display device using the photosensitive resin composition.

In order to achieve the above object, a photosensitive resin composition is provided herein, comprising: a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the following Chemical Formula 2, a repeating unit represented by the following Chemical Formula 3 and a repeating unit represented by the following Chemical Formula 4 Alkali-developable binder resin of unit; photopolymerization initiator; and photopolymerizable compound, wherein the photosensitive resin composition satisfies any one of the following (a) or (b): (a) For a resist pattern obtained by exposing and developing a photosensitive resin layer containing a photosensitive resin composition, the amount of the resist residue remaining on the bottom surface in the space between the lines of the photosensitive resin layer adjacent to each other Maximum foot length of 1 micron or less meters, or (b) For a film sample in which a photosensitive resin layer containing a photosensitive resin composition is laminated on a substrate, when nickel plating is performed with an aqueous solution containing nickel for 20 minutes or more, the adhesive force defined by the following Equation 1 90% or more.

[Equation 1] Adhesion (%)=(surface area of the photosensitive resin layer containing the photosensitive resin composition after nickel plating in contact with the substrate/surface area of the photosensitive resin layer containing the photosensitive resin composition in contact with the substrate before nickel plating)×100 ,

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

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

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

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

Also provided herein is a dry film photoresist comprising a photosensitive resin layer containing a photosensitive resin composition.

Further provided herein is a photosensitive element comprising a polymer substrate and a photosensitive resin layer formed on the polymer substrate, and satisfying any one of the following (a) or (b): (a) for the photosensitive resin layer through exposure and development The obtained resist pattern, in the space between the mutually adjoining photosensitive resin layer lines, has a maximum foot length of the resist residue remaining on the bottom surface of 1 micrometer or less, or (b) for wherein The film sample in which the photosensitive resin layer was laminated on the substrate, when nickel-plated with an aqueous solution containing nickel for 20 minutes or more, had an adhesion force defined by the following Equation 3 of 90% or more.

[Equation 3] Adhesion (%) = (The photosensitive resin layer of the photosensitive element is in contact with the substrate after nickel plating Surface area/surface area of the photosensitive resin layer of the photosensitive element in contact with the substrate before nickel plating) × 100.

This document further provides a circuit board and a display device, comprising a photosensitive resin layer containing a photosensitive resin composition.

Hereinafter, the photosensitive resin composition and the dry film photoresist, photosensitive element, circuit board and display device using the same according to specific embodiments of the present disclosure will be described in more detail.

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

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

The terms "comprising" or "comprising" as used herein specify particular features, regions, integers, steps, acts, elements and/or components, but do not exclude different particular features, regions, integers, steps, acts, elements, groups The presence or addition of fractions and/or groups.

Furthermore, terms including ordinal numbers such as "first", "second", etc. are used only for the purpose of distinguishing one component from another and are not limited by ordinal numbers. For example, a first component could be termed a second component, or, similarly, a second component could be termed a first component, without departing from the scope of the present disclosure.

In this specification, examples of substituents are described below, but are not limited thereto.

In the present specification, the term "substituted" means other functional groups that replace hydrogen atoms in the bonding compound, and the positions to be substituted are not limited as long as the positions are positions where hydrogen atoms are substituted, that is, the substituents may be substituted. The substituted positions, and when two or more than two substituents are substituted, may be the same or different from each other.

In this specification, the term "substituted or unsubstituted" means unsubstituted Substituted or substituted with one or more substituents selected from the group consisting of: deuterium; halo; cyano; nitro; hydroxyl; carbonyl; ester; imino; imino; primary amine ; carboxyl group; sulfonic acid group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; alkylthiol group; arylthiol group; alkylthiooxy; arylthiooxy; silicon boryl; alkyl; cycloalkyl; alkenyl; aryl; aralkyl; aralkenyl; alkaryl; alkoxysilylalkyl; arylphosphino or containing N, O and S atoms A heterocyclyl group of at least one of, or unsubstituted or substituted with a substituent to which two or more of the substituents exemplified above are attached. For example, "a substituent to which two or more substituents are attached" can be biphenyl. That is, a biphenyl group can also be an aryl group, and can be interpreted as a substituent to which two phenyl groups are attached.

或

意謂與另一取代基連接的鍵，且直接鍵意謂其中在表示為L的部分中不存在其他原子的情況。 In this manual, the symbol

or

means a bond to another substituent, and a direct bond means a case where no other atoms are present in the moiety denoted L.

In this specification, a (meth)propenyl group means that both a propenyl group and a methacryl group are included.

In the present specification, an alkyl group is a monovalent functional group derived from an alkane, and may be linear or branched. The number of carbon atoms of the straight-chain alkyl group is not particularly limited, but preferably 1 to 20. In addition, the branched chain alkyl group has 3 to 20 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tertiary butyl, tertiary butyl, 1-methyl-butyl , 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tertiary 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, tertiary 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, but not limited to this. Alkyl groups can be substituted or unsubstituted, and when they are substituted, examples of substituents are the same as described above.

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

In the following, the present disclosure will be described in more detail.

1. Photosensitive resin composition.

According to one embodiment of the present disclosure, there can be provided a photosensitive resin composition comprising: a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the following Chemical Formula 2, a repeating unit represented by the following Chemical Formula 3, and a repeating unit represented by the following Chemical formula The alkali-developable binder resin of the repeating unit represented by 4; a photopolymerization initiator; and a photopolymerizable compound, wherein the photosensitive resin composition satisfies any one of the following (a) or (b): (a) For a resist pattern obtained by exposing and developing a photosensitive resin layer containing a photosensitive resin composition, the amount of the resist residue remaining on the bottom surface in the space between the lines of the photosensitive resin layer adjacent to each other Maximum foot length of 1 micron or less meters, or (b) For a film sample in which a photosensitive resin layer containing a photosensitive resin composition is laminated on a substrate, when nickel plating is performed with an aqueous solution containing nickel for 20 minutes or more, the adhesive force defined by the following Equation 1 90% or more.

[Equation 1] Adhesion (%)=(surface area of the photosensitive resin layer containing the photosensitive resin composition after nickel plating in contact with the substrate/surface area of the photosensitive resin layer containing the photosensitive resin composition in contact with the substrate before nickel plating)×100 ,

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

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

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

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

The inventors have found through experiments that the photosensitive resin composition of one embodiment contains repeating units represented by Chemical Formula 1 in the alkali-developable binder resin, so that the photosensitive resin composition is formed by exposing and developing a dry film photoresist using the photosensitive resin composition. When patterning, the length of the resist residue can be minimized at the lower end portion of the resist residue, thus realizing a fine pattern with high resolution and completing the present disclosure.

In addition, the present inventors found through experiments that since the photosensitive resin composition of one embodiment contains a repeating unit represented by Chemical Formula 1 in the alkali-developable adhesive resin to improve the electroplating resistance of the alkali-developable adhesive resin, therefore The detachment phenomenon due to hydrogen bubbles can be minimized during nickel plating of a dry film photoresist using a photosensitive resin composition, and the present disclosure is completed.

(1) Alkaline developable binder resin

The alkali-developable binder resin of the present disclosure may include: by Chemical Formula 1 The repeating unit represented by Chemical Formula 2, the repeating unit represented by Chemical Formula 3, and the repeating unit represented by Chemical Formula 4.

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

Since the repeating unit represented by Chemical Formula 1 is contained in the alkali-developable binder resin to thereby increase the hydrophobicity of the alkali-developable binder resin, it inhibits the use of a dry film type photoresist using a photosensitive resin composition. Foam is generated during the development process, and thus exhibits excellent development properties and has the potential to improve substrate adhesion and thus ensure proper physical properties (resolution, fine line adhesion, etc.).

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

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

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

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

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

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

The repeating unit represented by Chemical Formula 1 may be contained in an amount of 5 mol % or more and 40 mol % based on 100 mol % of the total repeating units contained in the alkali-developable binder resin or less than 40 mol%, 5 mol% or more than 5 mol% and 30 mol% or less than 30 mol%, 5 mol% or more than 5 mol% and 25 mol% or less than 25 mol% or 10 mol% or more and 25 mol% or less.

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

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

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

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

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

In Chemical Formula 2-1, R ₃ is hydrogen or an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 2-1, R ₃ is the same as described above for Chemical Formula 2. Specific examples of the monomer represented by Chemical 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.

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

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

[Chemical formula 4-1]

In Chemical Formula 4-1, Ar is an aryl group having 6 to 20 carbon atoms. In Chemical Formula 4-1, the content of Ar is the same as that described above for Chemical Formula 4. Specific examples of the monomer represented by Chemical Formula 4-1 may include styrene (SM).

The alkaline developable binder resin may contain 20 mol % or more and 60 mol % or less, based on 100 mol % of the total repeating units contained in the alkali developable binder resin %, 20 mol% or greater than 20 mol% and 50 mol% or less than 50 mol% or 30 mol% or greater than 30 mol% and 40 mol% or less than 40 mol% by Chemical formula 2 Represents a repeating unit.

In addition, the alkaline developable binder resin may contain 1 mol % or more and 30 mol % or less based on 100 mol % of the total repeating units contained in the alkali developable binder resin 30 mol % or 5 mol % or more and 30 mol % or less of the repeating unit represented by Chemical Formula 3, and 30 mol % or more and 60 mol % % or less than 60 mol%, 30 mol% or more than 30 mol% and 50 mol% or less than 50 mol% or 30 mol% or more than 30 mol% and 40 mol% or less than 40 mol% % of the repeating unit represented by Chemical Formula 4.

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

Thus, as the content of the repeating unit represented by Chemical Formula 4 having hydrophobicity increases, the degree of hydrophobicity of the alkali-developable binder resin also increases, thereby inhibiting the development process of the dry film type photoresist using the photosensitive resin composition generation of bubbles.

The alkaline 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 20°C or more and 150°C or less Glass transition temperature of 150°C. Thereby, the coating characteristics and followability of the dry film type photoresist and the mechanical strength of the resist itself after circuit formation can be improved.

As used herein, weight average molecular weight refers to polystyrene converted weight average molecular weight as measured by gel permeation chromatography (GPC). In the process of measuring polystyrene-converted weight average molecular weight by GPC, detectors and analytical columns such as commonly known analytical equipment and differential refractive index detectors can be used, and commonly used The temperature conditions, solvents, and flow rates of the application.

Specific examples of measurement conditions are as follows. The alkaline developable binder resin was dissolved in tetrahydrofuran to have a concentration of 1.0 (w/w) % in THF (approximately 0.5 (w/w) % by solids), filtered using a 0.45 micron pore size syringe was filtered and then injected into GPC in an amount of 20 microliters, and tetrahydrofuran (THF) was used as the mobile phase of GPC and the flow rate was 1.0 mL/min. The column was configured with one Agilent Plagal 5-micron guard (7.5 x 50 mm) and two Agilent Plagal 5-micron Mixed D (7.5 x 300 mm) connected in series and stored at 40°C by using an Agilent The 1260 Infinity II system and RI detector perform the measurements.

Polystyrene standard samples (STD A, STD B, STD C, STD D) and then injected into GPC, and the value of the weight average molecular weight (Mw) of the alkaline developable binder resin was determined using a calibration curve.

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

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

STD C(MP): 126,000/4430/370

STD D(MP): 51,200/1920/162

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

Alkaline developable binder resins may have 120 mg KOH/gram or greater than 120 mg KOH/gram and 200 mg KOH/gram or less than 200 mg KOH/gram or 140 mg KOH/gram or greater than 140 mg KOH/gram and 160 mg Acid value of KOH/gram or less than 160 mg KOH/gram. Measure the acid value by the following procedure: sample about 1 gram of alkaline developable binder resin, dissolve it in 50 ml of mixed solvent (MeOH 20%, acetone 80%), add two drops of 1% phenolphthalein indicator to it, and The acid value was then measured by titration with 0.1N-KOH.

The alkali-developable binder resin is contained in an amount of 20 wt % or more and 80 wt % or less with respect to the total weight of the photosensitive resin composition in terms of solid content. When the content of the alkali-developable binder resin is within the above-mentioned range, it is possible to obtain the effect of enhancing the adhesion of fine lines after circuit formation. The solid content by weight means the remaining components excluding the solvent from the photosensitive resin composition.

The content of the alkaline developable binder resin of the present disclosure may be 40 wt % or more and 70 wt % or less with respect to the total weight of the photosensitive resin composition. When the content of the alkali-developable binder resin is less than 40% by weight with respect to the total photosensitive resin composition, there is a risk of contamination due to development There are disadvantages such as short circuit defects, and when the content of the alkali-developable binder resin exceeds 70% by weight, there are problems such as deterioration of circuit characteristics such as adhesion and resolution.

Meanwhile, the alkali-developable binder resin may further include a repeating unit represented by the following Chemical Formula 13, a repeating unit represented by the following Chemical Formula 14, a repeating unit represented by the following Chemical Formula 15, a repeating unit represented by the following Chemical Formula 16, and A first alkali-developable binder resin comprising a repeating unit represented by the following Chemical Formula 17; and a second alkali-developable binder resin 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 Alkaline developable binder resin.

In Chemical Formula 13, R ₃ " is hydrogen,

In Chemical Formula 14, R ₃ ' is an alkyl group having 1 to 10 carbon atoms, [Chemical Formula 15]

In Chemical Formula 15, R ₄ " is an alkyl group having 1 to 10 carbon atoms, and R ₅ " is an alkyl group having 1 to 10 carbon atoms,

In Chemical Formula 16, _Ar is an aryl group having 6 to 20 carbon atoms,

And in Chemical Formula 17, R ₄ ' is hydrogen, and R ₅ ' is an alkyl group having 1 to 10 carbon atoms.

Specifically, the first alkali-developable binder resin may include a repeating unit represented by Chemical Formula 13, a repeating unit represented by Chemical Formula 14, a repeating unit represented by Chemical Formula 15 A random copolymer of the repeating unit represented by Chemical Formula 16, the repeating unit represented by Chemical Formula 16, and the repeating unit represented by Chemical Formula 17.

In Chemical Formula 13 to Chemical Formula 17, specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group.

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

The repeating unit represented by Chemical Formula 14 may be a repeating unit derived from a monomer represented by the following Chemical Formula 14-1.

In Chemical Formula 14-1, R ₃ " is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 14-1, the content of R ₃ " is the same as described above for Chemical Formula 14. Specific examples of the monomer represented by Chemical Formula 14-1 may include methacrylic acid (MAA).

The repeating unit represented by Chemical Formula 15 may be a repeating unit derived from a monomer represented by the following Chemical Formula 15-1.

In Chemical Formula 15-1, R ₄ " is an alkyl group having 1 to 10 carbon atoms, and R ₅ " is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 15-1, the definitions of R ₄ " and R ₅ " are the same as described above for Chemical Formula 15. Specific examples of the monomer represented by Chemical Formula 15-1 may include methyl methacrylate (MMA).

The repeating unit represented by Chemical Formula 16 may be a repeating unit derived from a monomer represented by the following Chemical Formula 16-1.

In Chemical Formula 16-1, Ar is an aryl group having 6 to 20 carbon atoms. In Chemical Formula 16-1, the definition of Ar is the same as that described for Chemical Formula 16. Specific examples of the monomer represented by Chemical Formula 16-1 may include styrene (SM).

The first alkaline developable binder resin may have a weight average molecular weight of 30000 g/mol or more and 150000 g/mol or less and 20°C or more and 150°C or a glass transition temperature of less than 150°C. Thereby, the coating characteristics and traceability of the dry film type photoresist and the mechanical strength of the resist itself after circuit formation can be improved. Additionally, the first alkaline developable binder resin may have an acid value of 140 mg potassium hydroxide/gram or greater and 160 mg potassium hydroxide/gram or less.

In addition, the second alkaline developable binder resin may have a weight average molecular weight of 20,000 g/mol or more and 130,000 g/mol or less and 30°C or more and A glass transition temperature of 160°C or less. Thereby, the coating characteristics and traceability of the dry film type photoresist and the mechanical strength of the resist itself after circuit formation can be improved.

As used herein, weight average molecular weight refers to the (GPC) Measured weight average molecular weight of polystyrene converted. In the process of measuring the weight average molecular weight of polystyrene conversion by GPC, detectors and analytical columns, such as commonly known analytical equipment and differential refractive index detectors, can be used, and commonly applied temperature conditions, solvents, and flow rates.

Specific examples of measurement conditions are as follows. The alkaline developable binder resin was dissolved in tetrahydrofuran to have a concentration of 1.0 (w/w) % in THF (approximately 0.5 (w/w) % by solids), filtered using a 0.45 micron pore size syringe was filtered and then injected into GPC in an amount of 20 microliters, and tetrahydrofuran (THF) was used as the mobile phase of the GPC and the flow rate was 1.0 ml/min. The column was configured with one Agilent Plagal 5 micron guard (7.5 x 50 mm) and two Agilent Plagal 5 micron Mixed D (7.5 x 300 mm) connected in series, and was heated at 40°C by using an Agilent 1260 Infinity II The system and the RI detector perform the measurements.

Polystyrene standard samples (STD A, STD B, STD C, STD D) and then injected into GPC, and the value of the weight average molecular weight (Mw) of the alkaline developable binder resin was determined using a calibration curve.

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

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

STD C(Mp): 126,000/4430/370

STD D(Mp): 51,200/1920/162

The glass transition temperatures of the reference and binder polymers were compared by differential scanning calorimeter (DSC) (Perkin Elmer, DSC-7). can be achieved by maintaining the temperature at 20°C for 15 minutes and then increasing the temperature to 200°C at a rate of 1°C/minute Perform measurements.

The acid value of the alkali-developable adhesive resin was measured by the following process: sample about 1 gram of the alkali-developable adhesive resin, dissolve it in 50 ml of mixed solvent (MeOH 20%, acetone 80%), add two 1% phenolphthalein indicator was dropped, and then the acid value was measured by titration with 0.1N-KOH.

The first alkaline developable binder resin may have an acid value of 140 mg potassium hydroxide/gram or greater and 160 mg potassium hydroxide/gram or less. Additionally, the second alkaline developable binder resin may have an acid value of 160 mg potassium hydroxide/gram or greater and 200 mg potassium hydroxide/gram or less.

Specifically, the ratio of the glass transition temperature of the first alkaline developable binder resin to the second alkaline developable binder resin may be 1:1.5 or more and 1:5 or less than 1:5, 1 : 1.5 or more than 1: 1.5 and 1: 3 or less than 1: 3, 1: 1.5 or more than 1: 1.5 and 1: 2 or less than 1: 2, 1: 1.5 or more than 1: 1.5 and 1: 1.8 or less than 1 : 1.8, 1:1.5 or greater than 1:1.5 and 1:1.75 or less than 1:1.75 or 1:1.5 or greater than 1:1.5 and 1:1.6 or less than 1:1.6.

In addition, the acid value ratio of the first alkali-developable binder resin to the second alkali-developable binder resin may be 1:1.01 or more and 1:1.5 or less, 1:1.01 or more 1:1.01 and 1:1.25 or less than 1:1.25, 1:1.01 or more than 1:1.01 and 1:1.2 or less than 1:1.2 or 1:1.01 or more than 1:1.01 and 1:1.1 or less than 1:1.1.

Meanwhile, the first alkali-developable binder resin contained in the photosensitive resin composition of one embodiment may contain 1.2 mol or more and 3 mol or less of the repeating unit represented by Formula 3 with respect to 1 mol 3 moles, 1.2 moles or more and 2 moles or less, 1.5 moles or more than 1.5 moles and 2 moles or The repeating unit represented by Chemical Formula 4 is less than 2 moles or 1.5 moles or more than 1.5 moles and 1.6 moles or less.

In addition, the first alkali-developable binder resin contained in the photosensitive resin composition of one embodiment may be 2 mol or more and 10 mol or more of the repeating unit represented by Chemical Formula 17 with respect to 1 mol. less than 10 moles, 3 moles or greater than 3 moles and 10 moles or less than 10 moles, 3 moles or greater than 3 moles and 5 moles or less than 5 moles or 4 moles or greater than 4 moles and The amount of 5 mol or less includes the repeating unit represented by Chemical Formula 15.

Meanwhile, the second alkaline developable binder resin may include a random copolymer of a repeating unit represented by the following Chemical Formula 14, a repeating unit represented by the following Chemical Formula 15, and a repeating unit represented by the following Chemical Formula 16.

In Chemical Formula 14, R ₃ ′ is an alkyl group having 1 to 10 carbon atoms.

In Chemical Formula 15, R ₄ " is an alkyl group having 1 to 10 carbon atoms, and R ₅ " is an alkyl group having 1 to 10 carbon atoms.

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

The repeating unit represented by Chemical Formula 14 may be a repeating unit derived from a monomer represented by the following Chemical Formula 14-1.

In Chemical Formula 14-1, R ₃ " is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 14-1, the definition of R ₃ " is the same as that described for Chemical Formula 14. Specific examples of the monomer represented by Chemical Formula 14-1 may include methacrylic acid (MAA).

The repeating unit represented by Chemical Formula 15 may be a repeating unit derived from a monomer represented by the following Chemical Formula 15-1.

In Chemical Formula 15-1, R ₄ " is an alkyl group having 1 to 10 carbon atoms, and R ₅ " is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 15-1, the definitions of R ₄ " and R ₅ " are the same as those described for Chemical Formula 15. Specific examples of the monomer represented by Chemical Formula 15-1 may include methyl methacrylate (MMA).

The repeating unit represented by Chemical Formula 16 may be a repeating unit derived from a monomer represented by the following Chemical Formula 16-1.

In Chemical Formula 16-1, Ar is an aryl group having 6 to 20 carbon atoms. In Chemical Formula 16-1, the definition of Ar is the same as that described for Chemical Formula 16. Specific examples of the monomer represented by Chemical Formula 16-1 may include styrene (SM).

Specifically, the first alkali developable binder resin may be 1:(2 or more and 5 or less than 5):(0.2 or more and 0.9 or less than 0.9), 1:(2 or more and 3 or Less than 3): (0.5 or greater than 0.5 and 0.9 or less than 0.9), 1: (2.5 or greater than 2.5 and 3 or less than 3): (0.6 or greater than 0.6 and 0.9 or less than 0.9) or 1: (2.75 or greater than 2.75 and 3 or less than 3): The ratio of (0.6 or more and 0.75 or less than 0.75) includes the repeating unit represented by Chemical Formula 14: the repeating unit represented by Chemical Formula 15: the repeating unit represented by Chemical Formula 16.

In addition, the second alkali developable binder resin may be 1:(1.1 or more and 2 or less than 2):(0.2 or more and 0.99 or less than 0.99), 1:(1.5 or more and 2 or less than 2 ): (0.5 or more and 0.99 or less than 0.99) or 1: (1.5 or more and 1.75 or less than 1.75): (0.75 or more and 0.99 or less than 0.99) at a ratio including the repeating unit represented by Chemical Formula 14: Repeating unit represented by Chemical Formula 15: Repeating unit represented by Chemical Formula 16.

Meanwhile, based on 100 parts by weight of the first alkali developable binder resin, The photosensitive resin composition of one embodiment of the present disclosure may include 500 parts by weight or more and 1000 parts by weight or less than 1000 parts by weight, 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 second alkali developable binder resin.

As described above, since the second alkaline developable binder resin is added in an excessive amount of 500 parts by weight or more based on 100 parts by weight of the first alkaline developable binder resin, it is possible to achieve imparting The hydrophobic function of the photosensitive resin increases the resistance to the developer solution and the technical effect of improving the circuit characteristics.

(2) Photopolymerization initiator

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

Compounds that can be used as photopolymerization initiators can include anthraquinone derivatives such as 2-methylanthraquinone and 2-ethylanthraquinone; and benzoin derivatives such as benzoin methyl ether, benzophenone, phenanthraquinone and 4,4'-bis(dimethylamino)benzophenone.

In addition, from 2,2'-bis(2-chlorophenyl)-4,4'-5,5'-tetraphenylbisimidazole, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy -1,2-Diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-N-morpholinopropan-1-one, 2-benzyl yl-2-dimethylamino-1-[4-N-morpholinophenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4 ,6-Trimethylbenzyldiphenylphosphine oxide, 1-[4-(2-hydroxymethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, 2,4 -Diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1 -Chloro-4-propoxythioxanthone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl) -2-Hydroxy -2-Methylpropan-1-one, 4-benzyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate , 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid butyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 4-dimethylaminobenzoic acid 2-Isoamyl ester, 2,2-diethoxyacetophenone, benzyl ketone dimethyl acetal, benzyl ketone β-methoxydiethyl acetal, 1-phenyl-1,2 -Propyldioxime-o,o'-(2-carbonyl)ethoxy ether, methyl o-benzylbenzoate, bis[4-dimethylaminophenyl)ketone, 4,4'-bis (Diethylamino)benzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin , isobutoxybenzoin, tertiary butoxybenzoin, p-dimethylaminoacetophenone, p-tertiary butyl trichloroacetophenone, p-tertiary butyl dichloroacetophenone, thioxanthone, 2 - Methyl thioxanthone, 2-isopropyl thioxanthone, dibenzocycloheptanone, α,α-dichloro-4-phenoxyacetophenone, and amyl 4-dimethylaminobenzoate Compounds selected from these can be used as photopolymerization initiators, but are not limited thereto.

The photopolymerization initiator is contained in an amount of 1 wt % or more and 10 wt % or less with respect to the total weight of the photosensitive resin composition in terms of solid content. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity can be obtained. The solid content by weight means the remaining components excluding the solvent from the photosensitive resin composition.

When the content of the photopolymerization initiator is less than 1% by weight, light efficiency is low and a large amount of exposure must be applied, and thus there is a disadvantage that production efficiency is extremely lowered. When the content of the photopolymerization initiator exceeds 10% by weight, there is a problem that the film is brittle and the contamination of the developer solution increases, causing short-circuit or the like defects.

(3) Photopolymerizable compounds

The photopolymerizable compounds of the present disclosure have a Resistant to developer solutions and enables patterning.

The photopolymerizable compound may include a bifunctional (meth)acrylate compound. The bifunctional (meth)acrylate compound may contain 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 5 can be used.

In Chemical Formula 5, l+n is an integer of 2 or 3, and m is an integer of 12 to 18.

The compound represented by Chemical Formula 5 can improve the hydrophobicity of the photosensitive resin composition, significantly improve the resistance to developer solutions and plating solutions, and shorten the peeling time of the cured film.

In the present disclosure, the compound represented by Chemical Formula 5 may be 10 wt % or more and 60 wt % or less than 60 wt % or 20 wt % or more based on the total weight of the solid content of the photosensitive resin composition 20% by weight and 40% by weight or less.

If the content of the compound represented by Chemical Formula 5 is less than 10% by weight based on the total weight of the solid content of the photosensitive resin composition, the effect due to the addition of the compound represented by Chemical Formula 5 is insufficient, and if the content exceeds 60% by weight , there may be problems that the hydrophobicity increases and the development time of the development process increases rapidly after exposure.

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

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

Examples of bisphenolic di(meth)acrylates containing greater than 8 moles and 16 moles or less of ethylene oxide may include Miramer M2100 (BPA(EO) ₁₀ manufactured by American Source Specialty Chemicals, Inc. DA, Bisphenol A(EO) ₁₀ Diacrylate), Miramer M2200 (BPA(EO) ₂₀ DA, Bisphenol A(EO) ₂₀ Diacrylate) and Miramer M2101 (Bisphenol A(EO) ₁₀ Dimethacrylate) ester).

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

Meanwhile, the photopolymerizable compound may contain a trifunctional or higher polyfunctional (meth)acrylate compound.

The trifunctional or higher polyfunctional (meth)acrylate compound may have three or more alkylene oxide groups having 1 to 10 carbon atoms therein and three or more (meth)acrylates The functional group is bonded to a structure having a central group of 1 to 20 carbon atoms.

The trifunctional or higher polyfunctional (meth)acrylate compound may include a compound represented by the following Chemical Formula 12.

In Chemical Formula 12, R ₁₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₁₅ is an alkylene group having 1 to 10 carbon atoms, and R ₁₆ is an alkylene group having 1 to 20 carbon atoms The p-valent functional group of the central group, n12 is an integer of 1 to 20 and p is the number of functional groups substituted for _R16 and is an integer of 3 to 10.

The photopolymerizable compound may further contain a monofunctional (meth)acrylate compound. That is, the photosensitive resin composition according to one embodiment of the present disclosure may include a mixture of a monofunctional (meth)acrylate compound and a trifunctional or higher polyfunctional (meth)acrylate compound.

The monofunctional (meth)acrylate compound may contain a (meth)acrylate containing an alkylene oxide group having 1 to 10 carbon atoms.

More specifically, the monofunctional (meth)acrylate compound may include a compound represented by the following Chemical Formula 11.

[Chemical formula 11]

In Chemical Formula 11, R ₁₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₁₂ is an alkylene group having 1 to 10 carbon atoms, and R ₁₃ is an alkylene group having 1 to 10 carbon atoms The alkyl group and n11 are integers from 1 to 20.

By including the monofunctional (meth)acrylate compound represented by Chemical Formula 11 and the trifunctional or higher polyfunctional (meth)acrylate compound represented by Chemical Formula 12, the circuit characteristics are equivalent to those of the existing product, However, the photocuring speed is increased so that, for technical reasons of accelerating the color development time of the resulting film and increasing the amount of color change, the time required to change the contrast is increased, thereby ensuring excellent development characteristics.

Specifically, in Chemical Formula 11, n11 may be an integer of 1 to 20, an integer of 1 to 10, or an integer of 5 to 10. Examples of the monofunctional (meth)acrylate compound represented by Chemical Formula 11 are not particularly limited, but may be, for example, methoxypropanediol [400]acrylate (A040) represented by Chemical Formula A below.

Since the photosensitive resin composition of one embodiment contains the monofunctional (meth)acrylate compound represented by Chemical Formula 11, it is possible to realize a method of rapidly implementing the color change of the film in the exposed portion due to the technical reason of increasing the photocuring speed. Effect.

In addition, in Chemical Formula 12, n12 is an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to 5, and p means the number of functional groups substituted for R ₁₆ and may be an integer of 3 to 10, an integer of 3 to 10 An integer of 5 or an integer of 3 to 4.

That is, in Chemical Formula 12, since p meaning the number of functional groups substituted for R ₁₆ is an integer of 3 to 10, it may be a trifunctional or higher polyfunctional (meth)acrylate represented by Chemical Formula 12 compound.

Specifically, the trifunctional or higher polyfunctional (meth)acrylate compound may be represented by the following Chemical Formula 12-1.

In Chemical Formula 12-1, R ₂₀ is a trivalent organic group, R ₂₁ to R ₂₃ are each independently an alkylene group having 1 to 10 carbon atoms, and R ₂₄ to R ₂₆ are each independently hydrogen or have The alkyl group of 1 to 10 carbon atoms, and n to n5 are each independently an integer of 1 to 20.

In Chemical Formula 12-1, n13 to n15 may be an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to 5.

Examples of the trifunctional or higher polyfunctional (meth)acrylate compound represented by Chemical Formula 12 are not limited, but may be, for example, T063 (trimethylolpropane [EO] ₆ triacrylate) represented by the following Chemical Formula B .

[Chemical formula B]

Since the photosensitive resin composition of one embodiment includes the trifunctional or higher polyfunctional (meth)acrylate compound represented by Chemical Formula 12, the trifunctional or higher polyfunctional (meth)acrylate compound represented by Chemical Formula 12 has a Functional or higher polyfunctional (meth)acrylate compounds have increased crosslinking during photocuring, and reactive groups prevent degradation of circuit characteristics due to various technical reasons and can achieve the effect of increasing the amount of color development change .

Meanwhile, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photosensitive resin composition of one embodiment may be 110 parts by weight or more and 500 parts by weight or less, 110 parts by weight or more 110 parts by weight and 300 parts by weight or less, 110 parts by weight or more and 200 parts by weight or less or 150 parts by weight or more and 200 parts by weight or less Contains trifunctional or higher polyfunctional (meth)acrylate compounds.

Since the photosensitive resin composition of one embodiment contains the trifunctional or higher polyfunctional (meth)acrylate compound in excess relative to the monofunctional (meth)acrylate compound, it is possible to simultaneously achieve an increase in the amount represented by Chemical Formula 11. The photo-curing speed of the monofunctional (meth)acrylate compound and thus the effect of rapidly implementing the color change of the film and the increase in cross-linking during photocuring of the trifunctional or higher polyfunctional (meth)acrylate compound represented by Chemical Formula 12 and thus prevent the decrease in circuit characteristics that occurs when only monofunctional materials are added and the increase in color change by increasing the amount of reactive groups amount of effect.

When the photosensitive resin composition of one embodiment contains less than 100 parts by weight of a trifunctional or higher polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound, there may be a circuit The technical problem is that the characteristics are deteriorated and the amount of color development change is reduced.

In addition, the photopolymerizable compound may include a bifunctional (meth)acrylate compound, a monofunctional (meth)acrylate compound represented by Chemical Formula 11, and a trifunctional or higher polyfunctional (meth)acrylic acid represented by Chemical Formula 12 ester compound.

That is, the photosensitive resin composition of one embodiment includes a photopolymerizable compound, and the photopolymerizable compound may include a monofunctional (meth)acrylate compound, a trifunctional or higher polyfunctional (meth)acrylate compound, and a difunctional (meth)acrylate compound. Functional (meth)acrylate compounds.

Specifically, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photosensitive resin composition of one embodiment may be 500 parts by weight or more and 1500 parts by weight or less, 500 parts by weight or more than 500 parts by weight and 1000 parts by weight or less than 1000 parts by weight, 750 parts by weight or more than 750 parts by weight and 1000 parts by weight or less than 1000 parts by weight or 800 parts by weight or more than 800 parts by weight and 900 parts by weight or less than 900 parts by weight contains a difunctional (meth)acrylate compound.

That is, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photosensitive resin composition of one embodiment may contain 110 parts by weight or more of trifunctional or higher polyfunctional (meth)acrylic acid An ester compound and 500 parts by weight or more and 1500 parts by weight or less of a bifunctional (meth)acrylate compound.

In addition, based on 100 parts by weight of the trifunctional or higher polyfunctional (meth)acrylate compound, the photosensitive resin composition of one embodiment may be 500 parts by weight or more and 1000 parts by weight or less, 500 parts by weight or more and 800 parts by weight or less, 500 parts by weight or more and 750 parts by weight or less, 500 parts by weight or more and 700 parts by weight or less The bifunctional (meth)acrylate compound is contained in an amount of 700 parts by weight or 500 parts by weight or more and 600 parts by weight or less.

As described above, since a monofunctional (meth)acrylate compound, a trifunctional or higher polyfunctional (meth)acrylate compound, and a bifunctional (meth)acrylate compound are contained while satisfying the above weight range, a The photosensitive resin composition of the embodiment can exhibit appropriate circuit characteristics, and when a light intensity of 10 mJ/cm 2 or more is applied, a technology capable of rapid color development and color change of an exposed portion can be realized Effect.

More specifically, based on 100 parts by weight of the bifunctional (meth)acrylate compound, the photosensitive resin composition of one embodiment may be 100 parts by weight or less, 50 parts by weight or less, 1 part by weight part by weight or more and 50 parts by weight or less or 1 part by weight or more and 100 parts by weight or less containing the monofunctional (meth)acrylate compound represented by Chemical Formula 11 and a trifunctional or higher polyfunctional (meth)acrylate compound represented by Chemical Formula 12.

The content of the photopolymerizable compound may be 10 wt % or more and 70 wt % or less with respect to the total weight of the photosensitive resin composition in terms of solid content. When the content of the photopolymerizable compound is within the above range, there may be The effect of enhancing photosensitivity, resolution, adhesion and the like can be obtained. The solid content by weight means the remaining components excluding the solvent from the photosensitive resin composition.

(4) Photosensitive resin composition

The photosensitive resin composition may satisfy any one of the following (a) or (b): (a) For the resist pattern obtained by exposing and developing the photosensitive resin layer containing the photosensitive resin composition, in the photosensitive resin adjacent to each other; In the space between the layer lines, the maximum foot length of the resist residue remaining on the bottom surface is 1 micrometer or less, or (b) for the photosensitive resin layer in which the photosensitive resin composition is laminated on the The film sample on the substrate, when nickel-plated with an aqueous solution containing nickel for 20 minutes or more, had an adhesion of 90% or more as defined by Equation 1 below.

[Equation 1] Adhesion (%)=(surface area of the photosensitive resin layer containing the photosensitive resin composition after nickel plating in contact with the substrate/surface area of the photosensitive resin layer containing the photosensitive resin composition in contact with the substrate before nickel plating)×100 .

Specifically, for a resist pattern obtained by exposing and developing a photosensitive resin layer containing a photosensitive resin composition, the resist residue remaining on the bottom surface in the space between the lines of the photosensitive resin layer adjacent to each other The maximum foot length can be 1 micron or less, 0.7 microns or less than 0.7 microns, 0.1 microns or more than 0.1 microns and 1 microns or less, 0.1 microns or more than 0.1 microns and 0.7 microns or less than 0.7 microns, 0.4 microns or greater than 0.4 microns and 0.7 microns or less than 0.7 microns or 0.5 microns or greater than 0.5 microns and 0.6 microns or less than 0.6 microns.

A resist pattern is obtained by selectively exposing and developing the photosensitive resin composition, so that a part of the photosensitive resin composition remains as a photosensitive resin layer to form a photosensitive resin composition The resin layer lines and a portion thereof may be removed by development to form spaces between the photosensitive resin layer lines.

At this time, a resist residue remaining without being removed by development may exist on the bottom surface in the space between the photosensitive resin layer lines adjacent to each other, and when the foot length of this resist residue is excessively raised Above 1 micron, the footing phenomenon may occur excessively at the bottom portion of the pattern, making it difficult to implement a resist pattern with high resolution.

Specifically, the full length of the resist residue may be the shortest straight-line distance between the following points: a point on the boundary line formed by the contact of one side of the photosensitive resin layer line with the bottom surface and the resist residue, The cross-section of the plane formed by the vertical line on one side of the photosensitive resin layer line from one point and the vertical line on the bottom surface from one point with the resist residue and the bottom surface and the resist residue The intersection formed where the dividing line crosses.

The full length of the resist residue will be described with reference to the schematic cross-sectional view of the resist pattern in FIG. 2 below. One point on the boundary line formed by the contact of one side of the photosensitive resin layer line with the bottom surface and the resist residue corresponds to the point indicated by d1, and the resist residue is on the photosensitive resin layer starting from one point. The cross-section of the plane formed by the vertical line on one side of the line and the vertical line of the bottom surface from one point intersects the dividing line formed by the bottom surface and the resist residue. The intersection corresponds to the point indicated by d2. The shortest straight-line distance between d1 and d2 corresponds to the full length of the resist residue.

The full length of the resist residue can be measured via an optical microscope (ZEISS AXIOPHOT Microscope) as shown in FIG. 1 .

More specifically, in a resist used to measure the full length of the resist residue In the agent pattern, the ratio between the line width of the upper end of the photosensitive resin layer line and the interval between the upper end portions of the photosensitive resin layer line adjacent to each other may be 1:0.5 to 1:2 or 1:0.9 to 1:1.1. In other words, the line width of the upper end of the photosensitive resin layer line corresponds to L in Fig. 2 below, and the interval between the upper end portions of the photosensitive resin layer lines adjacent to each other corresponds to S in Fig. 2 below.

In addition, the line width of the upper end of the photosensitive resin layer line for measuring the full length of the resist residue may be 5 micrometers or more and 15 micrometers or less than 15 micrometers or 9 micrometers or more than 9 micrometers and 11 micrometers or less than 11 microns. The line width of the upper end of the photosensitive resin layer line can be measured through an optical microscope.

The thickness of the photosensitive resin layer for measuring the full length of the resist residue may be 20 microns or more and 30 microns or less or 24 microns or more and 26 microns or less. The thickness of the photosensitive resin layer corresponds to T in Fig. 2 below. The thickness of the photosensitive resin layer can be measured through an optical microscope.

The exposure conditions for measuring the full length of the resist residue are 35 mJ/cm 2 or more and 45 mJ/cm 2 or less than 45 mJ/cm 2 or The exposure dose of 39 mJ/cm 2 or more and 41 mJ/cm 2 or less is used to irradiate ultraviolet rays. The exposure time can be 1 minute or more and 10 minutes or less.

The development conditions when measuring the full length of the resist residue are that a concentration of 0.5 wt % or more and 1.5 wt % or less than 1.5 wt % or 0.9 wt % or more and 1.1 wt % or more can be used. Less than 1.1 wt% alkaline aqueous solution. The pH of the alkaline aqueous solution may be in the range of 9 or more and 11 or less, and the temperature may be adjusted according to the developing characteristics of the photosensitive resin layer. Specificity of alkaline aqueous solution Examples may include aqueous sodium carbonate, aqueous potassium carbonate, and aqueous sodium hydroxide.

The development may be performed using a method of contacting an alkaline aqueous solution with the photosensitive resin layer, and as an example of a specific contact method, spraying or immersion may be used. The development time may be 1 minute or more and 10 minutes or less.

Meanwhile, the photosensitive resin composition may have the following characteristics: with respect to a film sample in which a photosensitive resin layer containing the photosensitive resin composition is laminated on a substrate, when nickel plating is performed with an aqueous solution containing nickel for 20 minutes or more, by The adhesive force defined by Equation 1 below is 90% or more or 90% or more and 100% or less.

[Equation 1] Adhesion (%)=(surface area of the photosensitive resin layer containing the photosensitive resin composition after nickel plating in contact with the substrate/surface area of the photosensitive resin layer containing the photosensitive resin composition in contact with the substrate before nickel plating)×100.

Adhesion defined by Equation 1 means the percentage ratio of the surface area of the photosensitive resin layer containing the photosensitive resin composition after nickel plating in contact with the substrate to the surface area of the photosensitive resin layer containing the photosensitive resin composition before nickel plating in contact with the substrate.

The surface area used to determine adhesion can be measured via optical microscope images.

The specific conditions for nickel plating are not particularly limited, but for example, by using an aqueous solution of ICP NICORON GIB (a mixture of 100 cubic centimeters of ICP NICORON GIB-M and 50 cubic centimeters of ICP NICORON GIB-1 in 850 cubic centimeters of distilled water) as a An aqueous solution of nickel, immersing a film sample in which a photosensitive resin layer containing a photosensitive resin composition is laminated on a substrate under the conditions of 50°C or more and 100°C or less than 100°C for 20 minutes or more or 20 minutes or more 20 minutes or more and 30 minutes or less, thereby performing electroplating.

Before nickel plating, the immersion process with the aqueous catalyst solution must be further performed before the immersion process with the aqueous solution containing nickel. The specific conditions of the immersion process by the catalyst aqueous solution are not particularly limited, but for example, by using a hydrochloric acid-based palladium catalyst, ICP ACCERA H aqueous solution (90 cubic centimeters of 35% hydrochloric acid aqueous solution and 40 cubic centimeters of ICP ACCERA H is charged in 870 cubic centimeters). mixture in distilled water) as an aqueous catalyst solution, the film sample in which the photosensitive resin layer containing the photosensitive resin composition is laminated on the substrate can be immersed for 0.1 minute at 10°C or more and 40°C or less or more than 0.1 minutes and 10 minutes or less.

In addition, if necessary, after the immersion process with the nickel-containing aqueous solution, the immersion process with the gold-containing aqueous solution may be further performed. The specific conditions of the immersion process by the gold-containing aqueous solution are not particularly limited, but for example, under the conditions of 70°C or more and 100°C or less, by using the gold-containing aqueous solution The film sample in which the photosensitive resin layer of the photosensitive resin composition is laminated on the substrate is immersed for 1 minute or more and 20 minutes or less.

A specific example of the gold-containing aqueous solution may be IM GOLD IB MAKE UP SALT aqueous solution (a mixed solution of 80 grams of IM GOLD IB MAKE UP SALT and 2.92 grams of potassium gold cyanide charged in 1000 cubic centimeters of distilled water).

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 an arbitrary substrate, and is used for measurement by the equation An example of a substrate with defined adhesion may be a copper clad laminate on which a copper layer having a thickness of 10 microns or more and 100 mm or less is disposed on the surface.

The photosensitive resin layer may include a dried product or a cured product of the photosensitive resin composition of one embodiment. The dried product means the material obtained through the drying process of the photosensitive resin composition of one embodiment. The cured product refers to the material obtained through the curing process of the photosensitive resin composition of one embodiment.

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

Examples of the method of forming the pattern-shaped photosensitive resin layer may include a method of performing exposure and development after laminating the photosensitive resin layer of the dry film type photoresist of another embodiment described later on a substrate. In addition, a method of laminating a photosensitive resin layer of a photosensitive element of another embodiment described later on a substrate and then performing exposure and development can be mentioned.

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

In addition, when the dry film type photoresist or photosensitive element of another embodiment has a polymer substrate or a substrate film laminated on one side of the photosensitive resin layer, it may be further performed to remove the polymer substrate immediately after the exposure process or Process of substrate film.

The exposure conditions for measuring the adhesion defined by Equation 1 are that 20 mJ/cm 2 or more and 200 mJ/cm 2 or less or less using an exposure machine. The exposure dose of 50 mJ/cm2 or more and 100 mJ/cm2 or less is used to irradiate ultraviolet rays. The exposure time may be 1 second or more and 10 minutes or less or 1 second or more and 10 seconds or less.

The developing condition when measuring the adhesion defined by Equation 1 is the usable concentration 0.5 wt % or more and 1.5 wt % or less of 1.5 wt % or 0.9 wt % or more and 1.1 wt % or less of an alkaline aqueous solution. The pH of the alkaline aqueous solution may be in the range of 9 or more and 11 or less, and the temperature thereof may be adjusted according to the developing characteristics of the photosensitive resin layer. Specific examples of the alkaline aqueous solution may include an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, and an aqueous sodium hydroxide solution.

The development may be performed using a method of contacting an alkaline aqueous solution with the photosensitive resin layer, and as an example of a specific contact method, spraying or immersion may be used. The development time may be 30 seconds or more and 10 minutes or less or 30 seconds or more and 2 minutes or less.

The thickness of the photosensitive resin layer used to measure the adhesion defined by Equation 1 may be 20 micrometers or more and 80 micrometers or less or 30 micrometers or more than 30 micrometers and 60 micrometers or less. In addition, the photosensitive resin layer used to measure the adhesive force defined by Equation 1 may have parallel to 0.10 square meters or more and 1.00 square meters or less than 1.00 square meters or 0.15 square meters or more The cross-sectional area of the ground that is 0.15 square meters and 0.30 square meters or less. The thickness or cross-sectional area of the photosensitive resin layer can be measured through an optical microscope.

When the adhesion defined by Equation 1 is excessively reduced to less than 90% due to air bubbles generated during the electroplating process, undesirable circuits can be configured in the resulting circuit board or display.

In terms of solid content, the photosensitive resin composition may comprise 20 wt % or more and 80 wt % or less of an alkali developable binder resin, 1 wt % or more and 10 wt % or Less than 10% by weight of photopolymerization initiator and 10% by weight or more and 70% by weight or less photopolymerizable compounds.

The photosensitive resin composition may further contain a solvent. The solvent is generally selected from methyl ethyl ketone (MEK), methanol, THF, toluene and acetone and is not particularly limited thereto, and its content may also be determined according to the photopolymerization initiator, alkali developable adhesive The content of the resin and the photopolymerizable compound is adjusted.

In addition, the photosensitive resin composition may further contain other additives as necessary. Other additives are plasticizers and may contain dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate in the form of phthalates ; triethylene glycol diacetate, tetraethylene glycol diacetate in the form of glycol esters; p-toluenesulfonamide, benzenesulfonamide, n-butylbenzenesulfonamide in the form of acid amides; Triphenyl phosphate, etc.

In the present disclosure, leuco dyes or coloring materials may be added to improve the handling characteristics of the photosensitive resin composition. Examples of leuco dyes include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, and fluorane dyes. Among them, when leuco crystal violet is used, the contrast ratio is good, which is preferable. When the leuco dye is contained, the content based on the photosensitive resin composition may be 0.1% by weight or more and 10% by weight or less. From the viewpoint of exhibiting contrast, 0.1% by weight or more is preferable, and from the viewpoint of maintaining storage stability, 10% by weight or less is preferable.

Examples of the coloring material may include toluenesulfonic acid monohydrate, magenta, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile blue 2B, victoria blue blue), malachite green, diamond green, basic blue 20 and the like. When the coloring material is included, the added amount may be 0.001 wt % or more and 1 wt % or less based on the photosensitive resin composition weight%. When the content is 0.001% by weight or more, it has the effect of improving handleability, and when the content is 1% by weight or less, it has the effect of maintaining storage stability.

In addition, other additives may further include thermal polymerization inhibitors, dyes, discoloration agents, and adhesion accelerators.

2. Dry film photoresist

According to another embodiment of the present disclosure, a dry film photoresist can be provided, including a photosensitive resin layer including the photosensitive resin composition of one embodiment. Details about the photosensitive resin composition include all the content described above in one embodiment.

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

For example, the photosensitive resin layer may include: an alkali developable binder resin including a repeating unit represented by Chemical Formula 1; a repeating unit represented by Chemical Formula 2; a repeating unit represented by Chemical Formula 3; and a repeating unit represented by Chemical Formula 4 Repeating units, and photopolymerizable compounds. Details on the alkaline developable binder resin comprising the repeating unit represented by Chemical Formula 1; the repeating unit represented by Chemical Formula 2; the repeating unit represented by Chemical Formula 3; and the repeating unit represented by Chemical Formula 4; and the photopolymerizable compound Contains everything described above in one embodiment.

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

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

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

The protective film prevents damage to the resist during processing and serves as a protective cover to protect the photosensitive resin layer from foreign substances such as dust, and is laminated on the backside of the photosensitive resin layer on which the substrate film is not formed. The protective film is used to protect the photosensitive resin layer from external influences. When the dry film photoresist is applied to the back end process, it needs to be easily released and it needs to have proper separation and adhesion so that it does not deform during storage and distribution.

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

Meanwhile, the dry film photoresist may satisfy either of the following (a) or (b): (a) For the resist pattern obtained by exposing and developing the photosensitive resin layer, in The maximum foot length of the resist residue remaining on the bottom surface in the space between the lines of photosensitive resin layers adjacent to each other is 1 μm or less, or (b) for the photosensitive resin in which the dry film type photoresist is applied The film sample in which the resin layer is laminated on the substrate, when nickel-plated with an aqueous solution containing nickel for 20 minutes or more, has an adhesion force defined by the following Equation 2 of 90% or more.

[Equation 2] Adhesion (%)=(surface area of photosensitive resin layer of dry film photoresist in contact with substrate after nickel plating/surface area of photosensitive resin layer of dry film photoresist in contact with substrate before nickel plating)×100 .

Specifically, for a resist pattern obtained by exposing and developing the photosensitive resin layer, the maximum foot length of the resist residue remaining on the bottom surface in the space between the mutually adjacent photosensitive resin layer lines may be 1 micron or less, 0.7 microns or less than 0.7 microns, 0.1 microns or more than 0.1 microns and 1 micron or less, 0.1 microns or more than 0.1 microns and 0.7 microns or less than 0.7 microns, 0.4 microns or more than 0.4 microns and 0.7 microns microns or less than 0.7 microns or 0.5 microns or more than 0.5 microns and 0.6 microns or less than 0.6 microns.

The resist pattern is obtained by selectively exposing and developing the photosensitive resin composition, so that a part of the photosensitive resin composition remains as the photosensitive resin layer to form the photosensitive resin layer line and a part thereof can be removed by developing to be in the photosensitive resin layer line. form space.

At this time, a resist residue remaining without being removed by development may exist on the bottom surface in the space between the photosensitive resin layer lines adjacent to each other, and when the foot length of this resist residue is excessively raised Above 1 micron, the footing phenomenon may occur excessively at the bottom portion of the pattern, making it difficult to implement a resist pattern with high resolution.

Specifically, the full length of the resist residue may be a point on the boundary line formed by the contact of one side of the photosensitive resin layer line with the bottom surface and the resist residue and the resist residue on the boundary formed by a free one Between a cross section of a plane formed by a vertical line on one side of the photosensitive resin layer line starting from a point and a vertical line on the bottom surface starting from a point and the intersection point where the dividing line formed by the bottom surface and the resist residue intersects the shortest straight-line distance.

The full length of the resist residue is described with reference to the schematic cross-sectional view of the resist pattern in FIG. 2 below. One point on the boundary line formed by the contact of one side of the photosensitive resin layer line with the bottom surface and the resist residue corresponds to the point indicated by d1, and the resist residue is on the photosensitive resin layer starting from one point. The cross-section of the plane formed by the vertical line on one side of the line and the vertical line of the bottom surface from one point intersects the dividing line formed by the bottom surface and the resist residue. The intersection corresponds to the point indicated by d2. The shortest straight-line distance between d1 and d2 corresponds to the full length of the resist residue.

The full length of the resist residue can be measured via an optical microscope (Zeiss AXIOPHOT microscope) as shown in FIG. 1 .

More specifically, in the resist pattern for measuring the full length of the resist residue, the difference between the line width of the upper end of the photosensitive resin layer line and the interval between the upper end portions of the photosensitive resin layer lines adjacent to each other. The ratio can be 1:0.5 to 1:2 or 1:0.9 to 1:1.1 Specifically, the line width of the upper end of the photosensitive resin layer line corresponds to L in Figure 2 below, and the photosensitive resin layer lines adjacent to each other The interval between the upper end parts of , corresponds to S in Figure 2 below.

In addition, the line width of the upper end of the photosensitive resin layer line for measuring the full length of the resist residue may be 5 micrometers or more and 15 micrometers or less or 9 microns or more and 11 microns or less.

The thickness of the photosensitive resin layer for measuring the full length of the resist residue may be 20 microns or more and 30 microns or less or 24 microns or more and 26 microns or less. The thickness of the photosensitive resin layer corresponds to T in Fig. 2 below.

The exposure conditions for measuring the full length of the resist residue are 35 mJ/cm 2 or more and 45 mJ/cm 2 or less than 45 mJ/cm 2 or The exposure dose of 39 mJ/cm 2 or more and 41 mJ/cm 2 or less is used to irradiate ultraviolet rays. The exposure time can be 1 minute or more and 10 minutes or less.

The development conditions when measuring the full length of the resist residue are that a concentration of 0.5 wt % or more and 1.5 wt % or less than 1.5 wt % or 0.9 wt % or more and 1.1 wt % or more can be used. Less than 1.1 wt% alkaline aqueous solution. The pH of the alkaline aqueous solution may be in the range of 9 or more and 11 or less, and the temperature thereof may be adjusted according to the developing characteristics of the photosensitive resin layer. Specific examples of the alkaline aqueous solution may include an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, and an aqueous sodium hydroxide solution.

The development may be performed using a method of contacting an alkaline aqueous solution with the photosensitive resin layer, and as an example of a specific contact method, spraying or immersion may be used. The development time may be 1 minute or more and 10 minutes or less.

Meanwhile, the dry film type photoresist may have the following characteristics: for a film sample in which the photosensitive resin layer of the dry film type photoresist is laminated on the substrate, when nickel plating is performed with an aqueous solution containing nickel for 20 minutes or more, The adhesive force defined by the following Equation 2 is 90% or more or 90% or more and 100% or less.

[Equation 2] Adhesion (%)=(surface area of photosensitive resin layer of dry film photoresist in contact with substrate after nickel plating/surface area of photosensitive resin layer of dry film photoresist in contact with substrate before nickel plating)×100.

Adhesion defined by Equation 2 means the percentage ratio of the surface area of the photoresist layer of the dry film photoresist in contact with the substrate after nickel plating relative to the surface area of the photoresist layer of the dry film photoresist in contact with the substrate before nickel plating.

The surface area used to determine adhesion can be measured via optical microscope images.

The specific conditions for nickel plating are not particularly limited, but for example, by using an aqueous solution of ICP NICORON GIB (a mixture of 100 cc of ICP NICORON GIB-M and 50 cc of ICP NICORON GIB-1 in 850 cc of distilled water) as a nickel-containing Aqueous solution, immersing a film sample in which a photosensitive resin layer containing a photosensitive resin composition is laminated on a substrate under the conditions of 50°C or more and 100°C or less than 100°C for 20 minutes or more or 20 minutes or More than 20 minutes and 30 minutes or less, thereby performing electroplating.

Before nickel plating, the immersion process with the aqueous catalyst solution must be further performed before the immersion process with the aqueous solution containing nickel. The specific conditions of the immersion process by the catalyst aqueous solution are not particularly limited, but for example, by using a hydrochloric acid-based palladium catalyst, ICP ACCERA H aqueous solution (90 cubic centimeters of 35% hydrochloric acid aqueous solution and 40 cubic centimeters of ICP ACCERA H is charged in 870 cubic centimeters). mixture in distilled water) as an aqueous catalyst solution, the film sample in which the photosensitive resin layer containing the photosensitive resin composition is laminated on the substrate can be immersed for 0.1 minute at 10°C or more and 40°C or less or more than 0.1 minutes and 10 minutes or less.

In addition, if necessary, after the immersion process with the nickel-containing aqueous solution, the immersion process with the gold-containing aqueous solution may be further performed. The specific conditions of the immersion process by the gold-containing aqueous solution are not particularly limited, but for example, by using the gold-containing aqueous solution, the immersion process can be carried out at 70°C or more and 100°C or less. The film sample in which the photosensitive resin layer containing the photosensitive resin composition was laminated on the substrate was immersed for 1 minute or more and 20 minutes or less.

A specific example of the gold-containing aqueous solution may be IM GOLD IB MAKE UP SALT aqueous solution (a mixed solution of 80 grams of IM GOLD IB MAKE UP SALT and 2.92 grams of potassium gold cyanide charged in 1000 cubic centimeters of distilled water).

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 an arbitrary substrate, and is used for measurement by the equation 2 An example of a substrate with defined adhesion may be a copper clad laminate on which a copper layer having a thickness of 10 microns or more and 100 mm or less is disposed on the surface.

The photosensitive resin layer may include a dried product or a cured product of the photosensitive resin composition of one embodiment. The dried product means the material obtained through the drying process of the photosensitive resin composition of one embodiment. The cured product refers to the material obtained through the curing process of the photosensitive resin composition of one embodiment.

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

An example of the method of forming the patterned photosensitive resin layer may include a method of laminating a photosensitive resin layer of a dry film type photoresist of another embodiment described later on a substrate and then performing exposure and development. In addition, light of another embodiment to be described later may be mentioned The photosensitive resin layer of the sensitive element is laminated on the substrate and then a method of exposing and developing is performed.

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

In addition, when the dry film type photoresist or photosensitive element of another embodiment has a polymer substrate or a substrate film laminated on one side of the photosensitive resin layer, it may be further performed to remove the polymer substrate immediately after the exposure process or Process of substrate film.

The exposure conditions for measuring the adhesion defined by Equation 2 are that 20 mJ/cm 2 or more and 200 mJ/cm 2 or less or less than 200 mJ/cm 2 or The exposure dose of 50 mJ/cm2 or more and 100 mJ/cm2 or less is used to irradiate ultraviolet rays. The exposure time may be 1 second or more and 10 minutes or less or 1 second or more and 10 seconds or less.

The developing conditions when measuring the adhesive force defined by Equation 2 are that a concentration of 0.5 wt % or more and 1.5 wt % or less than 1.5 wt % or 0.9 wt % or more and 1.1 wt % or more can be used. Less than 1.1 wt% alkaline aqueous solution. The pH of the alkaline aqueous solution may be in the range of 9 or more and 11 or less, and the temperature thereof may be adjusted according to the developing characteristics of the photosensitive resin layer. Specific examples of the alkaline aqueous solution may include an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, and an aqueous sodium hydroxide solution.

The development may be performed using a method of contacting an alkaline aqueous solution with the photosensitive resin layer, and as an example of a specific contact method, spraying or immersion may be used. The development time may be 30 seconds or more and 10 minutes or less or 30 seconds or more and 2 minutes or less.

The thickness of the photosensitive resin layer used to measure the adhesion defined by Equation 2 may be 20 micrometers or more and 80 micrometers or less or 30 micrometers or more than 30 micrometers and 60 micrometers or less. In addition, the photosensitive resin layer used to measure the adhesive force defined by Equation 2 may have parallel to 0.10 square meters or more and 1.00 square meters or less than 1.00 square meters or 0.15 square meters or more The cross-sectional area of the ground that is 0.15 square meters and 0.30 square meters or less. The thickness or cross-sectional area of the photosensitive resin layer can be measured through an optical microscope.

When the adhesion defined by Equation 2 is excessively reduced to less than 90% due to air bubbles generated during the electroplating process, undesirable circuits can be configured in the resulting circuit board or display.

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

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

The step of drying the coated photosensitive resin composition may be performed by a heating member such as a hot air oven, a hot plate, a hot air circulation oven, and an infrared oven, and may be performed at 50° C. or more and 100° C. or less than 100° C. performed at the temperature.

3. Photosensitive element

According to another embodiment of the present disclosure, a photosensitive element can be provided, which includes a polymer substrate and a photosensitive resin layer formed on the polymer substrate; and satisfies the following either (a) or (b): (a) For the resist pattern obtained by exposing and developing the photosensitive resin layer, the maximum foot length of the resist residue remaining on the bottom surface in the space between the mutually adjoining photosensitive resin layer lines is 1 μm or less than 1 micron, or (b) For a film sample in which a photosensitive resin layer is laminated on a substrate, when nickel plating is performed with an aqueous solution containing nickel for 20 minutes or more, the adhesion defined by the following Equation 3 is 90% or more %.

[Equation 3] Adhesion (%)=(surface area of the photosensitive resin layer of the photosensitive element in contact with the substrate after nickel plating/surface area of the photosensitive resin layer of the photosensitive element in contact with the substrate before nickel plating)×100.

Details regarding the full length and adhesion of the photosensitive resin layer and the resist residue include all those described above in one embodiment and another. That is, the photosensitive resin layer may include: an alkali developable binder resin including a repeating unit represented by Chemical Formula 1; a repeating unit represented by Chemical Formula 2; a repeating unit represented by Chemical Formula 3; and a repeating unit represented by Chemical Formula 4 unit; and a photopolymerizable compound.

Details on the alkaline developable binder resin comprising the repeating unit represented by Chemical Formula 1; the repeating unit represented by Chemical Formula 2; the repeating unit represented by Chemical Formula 3; and the repeating unit represented by Chemical Formula 4; and the photopolymerizable compound Contains everything described above in one embodiment.

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

A specific example of the polymer substrate may be a polyester film, wherein the release layer is a surface of which is coated with a coating solution containing a binder resin and organic particles by uniaxially stretching an unstretched polyester film Formed by a tandem coating method that stretches the remainder uniaxially.

Polymer substrates are typically fabricated by an inline coating method instead of adding a release agent (generally added to take into account flowability and winding properties during fabrication), and have a layer of organic particles using alternative particles that do not compromise transparency.

Here, examples of organic particles used as particles that do not impair transparency while considering fluidity and winding properties may include organic particles such as multilayered multicomponent particles in which formations such as methyl methacrylate, ethyl methacrylate, etc. are formed. Acrylic particles of ester, isobutyl methacrylate, n-butyl methacrylate, n-butyl methacrylate, acrylic acid, methacrylic acid copolymer or terpolymer; such as polyethylene, polystyrene or Olefinic particles of polypropylene; acrylic and olefinic copolymers; or homopolymer particles and then another type of monomer is coated on the layer.

a2+b2定義。且，六面體中的頂點之間具有最長距離的軸(f)與除a軸及b軸以外的c軸之間的關係由f2

c2+a2+b2定義。粒子的形狀應為球形的，其關於流動性為較佳的。 These organic particles should be specifically spherical and also have a difference in refractive index from the binder resin. Here, "spherical" means that the ratio of the short axis (a) to the long axis (b) in the ellipse is 0.5<a/b<2, and the relationship with the diagonal (d) in the rectangle is given by d2

a2+b2 definition. Also, the relationship between the axis (f) having the longest distance between the vertices of the hexahedron and the c-axis other than the a-axis and the b-axis is given by f2

c2+a2+b2 definition. The shape of the particles should be spherical, which is preferable with regard to flowability.

and is characterized by the difference in refractive index between the organic particles and the binder resin is 0.05 or less. When the difference in refractive index is greater than 0.05, the haze increases. This means that there is a large amount of scattered light, and when there is a large amount of such scattered light, the sidewall smoothing effect is reduced. This also depends on the size and amount of organic particles. Preferably, the organic particles have an average particle size of about 0.5 microns to 5 microns. When it is smaller than this particle size, fluidity and winding characteristics are deteriorated, and when it is larger than 5 micrometers, haze increases, which is unfavorable in view of the occurrence of drop problems. The content of the organic particles is preferably 1 wt % to 10 wt % based on the total amount of the binder resin.

When the content of the organic particles is less than 1% by weight based on the total amount of the binder resin, the anti-blocking effect is insufficient and easily affected by scratches, and the fluidity and winding properties are deteriorated, and when it exceeds 10% by weight, there may be There are problems of increased haze and cracked transparency properties.

Meanwhile, in addition to the above-mentioned organic particles, inorganic particles may also be added. At this time, it is not inclined to increase the common inorganic anti-blocking agent, and it is preferable to increase the colloidal silica with a particle size of 100 nm or less. Based on 100 parts by weight of the binder resin, its content is preferably 10 parts by weight or less. When the particle sizes and contents as described above are satisfied, it is possible to prevent sidewall defects or grooves, such as pits caused by the release layer, from occurring when patterning using a dry film type photoresist.

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

The solvent that can be used in the preparation of the coating solution using the binder resin and organic particles is preferably water.

As described above, an unstretched polyester film obtained by melt-extruding PET pellets was uniaxially stretched, and then a coating solution containing organic particles in a binder resin was applied to the uniaxially stretched on the stretched membrane. The coating may be performed on at least one side of the uniaxially stretched film, and preferably has a thickness of about 30 nm to 200 nm in terms of thickness after final drying. If a coating solution containing organic particles is applied to a uniaxially stretched film with a thickness of more than 30 nm, there are problems that the organic particles are easily detached and are easily affected by scratches and white powder is generated. When the coating thickness is greater than 200 nm, coating streaks are generated in the coating direction in the tandem coating with high coating speed due to the increased viscosity of the coating solution.

The polymer substrate obtained by coating with organic particles other than the general release agent by the tandem coating method as described above is a substrate film that maintains fluidity and winding characteristics due to the particle layer, and has excellent The light transmittance of organic particles has excellent transparency.

Since the lamination of the photosensitive resin layer is performed on the opposite surface of the organic particle-containing layer in the polymer substrate, and the photosensitive resin layer is formed on the opposite surface of the organic particle-containing layer in this way. Therefore, there is no pit-like defect that occurs when the substrate film containing the release agent is laminated as described above. Since particles such as silica are not only larger in size than organic particles, but are also distributed throughout the substrate film, the effect of silica does not seem to be significant even in regions adjacent to the photosensitive resin layer.

On the other hand, in the polymer substrate used in the present disclosure, the organic particles have a size of 0.5 micrometers to 5 micrometers, and the organic particle layer is not adjacent to the photosensitive resin layer, so that the physical effect of the organic particles does not occur. In addition, by using the excellent Transmittance organic particles that reduce sidewall defects without compromising other circuit properties.

The photosensitive element may further include a protective film formed on the photosensitive resin layer. The protective film prevents damage to the photosensitive resin layer during handling, and serves as a protective cover to protect the photosensitive resin layer from foreign substances such as dust. A protective film is laminated on the back side of the photosensitive resin layer on which the polymer substrate is not formed. The protective film is used to protect the photosensitive resin layer from external influences. When the dry film photoresist is applied to the back end process, it needs to be easily released and it needs to have proper separation and adhesion so that it does not deform during storage and distribution.

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

4. Circuit board, display device

According to another embodiment of the present disclosure, a circuit board or a display device can be provided, including a photosensitive resin layer including the photosensitive resin composition of one embodiment. Details about the photosensitive resin composition include all the content described above in one embodiment.

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

The photosensitive resin layer included in the circuit board or the display device may be in the form of a film without openings or in the form of a pattern with openings.

An example of a method of forming a patterned photosensitive resin layer includes combining another embodiment A method of laminating a photosensitive resin layer of a dry film photoresist on a circuit board or a display device manufacturing substrate and then performing exposure and development. In addition, a method of laminating a photosensitive resin layer of a photosensitive element according to another embodiment to a circuit board or a display device manufacturing substrate and then performing exposure and development can be mentioned.

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

An example of the method of forming the patterned photosensitive resin layer may include a method of laminating a photosensitive resin layer of a dry film type photoresist of another embodiment described later on a substrate and then performing exposure and development. In addition, a method of laminating a photosensitive resin layer of a photosensitive element of another embodiment described later on a substrate and then performing exposure and development can be mentioned.

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

In addition, when the dry film type photoresist or photosensitive element of another embodiment has a polymer substrate or a substrate film laminated on one side of the photosensitive resin layer, it may be further performed to remove the polymer substrate immediately after the exposure process or Process of substrate film.

Therefore, the photosensitive resin layer contained in the dry film photoresist or the photosensitive element of another embodiment can be included in a circuit board or a display device.

According to the present disclosure, a photosensitive resin composition capable of reducing cavities during pattern plating and realizing high-resolution patterns, and a dry film photoresist, a circuit board, and a display device using the same can be provided.

Furthermore, according to the present disclosure, it is possible to provide a Photosensitive resin composition and dry film photoresist, circuit board and display device using the same.

L: Line width at the upper end of the line

S: space between lines

T: Thickness of the photosensitive resin layer

d1: The point on the boundary line formed by the contact of one side of the photosensitive resin layer line with the bottom surface and the resist residue

d2: wherein the cross section of the resist residue of the plane formed by the vertical line from d1 to one side of the photosensitive resin layer line and the vertical line from d1 to the bottom surface line and the difference between the bottom surface and the resist residue point of intersection

F: Foot length

FIG. 1 shows an optical microscope image of the foot length measured in Example 1. FIG.

FIG. 2 is a schematic cross-sectional view of the resist pattern obtained in Example 1. FIG.

3 shows optical microscope images of the adhesion between the substrate and the photosensitive resin layer measured in Examples 5 to 8.

4 shows an optical microscope image of the adhesive force between the substrate and the photosensitive resin layer measured in Comparative Example 3 (20-minute immersion condition).

5 is an optical microscope image of the adhesion between the substrate and the photosensitive resin layer measured in Comparative Example 3 (30-minute immersion condition) and Comparative Example 4 (20-minute immersion condition).

6 shows an optical microscope image of the adhesive force between the substrate and the photosensitive resin layer measured in Comparative Example 4 (30-minute immersion condition).

The present disclosure will be described in more detail with the aid of the examples shown below. However, these examples are only given to illustrate the invention and are not intended to limit the scope of the invention thereto.

<Preparation Example and Comparative Preparation Example: Preparation of Alkaline Developable Binder Resin>

Preparation Example 1

The four-necked round bottom flask was equipped with a mechanical stirrer and a reflux device, and then the interior of the flask was purged with nitrogen. Mix 68 grams of methyl ethyl ketone (MEK) and 5 grams of methyl ethyl ketone (MEK) Alcohol (MeOH) was added to the nitrogen purged flask, and then 0.9 grams of azobisisobutyronitrile (AIBN) was added and dissolved completely. To this was added a monomer mixture of 24 grams of methacrylic acid (MAA), 6 grams of methyl methacrylate (MMA), 30 grams of styrene (SM), and 40 grams of 2-phenoxyethyl methacrylate (PHEMA) As a monomer, heated up to 80°C, and then polymerized for 6 hours to prepare an alkaline developable binder resin (weight average molecular weight: 68,900 g/mol, solid content: 47.9 wt %, acid value: 154 mg potassium hydroxide/ grams).

The alkaline developable binder resin prepared in the above preparation example was dissolved in tetrahydrofuran so as to have a concentration of 1.0 (w/w) % in THF (about 0.5 (w/w) % by solids content), and Filtration using a 0.45 micron pore size syringe filter followed by injection into GPC in 20 microliter volumes. Tetrahydrofuran (THF) was used as the mobile phase for GPC and the flow rate was 1.0 mL/min. The column was configured with one Agilent Plagal 5 micron guard (7.5 x 50 mm) and two Agilent Plagal 5 micron Mixed D (7.5 x 300 mm) connected in series, and was heated at 40°C by using an Agilent 1260 Infinity II The system and the RI detector perform measurements as detectors.

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

The solids content is based on the weight of the alkaline developable binder resin prepared in the above preparation example and heated in an oven at 150°C for 120 minutes, and then the weight percent ratio of remaining solids is measured.

Preparation Example 2

The four-necked round bottom flask was equipped with a mechanical stirrer and reflux device, and was then used Nitrogen purges the inside of the flask. 68 grams of methyl ethyl ketone (MEK) and 5 grams of methanol (MeOH) were added to a nitrogen purged flask, and then 0.9 grams of azobisisobutyronitrile (AIBN) was added and dissolved completely. To this was added a monomer mixture of 24 grams of methacrylic acid (MAA), 26 grams of methyl methacrylate (MMA), 30 grams of styrene (SM), and 20 grams of 2-phenoxyethyl methacrylate (PHEMA) As a monomer, it was heated to 80°C, and then polymerized for 6 hours to prepare an alkaline developable binder resin (weight average molecular weight: 52,500 g/mol, solid content: 48.3 wt %, acid value: 154 mg potassium hydroxide/ grams).

Preparation Example 3

The four-necked round bottom flask was equipped with a mechanical stirrer and a reflux device, and then the interior of the flask was purged with nitrogen. 80 grams of methyl ethyl ketone (MEK) and 7.5 grams of methanol (MeOH) were added to a nitrogen purged flask, and then 0.45 grams of azobisisobutyronitrile (AIBN) was added and dissolved completely. To this were added 8 g of acrylic acid (AA), 15 g of methacrylic acid (MAA), 15 g of butyl acrylate (BA), 52 g of methyl methacrylate (MMA) and 10 g of styrene (SM). The monomer mixture was used as a monomer, heated up to 80°C, and then polymerized for 6 hours to prepare an alkaline developable binder resin.

The alkaline 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 solids content of 51.4 wt %, and an acid value of 156.3 mg potassium hydroxide/g.

Preparation Example 4

The four-necked round bottom flask was equipped with a mechanical stirrer and a reflux device, and then the interior of the flask was purged with nitrogen. 110 grams of methyl ethyl ketone (MEK) and 10 grams of methanol (MeOH) were added to a nitrogen purged flask, followed by 1 gram of azobisisobutyronitrile (AIBN) and dissolved completely. A monomer mixture of 30 g of methacrylic acid (MAA), 100 g of methyl methacrylate (MMA), and 30 g of styrene (SM) was added thereto as monomers, heated to 80° C., and then polymerized for 6 hours to prepare Alkaline developable binder resin (weight average molecular weight: 49,852 g/mol, glass transition temperature: 125°C, solids content: 48.5 wt% and acid value: 163.17 mg potassium hydroxide/g).

Comparative Preparation Example 1

The four-necked round bottom flask was equipped with a mechanical stirrer and a reflux device, and then the interior of the flask was purged with nitrogen. 90 grams of methyl ethyl ketone (MEK) and 10 grams of propylene glycol monomethyl ether acetate (PGMEA) were added to a nitrogen purged flask, followed by 0.8 grams of azodiisobutylene Nitrile (AIBN) and completely dissolved. A monomer mixture of 20 grams of methacrylic acid (MAA), 70 grams of methyl methacrylate, and 10 grams of styrene was added thereto as monomers, heated up to 80° C., and then polymerized for 6 hours to prepare an alkaline developable adhesive Resin (weight average molecular weight: 60,000 g/mol).

Comparative Preparation Example 2

The four-necked reaction flask jacketed set was equipped with a mechanical stirrer and a reflux device, and then the inside of the flask was purged with nitrogen. 90 grams of methyl ethyl ketone (MEK) and 10 grams of methanol were added to a nitrogen purged flask, and then 0.8 grams of azobisisobutyronitrile (AIBN) was added and dissolved completely. Thereto was added a monomer mixture of 24 g of methacrylic acid, 46 g of methyl methacrylate and 30 g of styrene as monomers, heated up to 80°C, and then polymerized for 6 hours to prepare an alkaline developable binder resin (heavy weight). Average molecular weight: 49,000 g/mol, solids content: 50.0% by weight and acid value: 155 mg potassium hydroxide/g).

<Example and Comparative Example: Preparation of Photosensitive Resin Composition and Dry Film Photoresist>

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

The obtained photosensitive resin composition was coated on a 20-micrometer PET film using a coating bar. The coated photosensitive resin composition layer was dried using a hot air oven. At this time, the drying temperature was 80° C., the drying time was 5 minutes, and the thickness of the photosensitive resin composition layer after drying was 25 μm.

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

The PET film was produced through the following process.

PET is prepared by performing transesterification and polycondensation using ethylene glycol and terephthalic acid. The PET pellets were dried under reduced pressure at 120°C for 8 hours, then fed into an extruder and melted at 280°C. This was wound on a casting drum with a surface temperature of 20°C using an electrostatic coating casting method, and cooled and solidified to form an unstretched film. The thickness of the unstretched film was adjusted to 250 microns by adjusting the discharge of the extruder. Next, the unstretched film was stretched four times in the longitudinal direction, and finally dried using a concave plate. cloth solution, and then coated on one side thereof to have a thickness of 50 nm. The polymethyl methacrylate used here is polymethyl methacrylate coated with polystyrene on its surface, which is spherical and has a refractive index difference of 0.03 with the acrylic resin.

The longitudinal direction of the coating solution containing the organic particles was preheated at 120°C. The film was uniaxially stretched and stretched four times in the transverse direction.

The film was heat set at a maximum temperature of 230°C for 10 seconds at a predetermined length and cooled to room temperature to obtain a polyester film with a total thickness of 20 microns and a coating thickness of 50 nm.

<Experimental example>

For the dry film photoresists prepared in the Examples and Comparative Examples, physical properties were measured by the following methods and the results are shown in Tables 3 to 5 below.

1. Foot length (unit: micron)

Dry film photoresist peeling protective films prepared from Examples 1 to 4 and Comparative Example 1 and Comparative Example 2, and the photosensitive resin layer of the dry film photoresist was laminated using HAKUTO MACH 610i so as to contact 1.6 The surface of the copper layer of the thick copper-clad laminate with a thickness of millimeters is brushed under the following conditions: the temperature of the substrate preheating roller is 120°C, the temperature of the laminator roller is 115°C, the roller pressure is 4.0 kgf/cm2 and the roller The rotation rate was 2.0 min/m, thereby forming a laminate.

The supporting PET film for dry film photoresist was peeled off from the laminate, and then irradiated with ultraviolet rays through a photomask using a parallel exposure machine (EXM-1201, manufactured by ORC Manufacturing Co., Ltd.) to Circuit evaluations (10 microns wide openings and 10 microns spacing between openings) were performed until an exposure dose of 40 mJ/cm 2 was reached and then allowed to stand for 15 minutes. Thereafter, development was performed at 30±1° C. with a 1.0 wt % Na ₂ CO ₃ aqueous solution under the jet-type developing condition of a jet pressure of 1.5 kgf/cm 2 for twice the minimum developing time. Thus, a resist pattern is produced in which the ratio L/S of the line width (L) of the upper end of the photosensitive resin layer line to the space interval (S) between the photosensitive resin layer line is 1:1, and the photosensitive resin layer line is The line width (L) of the upper end is 10 μm, as shown in Figure 2 below.

After that, as shown in FIG. 2 below, in the surface of the copper-clad laminate, which is the bottom surface of the space between the photosensitive resin layer lines adjacent to each other, for the bottom surface and the upper part of the photosensitive resin layer line side in contact with it The remaining undeveloped resist residue, the boundary line formed by the contact of one side of the photosensitive resin layer line with the bottom surface and the resist residue A point on (d1) to a cross-section of the resist residue in a plane formed by a vertical line on one side of the photosensitive resin layer line from one point and a vertical line on the bottom surface from one point and The shortest straight-line distance from the intersection (d2) where the dividing line between the bottom surface and the resist residue intersects was measured using a Zeiss AXIOPHOT microscope and the maximum value of the foot length is shown in Table 2 below.

2. Thin wire adhesion (unit: microns)

The dry film photoresist peeling protective films were prepared from Examples 1 to 4 and Comparative Example 1 and Comparative Example 2, and the photosensitive resin layer of the dry film photoresist was laminated using Bodong MACH 610i so as to contact a thickness of 1.6 mm. The copper layer surface of the thick copper-clad laminate is brushed under the following conditions: the temperature of the substrate preheating roller is 120°C, the temperature of the laminator roller is 115°C, the roller pressure is 4.0 kgf/cm2 and the rolling rate is 2.0 min/m, thereby forming a laminate.

The supporting PET film of the dry film photoresist was peeled off from the laminate, and then irradiated with ultraviolet rays through the reticle using a parallel exposure machine (EXM-1201, manufactured by ORC Manufacturing Co., Ltd.) for circuit evaluation up to 40 mJ/square centimeter exposure dose and then allowed to stand for 15 minutes. Thereafter, development was performed at 30±1° C. with a 1.0 wt % Na ₂ CO ₃ aqueous solution under the jet-type developing condition of a jet pressure of 1.5 kgf/cm 2 for twice the minimum developing time.

In the developed laminate, the minimum line width of the photosensitive resin layer was measured with a Zeiss AXIOPHOT microscope and evaluated as fine line adhesion. It can be estimated that the smaller the value, the better the adhesion of thin lines.

3.1:1 resolution (unit: microns)

Dry film photoresist release protective films prepared from Examples 1 to 4 and Comparative Example 1 and Comparative Example 2, and laminated dry film using Bodong MACH 610i The photosensitive resin layer of the photoresist is thus brushed in contact with the copper layer surface of a thick copper-clad laminate with a thickness of 1.6 mm under the following conditions: the temperature of the substrate preheating roller is 120 °C, the temperature of the laminator roller is 115 °C, and the roller temperature is 115 °C. The pressure was 4.0 kgf/cm 2 and the tumble rate was 2.0 min/m, thereby forming a laminate.

The supporting PET film for dry film type photoresist was peeled off from the laminate, and then irradiated with ultraviolet rays through the photomask using a parallel exposure machine (EXM-1201, manufactured by ORC Manufacturing Co., Ltd.) for circuit evaluation up to 40 millimetres The exposure dose of J/cm2, so that the width of the circuit lines and the space interval between the circuit lines can be changed to 1:1, and then it was allowed to stand for 15 minutes. Thereafter, development was performed at 30±1° C. with a 1.0 wt % Na ₂ CO ₃ aqueous solution under the jet-type developing condition of a jet pressure of 1.5 kgf/cm 2 for twice the minimum developing time.

In the developed laminate, the minimum value of the spacing between the photosensitive resin layers was measured with a ZEISS AXIOPHOT microscope and evaluated as 1:1 resolution. It can be estimated that the smaller the value, the better the 1:1 resolution value.

4. Minimum development time (unit: seconds)

The dry film photoresist peeling protective films were prepared from Examples 1 to 4 and Comparative Example 1 and Comparative Example 2, and the photosensitive resin layer of the dry film photoresist was laminated using Bodong MACH 610i so as to contact a thickness of 1.6 mm. The surface of the copper layer of the copper-clad laminate is brushed under the following conditions: the temperature of the substrate preheating roller is 120°C, the temperature of the laminator roller is 115°C, the roller pressure is 4.0 kgf/cm 2 and the rolling rate is 2.0 min/m, thereby forming a laminate.

Subsequently, development was performed at 30±1° C. with a 1.0 wt % Na ₂ CO ₃ aqueous solution under the jet-type development conditions of a jet pressure of 1.5 kgf/cm 2 for twice the minimum development time.

A stopwatch was used to measure the time (minimum development time) required to completely wash the photosensitive resin layer on the copper-clad laminate in the developer solution.

As shown in Table 3 above, it was confirmed that the development characteristics of the Examples were excellent compared to the Comparative Examples since the foot length was very short while maintaining similar levels of development time, fine wire adhesion, and resolution.

5. Electroplating resistance

The dry film photoresist peel-off protective films were prepared from Examples 5 to 8 and Comparative Examples 3 and 4, and the photosensitive resin layer of the dry film photoresist was laminated using Bodong MACH 610i so as to contact a thickness of 1.6 mm. The surface of the copper layer of the copper-clad laminate is brushed under the following conditions: the temperature of the substrate preheating roller is 120°C, the temperature of the laminator roller is 115°C, the roller pressure is 4.0 kgf/cm 2 and the rolling rate is 2.0 min/m, thereby forming a laminate.

The supporting PET film for dry film resist was peeled off from the laminate, and then the front surface was irradiated with ultraviolet rays at an exposure dose of 80 mJ/cm 2 using a parallel exposure machine (EXM-1201, manufactured by ORC Manufacturing Co., Ltd.), This was continued for 4 seconds and then allowed to stand for 15 minutes. Thereafter, development was performed for one minute at 30±1° C. with a 1.0 wt % Na ₂ CO ₃ aqueous solution under the jet-type developing conditions of a jet pressure of 1.5 kgf/cm 2 .

The developed laminate was cut to a size of 5 cm in width and 5 cm in length to prepare samples, which were loaded on wafer carriers made of PFA material of the same size and then immersed in 1 liter of aqueous nickel solution to perform nickel plating.

More specifically, nickel plating is performed as follows. The cured film was immersed in an aqueous solution of hydrochloric acid-based palladium catalyst ICP ACCERA H (90 cubic centimeters of 35% hydrochloric acid and 40 cubic centimeters of ICP ACCERA H) at 25°C according to the dry bath conditions of MK Chem & Tech. 870 cm3 of distilled water) for 1 min, and then the cured film was immersed in an aqueous solution of electroless Ni-P drug ICP NICORON GIB (100 cm3 ICP NICORON GIB-M and 50 cm3 ICP NICORON GIB- 1 in 850 cubic centimeters of distilled water) for 10 minutes, 20 minutes, and 30 minutes, respectively, for the immersion times shown in Table 2 below. (As nickel plating solutions, ICP ACCERA H, ICP NICORON GIB-M, and ICP NICORON GIB-1 were purchased from MK Chemical & Technology.)

When the nickel plating was completed, the adhesion of the dry film photoresist to the copper clad laminate was measured by optical microscope images to evaluate the plating resistance, and the results are shown in Table 2 below. The adhesion of the dry film photoresist means that the surface area of the photosensitive resin layer of the dry film photoresist in contact with the copper clad laminate after nickel plating is relative to the contact between the photosensitive resin layer of the dry film photoresist and the copper clad laminate before nickel plating percentage of surface area.

[Equation 4] Adhesion (%) = (the surface area of the photosensitive resin layer of the dry film photoresist in contact with the copper clad laminate after nickel plating / the photosensitive resin layer of the dry film photoresist and the copper clad laminate before nickel plating Contact surface area)×100

[Table 4]

As depicted in Table 4, it can be demonstrated that the examples maintain adhesion to the substrate during nickel plating by means of ENIG electroplating and have superior plating resistance compared to the comparative examples.

6. Thin wire adhesion (unit: microns)

The dry film photoresist peel-off protective films were prepared from Examples 5 to 8 and Comparative Examples 3 and 4, and the photosensitive resin layer of the dry film photoresist was laminated using Bodong MACH 610i so as to contact a thickness of 1.6 mm. The copper layer surface of the thick copper-clad laminate is brushed under the following conditions: the temperature of the substrate preheating roller is 120°C, the temperature of the laminator roller is 115°C, the roller pressure is 4.0 kgf/cm2 and the rolling rate is 2.0 min/m, thereby forming a laminate.

The supporting PET film for dry film photoresist was peeled off from the laminate, and then irradiated with ultraviolet rays through a photomask at an exposure dose of 40 mJ/cm 2 using a parallel exposure machine (EXM-1201, manufactured by ORC Manufacturing Co., Ltd.) seconds for circuit evaluation, and then allowed to stand for 15 minutes. Thereafter, development was performed at 30±1° C. with a 1.0 wt % Na ₂ CO ₃ aqueous solution under the jet-type developing condition of a jet pressure of 1.5 kgf/cm 2 for twice the minimum developing time.

In the developed laminate, the minimum line width of the photosensitive resin layer was measured with a Zeiss AXIOPHOT microscope and evaluated as fine line adhesion. It can be estimated that the smaller the value, the better the adhesion of thin lines.

7.1:1 resolution (unit: microns)

The protective film was peeled off from the protective films of the dry film photoresists prepared in Examples 5 to 8 and Comparative Examples 3 and 4, and the photosensitive resin layer of the dry film photoresist was laminated using Bodong MACH 610i so as to contact The copper layer surface of the thick copper-clad laminate with a thickness of 1.6 mm is brushed under the following conditions: the temperature of the substrate preheating roll is 120 °C, the temperature of the laminator roll is 115 °C, the roll pressure is 4.0 kgf/cm² and The tumble rate was 2.0 min/m, thereby forming a laminate.

The supporting PET film for dry film type photoresist was peeled off from the laminate, and then a parallel exposure machine (EXM-1201, manufactured by ORC Manufacturing Co., Ltd.) was used for circuit evaluation by irradiating ultraviolet rays through a photomask for 4 seconds until reaching An exposure dose of 80 mJ/cm 2 made the width of the circuit lines and the spacing between the circuit lines become 1:1, and then allowed to stand for 15 minutes. Thereafter, development was performed for one minute at 30±1° C. with a 1.0 wt % Na ₂ CO ₃ aqueous solution under the jet-type developing conditions of a jet pressure of 1.5 kgf/cm 2 .

In the developed laminate, the minimum value of the spacing between the photosensitive resin layers was measured with a ZEISS AXIOPHOT microscope and evaluated as 1:1 resolution. It can be estimated that the smaller the value, the better the 1:1 resolution value.

As shown in Table 5, it can be confirmed that the examples have excellent fine line adhesion and resolution compared to the comparative examples.

Claims (16)

A photosensitive resin composition comprising: an alkali-developable adhesive comprising a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the following Chemical Formula 2, a repeating unit represented by the following Chemical Formula 3, and a repeating unit represented by the following Chemical Formula 4 agent resin; a photopolymerization initiator; and a photopolymerizable compound, wherein based on 100 mol% of all repeating units contained in the alkaline developable binder resin, the alkaline developable binder resin contains 5 mol% or more and 40 mol% or less of the repeating unit represented by Chemical Formula 1, 20 mol% or more and 60 mol% or less mol% of the repeating unit represented by Chemical Formula 2, 1 mol% or more and 30 mol% or less of the repeating unit represented by Chemical Formula 3, and 30 mol% or more than 30 mol% and 60 mol% or less of the repeating unit represented by Chemical Formula 4, wherein the photosensitive resin composition satisfies any one of the following (a) or (b): (a) For a resist pattern obtained by exposing and developing a photosensitive resin layer containing the photosensitive resin composition, the resist residue remaining on the bottom surface in the space between the lines of the photosensitive resin layer adjacent to each other The maximum foot length of the material is 1 micrometer or less, or (b) for a film sample in which the photosensitive resin layer containing the photosensitive resin composition is laminated on a substrate, when the film sample is plated with an aqueous solution containing nickel When nickel is 20 minutes or more, the adhesion defined by the following equation 1 is 90% or more: [Equation 1] Adhesion (%) = (the photosensitive resin composition containing the photosensitive resin composition after the nickel plating The surface area of the photosensitive resin layer in contact with the substrate/the surface area of the photosensitive resin layer containing the photosensitive resin composition before the nickel plating in contact with the substrate) × 100,

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

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

In Chemical Formula 3, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₅ is an alkyl group having 1 carbon atom,

In Chemical Formula 4, Ar is an aryl group having 6 to 20 carbon atoms. The photosensitive resin composition of claim 1, wherein the full length of the resist residue is such that one side of the photosensitive resin layer line contacts the bottom surface and the resist residue A point on the formed boundary line and a vertical line of the resist residue on one side of the line of the photosensitive resin layer from the one point and the bottom surface from the one point. The shortest straight-line distance between the cross-section of the plane formed by the vertical line and the intersection point where the dividing line formed by the bottom surface and the resist residue intersects. The photosensitive resin composition according to claim 1, wherein a molar ratio of the repeating unit represented by Chemical Formula 3 to 100 mol of the repeating unit represented by Chemical Formula 4 is 10 mol or more and 99 moles or less. The photosensitive resin composition according to claim 1, wherein the photopolymerizable compound comprises a bifunctional (meth)acrylate compound. The photosensitive resin composition according to claim 1, wherein the photopolymerizable compound comprises trifunctional or higher polyfunctional (meth)propane alkenoate compounds. The photosensitive resin composition according to claim 5, wherein the trifunctional or higher polyfunctional (meth)acrylate compound has three or more epoxy alkyl groups in which three or more have 1 to 10 carbon atoms groups and three or more (meth)acrylate functional groups are bonded to structures having a central group of 1 to 20 carbon atoms. The photosensitive resin composition according to claim 5, wherein the trifunctional or higher polyfunctional (meth)acrylate compound comprises a compound represented by the following Chemical Formula 12:

In Chemical Formula 12, R ₁₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₁₅ is an alkylene group having 1 to 10 carbon atoms, and R ₁₆ is an alkylene group having 1 to 20 carbon atoms The p-valent functional group of the central group, n12 is an integer from 1 to 20, and p is the number of functional groups substituted for _R16 , and is an integer from 3 to 10. The photosensitive resin composition according to claim 5, wherein the photopolymerizable compound further comprises a monofunctional (meth)acrylate compound. The photosensitive resin composition according to claim 8, wherein the monofunctional (meth)acrylate compound contains a (meth)acrylate containing a carbon atom having 1 to 10 carbon atoms. alkylene oxide group. The photosensitive resin composition according to claim 8, wherein the monofunctional (meth)acrylate compound comprises a compound represented by the following Chemical Formula 11:

In Chemical Formula 11, R ₁₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₁₂ is an alkylene group having 1 to 10 carbon atoms, and R ₁₃ is an alkylene group having 1 to 10 carbon atoms alkyl, and n11 is an integer from 1 to 20. The photosensitive resin composition as claimed in claim 1, further comprising: a first alkali-developable binder resin comprising a repeating unit represented by the following chemical formula 13, a repeating unit represented by the following chemical formula 14, and a repeating unit represented by the following chemical formula 15 a repeating unit, a repeating unit represented by the following Chemical Formula 16, and a repeating unit represented by the following Chemical Formula 17; and a second alkaline developable binder resin 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:

In Chemical Formula 13, R ₃ " is hydrogen,

In Chemical Formula 14, R ₃ ' is an alkyl group having 1 to 10 carbon atoms,

In Chemical Formula 15, R ₄ " is an alkyl group having 1 to 10 carbon atoms, and R ₅ " is an alkyl group having 1 to 10 carbon atoms, [Chemical Formula 16]

In Chemical Formula 16, Ar is an aryl group having 6 to 20 carbon atoms, and

In Chemical Formula 17, R ₄ ' is hydrogen, and R ₅ ' is an alkyl group having 1 to 10 carbon atoms. A dry film photoresist comprising a photosensitive resin layer containing the photosensitive resin composition of claim 1. The dry film type photoresist of claim 15, wherein the dry film type photoresist satisfies any one of the following (a) or (b): (a) For obtaining by exposing and developing the photosensitive resin layer A resist pattern in which the maximum foot length of the resist residue remaining on the bottom surface in the space between the mutually adjoining photosensitive resin layer lines is 1 micrometer or less, or (b) for the A film sample in which the photosensitive resin layer of the dry film type photoresist is laminated on a substrate, when nickel plating is performed with an aqueous solution containing nickel for 20 minutes or more, the adhesion defined by the following equation 2 is 90 % or greater than 90%: [Equation 2] Adhesion (%)=(surface area of the photosensitive resin layer of the dry film type photoresist in contact with the substrate after the nickel plating/the dry film type photoresist before the nickel plating The surface area of the photosensitive resin layer in contact with the substrate)×100. A photosensitive element, comprising a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, and satisfying any one of the following (a) or (b): (a) for the photosensitive by exposure and development A resist pattern obtained from a resin layer in which the resist residue remaining on the bottom surface has a maximum foot length of 1 micrometer or less in the space between the mutually adjoining photosensitive resin layer lines, or (b) For the film sample in which the photosensitive resin layer was laminated on the polymer substrate, the adhesion defined by the following Equation 3 was 90% when nickel plating was performed with an aqueous solution containing nickel for 20 minutes or more or more than 90%: [Equation 3] Adhesion (%)=(surface area of the photosensitive resin layer of the photosensitive element in contact with the polymer substrate after the nickel plating/the photosensitive resin before the nickel plating The surface area of the photosensitive resin layer of the element in contact with the polymer substrate) × 100, wherein the photosensitive resin composition comprises: a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the following Chemical Formula 2, by the following A repeating unit represented by Chemical Formula 3 and an alkali-developable binder resin of a repeating unit represented by the following Chemical Formula 4; and a photopolymerizable compound, wherein all repeating units contained in the alkali-developable binder resin are 100 In terms of mol%, the alkaline developable binder resin contains 5 mol% or more and 40 mol% or less of the repeating unit represented by Chemical Formula 1, 20 mol% % or more and 60 mol % or less of the repeating unit represented by Chemical Formula 2, 1 mol % or more and 30 mol % or less than 30 mol % of the repeating unit represented by Chemical Formula 3 and 30 mol % or more and 60 mol % or less of the repeating unit represented by Chemical Formula 4:

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

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

In Chemical Formula 3, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₅ is an alkyl group having 1 carbon atom,

And in Chemical Formula 4, Ar is an aryl group having 6 to 20 carbon atoms. A circuit board comprising a photosensitive resin layer containing the photosensitive resin composition of claim 1. A display device comprising a photosensitive resin layer containing the photosensitive resin composition of claim 1.

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