TWI819260B - Photosensitive resin layer, and dry film photoresist, photosensitive element using the same - Google Patents

Abstract

The present disclosure relates to a photosensitive resin layer including a photopolymerizable compound and a trifunctional or higher polyfunctional (meth)acrylate compound, and having excellent substrate adhesion, and a dry film photoresist, and a photosensitive element using the same.

Description

Photosensitive resin layer and dry film photoresist and photosensitive element using it pieces

[Cross-reference to related applications]

This application claims Korean Patent Application No. 10-2019-0179945 filed on December 31, 2019 and Korean Patent Application No. 10-2020 filed on July 30, 2020 in the Korean Intellectual Property Office -0095387, the full text of each of the Korean patent applications described is hereby incorporated by reference.

The present disclosure relates to a photosensitive resin layer, a dry film photoresist (DFR) using the photosensitive resin layer, and a photosensitive element using the photosensitive resin layer.

Photosensitive resin compositions are used in dry film photoresist (DFR), liquid photoresist ink (liquid photoresist ink) or the like for printed circuit boards (PCB) or lead frames (lead frames). form is used.

Currently, dry film photoresist is widely used not only in manufacturing printed circuit boards (PCBs) and lead frames, but also in manufacturing rib barriers for plasma display panels (PDP) and other applications. Display indium tin oxide (ITO) electrodes, bus address electrodes, black matrix (black matrix) and the like.

Generally speaking, this type of dry film photoresist is often used in applications where it is laminated on a copper clad laminate. In connection with this, as an example of a manufacturing process of a printed circuit board (PCB), a preprocessing process is first performed to laminate a copper-clad laminate as a raw board material of the PCB. The pretreatment process is performed in the order of drilling, deburring, and surface conditioning in the outer layer process, and surface conditioning or pickling is performed in the inner layer process. In surface modification, bristle brush and jet pumice process are mainly used, and pickling can undergo soft etching and 5 wt% sulfuric acid pickling.

In order to form a circuit on a copper-clad laminate that has undergone a pretreatment process, dry film photoresist (hereinafter referred to as DFR) is generally laminated on the copper layer of the copper-clad laminate. In this process, the DFR photoresist layer is laminated on the copper surface, and a laminator is used to peel off the DFR protective film. Generally speaking, lamination is performed at a speed of 0.5 m/min to 3.5 m/min, a temperature of 100°C to 130°C, and a heated roller pressure of 10 pounds per square inch (psi) to 90 psi. (heating roll pressure) execution.

Allow printed circuit boards that have undergone the lamination process to rest for 15 minutes or more. The board was allowed to stabilize for 15 minutes, and the DFR photoresist was then exposed through a photomask with the desired circuit pattern formed on it. When ultraviolet (UV) rays are used to irradiate the photomask in this process, the photoresist irradiated with ultraviolet rays starts to polymerize through the photoinitiator contained in the irradiated part. First, the oxygen in the photoresist is initially consumed, and then the activated monomer is polymerized to cause a cross-linking reaction. Thereafter, the polymerization reaction continues while consuming a large amount of monomer. At the same time, the unexposed portion exists in a state where the cross-linking reaction does not progress.

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

Next, depending on the inner layer process and the outer layer process, the circuit is formed through different processes. However, in the inner layer process, a circuit is formed on the board through an etching and stripping 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.

Recently, there has been a need to develop a photosensitive resin composition that has high sensitivity to ultrahigh-pressure mercury lamp or laser direct exposure, increases resistance to developer solutions, and thus can be used during development High-density circuits are formed during the process. The photosensitive resin composition has excellent color development and can be used as a UV mark for setting the exposure position of the substrate. It also shortens the peeling time of the cured film and has a small of the peeled sample and therefore does not clog the filter.

An object of the present disclosure is to provide a photosensitive resin layer that can achieve excellent substrate adhesion.

Another object of the present disclosure is to provide a dry film photoresist and photosensitive element including the photosensitive resin layer.

To achieve the above purpose, this article provides a photosensitive resin layer, which includes: a photopolymerizable compound containing a trifunctional or higher polyfunctional (meth)acrylate compound; and an alkaline developable binder resin. , wherein the adhesion force defined by the following Equation 1 is 90% or greater during a tape peeling test using a peel tester on a film sample in which the photosensitive resin layer is laminated on a substrate: [Equation 1] Adhesion (%) = (surface area of the substrate and the photosensitive resin layer after the tape peeling test/surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test) * 100.

The trifunctional or higher polyfunctional (meth)acrylate compound may have three or more epoxyalkyl groups having 1 to 10 carbon atoms and three or more (meth)acrylate functional group bonds to a central group having 1 to 20 carbon atoms structure.

The trifunctional or higher polyfunctional (meth)acrylate compound may include the compound of Chemical Formula 2.

The trifunctional or higher polyfunctional (meth)acrylate compound may include the compound of Chemical Formula 2-1. The compound of Chemical Formula 2-1 is as follows.

The photopolymerizable compound may further include a monofunctional (meth)acrylate compound.

The photopolymerizable compound may contain 100 parts by weight or more of the multifunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound.

The monofunctional (meth)acrylate compound may include a (meth)acrylate containing an epoxyalkyl group having 1 to 10 carbon atoms.

The monofunctional (meth)acrylate compound may include the compound of Chemical Formula 1.

The photopolymerizable compound may include: a monofunctional (meth)acrylate compound containing a (meth)acrylate containing an epoxyalkyl group having 1 to 10 carbon atoms; and a trifunctional or higher polyfunctional (meth)acrylate compounds having three or more epoxyalkyl groups having 1 to 10 carbon atoms and three or more (meth)acrylate functional groups bonded to Structures with a central group of 1 to 20 carbon atoms.

The alkaline developable binder resin may have a weight average molecular weight of 20,000 grams per mole (g/mol) or greater and 150,000 g/mol or less.

Based on 100 parts by weight of the monofunctional (meth)acrylate compound, the polyfunctional The (meth)acrylate compound may be contained in an amount of less than 100 parts by weight.

The polyfunctional (meth)acrylate compound may be contained in an amount of 30 parts by weight or more and 90 parts by weight or less based on 100 parts by weight of the monofunctional (meth)acrylate compound.

The alkaline developable binder resin may include: a first alkaline developable binder resin including a repeating unit represented by Chemical Formula 3, a repeating unit represented by Chemical Formula 4, a repeating unit represented by Chemical Formula 5, a repeating unit represented by Chemical Formula 6 a repeating unit and a repeating unit represented by Chemical Formula 7; and a second alkaline developable binder resin including a repeating unit represented by Chemical Formula 4, a repeating unit represented by Chemical Formula 5, and a repeating unit represented by Chemical Formula 6. Chemical formulas 3 to 7 are as follows.

The second alkaline developable binder resin may be contained in an amount of 500 parts by weight or more and 1000 parts by weight or less based on 100 parts by weight of the first alkaline developable binder resin.

The ratio of the glass transition temperature of the first alkali developable binder resin to the glass transition temperature of the second alkali developable binder resin may be 1:1.5 or greater and 1:5 or less.

The ratio of the acid value of the first alkaline developable binder resin to the acid value of the second alkaline developable binder resin may be 1:1.01 or greater than 1:1.01 and 1:1.5 or less than 1:1.5.

The photosensitive resin layer may have a thickness of 1 micron or more and 1000 microns or less.

The photosensitive resin layer may have a thickness of 0.10 square centimeters or greater than 0.10 square centimeters. A cross-sectional area of 5.00 square centimeters or less than 5.00 square centimeters.

This article further provides a dry film photoresist including the photosensitive resin layer containing the photosensitive resin composition.

This article further provides a photosensitive element, which includes: a polymer substrate; and the photosensitive resin layer formed on the polymer substrate.

This article further provides a photosensitive element, the photosensitive element comprising: a polymer substrate; and the photosensitive resin layer formed on the polymer substrate, wherein the photosensitive resin layer is laminated on the polymer substrate using a peel tester. During a tape peeling test of a film sample on a substrate, the adhesion defined by the following Equation 1 is 90% or greater: [Equation 1] Adhesion (%) = (After the tape peeling test the substrate and Surface area of the photosensitive resin layer/surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test)*100.

In the following, a photosensitive resin composition, a photosensitive resin layer, a dry film photoresist and a photosensitive element using the photosensitive resin layer according to specific embodiments of the present disclosure will be described in more detail.

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

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

The terms "including" or "comprising" are used herein to specify specific features, regions, integers, steps, actions, components and/or components, but does not exclude the existence or addition of different specific features, regions, integers, steps, actions, elements, components and/or groups.

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

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

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

In this specification, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; halogen group; cyano group ; Nitro; hydroxyl; carbonyl; ester group; amide group; amide group; primary amine group; carboxyl group; sulfonate group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; alkyl sulfide Oxygen; arylsulfoxy; alkylsulfonateoxy; arylsulfonateoxy; silyl; boron; alkyl; cycloalkyl; alkenyl; aryl; aralkyl; arylalkenyl; Alkylaryl; alkoxysilylalkyl; arylphosphinoyl; or heterocyclyl, containing at least one of N, O and S atoms, or meaning unsubstituted or among the substituents exemplified above Substitution with a substituent bonded to two or more substituents. For example, the "substituent bonded to two or more substituents" may be a biphenyl group. That is, biphenyl is also Can be an aryl group and can be interpreted as a substituent bonded to two phenyl groups.

或

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

or

It means a bond to another substituent, and a direct bond means that there are no other atoms in the moiety represented by L.

In this specification, (meth)acrylic acid groups are intended to include both acrylic acid groups and methacrylic acid groups. For example, (meth)acrylate is intended to include both acrylates and methacrylates.

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

基、芴基及類似物，但不限於此。芳基可為經取代或未經取代的，且當其經取代時，取代基的實例與上述者相同。 In this specification, an aryl group is a monovalent functional group derived from an arene, and is not particularly limited, but preferably has 6 to 20 carbon atoms, and can be a monocyclic aryl group or a polycyclic aryl group. Specific examples of the monocyclic aryl group may include phenyl, biphenyl, terphenyl and the like, but are not limited thereto. Specific examples of the polycyclic aromatic group may include naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylene,

base, fluorenyl base and the like, but are not limited thereto. The aryl group may be substituted or unsubstituted, and when it is substituted, examples of the substituents are the same as above.

In this specification, the alkylene group is a divalent functional group derived from an alkane (alkane), and the description for the alkyl group as defined above is applicable except that the alkylene group is a divalent functional group. For example, the alkylene group may be linear or branched, methylene, vinyl, propenyl, isobutenyl, sec-butenyl, tert-butenyl, pentenyl, hexenyl or the like. things. Alkylene groups may be substituted or unsubstituted.

In this specification, a multivalent functional group is a residue in which a plurality of hydrogen atoms bonded to any compound are removed, and, for example, it may be a divalent functional group, a trivalent functional group, and a tetravalent functional group . As an example, a tetravalent functional group derived from cyclobutane means a residue in which any four hydrogen atoms bonded to cyclobutane have been removed.

In this specification, direct bonding or single bonding means connecting to a bond line where no atom or atomic group exists at the corresponding position. Specifically, direct bonding or single bonding means a situation in which no other atoms are present in the part represented by R _a or L _b (where a and b are respectively integers from 1 to 20) in the chemical formula.

In this specification, the term "(photo)cured product" or "(photo)cured" means not only a component in which a component having a curable or crosslinkable unsaturated group in the chemical structure is completely cured, crosslinked or polymerized situations, and includes situations in which such components are partially cured, cross-linked or polymerized.

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

1. Photosensitive resin composition

According to one embodiment of the present disclosure, a photosensitive resin layer may be provided, the photosensitive resin layer comprising: a photopolymerizable compound containing a trifunctional or higher polyfunctional (meth)acrylate compound; and an alkaline developable adhesive agent resin, wherein the adhesive force defined by Equation 1 is 90% or greater during a tape peeling test using a peel tester on a film sample in which the photosensitive resin layer is laminated on a substrate.

The inventor discovered through experiments that because the photosensitive resin layer of one embodiment has an adhesion force defined by Equation 1 of 90% or greater, excellent physical properties (resolution, fine line adhesion, etc.) can be ensured. , and complete this disclosure.

(1)Alkaline developable binder resin

The photosensitive resin layer of the present disclosure may include an alkaline developable binder resin.

Specifically, the alkaline developable binder resin may include at least two or more alkaline developable binder resins. The at least two or more alkaline developable binder resins may mean a mixture composed of two or more alkaline developable binder resins.

The at least two or more alkaline developable binder resins may include: a first alkaline developable binder resin including a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by 5, a repeating unit represented by the following Chemical Formula 6, and a repeating unit represented by the following Chemical Formula 7; and a second alkaline developable binder resin including a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5 and a repeating unit represented by the following Chemical Formula 6.

In Chemical Formula 3, R ₃ " is hydrogen,

In Chemical Formula 4, R ₃ ' is an alkyl group having 1 to 10 carbon atoms,

In Chemical Formula 5, 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 6]

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

In Chemical Formula 7, R ₄ ' is hydrogen, and R ₅ ' is an alkyl group having 1 to 10 carbon atoms.

Specifically, the alkaline developable binder resin may include a random copolymer composed of a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5, The repeating unit represented by Chemical Formula 6 and the repeating unit represented by Chemical Formula 7 below.

In Chemical Formula 3, R ₃ " is hydrogen,

In Chemical Formula 4, R ₃ ' is an alkyl group having 1 to 10 carbon atoms,

In Chemical Formula 5, 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 6, Ar is an aryl group having 6 to 20 carbon atoms, [Chemical Formula 7]

In Chemical Formula 7, R ₄ ' is hydrogen, and R ₅ ' is an alkyl group having 1 to 10 carbon atoms.

In Chemical Formulas 3 to 7, 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 4 may be a repeating unit derived from a monomer represented by Chemical Formula 4-1 below.

In Chemical Formula 4-1, R ₃ ' is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 4-1, the definition of R ₃ ' is the same as that set forth for Chemical Formula 4. Specific examples of the monomer represented by Chemical Formula 4-1 may include methacrylic acid (MAA).

The repeating unit represented by Chemical Formula 5 may be a repeating unit derived from a monomer represented by Chemical Formula 5-1 below.

In Chemical Formula 5-1, 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 5-1, the definitions of R ₄ " and R ₅ " are the same as those set forth for Chemical Formula 5. Specific examples of the monomer represented by Chemical Formula 5-1 may include methylmethacrylate (MMA).

The repeating unit represented by Chemical Formula 6 may be a repeating unit derived from a monomer represented by Chemical Formula 6-1 below.

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

The alkaline developable binder resin may have a weight average molecular weight of 30,000 g/mol or greater and 150,000 g/mol or less and have a weight average molecular weight of 20°C or greater and a glass transition temperature of 150°C or less. Thereby, the coating properties and followability of the dry film photoresist can be improved, as well as the mechanical strength of the photoresist itself after the circuit is formed. Additionally, the alkaline developable binder resin may have 140 milligrams of potassium hydroxide per gram (mg KOH/g) or more and 160 mg KOH/g or less. /g acid value.

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

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

Specific examples of measurement conditions are as follows: the alkaline developable binder resin is dissolved in tetrahydrofuran (THF), so that the alkaline developable binder resin in THF has a value of 1.0 (weight/weight (w/w) )% concentration (in solid Body content, about 0.5 (weight/weight)%); filtered using a syringe filter with a pore size of 0.45 microns; and then injected into the GPC in an amount of 20 microliters, tetrahydrofuran ( THF) was used as the mobile phase of GPC, and the flow rate was 1.0 mL/min. The column is composed of an Agilent PL gel 5 micron (μm) guard (7.5 × 50 millimeters (mm)) and two Agilent PL gel 5 micron mixed tubes (mixed) D ( 7.5 × 300 mm) configured, and the measurement was performed at 40°C using the Agilent 1260 Infinity II System RI Detector as the detector.

Polyphenyls in which polystyrenes with various molecular weights were dissolved in tetrahydrofuran at a concentration of 0.1 (weight/weight) (w/w)% were analyzed through a syringe filter with a pore size of 0.45 microns. Ethylene standards (STD A, B, C, D) were filtered and then injected into the GPC and the weight average molecular weight (Mw) value 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)：126,000/4,430/370

STD D(MP)：51,200/1,920/162

The glass transition temperature of the reference polymer and the glass transition temperature of the binder polymer were measured using a Differential Scanning Calorimeter (DSC) (Perkin-Elmer, DSC-7). compared Compare. The measurement 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.

The acid value of the alkaline developable binder resin was measured by the following process: In the process, approximately 1 gram of the alkaline developable binder resin was sampled and dissolved in two drops of 1% phenolphthalein indicator in 50 milliliters (ml) of a mixed solvent (MeOH 20%, acetone (80%)), and then titrated using 0.1 normal concentration (N) KOH to measure the acid value.

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 content of 160 mg potassium hydroxide/gram or more and 200 mg potassium hydroxide/gram or less. value.

Specifically, the ratio of the glass transition temperature of the first alkali developable binder resin to the glass transition temperature of the second alkali developable binder resin may be 1:1.5 or greater and 1:5 or less. 1.5, 1:1.5 or greater than 1:1.5 and 1:3 or less than 1:3, 1:1.5 or greater than 1:1.5 and 1:2 or less than 1:2, 1:1.5 or greater 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 1:1.6 or greater than 1:1.6 and 1:1.7 or less than 1:1.7.

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

Meanwhile, based on 1 mol of the repeating unit represented by Chemical Formula 3, the first alkaline developable binder resin contained in the photosensitive resin composition of one embodiment may be 1.2 mol or greater than 1.2 mol and 3 mol 1 mole or less, 1.2 mole or more than 1.2 mole and 2 mole or less, 1.5 mole or more than 1.5 mole and 2 mole or less, or 1.5 mole or An amount of more than 1.5 mole and 1.6 mole or less than 1.6 mole includes the repeating unit represented by Chemical Formula 4.

In addition, the second alkaline developable binder resin contained in the photosensitive resin composition of one embodiment may be 2 moles or greater than 2 moles and 10 moles based on 1 mole of the repeating unit represented by Chemical Formula 7. 10 moles or less, 3 moles or more and 10 moles or less, 3 moles or more than 3 moles and 5 moles or less, or 4 moles or An amount of more than 4 moles and 5 moles or less includes the repeating unit represented by Chemical Formula 5.

Meanwhile, the second alkaline developable binder resin may include a random copolymer composed of a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5, and a repeating unit represented by the following Chemical Formula 6.

In Chemical Formula 4, R ₃ ' is an alkyl group having 1 to 10 carbon atoms.

In Chemical Formula 5, 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 6, Ar is an aryl group having 6 to 20 carbon atoms.

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

[Chemical formula 4-1]

In Chemical Formula 4-1, R ₃ ' is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 4-1, the definition of R ₃ ' is the same as that set forth for Chemical Formula 4. Specific examples of the monomer represented by Chemical Formula 4-1 may include methacrylic acid (MAA).

The repeating unit represented by Chemical Formula 5 may be a repeating unit derived from a monomer represented by Chemical Formula 5-1 below.

In Chemical Formula 5, 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 5-1, the definitions of R ₄ " and R ₅ " are the same as those set forth for Chemical Formula 5. Specific examples of the monomer represented by Chemical Formula 5-1 may include methyl methacrylate (MMA).

The repeating unit represented by Chemical Formula 6 may be derived from the following Chemical Formula 6- 1 represents the repeating unit of the monomer.

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

Specifically, the first alkaline developable binder resin may include the repeating unit represented by Chemical Formula 4 in the following ratio: the repeating unit represented by Chemical Formula 5: the repeating unit represented by Chemical Formula 6: 1: (2 or more than 2 and is 5 or less than 5): (0.2 or greater than 0.2 and 0.9 or less than 0.9), 1: (2 or greater than 2 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): (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): (0.6 or greater than 0.6 and 0.75 or less 0.75).

In addition, the second alkaline developable binder resin may include a repeating unit represented by Chemical Formula 4: a repeating unit represented by Chemical Formula 5: a repeating unit represented by Chemical Formula 6: 1: (1.1 or more than 1.1 and 2 or less than 2): (0.2 or greater than 0.2 and 0.99 or less than 0.99), 1: (1.5 or greater than 1.5 and 2 or less than 2): (0.5 or greater than 0.5 and 0.99 or less than 0.99) or 1: (1.5 or Greater than 1.5 and 1.75 or less than 1.75): (0.75 or greater than 0.75 and 0.99 or less than 0.99).

At the same time, based on 100 parts by weight of the first alkaline developable binder resin, The photosensitive resin layer of an embodiment of the present disclosure may be 500 parts by weight or greater than 500 parts by weight and 1000 parts by weight or less than 1000 parts by weight, 600 parts by weight or greater than 600 parts by weight and 800 parts by weight or less, The second alkaline developable binder resin is included in an amount of 700 parts by weight or more and 800 parts by weight or less.

As mentioned above, since 500 parts by weight or more of the second alkaline developable binder resin is excessively added based on 100 parts by weight of the first alkaline developable binder resin, it is possible to impart hydrophobicity to the photosensitive resin. function, the technical effect of increasing tolerance to developer solutions and improving circuit properties.

In terms of solid content, the alkaline developable binder resin is contained in an amount of 20% by weight or more and 80% by weight or less than 80% by weight relative to the total weight of the photosensitive resin composition. When the content of the alkaline developable binder resin is within the above range, the effect of enhancing the adhesion of thin wires after circuit formation can be obtained. The solid content on a weight basis 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% by weight or greater than 40% by weight and 70% by weight or less than 70% by weight relative to the total weight of the photosensitive resin composition forming the photosensitive resin layer. When the content of the alkaline developable binder resin is less than 40% by weight relative to the total photosensitive resin composition, there is a disadvantage that defects such as short circuits may occur due to contamination during development, and when the content of the alkaline developable binder resin is When the content exceeds 70% by weight, there is a problem of deterioration in circuit properties such as adhesive strength and resolution.

(2) Photopolymerization initiator

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

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

In addition, one selected from the group consisting of 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 1-hydroxycyclohexylphenylketone, 2,2-di Methoxy-1,2-diphenylethyl-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1-[4-morpholinophenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4 ,6-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-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzene Methyl formate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylamine 2-isoamyl benzoate, 2,2-diethoxyacetophenone, benzyl ketone dimethyl acetal, benzyl ketone β-methoxy diethyl acetal, 1-phenyl-1 ,2-propyldioxime-o,o'-(2-carbonyl)ethoxy ether (1-phenyl-1,2-propyldioxime-o,o'-(2-carbonyl)ethoxy ether), o-phenyldioxime Methyl benzoate, bis[4-dimethylaminophenyl]one, 4,4'-bis(diethyl) Amino)benzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, isobutoxy Benzoin, tert-butoxybenzoin, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methyl Compounds in thioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, α,α-dichloro-4-phenoxyacetophenone and amyl 4-dimethylaminobenzoate As a photopolymerization initiator, it is not limited to this.

In terms of solid content, the photopolymerization initiator is contained in an amount of 2 wt% or more and 10 wt% or less with respect to the total weight of the photosensitive resin composition used to form the photosensitive resin layer. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity can be obtained. The solid content on a weight basis means the remaining components excluding the solvent from the photosensitive resin composition.

When the content of the photopolymerization initiator is less than 2% by weight, the light efficiency is low, and a large amount of exposure must be applied and therefore, there is a disadvantage that the production efficiency is greatly reduced. When the content of the photopolymerization initiator exceeds 10% by weight, there are problems that the film becomes brittle and contamination of the developer solution increases, leading to defects such as short circuits.

(3) Photopolymerizable compounds

The photopolymerizable compounds of the present disclosure are resistant to developer solutions after UV exposure and are therefore capable of patterning.

Photopolymerizable compounds of the present disclosure may include trifunctional or higher polyfunctional (meth)acrylate compounds.

Specifically, the trifunctional or higher polyfunctional (meth)acrylate compound may have three or more epoxyalkyl groups having 1 to 10 carbon atoms and three A structure in which one or more (meth)acrylate functional groups are bonded to a central group having 1 to 20 carbon atoms.

More specifically, the trifunctional or higher polyfunctional (meth)acrylate compound may include the polyfunctional (meth)acrylate compound of the following Chemical Formula 2:

In Chemical Formula 2, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₅ is an alkylene group having 1 to 10 carbon atoms, and R ₆ is a central group containing 1 to 20 carbon atoms. For p-valent functional groups, n2 is an integer ranging from 1 to 20, and p is the number of functional groups replacing R ₆ and is an integer ranging from 3 to 10.

Furthermore, in Chemical Formula 2, n2 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 substituting R ₆ and may be an integer of 3 to 10, is an integer from 3 to 5 or an integer from 3 to 4.

That is, in Chemical Formula 2, since p which means the number of functional groups substituting R ₆ is an integer of 3 to 10, the trifunctional or higher polyfunctional (meth)acrylate compound represented by Chemical Formula 2 can It is a trifunctional or higher polyfunctional (meth)acrylate compound.

Specifically, multifunctional (meth)acrylate compounds can be formed by the following chemical Expressed in Formula 2-1.

In Chemical Formula 2-1, R ₆ ' is a trivalent functional group having 1 to 10 carbon atoms, R ₇ to R ₉ are each independently an alkylene group having 1 to 10 carbon atoms, and R ₁₀ to R ₁₂ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, and n3 to n5 are each independently an integer of 1 to 20.

In Chemical Formula 2-1, n3 to n5 may be an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to 5.

Examples of the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 are not particularly limited, but may be, for example, T063 (Trimethylolpropane [EO] ₆ triacrylate (Trimethylolpropane [EO]) represented by the following Chemical Formula B ₆ triacrylate)).

Since the photosensitive resin composition of one embodiment includes the multifunctional (meth)acrylate compound represented by Chemical Formula 2, the photocuring speed and degree of curing are improved, contrast can be ensured, and excellent fine line adhesion can be achieved.

Meanwhile, the photosensitive resin layer of one embodiment may further include a monofunctional (meth)acrylate compound.

Specifically, the monofunctional (meth)acrylate compound may include (meth)acrylate containing an epoxyalkyl group having 1 to 10 carbon atoms.

That is, the photopolymerizable compound may include: a monofunctional (meth)acrylate compound containing a (meth)acrylate containing an epoxyalkyl group having 1 to 10 carbon atoms; and Trifunctional or higher polyfunctional (meth)acrylate compounds having three or more (meth)acrylate functional groups having 1 to 10 carbon atoms and three or more (meth)acrylic acids Structures in which the ester functionality is bonded to a central group having 1 to 20 carbon atoms.

More specifically, the monofunctional (meth)acrylate compound may include a monofunctional (meth)acrylate compound represented by the following Chemical Formula 1.

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, R ₃ is an alkyl group having 1 to 10 carbon atoms, And n1 is an integer from 1 to 20.

Specifically, in Chemical Formula 1, n1 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 1 are not particularly limited, but may be, for example, A040 (methoxypropylene glycol [400] acrylate) represented by the following Chemical Formula A.

Since the photosensitive resin layer of one embodiment includes the monofunctional (meth)acrylate compound represented by Chemical Formula 1, the photosensitive resin layer has a low glass transition temperature due to the low glass transition temperature of the monofunctional (meth)acrylate compound represented by Chemical Formula 1. The resin layer has relatively large fluidity at the lamination temperature of the dry film photoresist, and thereby can achieve the effect of improving physical adhesion to substrates with high surface roughness and non-uniformity.

Meanwhile, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photosensitive resin layer of one embodiment may be less than 100 parts by weight, 30 parts by weight or more than 30 parts by weight, and 90 parts by weight or less than 90 parts by weight. parts by weight, 50 parts by weight or more and 90 parts by weight or less, 50 parts by weight or more than 50 parts by weight and 80 parts by weight or less, or 50 parts by weight or more The polyfunctional (meth)acrylate compound is contained in an amount of 50 parts by weight and 75 parts by weight or less.

Since the photosensitive resin layer of one embodiment contains a small amount of the multifunctional (meth)acrylate compound relative to the monofunctional (meth)acrylate compound, an improvement in the monofunctional (meth)acrylic acid represented by Chemical Formula 1 is simultaneously achieved. Physical adhesion of the ester compound to the substrate, ensuring contrast of the multifunctional (meth)acrylate compound represented by Chemical Formula 2, and improving fine line adhesion, thereby exhibiting excellent developability, thereby improving adhesion to the substrate and Ensure excellent physical properties (resolution, fine line adhesion, etc.).

When the photosensitive resin layer of one embodiment contains 100 parts by weight or more of a multifunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound, there may be damage to the substrate. Technical issues with reduced adhesion.

Meanwhile, the photopolymerizable compound may include a bifunctional (meth)acrylate compound including an alkylene glycol-based di(meth)acrylate and a urethane-based Di(meth)acrylate.

That is, the photosensitive resin layer of one embodiment includes a photopolymerizable compound, and the photopolymerizable compound may include a monofunctional (meth)acrylate compound, a multifunctional (meth)acrylate compound, or an alkylene glycol. It is a bifunctional (meth)acrylate of di(meth)acrylate and urethane di(meth)acrylate.

Alkylene glycol di(meth)acrylates may include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate (meth)acrylate), tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate (meth)acrylate (polyethylene glycol di(meth)acrylate), polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate meth)acrylate), ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate (diethylene glycol diglycidyl ether di(meth)acrylate), such as Miramer M244 (Bisphenol A (EO) ₃ DA, bisphenol A manufactured by Miwon Specialty Chemical Co., Ltd. (EO) ₃ Diacrylate), Miramer M240 (Bisphenol A (EO) ₄ DA, Bisphenol A (EO) ₄ Diacrylate), Miramer M241 (Bisphenol A (EO) ₄ Dimethacrylate), Miramer M2100 (Bisphenol A (EO) ₁₀ DA, Bisphenol A (EO) ₁₀ Diacrylate), Miramer M2200 (Bisphenol A (EO) ₂₀ DA, Bisphenol A (EO) ₂₀ diacrylate), Miramer M2101 (bisphenol A (EO) ₁₀ dimethacrylate) and other commercially available products.

In addition, KUA-1330h or the like can be used as the urethane di(meth)acrylate.

The molecular weight of the urethane di(meth)acrylate can be larger than the existing simple alkylene oxide and has a linear structure, thereby imparting flexibility. This results in improved hole-capping properties required for the outer dry film resist (DFR) and as a urethane The hydrophobicity of the polyol, one of the components of ester acrylate, improves the resistance to the plating solution which is a strong acid, thereby not contaminating the plating solution.

Urethane di(meth)acrylate can be obtained by reacting a diisocyanate compound with a polyether compound having a hydroxyl group or a polyester compound having a hydroxyl group to obtain a urethane compound, And then the obtained urethane compound is reacted with a compound having both a hydroxyl group and an ethylenically unsaturated group.

The polyether compound having a hydroxyl group is a polyether glycol, and glycols such as polytetramethylene glycol, polyoxyethylene, polyoxypropylene, and polyoxytetrahydrofuran are used. As the polyester compound having a hydroxyl group, a compound obtained by condensing adipic acid and 1,4-butanediol is used.

The diisocyanate compound (a-2) may include an aliphatic diisocyanate compound having a divalent aliphatic group (such as an alkylene group), an alicyclic diisocyanate compound having a divalent alicyclic group (such as a cycloalkylene group) , aromatic diisocyanate compounds and their isocyanurate modified components, carbodiimide modified components, buret-modified components and the like.

At this time, examples of the aliphatic diisocyanate compound include hexamethylene isocyanate, trimethylhexamethylene diisocyanate and the like.

Alicyclic diisocyanate compounds may include isophorone diisocyanate, methylene bis(cyclohexyl)diisocyanate, 1,3- or 1,4-bis(methylisocyanate)cyclohexane, and the like.

Aromatic diisocyanate compounds may include 2,4-toluene diisocyanate, 2,6-Toluene diisocyanate, 2,4-toluene diisocyanate or dimer polymer of 2,6-toluene diisocyanate, (o-, para- or meta-)xylene diisocyanate, diphenylmethane diisocyanate, 1, 5-Naphthalene diisocyanate and the like.

The compounds may be used alone or in combination of two or more. Furthermore, it may include isocyanate compounds having two or more isocyanate groups, such as triphenylmethane triisocyanate and tris(phenyl isocyanate)phosphorothioate. Among these, the alicyclic diisocyanate compound is preferable from the viewpoint of improving the flexibility and toughness of the photocured product and thus improving the adhesion to the substrate.

A polyether compound or polyester compound having a hydroxyl group is reacted with a diisocyanate compound to prepare a urethane compound. In the above reaction, the diisocyanate compound is preferably used in a molar ratio of 1.01 to 2.0, more preferably in a molar ratio of 1.1 to 2.0 relative to 1 mol of the polyether compound or polyester compound having a hydroxyl group. If the content of the diisocyanate compound is less than 1.01 mol or more than 2.0 mol, the urethane compound having isocyanate groups at both ends may not be stably obtained.

Furthermore, in the reaction for synthesizing the urethane compound, it is preferable to add dibutyltin dilaurate as a catalyst.

The reaction temperature is preferably 60°C to 120°C. When the reaction temperature is less than 60°C, there is a tendency that the reaction does not proceed sufficiently, and when the reaction temperature exceeds 120°C, the reaction operation may be dangerous due to sudden generation of heat.

Compounds having both a hydroxyl group and an ethylenically unsaturated group used for reaction with the urethane compound thus prepared may include compounds having a hydroxyl group and a (methyl) group in the molecule. Acrylyl compound. These compounds include hydroxy(meth)acrylates, hydroxy(meth)acrylate-caprolactone adducts or alkylene oxide adducts, by reacting a polyol (such as glycerol) with (meth)acrylic acid. The ester compound prepared by the reaction, and the glycidyl (meth)acrylate-acrylic acid adduct.

Hydroxy(meth)acrylates may include 2-hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, and hydroxybutyl(meth)acrylate.

Hydroxy(meth)acrylate-caprolactone adducts may include hydroxyethyl(meth)acrylate. Caprolactone adduct, hydroxypropyl (meth)acrylate. Caprolactone adduct, hydroxybutyl (meth)acrylate. Caprolactone adduct, and the alkylene oxide adduct may include hydroxyethyl (meth)acrylate. Alkylene oxide adduct, hydroxypropyl (meth)acrylate. Propylene oxide adduct, hydroxybutyl (meth)acrylate. Butylene oxide adduct.

Ester compounds may include, for example, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane mono(meth)acrylate, acrylate, ditrimethylolpropane tri(meth)acrylate, di(meth)acrylate of trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide Adduct of di(meth)acrylate. These may be used individually or in combination of two or more.

Urethane di(meth)acrylate is a compound derived from the addition reaction of a urethane compound and a compound having both a hydroxyl group and an ethylenically unsaturated group, and can be obtained by relatively A compound having both a hydroxyl group and an ethylenically unsaturated group is added at a molar ratio of 2.0 to 2.4 per mole of the urethane compound and then subjected to an addition reaction at 60°C to 90°C. obtain.

The urethane di(meth)acrylate preferably has a weight average molecular weight in the range of 1,000 g/mol to 60,000 g/mol. When the weight average molecular weight is less than 1,000 g/mol, it is difficult to sufficiently increase flexibility and toughness, so adhesion to the substrate may not be improved, and when the weight average molecular weight exceeds 60,000 g/mol, there is a possibility that the development properties may be deteriorated And the development time may be slowed down. Therefore, it is preferred that the urethane di(meth)acrylate according to the present disclosure has a weight average molecular weight of 1,000 g/mol to 60,000 g/mol.

In the present disclosure, the urethane di(meth)acrylate having a weight average molecular weight of 1,000 g/mol to 60,000 g/mol is 1 to 20 wt %, preferably 1.5 The photosensitive resin composition is included in an amount of % by weight to 15% by weight. When the content of the urethane di(meth)acrylate having a weight average molecular weight of 1,000 g/mol to 60,000 g/mol is less than 1% by weight, the effect produced thereby is insufficient, and when the content When it exceeds 20% by weight, there may be disadvantages that the development time increases rapidly during the development process after exposure and a large amount of scum and sludge are generated.

Based on 100 parts by weight of alkylene glycol di(meth)acrylate, the photosensitive resin layer of one embodiment may be 1 part by weight or more than 1 part by weight and 50 parts by weight or less than 50 parts by weight, 1 part by weight. 1 part by weight or more and 30 parts by weight or less, 1 part by weight or more and 10 parts by weight or less, or 1 part by weight or more than 1 part by weight and 5 parts by weight Or it is contained in an amount less than 5 parts by weight.

Since relative to 100 parts by weight of alkylene glycol di(meth)acrylic acid The ester and urethane di(meth)acrylate are contained in an amount of 1 part by weight or more and 50 parts by weight or less, so that the photosensitive resin composition of one embodiment can be achieved Reduce technical effects such as circuit property degradation, peeling and development time changes.

Specifically, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photosensitive resin layer of one embodiment may be 500 parts by weight or greater than 500 parts by weight and 1500 parts by weight or less than 1500 parts by weight, 500 parts by weight. 500 parts by weight or more and 1000 parts by weight or less, 750 parts by weight or more and 1000 parts by weight or less, or 800 parts by weight or more than 800 parts by weight and 900 parts by weight Or the bifunctional (meth)acrylate compound is included in an amount less than 900 parts by weight.

In addition, based on 100 parts by weight of the multifunctional (meth)acrylate compound, the photosensitive resin layer of one embodiment may be 500 parts by weight or greater than 500 parts by weight and 1000 parts by weight or less, 500 parts by weight or More than 500 parts by weight 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 than 500 parts by weight and 700 parts by weight or less The bifunctional (meth)acrylate compound is contained in an amount of 500 parts by weight or more and 600 parts by weight or less.

That is, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photosensitive resin layer of one embodiment may include less than 110 parts by weight of the multifunctional (meth)acrylate compound and 500 parts by weight or more than 500 parts by weight and is 1500 weight parts or less than 1500 parts by weight of a bifunctional (meth)acrylate compound.

As described above, since a monofunctional (meth)acrylate compound, a polyfunctional (meth)acrylate compound, and a bifunctional (meth)acrylate compound are contained simultaneously in such a manner that the above weight range is satisfied, one embodiment The photosensitive resin composition of the example can not only achieve excellent adhesion to the substrate, but also ensure contrast and implement excellent fine line adhesion.

In the present disclosure, the monofunctional photopolymerizable compound may be in an amount of 0.1% by weight or more and 2.5% by weight or less than 2.5% by weight based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer. is contained.

Furthermore, in the present disclosure, the multifunctional photopolymerizable compound may be 2.6% by weight or more and 5.0% by weight or less than 5.0% by weight based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer. amount is contained.

That is, the photosensitive resin composition used to form the photosensitive resin layer may contain 0.1% by weight or more and 2.5% by weight or less than 2.5% by weight based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer. of a monofunctional photopolymerizable compound and 2.6% by weight or greater than 2.6% by weight and 5.0% by weight or less of a multifunctional photopolymerizable compound.

When the content of the monofunctional photopolymerizable compound is less than 0.1% by weight or the content of the multifunctional photopolymerizable compound is less than 2.6% by weight based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer, due to the addition of Chemical Formula 1 The effect produced by the compounds represented by 2 and 2 is insufficient, and when the content of the monofunctional photopolymerizable compound is greater than 2.5% by weight or greater than 5.0% by weight or the content of the multifunctional photopolymerizable compound is When the content is greater than 5.0% by weight, there may be a problem of increased hydrophobicity and therefore, the development time in the development process after exposure is rapidly increased.

The photosensitive resin layer of one embodiment is an additional photopolymerizable compound and may include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, Tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate , neopentyl glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, trimethyolpropane trimethacrylate), trimethyolpropane triacrylate, glycerin dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dimethacrylate Pentaerythritol pentamethacrylate, 2,2-bis(4-methacryloxydiethoxyphenyl)propane, 2,2-bis(4-methacryloxydiethoxyphenyl)propane -Bis(4-methacryloxypolyethoxyphenyl)propane (2,2-bis(4-methacryloxypolyethoxyphenyl)propane), 2-hydroxy-3-methacryloxypolyethoxyphenyl methacrylic acid Ester (2-hydroxy-3-methacryloyloxypropyl methacrylate), ethylene glycol diglycidyl ether dimethacrylate (ethylene glycol diglycidyl ether dimethacrylate), diethylene glycol diglycidyl ether dimethacrylate, phthalic acid diglycidyl ester dimethacrylate, glycerol poly Glycerin polyglycidyl ether polymethacrylate, polyfunctional (meth)acrylates containing urethane groups and the like.

In terms of solid content, the content of the photopolymerizable compound may be 10% by weight or more and 70% by weight or less than 70% by weight relative to the total weight of the photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, effects of enhancing sensitivity, resolution, adhesion and similar properties can be obtained.

(4) Photosensitive resin composition

The photosensitive resin composition used to form the photosensitive resin layer may include: based on solid content, 20% by weight and greater than 20% by weight and 80% by weight or less than 80% by weight of an alkaline developable binder resin, 0.1% by weight or More than 0.1% by weight and 10% by weight or less of a photopolymerization initiator, and 10% by weight or more than 10% by weight and 70% by weight or less of a photopolymerizable compound. The solid content on a weight basis means the remaining components excluding the solvent from the photosensitive resin composition.

The photosensitive resin composition may further include 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 can also be determined based on the photopolymerization initiator, alkaline developable binder resin and content of the photopolymerizable compound.

In addition, the photosensitive resin composition may further contain other additives as needed. agent. Other additives are plasticizers and may include: dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate in the form of phthalates Esters; triethylene glycol diacetate and tetraethylene glycol diacetate in the form of glycol esters; p-toluenesulfonamide, benzenesulfonamide and n-butylbenzenesulfonamide in the form of acid amide; phosphoric acid triphenyl ester etc.

In the present disclosure, a colorless dye or a coloring material may be added in order to improve the handling properties of the photosensitive resin composition. Examples of leuco dyes include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2-methylphenyl)methane, and fluorane dye . Among these, when colorless crystal violet is used, the contrast is good, which is preferable. When a leuco dye is contained, the content may be 0.1% by weight or more and 10% by weight or less in the photosensitive resin composition. From the viewpoint of 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 coloring materials may include toluenesulfonic acid monohydrate, fuchsin, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl Orange, Nile blue 2B, Victoria blue, Malachite green, Diamond green, Basic blue 20 and the like. When a coloring material is included, the amount added may be 0.001% by weight or more and 1% by weight or less than 1% by weight based on the photosensitive resin composition. When the content is 0.001% by weight or greater than 0.001% by weight, it has improved disposability It has the effect of handleability, and when the content is 1% by weight or less than 1% by weight, it has the effect of maintaining storage stability.

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

Meanwhile, during a tape peeling test using a peel tester on a film sample in which the photosensitive resin layer is laminated on a substrate, the adhesive force defined by the following Equation 1 may be 90% or greater, It is 90% or more and 100% or less than 100%, or 95% or more and 100% or less. This can be implemented by including the above-mentioned photopolymerizable compound in the photosensitive resin layer of one embodiment.

[Equation 1] Adhesion (%) = (surface area of the substrate and the photosensitive resin layer after the tape peeling test/surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test)*100.

Specifically, since the photosensitive resin layer of one embodiment includes a monofunctional (meth)acrylate compound represented by Chemical Formula 1 and a multifunctional (meth)acrylate compound represented by Chemical Formula 2, the adhesion defined by Equation 1 The force can be 90% or greater.

Since the adhesion force defined by Equation 1 is 90% or greater, the effect of improving the substrate adhesion force of the dry film photoresist including the photosensitive resin layer of one embodiment can be achieved.

Specifically, in the film sample in which the photosensitive resin layer is laminated on the substrate, the substrate may be a reverse treated foil (RTF).

More specifically, the surface roughness of the substrate may be 1 micron or more and 10 microns or less, 3 microns or more and 7 microns or less, or 4 microns or more and 6 microns or less.

Meanwhile, the tape peeling test of Equation 1 can be performed using a peeling test after bonding a standard tape to a film sample in which a photosensitive resin layer is laminated on a substrate.

In the case where the adhesion force defined by Equation 1 is 90% or greater, since the photosensitive resin layer of one embodiment contains an excess of monofunctional (meth)acrylic acid relative to the multifunctional (meth)acrylate compound ester compound, therefore, the photosensitive resin layer has relatively large fluidity at the lamination temperature of the dry film type photoresist due to the low glass transition temperature of the monofunctional (meth)acrylate compound represented by Chemical Formula 1, and This can achieve the effect of improving physical adhesion to substrates with high surface roughness and non-uniformity.

2. Dry film photoresist

According to another embodiment of the present disclosure, a dry film photoresist including the photosensitive resin layer of the embodiment can be provided. Details about the photosensitive resin layer include all the contents explained above in the 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 dry product refers to the material obtained by the drying process of the photosensitive resin composition of one embodiment. The cured product means a material obtained through the curing process of the photosensitive resin composition of one embodiment.

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

Dry film photoresist can also include substrate film and protective film. The substrate film serves as a support for the photosensitive resin layer during the fabrication of the dry film photoresist and facilitates handling during exposure of the photosensitive resin layer with adhesive strength.

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

The protective film prevents damage to the photoresist during handling and serves as a protective cover to protect the photosensitive resin layer from foreign matter (such as dust), and is laminated on the photosensitive resin layer without forming on the backside of the substrate membrane. The protective film is used to protect the photosensitive resin layer from external influences. When dry film photoresist is used in post-processing, it needs to be easily detachable, and it needs proper releasability and adhesion to allow it to deform during storage and distribution.

Various plastic films can be used as the protective film, and examples thereof can include films selected from acrylic films, polyethylene (PE) films, polyethylene terephthalate (PET) At least one plastic film from the group consisting of triacetyl cellulose (TAC) film, polynorbornene (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 in the range of 0.01 micron to 1 mm.

Examples of methods for manufacturing dry film photoresists are not particularly limited, and for example, the photosensitive resin composition of one embodiment is coated onto a traditional substrate film (such as polyethylene terephthalate glycol) using a traditional coating method. ester), 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 is not particularly limited, and a method such as a coating bar can be used.

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

Meanwhile, the dry film type photoresist of one embodiment may be characterized by an adhesive force defined by the following Equation 2 during a tape peel test using a peel tester on a film sample in which a photosensitive resin layer is laminated on a substrate It can be 90% or more, 90% or more and 100% or less, or 95% or more and 100% or less. This can be implemented by including the above-mentioned photopolymerizable compound in the photosensitive resin layer of one embodiment.

[Equation 2] Adhesion (%) = (surface area of the photosensitive resin layer of the dry film photoresist in contact with the substrate after the tape peeling test/surface area of the photosensitive resin layer of the dry film photoresist in contact with the substrate before the tape peeling test)*100.

Details about adhesion include all of the above.

Since the adhesion force defined by Equation 2 is 90% or greater, the effect of improving the substrate adhesion force of the dry film photoresist in one embodiment can be achieved.

3. Photosensitive element

According to another embodiment of the present disclosure, a photosensitive element may be provided. The photosensitive element includes: a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, wherein the photosensitive resin is tested using a peeling tester. During a tape peeling test of a film sample laminated to a substrate, the adhesion force defined by the following Equation 1 is 90% or greater: [Equation 1] Adhesion force (%) = (during the tape peeling test The surface area of the substrate and the photosensitive resin layer afterward/the surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test)*100.

Details about adhesion include all of the above.

Since the adhesion force defined by Equation 1 is 90% or greater, a photosensitive element having excellent substrate adhesion force can be provided.

Meanwhile, the photosensitive resin layer includes an alkaline developable binder resin and a photopolymerizable compound, and the photopolymerizable compound may include a monofunctional (meth)acrylate compound represented by the following Chemical Formula 1 and a multifunctional (meth)acrylate compound represented by the following Chemical Formula 2 (meth)acrylate compounds.

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, R ₃ is an alkyl group having 1 to 10 carbon atoms, And n1 is an integer from 1 to 20,

In Chemical Formula 2, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₅ is an alkylene group having 1 to 10 carbon atoms, and R ₆ is a central group containing 1 to 20 carbon atoms. For p-valent functional groups, n2 is an integer ranging from 1 to 20, and p is the number of functional groups replacing R ₆ and is an integer ranging from 3 to 10.

Details about the photosensitive resin composition include all the contents explained above in the one embodiment and another embodiment.

That is, the photosensitive resin layer includes an alkaline developable binder resin and a photopolymerizable compound, and the photopolymerizable compound may include a monofunctional (meth)acrylate compound represented by the following Chemical Formula 1 and a polyfunctional (meth)acrylate compound represented by the following Chemical Formula 2 (meth)acrylate compounds.

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, R ₃ is an alkyl group having 1 to 10 carbon atoms, And n1 is an integer from 1 to 20,

In Chemical Formula 2, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₅ is an alkylene group having 1 to 10 carbon atoms, and R ₆ is a central group containing 1 to 20 carbon atoms. For p-valent functional groups, n2 is an integer ranging from 1 to 20, and p is the number of functional groups replacing R ₆ and is an integer ranging from 3 to 10.

Various plastic films can be used as the protective film, and examples thereof can include a film selected from the group consisting of acrylic film, polyethylene (PE) film, polyethylene terephthalate (PET) film, triacetyl cellulose (TAC) film, At least one plastic film from the group consisting of polynorbornene (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 in the range of 0.01 micron to 1 mm.

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

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

Here, examples of organic particles used as particles that do not impair transparency while taking feedability and winding characteristics into consideration may include, for example, organic particles in which, for example, methyl methacrylate, ethyl methacrylate, methyl methacrylate, etc. are formed. Acrylic particles, olefin particles (such as polyethylene, polystyrene or polyethylene) based on isobutyl acrylate, n-butyl methacrylate, n-butyl methyl methacrylate, acrylic acid, methacrylic acid copolymer or terpolymer multi-layer multi-component particles of acrylic), acrylic and olefin copolymers, or homopolymer particles and then coating another type of monomer on said layer multi-component particle).

a2+b2定義。並且，六面體中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。顆粒的形狀應為球形，此在走料性方面是較佳的。 Specifically, the organic particles should be spherical and also have a refractive index different from that of the binder resin. Here, "spherical" means that the ratio of the minor axis (a) to the major axis (b) in the ellipse is 0.5<a/b<2, and the relationship with the diagonal (d) in the rectangle is given by d2

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

c2+a2+b2 definition. The shape of the particles should be spherical, which is better in terms of conveyability.

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

When the content of organic particles is less than 1% by weight based on the total amount of binder resin, the anti-adhesive effect is insufficient and susceptible to scratches, and the feeding properties and winding characteristics are deteriorated, and when it exceeds 10% by weight , there may be problems of increased haze and deterioration of transparency properties.

At the same time, in addition to the above organic particles, inorganic particles can also be added. At this time, it is not preferable to add a commonly used inorganic anti-blocking agent, and it is preferable to add colloidal silica having a particle size of 100 nanometers or less. 100 parts by weight In terms of binder resin, its content is preferably 10 parts by weight or less. When the particle size and content as described above are met, the occurrence of sidewall defects or grooves (such as pits) caused by the anti-adhesion layer when patterning using dry film photoresist can be prevented.

As the binder resin serving as a binder for coating such organic particles onto an unstretched polyester film, a binder resin having excellent compatibility with the 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 methyl methacrylate , acrylic acid, methacrylic acid copolymer or terpolymer; urethane resin; epoxy resin; or melamine resin and the like, and acrylic resin is preferred.

The solvent that can be used to prepare 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 is uniaxially stretched, and then a coating solution containing organic particles in a binder resin is coated on the uniaxially stretched film superior. The coating may be performed on at least one side of the uniaxially stretched film, and the thickness after final drying is preferably about 30 nm to 200 nm. If the coating solution containing organic particles is applied to a uniaxially stretched film to a thickness thicker than 30 nanometers, there is a problem that the organic particles are easily dropped and scratched, and white powder is produced. When coating to a thickness thicker than 200 nm, coating streaks may occur in the coating direction during in-line coating with a high coating speed due to an increase in the viscosity of the coating solution.

By using an in-line coating method as described above, it is different from the general resist The polymer substrate obtained by coating the organic particles of the binder is a substrate film that maintains feedability and winding characteristics due to the particle layer and has excellent transparency due to the excellent light transmission of the organic particles. .

Since the lamination of the photosensitive resin layer is performed on the opposite surface of the layer containing organic particles in the polymer substrate, the photosensitive resin layer is formed on the opposite surface of the layer containing organic particles in this manner. Therefore, when the substrate film including the anti-blocking agent is laminated as before, pit-like defects do not occur. Since particles such as silicon dioxide are not only larger in size than organic particles but are also distributed throughout the substrate film, the influence of silicon dioxide is insignificant even in areas 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 microns to 5 microns, and the organic particle layer is not adjacent to the photosensitive resin layer so that the physical effect of the organic particles is not affected. In addition, by using organic particles with excellent light transmittance, sidewall defects can be reduced without compromising other circuit properties.

The photosensitive element may further include a protective film formed on the photosensitive resin layer. The protective film prevents damage to the photosensitive resin layer during handling and functions as a protective covering to protect the photosensitive resin layer from foreign matter such as dust. The 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 dry film resist is used for post-processing, it needs to be easily detachable, and it needs the right releasability and adhesion to allow it to deform during storage and distribution.

Various plastic films can be used as the protective film, and examples thereof can include a film selected from the group consisting of acrylic film, polyethylene (PE) film, polyethylene terephthalate (PET) film, triacetyl cellulose (TAC) film, At least one plastic film from the group consisting of polynorbornene (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 in the range of 0.01 micron to 1 mm.

4. Circuit boards and display devices

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

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

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

Examples of the method of forming the photosensitive resin in the form of a pattern layer include a method of laminating the photosensitive resin layer of the dry film type photoresist of another embodiment 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 on a circuit board or a display device manufacturing substrate and then performing exposure and development may be mentioned.

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

In addition, when the dry film photoresist or photosensitive element of another embodiment has a polymer substrate or substrate film laminated on one side of the photosensitive resin layer, the polymer substrate can be further removed immediately after the exposure process or Substrate film manufacturing process.

Therefore, the circuit board or the display device may include the dry film photoresist or the photosensitive resin layer contained in the photosensitive element of another embodiment.

According to the present disclosure, a photosensitive resin layer that can achieve excellent substrate adhesion, and a dry film photoresist, circuit board and display device using the photosensitive resin layer can be provided.

Figure 1 shows an optical microscope image of the adhesion between the substrate and the photosensitive resin layer during a tape peeling test measured in the Example.

2 shows an optical microscope image of the adhesion between the substrate and the photosensitive resin layer measured during a tape peeling test in Comparative Example 1.

3 shows an optical microscope image of the adhesion between the substrate and the photosensitive resin layer measured during a tape peeling test in Comparative Example 2.

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

<Preparation example: Preparation of alkaline developable binder resin>

Preparation Example 1

The four-neck round-bottom flask was equipped with a mechanical stirrer and a reflux device, and then the inside of the flask was purged with nitrogen. To the flask purged with nitrogen, 80 grams of methyl ethyl ketone (MEK) and 7.5 grams of methanol (MeOH) were added, and then 0.45 grams of azobisisobutyronitrile (AIBN) was added and allow it to dissolve completely. 8 grams of acrylic acid (AA), 15 grams of methacrylic acid (MAA), 15 grams of butyl acrylate (BA), and 52 grams of methyl methacrylate (MMA) were added to it. ) and 10 grams of styrene (SM) were used as monomers, heated to 80° C., and then polymerized for 6 hours to prepare an alkaline developable binder resin 1.

Alkaline Developable Binder Resin 1 was measured to have a weight average molecular weight of 71538 grams/mol, a glass transition temperature of 79°C, a solids content of 51.4 wt%, and 156.3 mg potassium hydroxide/gram of acid. value.

In a specific example of the measurement conditions of the weight average molecular weight, the alkali developable binder resin is dissolved in tetrahydrofuran so that the alkali developable binder resin has a concentration of 1.0 (weight/weight)% in THF ( Based on solid content, about 0.5 (weight/weight)%), filtered using a syringe filter with a pore size of 0.45 microns, and then injected into the GPC in an amount of 20 microliters, tetrahydrofuran ( Tetrahydrofuran (THF) was used as the mobile phase of GPC, and the flow rate was 1.0 ml/min. The column consists of an Agilent PL glue connected in series (Agilent PLgel) 5 micron guard (7.5 × 50 mm) is configured with two Agilent PL gel 5 micron mixed tubes (mixed) D (7.5 × 300 mm), and the measurement was performed using an Agilent 1260 An Agilent 1260 Infinity II System RI Detector was used as the detector and was performed at 40°C.

The acid value was measured by a process in which approximately 1 gram of alkaline developable binder resin was sampled and dissolved in 50 ml of a mixed solvent (MeOH) with two drops of 1% phenolphthalein indicator. 20%, acetone (80%), and then titrate with 0.1 normal KOH to measure the acid value.

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

Preparation Example 2

The four-neck round-bottom flask was equipped with a mechanical stirrer and a reflux device, and then the inside of the flask was purged with nitrogen. To the flask purged with nitrogen, 80 grams of methyl ethyl ketone (MEK) and 7.5 grams of methanol (MeOH) were added, and then 0.9 grams of azobisisobutyronitrile (AIBN) was added and allow it to dissolve completely. A monomer mixture of 25 grams of methacrylic acid (MAA), 47.5 grams of methyl methacrylate (MMA) and 27.5 grams of styrene (SM) was added as monomers and heated to 80 ℃, and then polymerized for 6 hours to prepare alkaline developable binder resin 2 (weight average molecular weight: 39000 g/mol, glass transition temperature: 128°C, solid content: 45.6% by weight, acid value: 163.1 mg hydrogen oxide potassium/g).

<Examples and Comparative Examples: Preparation of photosensitive resin composition and dry film photoresist>

According to the composition shown in Table 1 below, the photopolymerization initiator was dissolved in methyl ethyl ketone (MEK) as a solvent, and then the photopolymerization compound and the alkaline developable binder resin were added, and mechanical stirring was used Mix for about 1 hour to prepare a photosensitive resin composition.

The obtained photosensitive resin composition was applied to a 29-micron PET film using a coating rod. The applied 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 29 μm.

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

<Experimental example>

The physical properties of the dry film photoresists prepared in the Examples and Comparative Examples were measured by the following method, and the results are shown in Table 2 below.

1. Thin wire adhesion (unit: micron)

From the dry film type photoresist peel-off protective film prepared in the examples and comparative examples, and using Hakuto MACH 610i, the photosensitive resin layer of the dry film type photoresist was laminated into an RTF (Reverse Treated Foil, Reverse Treated Foil) with a contact thickness of 1.0 mm. The surface of the copper layer of the treatment foil) was subjected to soft etching under the following conditions, thereby forming a laminate: a laminator roll temperature of 110°C, a roll pressure of 4.0 kilograms of force per square centimeter (kgf/cm ³ ) and The roller speed is 2.0 meters/minute.

In the dry film photoresist laminated on RTF (Reverse Treated Foil, reverse treatment foil), the ORC FDi-3 (Laser Direct Image) exposure machine is used to achieve a photoresist temperature of 19 mJ/cm². Exposure Dosage A fine line bonding pattern (arranged so that the width increased from 10 microns to 58 microns in 2 micron increments with pattern intervals of 400 microns) was irradiated with UV rays and then allowed to stand for 15 minutes. Then, the supporting PET film for the dry film type photoresist was peeled off, and then developed using a 1.0 wt% Na ₂ CO ₃ aqueous solution at 30 ± 1° C. under spray type development conditions with a spray pressure of 1.5 kgf/cm2. 40 seconds.

In the developed laminate, the minimum value of the distance between the photosensitive resin layers was measured using a ZEISS AXIOPHOT Microscope, and the minimum value was taken as the resolution. evaluated. It can be evaluated that the smaller this value is, the better the resolution value is.

2. Resolution (unit: micron)

From the dry film type photoresist peel-off protective film prepared in the examples and comparative examples, and using Bodong MACH 610i, the photosensitive resin layer of the dry film type photoresist was laminated into an RTF (Reverse Treated Foil, reverse treated foil) with a contact thickness of 1.0 mm. ), the surface of the copper layer undergoes soft etching under the following conditions, thereby forming a laminate: the laminator roller temperature is 110°C, the roller pressure is 4.0 kgf/cm2, and the roller speed is 2.0 m/min.

In the dry film photoresist laminated on RTF (Reverse Treated Foil, reverse treated foil), an ORC FDi-3 (laser direct image exposure machine) was used to utilize ultraviolet rays for an exposure dose of 19 mJ/cm2 Resolution patterns (arranged so that the width increased from 10 to 58 microns in 2 micron increments, with pattern intervals of 400 microns) were illuminated and then allowed to stand for 15 minutes. Then, the supporting PET film for the dry film type photoresist was peeled off, and then developed using a 1.0 wt% Na ₂ CO ₃ aqueous solution at 30 ± 1° C. under spray type development conditions with a spray pressure of 1.5 kgf/cm2. 40 seconds.

In the developed laminate, the minimum value of the distance between the photosensitive resin layers was measured using a ZEISS AXIOPHOT Microscope, and the minimum value was taken as the resolution. evaluated. It can be evaluated that the smaller this value is, the better the resolution value is.

3. Peeling rate (unit: seconds)

From the dry film photoresist peeling protective film prepared in the examples and comparative examples, and using Bodong MACH 610i, the photosensitive resin layer of the dry film photoresist was laminated into an RTF (Reverse Treated Foil) with a contact thickness of 1.0 mm. The surface of the copper layer of the foil) was subjected to soft etching under the following conditions, thereby forming the laminate, whereby the laminator roller temperature was 110° C., the roller pressure was 4.0 kgf/cm2, and the roller speed was 2.0 m/min.

In the dry film photoresist laminated on RTF (Reverse Treated Foil, reverse treated foil), the ORC FDi-3 (Laser Direct Image) exposure machine is 19 mJ/cm2 The peeling pattern (50 mm x 50 mm) was irradiated with UV rays with an exposure dose of 100 % and then allowed to stand for 15 minutes. Then, the supporting PET film for the dry film type photoresist was peeled off, and then developed using a 1.0 wt% Na ₂ CO ₃ aqueous solution at 30 ± 1° C. under spray type development conditions with a spray pressure of 1.5 kgf/cm2. 40 seconds.

Then, peeling was performed using a 3% sodium hydroxide aqueous solution (temperature: 50°C). The peeling rate was evaluated by measuring the time required for the photocured layer to be released from the copper plate.

4. RTF (Reverse Treated Foil, reverse treated foil) adhesion

From the dry film photoresist peeling protective film prepared in the examples and comparative examples, and using Bodong MACH 610i, the photosensitive resin layer of the dry film photoresist was laminated into an RTF (Reverse Treated Foil) with a contact thickness of 1.0 mm. The laminate was formed from the matte side surface of the foil) which was subjected to soft etching under the following conditions: laminator roll temperature of 110°C, roll pressure of 4.0 kgf/cm2 and roll speed of 2.0 meters/minute.

The supporting PET film for dry film photoresist was peeled off from the laminate, and then standard tape 3M #610 tape was bonded to the photosensitive resin layer, and a SurTA peel tester (ChemiLab) was used. 3M #610 tape undergoes tape peeling testing to evaluate RTF adhesion. The results are shown in Table 2 below.

RTF adhesion refers to the surface area in contact between the photosensitive resin layer of the dry film photoresist and the substrate after the tape peeling test relative to the photosensitive resin layer of the dry film photoresist and the substrate before the tape peeling test. The percentage of surface area in contact, as shown in Equation 1 below.

[Equation 1] Adhesion (%) = (surface of substrate and photosensitive resin layer after tape peeling test Area/surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test)*100.

As shown in Table 2, it can be confirmed that the example exhibits excellent fine line adhesion and resolution, and at the same time, exhibits significant RTF adhesion. Different from the examples, it can be confirmed that in the case of Comparative Example 1 which does not contain the monofunctional (meth)acrylate compound, the RTF adhesion is significantly worse compared to the examples of the present disclosure.

In addition, it can be confirmed that in the case of Comparative Example 2, which does not contain the multifunctional (meth)acrylate compound, the fine line adhesion and resolution are significantly poorer compared to the examples of the present disclosure.

Claims (14)

A photosensitive resin layer comprising: a photopolymerizable compound containing trifunctional or higher polyfunctional (meth)acrylate compounds and monofunctional (meth)acrylate compounds; and an alkaline developable binder resin; wherein The trifunctional or higher polyfunctional (meth)acrylate compound is contained in an amount less than 100 parts by weight based on 100 parts by weight of the monofunctional (meth)acrylate compound, and wherein the peeling agent is used During the tape peeling test performed by the tester on a film sample in which the photosensitive resin layer is laminated on a substrate, the adhesion force defined by the following Equation 1 is 90% or greater: [Equation 1] Adhesion force (%) = (Surface area of the substrate and the photosensitive resin layer after the tape peeling test)/surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test)*100, wherein the monofunctional (meth)acrylate compound is A compound of the following Chemical Formula 1, wherein the trifunctional or higher polyfunctional (meth)acrylate compound includes a compound of the following Chemical Formula 2, wherein the alkali developable binder resin includes a first alkali developable binder resin and a second alkaline developable binder resin, wherein the first alkaline developable binder resin includes a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5 unit, a repeating unit represented by the following Chemical Formula 6, and a repeating unit represented by the following Chemical Formula 7; and the second alkaline developable binder resin includes a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5 and a repeating unit represented by the following Chemical Formula 6,

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, R ₃ is an alkyl group having 1 to 10 carbon atoms, And n1 is an integer from 1 to 20, [Chemical Formula 2]

In Chemical Formula 2, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₅ is an alkylene group having 1 to 10 carbon atoms, and R ₆ is a central group containing 1 to 20 carbon atoms. The p-valent functional group, n2 is an integer from 1 to 20, and p is the number of functional groups replacing R ₆ , and is an integer from 3 to 10,

In Chemical Formula 3, R ₃ " is hydrogen, [Chemical Formula 4]

In Chemical Formula 4, R ₃ ' is an alkyl group having 1 to 10 carbon atoms,

In Chemical Formula 5, 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 6, Ar is an aryl group having 6 to 20 carbon atoms,

In Chemical Formula 7, R ₄ ' is hydrogen, and R ₅ ' is an alkyl group having 1 to 10 carbon atoms. The photosensitive resin layer of claim 1, wherein the trifunctional or higher polyfunctional (meth)acrylate compound has three or more epoxyalkyl groups having 1 to 10 carbon atoms and three A structure in which one or more (meth)acrylate functional groups are bonded to a central group having 1 to 20 carbon atoms. The photosensitive resin layer according to claim 1, wherein the trifunctional or higher polyfunctional (meth)acrylate compound includes a compound of the following Chemical Formula 2-1: [Chemical Formula 2-1]

In Chemical Formula 2-1, R ₆ ' is a trivalent functional group having 1 to 10 carbon atoms, R ₇ to R ₉ are each independently an alkylene group having 1 to 10 carbon atoms, and R ₁₀ to R ₁₂ Each independently is hydrogen or an alkyl group having 1 to 10 carbon atoms, and n3 to n5 are each independently an integer of 1 to 3. The photosensitive resin layer of claim 1, wherein the monofunctional (meth)acrylate compound includes (meth)acrylate containing epoxy having 1 to 10 carbon atoms. alkyl. The photosensitive resin layer according to claim 1, wherein the photopolymerizable compound includes: the monofunctional (meth)acrylate compound contains (meth)acrylate, and the (meth)acrylate contains an epoxyalkyl group having 1 to 10 carbon atoms; and the trifunctional or higher polyfunctional (meth)acrylate compound having three or more epoxyalkyl groups having 1 to 10 carbon atoms and three or more A structure in which multiple (meth)acrylate functional groups are bonded to a central group having 1 to 20 carbon atoms. The photosensitive resin layer as claimed in claim 1, wherein the alkaline developable binder resin has an alkali density of 20,000 g/mol or greater than 20,000 g/mol and 150,000 g/mol or less than 150,000 g/mol. Weight average molecular weight. The photosensitive resin layer according to claim 2, wherein the trifunctional or higher polyfunctional (meth)acrylate compound is 30 parts by weight based on 100 parts by weight of the monofunctional (meth)acrylate compound. It is contained in an amount of 30 parts by weight or more and 90 parts by weight or less. The photosensitive resin layer as claimed in claim 1, wherein based on 100 parts by weight of the first alkaline developable binder resin, the second alkaline developable binder resin is 500 parts by weight or greater than 500 parts by weight. parts and is contained in an amount of 1,000 parts by weight or less. The photosensitive resin layer according to claim 1, wherein the ratio of the glass transition temperature of the first alkali developable binder resin to the glass transition temperature of the second alkali developable binder resin is 1:1.5 or Greater than 1:1.5 and 1:5 or less than 1:5. The photosensitive resin layer according to claim 1, wherein the ratio of the acid value of the first alkaline developable binder resin to the acid value of the second alkaline developable binder resin is 1:1.01 or greater than 1 :1.01 and 1:1.5 or less than 1:1.5. The photosensitive resin layer of claim 1, wherein the photosensitive resin layer has a thickness of 1 micron or more and 1000 microns or less. The photosensitive resin layer according to claim 1, wherein the photosensitive resin layer has a cross-sectional area of 0.10 square centimeters or more and 5.00 square centimeters or less. A dry film photoresist including the photosensitive resin layer according to claim 1. A photosensitive element includes: a polymer substrate; and the photosensitive resin layer according to claim 1, formed on the polymer substrate.