TW202142955A - Photosensitive resin layer, and dry film photoresist, photosensitive element using the same - Google Patents

Abstract

The present disclosure relates to a photosensitive resin composition including a photopolymerizable compound and a trifunctional or higher polyfunctional (meth)acrylate compound, and having excellent substrate adhesion.

Description

Photosensitive resin layer and dry film photoresist and photosensitive element using the same

[Cross reference of related applications] This application claims that the Korean Patent Application No. 10-2019-0179945 filed in the Korean Intellectual Property Office on December 31, 2019 and the Korean Patent Application No. 10-2020 filed on July 30, 2020 -0095387, the full text of each of the Korean patent applications is incorporated into this case for reference.

This 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.

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

At present, dry film photoresists are not only widely used in the manufacture of printed circuit boards (PCB) and lead frames, but also in the manufacture of rib barriers for plasma display panels (PDP) and other Display's Indium Tin Oxide (ITO) electrodes, bus address electrodes, black matrix and the like.

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

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

The printed circuit board that has undergone the lamination process is allowed to stand for 15 minutes or more than 15 minutes to stabilize the board, and then the photoresist of the DFR is exposed through a photomask on which a desired circuit pattern is formed. When the photomask is irradiated with ultraviolet (UV) rays in this process, the photoresist irradiated with ultraviolet rays starts to polymerize by 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, while consuming a large amount of monomers, the polymerization reaction continues. At the same time, the unexposed part exists in a state where the crosslinking reaction has not progressed.

Next, a development process of removing the unexposed part of the photoresist is performed. In the case of alkaline developable DFR, an aqueous solution of potassium carbonate and sodium carbonate of 0.8% to 1.2% by weight is used as a developer solution. In this process, the photoresist in the unexposed part is washed away in the developer solution by 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 by different processes. However, in the inner layer process, a circuit is formed on the board by 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 is a need to develop a photosensitive resin composition that has high sensitivity to ultra-high pressure mercury lamp or laser direct exposure, increases resistance to developer solutions, and can therefore be used in development. A high-density circuit is formed in the process. The photosensitive resin composition has an excellent degree of color development for use as a UV mark for setting the exposure position of the substrate, and shortens the peeling time of the cured film, has a small peeling sample, and therefore does not Clog the filter.

[ Technical Problem ] One 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.

[ Technical Solution ] In order to achieve the above objective, this article provides a photosensitive resin layer, the photosensitive resin layer comprising: a photopolymerizable compound containing a trifunctional or higher multifunctional (meth)acrylate compound; and a basic A developable adhesive resin, wherein during a tape peeling test (tape peeling test) performed on a film sample in which the photosensitive resin is laminated on a substrate using a peel tester, the adhesion force defined by the following Equation 1 is 90% Or greater than 90%:

[Equation 1] Adhesion (%) = (surface area of the substrate and 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 Joined to a structure with a central group of 1 to 20 carbon atoms.

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.

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

The monofunctional (meth)acrylate compound may include a (meth)acrylate including an epoxy 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 compound having three or more epoxyalkyl groups having 1 to 10 carbon atoms and three or more (meth)acrylate functional groups bonded to A structure 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/mole (g/mol) or greater than 20,000 grams/mole and 150,000 g/mole or less than 150,000 grams/mole.

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

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

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 The repeating unit and the repeating unit represented by Chemical formula 7; and the second alkaline developable binder resin, including the repeating unit represented by Chemical formula 4, the repeating unit represented by Chemical formula 5, and the repeating unit represented by Chemical formula 6. Chemical formulas 3 to 7 are as follows.

Based on 100 parts by weight of the first alkaline developable binder resin, 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.

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

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 micrometer or more and 1000 micrometers or less.

The photosensitive resin layer may have a cross-sectional area of 0.10 cm3 or more and 5.00 cm3 or less.

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

This document further provides a photosensitive element, the photosensitive element comprising: a polymer substrate; and the photosensitive resin layer formed on the polymer substrate.

This document 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 the tape peeling test of the film sample on the substrate, the adhesion force defined by the following equation 1 is 90% or greater:

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

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

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

Unless the context clearly indicates otherwise, the singular forms "a/an" and "the" used in this article also include plural references.

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

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

In this specification, examples of substituents are illustrated as follows, but are not limited thereto.

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

In this specification, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium; halogen; cyano ; Nitro; Hydroxyl; Carbonyl; Ester; Amino; Amino; Primary Amino; Carboxy; Sulfonic Acid; Sulfonamide; Phosphine Oxide; Alkoxy; Aryloxy; Alkyl Sulfur Oxy; arylthiooxy; alkylsulfonyloxy; arylsulfonyloxy; silyl; boron; alkyl; cycloalkyl; alkenyl; aryl; aralkyl; aralkenyl; Alkylaryl; alkoxysilylalkyl; arylphosphino; or heterocyclic group, containing at least one of N, O, and S atoms, or means unsubstituted or among the substituents exemplified above Substituents attached to two or more substituents are substituted. For example, the "substituent linked to two or more substituents" may be biphenyl. That is, the biphenyl group may also be an aryl group, and can be interpreted as a substituent connected 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 mark

or

It means a bond to another substituent, and direct bonding means that there are no other atoms in the part denoted as L.

In this specification, the (meth)acrylic group is intended to include both acrylic and methacrylic groups. For example, (meth)acrylate is intended to include both acrylate and methacrylate.

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

In this specification, the aryl group is a monovalent functional group derived from arenes and is not particularly limited, but preferably has 6 to 20 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. Specific examples of monocyclic aryl groups may include phenyl, biphenyl, terphenyl, and the like, but are not limited thereto. Specific examples of polycyclic aryl groups may include naphthyl, anthracenyl, phenanthryl, pyrenyl, perylene, eryl, fluorenyl, and the like, but are not limited thereto. The aryl group may be substituted or unsubstituted, and when it is substituted, examples of the substituent are the same as those described above.

In this specification, an alkylene group is a divalent functional group derived from an alkane, and the description of an alkyl group as defined above can be applied except that the alkylene group is a divalent functional group. For example, the alkylene group can be linear or branched, methylene, vinyl, propenyl, isobutenyl, second butenyl, third butenyl, pentylene, hexylene or the like Things. The alkylene group may be substituted or unsubstituted.

In this specification, a multivalent functional group is a residue in which multiple 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 are removed.

In this specification, a direct bond or a single bond means to connect to a bond line where no atom or atomic group is present at the corresponding position. Specifically, a direct bond or single bond wherein means desirable in the chemical formula represented as R _a or L _b (where a and b are respectively an integer of 1 to 20) is not part of the case of the presence of other atoms.

In this specification, the term "(light)cured product" or "(light)curable" means not only those in which the components with curable or crosslinkable unsaturated groups in the chemical structure are completely cured, crosslinked or polymerized Circumstances, and include those 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 an 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 multifunctional (meth)acrylate compound; and an alkaline developable adhesive An agent resin, wherein during a tape peeling test performed on a film sample in which the photosensitive resin is laminated on a substrate using a peel tester, the adhesion force defined by Equation 1 is 90% or more.

The inventors found through experiments that since the photosensitive resin layer of one embodiment has an adhesive force defined by Equation 1 of 90% or more, it can ensure excellent physical properties (resolution, fine-line adhesive force, etc.) , And completed 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 kinds of 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, and a repeating unit represented by the following chemical formula 4 The repeating unit represented by 5, the repeating unit represented by the following chemical formula 6, and the repeating unit represented by the following chemical formula 7; and the second alkaline developable binder resin, including the repeating unit represented by the following chemical formula 4, is represented by the following chemical formula 5 The repeating unit of and the repeating unit represented by the following Chemical Formula 6.

在化學式3中，R₃ "是氫， [化學式4]

在化學式4中，R₃ '是具有1至10個碳原子的烷基， [化學式5]

在化學式5中，R₄ "是具有1至10個碳原子的烷基，且R₅ "是具有1至10個碳原子的烷基， [化學式6]

在化學式6中，Ar是具有6至20個碳原子的芳基， [化學式7]

在化學式7中，R₄ '是氫，且R₅ '是具有1至10個碳原子的烷基。[Chemical formula 3]

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, [Chemical Formula 5]

In the 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, [Chemical Formula 7]

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.

在化學式3中，R₃ "是氫， [化學式4]

在化學式4中，R₃ '是具有1至10個碳原子的烷基， [化學式5]

在化學式5中，R₄ "是具有1至10個碳原子的烷基，且R₅ "是具有1至10個碳原子的烷基， [化學式6]

在化學式6中，Ar是具有6至20個碳原子的芳基， [化學式7]

在化學式7中，R₄ '是氫，且R₅ '是具有1至10個碳原子的烷基。[Chemical formula 3]

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, [Chemical Formula 5]

In the 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, [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 Formulae 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 the following Chemical Formula 4-1.

在化學式4-1中，R₃ '是具有1至10個碳原子的烷基。在化學式4-1中，R₃ '的定義與針對化學式4闡述的定義相同。由化學式4-1表示的單體的具體實例可包括甲基丙烯酸（methacrylic acid，MAA）。[Chemical formula 4-1]

In the 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 the definition 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 the following Chemical Formula 5-1.

在化學式5-1中，R₄ "是具有1至10個碳原子的烷基，且R₅ "是具有1至10個碳原子的烷基。在化學式5-1中，R₄ "及R₅ "的定義與針對化學式5闡述的定義相同。由化學式5-1表示的單體的具體實例可包括甲基丙烯酸甲酯（methylmethacrylate，MMA）。[Chemical formula 5-1]

In the 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 the chemical formula 5-1, _{the definitions of R 4} "and R ₅ " are the same as those set forth for the 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 the following Chemical Formula 6-1.

在化學式6-1中，Ar是具有6至20個碳原子的芳基。在化學式6-1中，Ar的定義與針對化學式6闡述的定義相同。由化學式6-1表示的單體的具體實例可包括苯乙烯（styrene，SM）。[Chemical formula 6-1]

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

In addition, the alkaline developable binder resin may have a weight average molecular weight of 20000 g/mol or more than 20000 g/mol and 130,000 g/mol or less than 130,000 g/mol, and having a weight average molecular weight of 30°C or more 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, and the mechanical strength of the resist itself after the circuit is formed.

The weight average molecular weight used herein refers to the weight average molecular weight converted from polystyrene measured by gel permeation chromatography (GPC). In the process of measuring the weight average molecular weight of polystyrene converted by GPC, detectors and analytical tubes (such as well-known analytical equipment and differential refractive index detectors) can be used ), and can use common temperature conditions, solvents and flow rate (flow rate).

A specific example of the measurement conditions is as follows: the alkaline developable binder resin is dissolved in tetrahydrofuran (tetrahydrofuran, THF) so that the alkaline developable binder resin has 1.0 (weight/weight (w/w) in THF) )% concentration (based on solid content, about 0.5 (weight/weight)%); filtered with a syringe filter with a pore size of 0.45 microns; and then injected in an amount of 20 microliters In GPC, tetrahydrofuran (THF) is used as the mobile phase of GPC, and the flow rate is 1.0 milliliters/minute (mL/min). The column consists of an Agilent PLgel 5 micron (µm) guard tube (7.5 × 50 mm (mm)) connected in series and two Agilent PL gel 5 micron mixed tubes (mixed) D ( 7.5 × 300 mm) configuration, and the measurement is performed using the Agilent 1260 Infinity II System RI detector (RI Detector) as the detector at 40°C.

A syringe filter with a pore size of 0.45 microns was used to dissolve polystyrene with various molecular weights in tetrahydrofuran at a concentration of 0.1 (weight/weight) (w/w)%. Ethylene standard samples (STD A, B, C, D) were filtered and then injected into GPC, and the value of the weight average molecular weight (Mw) of the alkaline developable binder resin was determined using a calibration curve. STD A (MP): 791,000 / 27,810 / 945 STD B (MP): 282,000 / 10,700 / 580 STD C (MP): 126,000 / 4,430 / 370 STD D (MP): 51,200 / 1,920 / 162

Use Differential Scanning Calorimeter (DSC) (Perkin-Elmer, DSC-7) to compare the glass transition temperature of the reference polymer and the glass transition temperature of the binder polymer A comparison was made. 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/min.

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

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

Specifically, the ratio of the glass transition temperature of the first alkaline developable adhesive resin to the glass transition temperature of the second alkaline developable adhesive resin may be 1:1.5 or greater than 1:1.5 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 being 1:1.8 or less than 1:1.8, 1:1.5 or greater than 1:1.5 and 1:75 or less than 1:75, or 1:1.6 or greater than 1:1.6 and 1:7 or less than 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 than 1:1.01 and being 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 an embodiment may be 1.2 mol or more than 1.2 mol and 3 mol. Ear or less than 3 mol, 1.2 mol or more than 1.2 mol and 2 mol or less than 2 mol, 1.5 mol or more than 1.5 mol and 2 mol or less than 2 mol, or 1.5 mol or An amount greater than 1.5 mol and 1.6 mol or less than 1.6 mol includes the repeating unit represented by Chemical Formula 4.

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

在化學式4中，R₃ '是具有1至10個碳原子的烷基。[Chemical formula 4]

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

在化學式5中，R₄ "是具有1至10個碳原子的烷基，且R₅ "是具有1至10個碳原子的烷基， [化學式6]

在化學式6中，Ar是具有6至20個碳原子的芳基。[Chemical formula 5]

In the 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.

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

在化學式4-1中，R₃ '是具有1至10個碳原子的烷基。在化學式4-1中，R₃ '的定義與針對化學式4闡述的定義相同。由化學式4-1表示的單體的具體實例可包括甲基丙烯酸（MAA）。[Chemical formula 4-1]

In the 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 the definition 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 the following Chemical Formula 5-1.

在化學式5中，R₄ "是具有1至10個碳原子的烷基，且R₅ "是具有1至10個碳原子的烷基。在化學式5-1中，R₄ "及R₅ "的定義與針對化學式5闡述的定義相同。由化學式5-1表示的單體的具體實例可包括甲基丙烯酸甲酯（MMA）。[Chemical formula 5-1]

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 the chemical formula 5-1, _{the definitions of R 4} "and R ₅ " are the same as those set forth for the 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 a repeating unit derived from a monomer represented by the following Chemical Formula 6-1.

在化學式6-1中，Ar是具有6至20個碳原子的芳基。在化學式6-1中，Ar的定義與針對化學式6闡述的定義相同。由化學式6-1表示的單體的具體實例可包括苯乙烯（SM）。[Chemical formula 6-1]

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 the chemical formula 4 in the following ratio: the repeating unit represented by the chemical formula 5: the repeating unit represented by the chemical formula 6: 1:(2 or more than 2 and 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 than 3): (0.6 or greater than 0.6 and 0.9 or less than 0.9) or 1: (2.75 or greater than 2.75 and 3 or less than 3): (0.6 or greater than 0.6 and 0.75 or less 0.75).

In addition, the second alkaline developable binder resin may include the repeating unit represented by Chemical Formula 4 in the following ratio: Repeating unit represented by Chemical Formula 5: 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 more and 1000 parts by weight or less than 1000 parts by weight, 600 parts by weight or more. Parts by weight or greater than 600 parts by weight and 800 parts by weight or less than 800 parts by weight, 700 parts by weight or greater than 700 parts by weight and 800 parts by weight or less than 800 parts by weight include the second alkaline developable binder resin.

As mentioned above, due to the excessive addition of 500 parts by weight or more of the second alkaline developable binder resin based on 100 parts by weight of the first alkaline developable binder resin, it is possible to impart hydrophobicity to the photosensitive resin. Function, increase the resistance to developer solution and improve the technical effect of circuit properties.

Based on the 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 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 fine lines 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.

Relative to the total weight of the photosensitive resin composition forming the photosensitive resin layer, the content of the alkaline developable binder resin of the present disclosure may be 40% by weight or more than 40% by weight and 70% by weight or less than 70% by weight. When the content of the alkaline developable binder resin is less than 40% by weight relative to the total photosensitive resin composition, there are defects such as short circuits due to contamination during development, and when the content of the alkaline developable binder resin When it exceeds 70% by weight, there are problems such as deterioration of circuit properties such as adhesion and resolution. (2) Photopolymerization initiator

The photopolymerization initiator contained in the photosensitive resin layer according to the present disclosure is a material that initiates the chain reaction of photopolymerizable monomers by UV and other radiation, and plays an important role in curing the 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, a group selected from 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl bisimidazole, 1-hydroxycyclohexyl phenyl ketone, 2,2-di Methoxy-1,2-diphenylethyl-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoprop-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-benzyl-4'-methyl dimethyl sulfide, 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-methoxydiethyl acetal, 1-phenyl-1 ,2-propanedioxime-o,o'-(2-carbonyl)ethoxy ether (1-phenyl-1,2-propyldioxime-o,o'-(2-carbonyl)ethoxy ether), o-benzyl Methyl benzoate, bis[4-dimethylaminophenyl] ketone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, Benzyl, benzoin, methoxy benzoin, ethoxy benzoin, isopropoxy benzoin, n-butoxy benzoin, isobutoxy benzoin, tertiary butoxy benzoin, p-dimethylamino acetophenone, P-tert-butyl trichloroacetophenone, p-tert-butyl dichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, Compounds among α,α-dichloro-4-phenoxyacetophenone and pentyl 4-dimethylaminobenzoate are used as photopolymerization initiators, but are not limited thereto.

In terms of solid content, the photopolymerization initiator is contained in an amount of 2% by weight or more and 10% by weight or less than 10% by weight relative 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 in that the film is brittle and contamination of the developer solution increases, resulting in defects such as short circuits. (3) Photopolymerizable compound

The photopolymerizable compound of the present disclosure is resistant to developer solutions after UV exposure, and thus can form a pattern.

The photopolymerizable compound of the present disclosure may include a trifunctional or higher multifunctional (meth)acrylate compound.

Specifically, 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)acrylic acid groups. The ester functional group is bonded to a structure having a central group of 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:

在化學式2中，R₄ 是氫或具有1至10個碳原子的烷基，R₅ 是具有1至10個碳原子的伸烷基，R₆ 是含有具有1至20個碳原子的中心基的p價官能基，n2是為1至20的整數，且p是取代R₆ 的官能基的數目且是為3至10的整數。[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 having 1 to 20 carbon atoms. N2 is an integer from 1 to 20, and p is _{the number of functional groups substituted for R 6} and is an integer from 3 to 10.

In addition, in Chemical Formula 2, n2 is an integer from 1 to 20, an integer from 1 to 10, or an integer from 1 to 5, and p means _{the number of functional groups substituted for R 6} and may be an integer from 3 to 10. It is an integer of 3 to 5 or an integer of 3 to 4.

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

Specifically, the multifunctional (meth)acrylate compound may be represented by the following Chemical Formula 2-1.

在化學式2-1中，R₆ '是具有1至10個碳原子的三價官能基，R₇ 至R₉ 各自獨立地是具有1至10個碳原子的伸烷基，R₁₀ 至R₁₂ 各自獨立地是氫或具有1至10個碳原子的伸烷基，且n3至n5各自獨立地是為1至20的整數。[Chemical formula 2-1]

In the 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 is independently hydrogen or an alkylene group having 1 to 10 carbon atoms, and n3 to n5 are each independently an integer of 1 to 20.

In the 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 Trimethylolpropane [EO] ₆ triacrylate)). [Chemical formula B]

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

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

Specifically, the monofunctional (meth)acrylate compound may include a (meth)acrylate containing an epoxy 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 epoxy group having 1 to 10 carbon atoms; and A trifunctional or higher polyfunctional (meth)acrylate compound having three or more (meth)acrylate functional groups having 1 to 10 carbon atoms and three or more (meth)acrylic acid among them The ester functional group is bonded to a structure having a central group of 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.

在化學式1中，R₁ 是氫或具有1至10個碳原子的烷基，R₂ 是具有1至10個碳原子的伸烷基，R₃ 是具有1至10個碳原子的烷基，且n1是為1至20的整數。[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 of 1-20.

Specifically, in Chemical Formula 1, n1 may be an integer from 1 to 20, an integer from 1 to 10, or an integer from 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. [Chemical formula A]

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

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

Compared with the monofunctional (meth)acrylate compound, the photosensitive resin layer of one embodiment contains a small amount of the polyfunctional (meth)acrylate compound, so it can improve the monofunctional (meth)acrylate represented by Chemical Formula 1 at the same time. The physical adhesion of the ester compound to the substrate, ensuring the contrast of the polyfunctional (meth)acrylate compound represented by the chemical formula 2, and improving the adhesion of fine lines, thereby exhibiting excellent developability, thereby improving the adhesion to the substrate and Ensure excellent physical properties (resolution, fine line adhesion, etc.).

Based on 100 parts by weight of the monofunctional (meth)acrylate compound, when the photosensitive resin layer of an embodiment contains 100 parts by weight or more of the multifunctional (meth)acrylate compound, there may be interference with the substrate Technical problems with reduced adhesion.

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

The alkylene glycol-based di(meth)acrylate may include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and 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 (polypropylene glycol di(meth)acrylate), butylene 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), 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, Commercially available products such as bisphenol A (EO) ₂₀ diacrylate) and Miramer M2101 (bisphenol A (EO) _{10 dimethacrylate).}

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

The molecular weight of the urethane-based di(meth)acrylate can be larger than the existing simple alkylene oxide and has a linear structure, thereby imparting flexibility. This results in improving the capping properties required for the dry film photoresist (DFR) of the outer layer and the hydrophobicity of the polyol as one of the components of the urethane acrylate, and improving the resistance to the plating solution as a strong acid Tolerance, so that it will not contaminate the plating solution.

The urethane-based 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 polyether glycol, and for example, 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 (for example, an alkylene group), an alicyclic diisocyanate compound having a divalent alicyclic group (for example, 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.

The alicyclic diisocyanate compound may include isophorone diisocyanate, methylene bis(cyclohexyl) diisocyanate, 1,3- or 1,4-bis(methyl isocyanate) cyclohexane, and the like.

Aromatic diisocyanate compounds may include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate or 2,6-toluene diisocyanate dimerized polymer, (ortho, pair or between ) Xylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate and the like.

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

A polyether compound or polyester compound having a hydroxyl group reacts with a diisocyanate compound to prepare a urethane compound. In the above reaction, the diisocyanate compound is preferably used at a molar ratio of 1.01 to 2.0, more preferably at a molar ratio of 1.1 to 2.0, relative to 1 mol of a 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, it may not be possible to stably obtain a urethane compound having isocyanate groups at both ends.

In addition, 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 will not proceed sufficiently, and when the reaction temperature exceeds 120°C, the reaction operation may be dangerous due to sudden heat generation.

The compound having both a hydroxyl group and an ethylenically unsaturated group used for reaction with the urethane compound thus prepared may include a compound having a hydroxyl group and a (meth)acryloyl group in the molecule. These compounds include hydroxy (meth) acrylate, hydroxy (meth) acrylate-caprolactone adduct or alkylene oxide adduct. The ester compound prepared by the reaction, and the glycidyl (meth)acrylate-acrylic acid adduct.

The hydroxy (meth)acrylate may include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate.

The hydroxy(meth)acrylate-caprolactone adduct 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 (methyl) Acrylate∙propylene oxide adduct, hydroxybutyl (meth)acrylate∙butylene oxide adduct.

The ester compound may include, for example, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane mono(meth)acrylate, Base) acrylate, ditrimethylolpropane tri(meth)acrylate, di(meth)acrylate of trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide Di(meth)acrylate of adduct. These can be used alone or in combination of two or more.

The urethane-based di(meth)acrylate is a compound derived by the addition reaction of a urethane compound and a compound having both a hydroxyl group and an ethylenically unsaturated group, and can be For 1 mol carbamate compound, add a compound having both a hydroxyl group and an ethylenically unsaturated group at a molar ratio of 2.0 to 2.4 and then subject it to an addition reaction at 60°C to 90°C. get.

It is preferable that the urethane-based di(meth)acrylate 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/mole, it is difficult to sufficiently increase the flexibility and toughness, and therefore the adhesion to the substrate may not be improved, and when the weight average molecular weight exceeds 60,000 g/mole, there is a possibility that the developing properties may be deteriorated. And the development time may become slower. Therefore, it is preferable that the urethane-based di(meth)acrylate according to the present disclosure has a weight average molecular weight of 1,000 g/mole to 60,000 g/mole.

In the present disclosure, the urethane-based di(meth)acrylate having a weight average molecular weight of 1,000 g/mol to 60,000 g/mol is considered to be 1 to 20% by weight, preferably 1.5 The amount of weight% to 15 weight% is included in the photosensitive resin composition. When the content of the urethane-based 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 resulting effect is insufficient, and when the content When it exceeds 20% by weight, the development time during the development process after exposure may increase rapidly and a large amount of scum and sludge may also be generated.

Based on 100 parts by weight of the alkylene glycol-based di(meth)acrylate, the photosensitive resin layer of an 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 Parts or more than 1 part by weight and 30 parts by weight or less than 30 parts by weight, 1 part by weight or more and 10 parts by weight or less than 10 parts by weight, 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 the alkylene glycol-based di(meth)acrylate, the urethane-based di(meth)acrylate is 1 part by weight or more and 50 parts by weight or less It is contained in an amount of 50 parts by weight, so the photosensitive resin composition of an embodiment can achieve technical effects such as reduction of 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 an embodiment may be 500 parts by weight or more and 1500 parts by weight or less than 1500 parts by weight, 500 parts by weight Parts or more than 500 parts by weight and 1000 parts by weight or less than 1000 parts by weight, 750 parts by weight or more than 750 parts by weight and 1000 parts by weight or less than 1000 parts by weight, or 800 parts by weight or more than 800 parts by weight and 900 parts by weight Or the bifunctional (meth)acrylate compound is contained in an amount of 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 more 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 than 800 parts by weight, 500 parts by weight or more than 500 parts by weight and 750 parts by weight or less than 750 parts by weight, 500 parts by weight or more than 500 parts by weight and 700 parts by weight or less than 700 The bifunctional (meth)acrylate compound is contained in an amount of parts by weight, 500 parts by weight or more and 600 parts by weight or less than 600 parts by weight.

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 polyfunctional (meth)acrylate compound and 500 parts by weight or more than 500 parts by weight And it is 1500 parts by weight or less of a bifunctional (meth)acrylate compound.

As described above, since the monofunctional (meth)acrylate compound, the multifunctional (meth)acrylate compound, and the bifunctional (meth)acrylate compound are contained and at the same time are contained so as to satisfy the above weight range, one implementation 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, based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer, the monofunctional photopolymerizable compound may be in an amount of 0.1% by weight or more than 0.1% by weight and 2.5% by weight or less than 2.5% by weight Is contained.

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

That is, based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer, 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 Of the monofunctional photopolymerizable compound and 2.6% by weight or more than 2.6% by weight and 5.0% by weight or less than 5.0% by weight of the 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, the addition is determined by the chemical formula 1 The effect produced by the compound represented by and 2 is insufficient, and when the content of the monofunctional photopolymerizable compound is more than 2.5% by weight or more than 5.0% by weight or the content of the multifunctional photopolymerizable compound is more than 5.0% by weight, there may be an increase in hydrophobicity Therefore, the development time in the development process after exposure is rapidly increasing.

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

Based on the solid content, relative to the total weight of the photosensitive resin composition, the content of the photopolymerizable compound may be 10% by weight or more and 70% by weight or less. 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 the solid content, 20% by weight and greater than 20% by weight and 80% by weight or less than 80% by weight of alkaline developable binder resin, 0.1% by weight or More than 0.1% by weight and 10% by weight or less than 10% by weight of the photopolymerization initiator, and 10% by weight or more than 10% by weight and 70% by weight or less than 70% by weight of the photopolymerizable compound. The solid content on the basis of weight 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 based on photopolymerization initiators, alkaline developable binder resins, and The content of the photopolymerizable compound can be adjusted.

In addition, the photosensitive resin composition may further contain other additives as necessary. Other additives are plasticizers and may include: dibutyl phthalate in the form of phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate Esters; triethylene glycol diacetate and tetraethylene glycol diacetate in the form of glycol esters; p-toluenesulfonamide, toluenesulfonamide, n-butylbenzenesulfonamide in the form of acid amides; phosphoric acid Triphenyl ester and so on.

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

Examples of 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 the 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 more, it has an effect of improving handleability, and when the content is 1% by weight or less, it has an effect of maintaining storage stability.

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

Meanwhile, during a tape peeling test performed on a film sample in which the photosensitive resin is laminated on a substrate using a peel tester, the adhesion force defined by the following Equation 1 may be 90% or more, It is 90% or more than 90% and 100% or less than 100%, or 95% or more than 95% and 100% or less than 100%. 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 photosensitive resin layer after the tape peeling test/surface area of the photosensitive resin layer and the substrate contacting the substrate before the tape peeling test) * 100.

Specifically, since the photosensitive resin layer of one embodiment includes the monofunctional (meth)acrylate compound represented by Chemical Formula 1 and the 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 adhesion of the substrate of the dry film photoresist including the photosensitive resin layer of one embodiment can be achieved.

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

More specifically, the surface roughness of the substrate may be 1 micrometer or more and 10 micrometers or less than 10 micrometers, 3 micrometers or more than 3 micrometers and 7 micrometers or less than 7 micrometers, or 4 micrometers or more than 4 micrometers and It is 6 microns or less.

Meanwhile, the tape peeling test of Equation 1 may 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 more than 90%, since the photosensitive resin layer of one embodiment contains an excessive amount of monofunctional (meth)acrylic acid relative to the polyfunctional (meth)acrylate compound An ester compound, therefore, due to the low glass transition temperature of the monofunctional (meth)acrylate compound represented by Chemical Formula 1, the photosensitive resin layer has relatively large fluidity at the lamination temperature of the dry film type photoresist, and Thereby, the effect of improving the physical adhesion to the substrate with high surface roughness and non-uniformity can be achieved. 2. Dry film photoresist

According to another embodiment of the present disclosure, a dry film photoresist including a photosensitive resin layer including the photosensitive resin layer of the one embodiment can be provided. The details about the photosensitive resin layer include all the contents set forth in the above-mentioned one embodiment.

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

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

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

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

The protective film prevents damage to the resist during handling, and functions as a protective cover that protects the photosensitive resin layer from foreign objects (such as dust), and is laminated on the photosensitive resin layer without being formed On the back side of the substrate film. The protective film is used to protect the photosensitive resin layer from external influences. When a dry film photoresist is applied to a post-process, it needs to be easily detached, and it needs proper releasability and adhesion to deform it during storage and distribution.

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

An example of a method of manufacturing a dry film photoresist is not particularly limited, and for example, the photosensitive resin composition of one embodiment is coated on a conventional substrate film (such as polyethylene terephthalate) using a conventional coating method. Ester), and then dried, and the upper surface of the dried photosensitive resin layer is laminated with a conventional protective film (for example, 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 a temperature of 50° C. or greater than 50° C. and a temperature of 100° C. Perform at a temperature of ℃ or less than 100℃.

At the same time, the dry film photoresist of one embodiment may have the following characteristics, that is, during a tape peel test using a peel tester on a film sample in which a photosensitive resin is laminated on a substrate, the adhesive force defined by the following equation 2 It can be 90% or more than 90%, 90% or more than 90% and 100% or less than 100%, or 95% or more than 95% and 100% or less than 100%. 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.

The 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 of the dry film photoresist of an embodiment can be achieved. 3. Photosensitive element

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

The details about adhesion include all of the above.

Since the adhesion force defined by Equation 1 is 90% or greater, a photosensitive element with excellent substrate adhesion 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 represented by the following Chemical Formula 2 (Meth)acrylate compound.

在化學式1中，R₁ 是氫或具有1至10個碳原子的烷基，R₂ 是具有1至10個碳原子的伸烷基，R₃ 是具有1至10個碳原子的烷基，且n1是為1至20的整數， [化學式2]

在化學式2中，R₄ 是氫或具有1至10個碳原子的烷基，R₅ 是具有1至10個碳原子的伸烷基，R₆ 是含有具有1至20個碳原子的中心基的p價官能基，n2是為1至20的整數，且p是取代R₆ 的官能基的數目且是為3至10的整數。[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, [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 having 1 to 20 carbon atoms. N2 is an integer from 1 to 20, and p is _{the number of functional groups substituted for R 6} and is an integer from 3 to 10.

The details of the photosensitive resin composition include all the contents described in the above-mentioned one embodiment and the other 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 multifunctional represented by the following Chemical Formula 2 (Meth)acrylate compound.

在化學式1中，R₁ 是氫或具有1至10個碳原子的烷基，R₂ 是具有1至10個碳原子的伸烷基，R₃ 是具有1至10個碳原子的烷基，且n1是為1至20的整數， [化學式2]

在化學式2中，R₄ 是氫或具有1至10個碳原子的烷基，R₅ 是具有1至10個碳原子的伸烷基，R₆ 是含有具有1至20個碳原子的中心基的p價官能基，n2是為1至20的整數，且p是取代R₆ 的官能基的數目且是為3至10的整數。[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, [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 having 1 to 20 carbon atoms. N2 is an integer from 1 to 20, and p is _{the number of functional groups substituted for R 6} and is an integer from 3 to 10.

Various plastic films can be used as the protective film, and examples thereof can include selected from acrylic film, polyethylene (PE) film, polyethylene terephthalate (PET) film, triacetyl cellulose (TAC) film, At least one plastic film in the group consisting of polynorbornene (PNB) film, cycloolefin polymer (COP) film, and polycarbonate (PC) film. The thickness of the protective film is not particularly limited, and for example, it can be freely adjusted in the range of 0.01 micrometers 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 applied to the polyester film by uniaxially stretching an unstretched polyester film An anti-blocking layer is formed on one surface and the remaining part by uniaxial stretching in-line coating method.

Polymer substrates are generally manufactured by in-line coating methods instead of adding anti-blocking agents (which are generally added taking into account the runnability and winding characteristics during manufacturing), and have the advantages of not impairing transparency. The organic particle layer of alternative particles.

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

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) of the ellipse is 0.5 <a/b <2, and the relationship with the diagonal (d) in the rectangle is d2≤a2+ b2 definition. In addition, the relationship between the axis (f) having the longest distance between the vertices of the hexahedron and the c axis other than the a axis and the b axis is defined by f2≦c2+a2+b2. The shape of the particles should be spherical, which is preferable in terms of feedability.

And, 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 preferable that the organic particles have an average particle diameter of about 0.5 to 5 microns. When it is less than this value, the material transportability and winding characteristics are deteriorated, and when it is greater than 5 microns, the haze increases, which is not preferable in consideration of the occurrence of falling problems. Based on the total amount of the binder resin, the content of the 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 the binder resin, the anti-blocking effect is insufficient and easy to be scratched (scratch), and the stripping and winding characteristics are deteriorated, and when it exceeds 10% by weight At this time, there may be a problem 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. Based on 100 parts by weight of the binder resin, the content is preferably 10 parts by weight or less. When the above-mentioned particle size and content are satisfied, the occurrence of sidewall defects or grooves (such as pits) caused by the anti-blocking layer when a dry film photoresist is used to form a pattern can be prevented.

As a binder resin serving as a binder for coating such organic particles on the unstretched polyester film, a binder resin having excellent compatibility with organic particles can be used. Examples of such resins may include: acrylic resins such as unsaturated polyester, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, n-butyl 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, the 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 applied to the uniaxially stretched film superior. The coating may be performed on at least one side of the uniaxially stretched film, and its thickness is preferably about 30 nm to 200 nm in terms of the thickness after the final drying. If a coating solution containing organic particles is applied to a uniaxially stretched film to be thicker than 30 nanometers, the organic particles are easy to fall off and are easily scratched, and white powder is generated. When the coating is thicker than 200 nanometers, due to the increase in the viscosity of the coating solution, in the in-line coating with high coating speed, coating streaks will occur in the coating direction.

The polymer substrate obtained by coating with organic particles different from general anti-blocking agents by the above-mentioned in-line coating method is due to the particle layer to maintain the feedability and winding characteristics and because the organic particles have extreme properties. Substrate film with excellent light transmission and excellent transparency.

Since the lamination of the photosensitive resin layer is performed on the opposite surface of the organic particle-containing layer in the polymer substrate, the photosensitive resin layer is formed on the opposite surface of the organic particle-containing layer in this manner. Therefore, when the substrate film including the anti-blocking agent is laminated as before, no pit-like defects will appear. Since particles such as silicon dioxide are not only larger in size than organic particles, but also distributed on the entire substrate film, the influence of silicon dioxide is negligible even in the area adjacent to the photosensitive resin layer.

On the other hand, in the polymer substrate used in the present disclosure, the organic particles have a size of 0.5 μm to 5 μm, and the organic particle layer is not adjacent to the photosensitive resin layer, so that the physical effect of the organic particles is not affected. In addition, by using organic particles with excellent light transmittance, sidewall defects can be reduced without damaging other circuit properties.

The photosensitive element may further include a protective film formed on the photosensitive resin layer. The protective film prevents damage to the photosensitive resin layer during handling, and functions as a protective cover that protects the photosensitive resin layer from foreign substances (for example, 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 a dry film photoresist is applied to post-processing, it needs to be easily detached, and it needs proper releasability and adhesion to make it deform during storage and distribution.

Various plastic films can be used as the protective film, and examples thereof can include selected from acrylic film, polyethylene (PE) film, polyethylene terephthalate (PET) film, triacetyl cellulose (TAC) film, At least one plastic film in the group consisting of polynorbornene (PNB) film, cycloolefin polymer (COP) film, and polycarbonate (PC) film. The thickness of the protective film is not particularly limited, and for example, it can be freely adjusted in the range of 0.01 micrometers to 1 mm. 4. Circuit board, display device

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 one embodiment can be provided. The details about the photosensitive resin layer include all the contents set forth in the above-mentioned one embodiment.

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

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

Examples of the method of forming the photosensitive resin in the form of a pattern layer include a method of laminating the photosensitive resin of the dry film 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 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 type photoresist or photosensitive element of another embodiment has a protective film on the photosensitive resin layer, the process of removing the protective film can be performed before the process of laminating the photosensitive resin on the circuit board or the display device manufacturing substrate .

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

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

[ Advantageous Effects ] 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.

The present disclosure will be explained in more detail with the examples shown below. However, these examples are given only to illustrate the present invention, and are not intended to limit the scope of the present 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 a 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) were added. And make it completely dissolve. 8 grams of acrylic acid (AA), 15 grams of methacrylic acid (MAA), 15 grams of butyl acrylate (BA), 52 grams of methyl methacrylate (MMA) were added to it. ) And 10 grams of styrene (SM) monomer mixture as monomers, heated to 80° C., and then polymerized for 6 hours to prepare alkaline developable binder resin 1.

The alkaline developable binder resin 1 was measured to have a weight average molecular weight of 71538 g/mol, a glass transition temperature of 79°C, a solid content of 51.4% by weight, and 156.3 mg of potassium hydroxide/g of acid. value.

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

The acid value was measured by the following process: In the process, about 1 g of alkaline developable binder resin was sampled and dissolved in 50 ml of mixed solvent (MeOH) added with two drops of 1% phenolphthalein indicator. 20%, 80% acetone), and then titrate with 0.1 equivalent KOH to measure the acid value.

The solid content is based on the weight of the alkaline developable binder resin prepared in the above preparation example, and the weight percentage of the solid content remaining after heating in an oven at 150° C. for 120 minutes is 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 a 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) were added. And make it completely dissolve. 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 to it 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 potassium hydroxide /gram). < 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 alkaline developable binder resin were added, and mechanical stirring was used The mixture was mixed for about 1 hour to prepare a photosensitive resin composition.

The obtained photosensitive resin composition was coated on a 29-micron PET film using a coating bar. The coated photosensitive resin composition layer was dried using a hot air oven. At this time, the drying temperature was 80° C., the drying time was 5 minutes, and the thickness of the photosensitive resin composition layer after drying was 29 μm.

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

（5）A040：甲氧基丙二醇[400]丙烯酸酯（n=9）

（6）KUA-1330h：二(甲基)丙烯酸胺基甲酸酯 （7）BMPS：三溴甲基碸 （8）BTCA：5-苯並三唑羧酸 （9）9-PA：9-苯基吖啶 ＜ 實驗例 ＞ [Table 1] Component Product name (or component name) Content (weight%) Example 1 Comparative example 1 Comparative example 2 Alkaline developable binder resin Preparation Example 1 12 12 12 Preparation Example 2 90 90 90 Photopolymerizable compound M-2101 17 17 17 M-280 7 7 7 M-241 3 3 3 T063 3 8 - A040 5 - 8 KUA-1330h 1 1 1 Photopolymerization initiator BMPS 1.25 1.25 1.25 N-phenylglycine 0.1 0.1 0.1 9-PA 0.5 0.5 0.5 additive N,N-Diethylbutylamine 0.7 0.7 0.7 Colorless crystal violet (Hodogaya Chemical Co Ltd, Japan) 0.148 0.148 0.148 Diamond Green GH (Hodogaya Chemical Co., Ltd., Japan) 0.025 0.025 0.025 Solvent MEK (methyl ethyl ketone) 12 12 12 Methanol (MeOH) 3 3 3 (1) M2101: Bisphenol A (EO) ₁₀ Dimethacrylate (Meiyuan Special Chemical Co., Ltd.) (2) M280: Polyethylene Glycol Dimethacrylate (Meiyuan Special Chemical Co., Ltd.) (3) M241: Bisphenol A (ethoxylate) ₄ dimethacrylate (Meiyuan Special Chemical Co., Ltd.) (4) T063: Trimethylolpropane [EO] ₆ triacrylate

(5) A040: Methoxypropylene glycol [400] acrylate (n=9)

(6) KUA-1330h: Di(meth)acrylate urethane (7) BMPS: Tribromomethyl sulfide (8) BTCA: 5-benzotriazole carboxylic acid (9) 9-PA: 9- Phenylacridine ＜ Experimental example ＞

The physical properties of the dry film photoresist prepared in the Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 2 below. 1. Thin wire adhesion (unit: micron)

From the dry film photoresist prepared in the examples and comparative examples, the protective film was peeled off, and Hakuto MACH 610i was used to laminate the photosensitive resin of the dry film photoresist into an RTF (Reverse Treated Foil) with a contact thickness of 1.0 mm. The surface of the copper layer of the processed foil) undergoes soft etching under the following conditions, thereby forming a laminate: the laminator roll temperature is 110°C, the roll pressure is 4.0 kgf/cm 2 (kgf/cm ³ ), and The roll speed is 2.0 minutes/meter.

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

In the developed laminate, the minimum value of the interval between the photosensitive resin layers was measured with a Zeiss AXIOPHOT Microscope, and the minimum value was used as the resolution did an evaluation. It can be evaluated that: the smaller the value, the better the resolution value. 2. Resolution (unit: micron)

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

In the dry film photoresist laminated on RTF (Reverse Treated Foil), ORC FDi-3 (laser direct image exposure machine) is used to use ultraviolet rays for an exposure dose of 19 mJ/cm² The resolution pattern (arranged so that the width increases from 10 micrometers to 58 micrometers in units of 2 micrometers, and the pattern interval is 400 micrometers) was irradiated, and then allowed to stand for 15 minutes. Then, the supporting PET film used for the dry film photoresist was peeled off, and then developed under spray-type development conditions with a spray pressure of 1.5 kgf/cm² using a 1.0 wt% Na ₂ CO ₃ aqueous solution at 30±1°C. 40 seconds.

In the developed laminate, the minimum value of the interval between the photosensitive resin layers was measured with a Zeiss AXIOPHOT Microscope, and the minimum value was used as the resolution did an evaluation. It can be evaluated that: the smaller the value, the better the resolution value. 3. Peeling rate (unit: second)

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

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

Then, peeling was performed using a 3% sodium hydroxide aqueous solution (at a temperature of 50°C). The peeling rate was evaluated by measuring the time required for the photocured layer to release from the copper plate. 4. RTF (Reverse Treated Foil) adhesion

From the dry film photoresist prepared in the example and the comparative example, the protective film was peeled off, and the photosensitive resin of the dry film photoresist was laminated into a RTF (Reverse Treated Foil, reverse treatment) with a contact thickness of 1.0 mm by Baidong MACH 610i The matte side surface of the foil) undergoes soft etching under the following conditions, thereby forming a laminate: the laminator roll temperature is 110°C, the roll pressure is 4.0 kgf/cm² and the roll speed is 2.0 minutes/meter.

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

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

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

[Table 2] category Fine line adhesion Resolution Peel rate RTF adhesion Example 1 20 15 35 100% bonding (see Figure 1) Comparative example 1 19 14 35 50% adhesion (see Figure 2) Comparative example 2 twenty three 17 35 100% bonding (see Figure 3)

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

In addition, it can be confirmed that, compared with the examples of the present disclosure, in the case of Comparative Example 2 which does not contain a polyfunctional (meth)acrylate compound, the adhesion and resolution of the thin wires are significantly poorer.

none

FIG. 1 shows an optical microscope image of the adhesion between the substrate and the photosensitive resin layer during the tape peeling test measured in the example. FIG. 2 shows an optical microscope image of the adhesion between the substrate and the photosensitive resin layer during the tape peeling test measured in Comparative Example 1. FIG. FIG. 3 shows an optical microscope image of the adhesion between the substrate and the photosensitive resin layer during the tape peeling test measured in Comparative Example 2. FIG.

Claims (20)

A photosensitive resin layer, comprising: a photopolymerizable compound containing a trifunctional or higher multifunctional (meth)acrylate compound; and an alkaline developable binder resin; Wherein during a tape peeling test performed on a film sample in which the photosensitive resin is laminated on a substrate using a peel tester, The adhesion force defined by the following equation 1 is 90% or greater: [Equation 1] Adhesion (%) = (surface area of the substrate and photosensitive resin layer after the tape peeling test)/surface area of the photosensitive resin layer and the substrate contacting the substrate before the tape peeling test) * 100. The photosensitive resin layer according to 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 or more (meth)acrylate functions The group is bonded to the structure of the 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: [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 having 1 to 20 carbon atoms. p-valent functional group, n2 is an integer from 1 to 20, and p is the number of the substituent R ₆ functional groups and is an integer of 3 to 10. 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, R ₁₀ to R ₁₂ Each is independently hydrogen or an alkylene having 1 to 10 carbon atoms, and n3 to n5 are each independently an integer of 1 to 3. The photosensitive resin layer according to claim 1, The photopolymerizable compound further includes a monofunctional (meth)acrylate compound. The photosensitive resin layer according to claim 5, Wherein, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photopolymerizable compound contains 100 parts by weight or more of the multifunctional (meth)acrylate compound. The photosensitive resin layer according to claim 5, Wherein, the monofunctional (meth)acrylate compound includes a (meth)acrylate, and the (meth)acrylate contains an epoxy group having 1 to 10 carbon atoms. The photosensitive resin layer according to claim 5, wherein the monofunctional (meth)acrylate compound is a photosensitive resin layer containing a compound of the following Chemical Formula 1: [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 of 1-20. The photosensitive resin layer according to claim 5, The photopolymerizable compound includes: A monofunctional (meth)acrylate compound containing a (meth)acrylate, the (meth)acrylate containing an alkylene oxide group having 1 to 10 carbon atoms; and A trifunctional or higher polyfunctional (meth)acrylate compound having three or more epoxyalkyl groups having 1 to 10 carbon atoms and three or more (meth)acrylate functional group bonds Joined to a structure with a central group of 1 to 20 carbon atoms. The photosensitive resin layer according to claim 1, The alkaline developable binder resin has a weight average molecular weight of 20000 g/mol or greater than 20000 g/mol and 150,000 g/mol or less than 150,000 g/mol. The photosensitive resin layer according to claim 5, Wherein, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the polyfunctional (meth)acrylate compound is considered to be contained in an amount of less than 100 parts by weight. The photosensitive resin layer according to claim 2, Wherein, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the multifunctional (meth)acrylate compound is 30 parts by weight or more and 90 parts by weight or less than 90 parts by weight The amount is contained. The photosensitive resin layer according to claim 1, comprising: 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, and a repeating unit represented by the following chemical formula 5 , The repeating unit represented by the following chemical formula 6 and the repeating unit represented by the following chemical formula 7; and the second alkaline developable binder resin, including the repeating unit represented by the following chemical formula 4, the repeating unit represented by the following chemical formula 5, and the The repeating unit represented by the following chemical formula 6, [chemical formula 3]

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, [Chemical Formula 5]

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, [Chemical Formula 7]

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 according to claim 13, 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 more and 1000 parts by weight or less than 1000 parts by weight The amount is contained. The photosensitive resin layer according to claim 13, Wherein the ratio of the glass transition temperature of the first alkaline developable binder resin to the glass transition temperature of the second alkaline developable binder resin is 1:1.5 or greater than 1:1.5 and 1:5 or less 1:5. The photosensitive resin layer according to claim 13, 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 according to claim 1, The photosensitive resin layer has a thickness of 1 micrometer or more and 1000 micrometers or less. The photosensitive resin layer according to claim 1, The photosensitive resin layer has a cross-sectional area of 0.10 cm2 or more and 5.00 cm2 or less. A dry film photoresist including the photosensitive resin layer according to claim 1. A photosensitive element, including: Polymer substrate; and The photosensitive resin layer according to claim 1 is formed on the polymer substrate.

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