TWI768604B - Photosensitive resin layer, and dry film photoresist, photosensitive element using the same - Google Patents

Abstract

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

Description

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

[Cross-reference to related applications]

This application claims Korean Patent Application No. 10-2019-0179944 filed on December 31, 2019 and Korean Patent Application No. 10-2020 filed on July 30, 2020 in the Korea Intellectual Property Office - the benefit of No. 0095386, each of which is incorporated herein by reference in its entirety.

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

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

At present, dry film photoresist is widely used not only in the manufacture of printed circuit boards (PCBs) and lead frames, but also in the manufacture of rib barriers for plasma display panels (PDPs), other Indium Tin Oxide (ITO) electrodes, bus address electrodes, black matrix and the like for displays.

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

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

Allows printed circuit boards that have undergone the lamination process to stand for 15 minutes or more The board was stabilized for 15 minutes and then the DFR photoresist was exposed through a photomask with the desired circuit pattern formed thereon. When the photomask is irradiated with ultraviolet (ultraviolet, UV) rays in this process, the photoresist irradiated with the ultraviolet rays starts to polymerize by a photoinitiator contained in the irradiated portion. First, the oxygen in the photoresist is initially consumed, and then the activating monomer is polymerized to cause a crosslinking reaction. Thereafter, the polymerization reaction proceeds while consuming a large amount of monomers. Meanwhile, the unexposed portion exists in a state in which the crosslinking reaction does not progress.

Next, a development process is performed to remove the unexposed portions of the photoresist. In the case of alkaline developable DFR, an aqueous solution of potassium carbonate and sodium carbonate of 0.8 to 1.2 wt % is used as the developer solution. In this process, the photoresist in the unexposed parts 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, circuits are formed by different processes. However, in the inner layer process, circuits are formed on the board by etching and stripping processes, and in the outer layer process, a plating process and a tenting process are performed, followed by etching and solder stripping to form predetermined circuits.

Recently, there has been 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 thus can be developed during development. High-density circuits are formed in the process, and the photosensitive resin composition has an excellent degree of color development to be used as a UV mark for setting the exposure position of the substrate, and shortens the peeling time of the cured film, has a small of the stripped sample and therefore does not clog the filter.

An object of the present disclosure is to provide a photosensitive resin layer, which can achieve excellent thin line adhesion and resolution, and can improve the alignment recognition rate of products during exposure ), and thus shorten the production time of the final product, reduce the defect rate and thus improve reliability.

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

In order to achieve the above objects, a photosensitive resin layer is provided herein, the photosensitive resin layer comprises: a photopolymerizable compound containing a trifunctional or higher polyfunctional (meth)acrylate compound; and an alkaline developable binder resin ; wherein the aromatic ring fraction value calculated by Equation 1 below is -0.015 or greater than -0.015 and -0.011 or less.

In Equation 1, Pc _n is the number of aromatic rings per (meth)acrylate compound, Oc _n is the number of O atoms and S atoms in each (meth)acrylate compound, and Wr _n is The weight percent of each (meth)acrylate compound relative to the total weight of each (meth)acrylate compound, and Mw _n is the weight average molecular weight of each (meth)acrylate compound .

In the present disclosure, the trifunctional or higher polyfunctional (meth)acrylate compound may have three or more epoxy alkyl groups having 1 to 10 carbon atoms therein and three or more (methyl) The acrylate functional group is bonded to a structure having a central group of 1 to 20 carbon atoms.

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

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

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

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

The monofunctional (meth)acrylate compound may contain a (meth)acrylate containing 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 epoxy alkyl group having 1 to 10 carbon atoms; and a trifunctional or higher polyfunctional (meth)acrylate compounds compounds having a structure in which three or more alkylene oxides having 1 to 10 carbon atoms and three or more (meth)acrylate functional groups are bonded to a central group having 1 to 20 carbon atoms .

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

In Equation 1, the ratio between the Oc ₁ of the monofunctional (meth)acrylate compound and the Oc ₂ of the polyfunctional (meth)acrylate compound may be 1:0.3 or greater than 1:0.3 and 1:0.9 or Less than 1:0.9.

In Equation 1, the ratio between the Mw ₁ of the monofunctional (meth)acrylate compound and the Mw ₂ of the multifunctional (meth)acrylate compound may be 1:1.1 or greater than 1:1.1 and 1:1.9 or Less than 1:1.9.

The polyfunctional (meth)acrylate compound may be contained in an amount of 110 parts by weight or more and 500 parts by weight or less based on 100 parts by weight of the monofunctional (meth)acrylate compound.

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

The difunctional (meth)acrylate compound may be contained in an amount of 500 parts by weight or more and 1500 parts by weight or less based on 100 parts by weight of the monofunctional (meth)acrylate compound.

The bifunctional (meth)acrylate compound may be contained in an amount of 500 parts by weight or more and 1000 parts by weight or less based on 100 parts by weight of the polyfunctional (meth)acrylate compound.

The alkali-developable binder resin may include: a first alkali-developable binder resin including a repeating unit represented by Chemical Formula 3, a repeating unit represented by Chemical Formula 4, a repeating unit represented by Chemical Formula 5, a repeating unit represented by Chemical Formula 6 a repeating unit and a repeating unit represented by Chemical Formula 7; and a second alkaline developable binder resin including a repeating unit represented by Chemical Formula 4, a repeating unit represented by Chemical Formula 5, and a repeating unit represented by Chemical Formula 6. Chemical formulae 3 to 7 are described below.

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

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

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

Further provided herein is a dry film photoresist including the photosensitive resin layer.

Further provided herein is a photosensitive element including the photosensitive resin layer.

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

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

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

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

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

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

In this specification, the term "substituted" means that another functional group is bonded in place 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 at which the substituent may be substituted) may be sufficient, 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; halo; cyano ; Nitro; Hydroxyl; Carbonyl; Ester; Imino; Amino; Primary Amino; Carboxyl; Sulfonic Acid; Sulfonamide; Phosphine Oxide; Alkoxy; Aryloxy; Alkylthiooxy; Arylthiooxy; Alkylsulfooxy; aryl; aralkyl; aralkenyl; alkylaryl; alkoxysilylalkyl; arylphosphino; or heterocyclyl, containing at least one of N, O, and S atoms, or meaning Unsubstituted or substituted with a substituent linked to two or more of the substituents exemplified above. For example, a "substituent attached to two or more substituents" can be biphenyl. That is, biphenyl may also be an aryl group, and may be interpreted as a substituent linked to two phenyl groups.

或

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

or

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

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

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

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

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

In the present specification, an alkylene group is a divalent functional group derived from an alkane, and the description of the alkylene group as defined above is applicable except that the alkylene group is a divalent functional group. For example, alkylene can be straight or branched chain, methylene, vinyl, propenyl, isobutenyl, second butenyl, third butenyl, pentylene, hexylene, or the like thing. Alkylene groups can be substituted or unsubstituted.

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

In this specification, a direct bond or a single bond means connection to a bond line where no atoms or groups of atoms are present at the corresponding positions. Specifically, a direct bond or a single bond means a situation in which other atoms do not exist in the moiety represented by R _a or L _b (where a and b are an integer of 1 to 20, respectively) in the chemical formula.

In this specification, the term "(photo)cured product" or "(photo)cured" is meant to include not only those in which a component having a curable or crosslinkable unsaturated group in its chemical structure is completely cured, crosslinked or polymerized situations, but also include situations in which such components are partially cured, cross-linked or polymerized.

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

1. Photosensitive resin composition

According to an embodiment of the present disclosure, a photosensitive resin layer can be provided, the photosensitive resin layer comprising: a photopolymerizable compound containing a trifunctional or higher polyfunctional (meth)acrylate compound; and an alkaline developable adhesive agent resin; wherein the aromatic ring fraction value calculated from Equation 1 below is -0.015 or greater and -0.011 or less.

In Equation 1, Pc _n is the number of aromatic rings per (meth)acrylate compound, Oc _n is the number of O atoms and S atoms in each (meth)acrylate compound, and Wr _n is The weight percent of each (meth)acrylate compound relative to the total weight of each (meth)acrylate compound, and Mw _n is the weight average molecular weight of each (meth)acrylate compound .

The inventors found through experiments that since the photosensitive resin layer of one embodiment has the aromatic ring fraction value calculated by Equation 1 which is -0.015 or greater than -0.015 and -0.011 or less than -0.011, it can ensure good resolution while maintaining It has the technical effect of excellent developability and peelability while maintaining high degree of strength and adhesion.

(1) Alkaline developable binder resin

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

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

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

Specifically, the alkali-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, a repeating unit represented by the following Chemical Formula 5 The repeating unit represented by Chemical Formula 6 and the repeating unit represented by the following Chemical Formula 7.

[Chemical formula 3]

In Chemical Formula 3, R ₃ " is hydrogen,

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

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

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

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

In Chemical Formulas 3 to 7, specific examples of the alkyl group having 1 to 10 carbon atoms may include a methyl group.

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

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

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

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

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

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

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

The first alkaline developable binder resin and the second alkaline developable binder resin may have a weight of 30000 g/mol or more and 150000 g/mol or less average molecular weight and having a glass transition temperature of 20°C or more and 150°C or less. Thereby, the coating properties and followability of the dry film photoresist as well as the mechanical strength of the photoresist itself after circuit formation can be improved. In the foregoing or below, weight average molecular weights were measured using a Waters 450 GPC with polystyrene used as standard and Shodex 105, 104, 103 columns. Glass transition temperatures were measured using a Perkin Elmer DSC 7.

The first alkaline developable binder resin may have 140 milligrams potassium hydroxide/gram (mgKOH/g) or greater and 160 milligrams potassium hydroxide/gram or less than 160 milligrams potassium hydroxide/gram acid value in grams. Additionally, the second alkaline developable binder resin may have an acid of 160 mg potassium hydroxide/gram or greater and 200 mg potassium hydroxide/gram or less than 200 mg potassium hydroxide/gram value.

Specifically, 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 may be 1:1.5 or more and 1:5 or less 1.5, 1:1.5 or greater than 1:1.5 and 1:3 or less, 1:1.5 or greater than 1:1.5 and 1:2 or less than 1:2, 1:1.5 or greater than 1:1.5 and 1: 1.8 or less than 1: 1.8, 1: 1.5 or more than 1: 1.5 and 1: 1.75 or less than 1: 1.75, Or 1:1.6 or greater and 1:1.7 or less than 1:1.7.

In addition, the ratio of the acid value of the first alkaline developable binder resin to the acid value of the second alkaline developable binder resin may be 1:1.01 or more and 1:1.5 or less than 1:1.5, 1:1.1 or greater than 1:1.1 and 1:1.5 or less, 1:1.25 or greater than 1:1.25 and 1:1.5 or less, or 1:1.4 or greater than 1:1.4 and 1 : 1.5 or less than 1: 1.5.

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

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

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

[Chemical formula 4]

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

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

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

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.

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

The repeating unit represented by Chemical Formula 5 may be a repeating unit derived from a monomer represented by the following 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 Chemical Formula 5-1, the definitions of R ₄ " and R ₅ " are the same as those set forth for Chemical Formula 5. Specific examples of the monomer represented by Chemical Formula 5-1 may include methyl methacrylate (MMA).

The repeating unit represented by Chemical Formula 6 may be a repeating unit derived from a monomer represented by the following 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 alkali-developable binder resin may include repeating units represented by Chemical Formula 4 in a ratio of: repeating units represented by Chemical Formula 5: repeating units represented by Chemical Formula 6: 1:(2 or more 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): (0.6 or greater than 0.6 and 0.9 or less) or 1: (2.75 or greater than 2.75 and 3 or less): (0.6 or greater than 0.6 and 0.75 or less 0.75).

In addition, the second alkali-developable binder resin may include the repeating unit represented by Chemical Formula 4 in the following ratio: the repeating unit represented by Chemical Formula 5: the repeating unit represented by Chemical Formula 6: 1:(1.1 or more 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): (0.75 or greater and 0.99 or less).

Meanwhile, based on 100 parts by weight of the first alkaline developable binder resin, the photosensitive resin composition of one embodiment of the present disclosure may be 500 parts by weight or more 500 parts by weight and 1000 parts by weight or less, 600 parts by weight or more and 800 parts by weight or less, 700 parts by weight or more and 800 parts by weight or less The amount of parts contains the second alkali developable binder resin.

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

A specific example of the measurement conditions is as follows: the alkali-developable binder resin is dissolved in tetrahydrofuran (THF) so that the alkali-developable binder resin has 1.0 (weight/weight (w/w) in THF) )% concentration (approximately 0.5 (w/w)% on a solids basis); filtered using a syringe filter with a pore size of 0.45 microns; and then injected in 20 microliters To GPC, tetrahydrofuran (THF) was used as the mobile phase of GPC, and the flow rate was 1.0 milliliters per minute (mL/min). The column consists of an Agilent PL gel 5 micron (μm) guard (7.5 x 50 mm) connected in series with two Agilent PL gel 5 micron mixed D (7.5 x 300 mm) millimeters (mm)) and the measurements were performed at 40°C using an Agilent 1260 Infinity II System RI Detector as detector.

Polystyrene in which polystyrene with various molecular weights was dissolved in tetrahydrofuran at a concentration of 0.1 (weight/weight) (w/w) % was filtered through a syringe filter with a pore size of 0.45 μm. Ethylene standards (STD A, B, C, D) were filtered and then injected into the 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

Glass transition temperature of reference polymer and glass transition temperature of binder polymer by Differential Scanning Calorimeter (DSC) (Perkin-Elmer, DSC-7) comparisons were 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/minute.

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

The alkali-developable binder resin is 20% by weight or more and 80% by weight in terms of solid content relative to the total weight of the photosensitive resin composition or is contained in an amount of less than 80% by weight. When the content of the alkali-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.

The content of the alkaline developable binder resin of the present disclosure may be 40 wt % or more and 70 wt % or less with respect to the total weight of the photosensitive resin composition used to form the photosensitive resin layer. When the content of the alkali-developable binder resin is less than 40% by weight with respect to the total photosensitive resin composition, there is a disadvantage that defects such as short circuits are caused due to contamination during development, and when the content of the alkali-developable binder resin is When it exceeds 70 weight%, there exists a problem that circuit properties, such as adhesive force and resolution, deteriorate.

(2) Photopolymerization initiator

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

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

In addition, can be selected from 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 1-hydroxycyclohexyl phenyl ketone, 2,2-bisimidazole Methoxy-1,2-diphenylethyl-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1-[4-morpholinophenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4 ,6-Three Methylbenzyldiphenylphosphine oxide, 1-[4-(2-hydroxymethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, 2,4-diethyl Thioxanthene, 2-Chlorothioxanthone, 2,4-Dimethylthioxanthone, 3,3-Dimethyl-4-methoxybenzophenone, Benzophenone, 1-Chloro-4- Propoxythioxanthone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy- 2-Methylpropan-1-one, 4-benzyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, Ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid 2 -Isoamyl ester, 2,2-diethoxyacetophenone, benzyl ketone dimethyl acetal, benzyl ketone β-methoxydiethyl acetal, 1-phenyl-1,2-propane Dioxime-o,o'-(2-carbonyl)ethoxy ether (1-phenyl-1,2-propyldioxime-o,o'-(2-carbonyl)ethoxy ether), methyl o-benzoyl benzoate Esters, bis[4-dimethylaminophenyl]ketone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin , methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, isobutoxybenzoin, tertiary butoxybenzoin, p-dimethylaminoacetophenone, p-tertiary butyl benzoin Trichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, α,α- The compounds in dichloro-4-phenoxyacetophenone and amyl 4-dimethylaminobenzoate are used as photopolymerization initiators, but are not limited thereto.

The photopolymerization initiator is contained in an amount of 0.1 wt % or more and 10 wt % or less in terms of solid content with respect to the total weight of the photosensitive resin composition for forming 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 0.1% by weight, the light efficiency is low, and a large amount of exposure must be applied and thus, there is a disadvantage that the production efficiency is greatly reduced. When the content of the photopolymerization initiator exceeds 10% by weight, there are problems that the film is brittle and the contamination of the developer solution increases, resulting in defects such as short circuits.

(3) Photopolymerizable compounds

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

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

Specifically, the trifunctional or higher polyfunctional (meth)acrylate compound may have three or more epoxy alkyl groups having 1 to 10 carbon atoms therein and three or more (meth)acrylic acid 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 compound of the following Chemical Formula 2:

In Chemical Formula 2, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₅ is an alkylene group having 1 to 10 carbon atoms, and R ₆ is a central group containing 1 to 20 carbon atoms of p-valent functional groups, n2 is an integer of 1 to 20, and p is the number of functional groups substituted for R6 and is an integer of ₃ to 10.

In addition, in Chemical Formula 2, n2 is an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to ₅ , p means the number of functional groups substituted for R6 and may be an integer of 3 to 10, 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 may be It is a trifunctional or higher polyfunctional (meth)acrylate compound.

Specifically, the polyfunctional (meth)acrylate compound can be represented by the following 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 are each 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 Chemical Formula 2-1, n3 to n5 may be an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to 5.

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

Since the photosensitive resin layer of one embodiment includes the polyfunctional (meth)acrylate compound represented by Chemical Formula 2, the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 is ) acrylate compounds have increased crosslinking and more reactive groups during photocuring. Due to these technical reasons, a reduction in circuit properties, which is a problem when only the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 is added, can be prevented, and an effect of increasing the amount of color development change can be achieved.

Meanwhile, the photopolymerizable compound may further contain a monofunctional (meth)acrylate compound.

Specifically, the monofunctional (meth)acrylate compound may include a (meth)acrylate containing an epoxy resin having 1 to 10 carbon atoms alkyl.

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 Trifunctional or higher polyfunctional (meth)acrylate compounds having three or more (meth)acrylate functional groups having 1 to 10 carbon atoms therein 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 monofunctional (meth)acrylate compound may include a monofunctional (meth)acrylate compound represented by Chemical Formula 1 below.

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 to 20.

That is, the photosensitive resin layer according to an embodiment of the present disclosure may include a mixture of a monofunctional (meth)acrylate compound and a polyfunctional (meth)acrylate compound.

Meanwhile, the photosensitive resin for forming the photosensitive resin layer of one embodiment may be 110 parts by weight based on 100 parts by weight of the monofunctional (meth)acrylate compound or more than 110 parts by weight and 500 parts by weight or less, 110 parts by weight or more and 300 parts by weight or less, 110 parts by weight or more and 200 parts by weight The trifunctional or higher polyfunctional (meth)acrylate compound is contained in an amount of or less than 200 parts by weight, or 150 parts by weight or more and 200 parts by weight or less.

Since the photosensitive resin layer of one embodiment contains the polyfunctional (meth)acrylate compound in excess with respect to the monofunctional (meth)acrylate compound, shortening of the monofunctional (meth)acrylic acid represented by Chemical Formula 1 can be achieved at the same time The effect of the peeling time of the ester compound and the effect of increasing the resistance of the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 to the developer solution and thus enhancing the adhesive force and resolution, thereby satisfying the calculated by Equation 1. The aromatic ring fraction value is -0.015 or more and -0.011 or less, and finally ensures excellent developing properties.

When the photosensitive resin layer of one embodiment contains less than 100 parts by weight of the polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound, the resistance to the developer solution is weakened , which may cause technical problems in achieving good adhesion and resolution.

Meanwhile, the photopolymerizable compound may include a bifunctional (meth)acrylate compound including 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 polyfunctional (meth)acrylate compound, including an alkylene glycol Di(meth)acrylates and amines Bifunctional (meth)acrylates of carbamate-based di(meth)acrylates.

The alkylene glycol-based di(meth)acrylate may include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate (meth)acrylate), tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate (Meth)acrylate (polyethylene glycol di(meth)acrylate), polypropylene glycol di(meth)acrylate (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 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 (Diacrylate), Miramer M240 (Bisphenol A (EO) ₄ DA, Bisphenol A (EO) ₄ Diacrylate), Miramer M241 (Bisphenol A (EO) ₄ Dimethacrylate), Miramer M2100 (Bisphenol A(EO) ₁₀ DA, Bisphenol A(EO) ₁₀ Diacrylate), Miramer M2200 (Bisphenol A(EO) ₂₀ DA, Bisphenol A(EO) ₂₀ diacrylate), Miramer M2101 (bisphenol A(EO) ₁₀ dimethacrylate) and other commercially available products.

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

The urethane-based di(meth)acrylate may have a larger molecular weight than the existing simple alkylene oxide and have a linear structure, thereby imparting flexibility. This results in improved hole capping properties required for dry film resist (DFR) of the outer layer and hydrophobicity of the polyol as one of the components of the urethane acrylate, and improved resistance to plating solutions as strong acids resistance, thereby not contaminating 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 a 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 may include aliphatic diisocyanate compounds having a divalent aliphatic group (eg, alkylene), alicyclic diisocyanate compounds having a divalent alicyclic group (eg, cycloalkylene), aromatic diisocyanates Compounds and 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, Methylenebis(cyclohexyl)diisocyanate, 1,3- or 1,4-bis(methylisocyanate)cyclohexane and the like.

The aromatic diisocyanate compound may include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, or dimer polymers of 2,6-toluene diisocyanate, (ortho, para, or meta) ) xylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate and the like.

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

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

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

The reaction temperature is preferably 60°C to 120°C. When the reaction temperature is less than 60°C, there is a tendency that the reaction does not proceed sufficiently, and when the reaction temperature exceeds 120°C At 0C, the operation of the reaction can be hazardous due to the sudden generation of heat.

The compound having both a hydroxyl group and an ethylenically unsaturated group 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)acrylates, hydroxy(meth)acrylate-caprolactone adducts or alkylene oxide adducts, by combining polyols such as glycerol with (meth)acrylic acid The ester compound prepared by the reaction, and the glycidyl (meth)acrylate-acrylic acid adduct.

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

Hydroxy (meth) acrylate - caprolactone adduct may include hydroxyethyl (meth) acrylate. Caprolactone adduct, hydroxypropyl (meth)acrylate. Caprolactone adduct, hydroxybutyl (meth) acrylate. Caprolactone adducts, and alkylene oxide adducts may include hydroxyethyl (meth)acrylate. Alkylene oxide adduct, hydroxypropyl (meth)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 The di(meth)acrylate of the adduct. These may be used alone or in combination of two or more.

Urethane-based di(meth)acrylates are derived from an addition reaction of a urethane compound with a compound having both a hydroxyl group and an ethylenically unsaturated group , and can be obtained by adding a compound having both hydroxyl and ethylenically unsaturated groups at a molar ratio of 2.0 to 2.4 relative to 1 molar carbamate compound and then at 60°C to 90°C It is obtained by subjecting it to an addition reaction.

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/mol, it is difficult to sufficiently increase flexibility and toughness, therefore, the adhesion to the substrate may not be improved, and when the weight average molecular weight exceeds 60,000 g/mol, developing properties exist Problems that may deteriorate and development time may become slow. 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/mol to 60,000 g/mol.

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 1 wt % to 20 wt %, preferably 1.5 The amount of % by weight to 15% by weight is contained in the photosensitive resin composition for forming the photosensitive resin layer. 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 wt%, there may be a disadvantage that the development time is rapidly increased in the development process after exposure, and a large amount of scum and sludge are also generated.

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

Specifically, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photosensitive resin composition for forming the photosensitive resin layer of one 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 or more and 1000 parts by weight or less, 750 parts by weight or more and 1000 parts by weight or less, or 800 parts by weight or more The bifunctional (meth)acrylate compound is contained in an amount of 800 parts by weight and 900 parts by weight or less.

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

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, 500 parts by weight or more and 750 parts by weight or less, 500 parts by weight or more and 700 parts by weight or less The bifunctional (meth)acrylate compound is contained in an amount of parts by weight, 500 parts by weight or more and 600 parts by weight or less.

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

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

That is, the photosensitive resin composition for forming the photosensitive resin layer may contain 0.1 wt % or more and 2.5 wt % or less of the monofunctional photopolymerizable compound based on the total weight of the photosensitive resin composition and 2.6 wt % or more and 5.0 wt % or less of a multifunctional photopolymerizable compound.

When the content of the monofunctional photopolymerizable compound is less than 0.1 wt % or the content of the polyfunctional photopolymerizable compound is less than 2.6 wt % based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer, due to the addition of the chemical formula 1 and the compounds represented by 2 are insufficient, and when the content of the monofunctional photopolymerizable compound is more than 2.5 wt % or more than 5.0 wt % or the content of the polyfunctional photopolymerizable compound is more than 5.0 wt %, there may be an increase in hydrophobicity and therefore, the development time in the development process after exposure increases rapidly.

The photosensitive resin composition for forming the photosensitive resin layer of one embodiment is an additional photopolymerizable compound, and may include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate ( diethylene glycol dimethacrylate), tetraethylene glycol dimethacrylate (tetraethylene glycol dimethacrylate), propylene glycol dimethacrylate (propylene glycol dimethacrylate), polypropylene glycol dimethacrylate (polypropylene glycol dimethacrylate), butylene glycol dimethacrylate (butylene glycol dimethacrylate), neopentyl glycol dimethacrylate Methacrylate (neopentyl glycol dimethacrylate,), 1,6-hexanediol dimethacrylate (1,6-hexane glycol dimethacrylate), trimethylolpropane trimethacrylate (trimethyolpropane trimethacrylate), trihydroxy Trimethyolpropane triacrylate, glycerin dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate Esters (dipentaerythritol pentamethacrylate), 2,2-bis(4-methacryloxydiethoxyphenyl)propane (2,2-bis(4-methacryloxydiethoxyphenyl)propane), 2,2-bis(4- Methacryloxypolyethoxyphenyl) propane (2,2-bis(4-methacryloxypolyethoxyphenyl)propane), 2-hydroxy-3-methacryloxypolyethoxyphenyl)propane -3-methacryloyloxypropyl methacrylate), ethylene glycol diglycidyl ether dimethacrylate (ethylene glycol diglycidyl ether dimethacrylate), diethylene glycol diglycidyl ether dimethacrylate (diethylene glycol diglycidyl ether dimethacrylate), phthalate Diglycidyl dicarboxylate dimethacrylate (phthalic acid diglycidyl ester dimethacrylate), glycerin polyglycidyl ether polymethacrylate (glycerin polyglycidyl ether polym ethacrylate), multifunctional urethane groups (Meth)acrylates and the like.

The content of the photopolymerizable compound may be 10 wt % or more and 70 wt % or less in terms of solid content with respect to the total weight of the photosensitive resin composition for forming the photosensitive resin layer. When the content of the photopolymerizable compound is within the above range, effects of enhancing sensitivity, resolution, adhesion, and the like can be obtained.

(4) Photosensitive resin composition

The photosensitive resin composition for forming the photosensitive resin layer may contain, in terms of solid content, 20 wt % and more than 20 wt % and 80 wt % or less of an alkali developable binder resin, 0.1 wt % or More than 0.1 wt % and 10 wt % or less of a photopolymerization initiator, and 10 wt % or more and 70 wt % or less of a photopolymerizable compound. The solid content on a weight basis means the remaining components excluding the solvent from the photosensitive resin composition.

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

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

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

Examples of the coloring material 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 added amount may be 0.001 wt % or more and 1 wt % or less based on the photosensitive resin composition. When the content is 0.001 wt % or more, it has an effect of improving handleability, and when the content is 1 wt % or less, it has an effect of maintaining storage stability.

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

Meanwhile, the photosensitive resin layer of one embodiment may have an aromatic ring fraction value calculated by Equation 1 below of -0.015 or more and -0.011 or less than -0.011.

In Equation 1, for the monofunctional (meth)acrylate compound represented by Chemical Formula 1 and the polyfunctional (meth)acrylate compound represented by Chemical Formula 2, Pc _n is the aromatic value of each (meth)acrylate compound The number of rings, Oc _n is the number of O atoms and S atoms in each (meth)acrylate compound, Wrn _is each (meth)acrylate compound relative to the monofunctional (meth)acrylate compound and The weight percent of the total weight of the multifunctional (meth)acrylate compound, and Mw _n is the weight average molecular weight of the (meth)acrylate compound.

Specifically, since the photosensitive resin composition of one embodiment includes a monofunctional (meth)acrylate compound represented by Chemical Formula 1 and a polyfunctional (meth)acrylate compound represented by Chemical Formula 2, the value calculated by Equation 1 The aromatic ring fraction value can be -0.015 or greater and -0.011 or less than -0.011.

More specifically, since the photosensitive resin layer of one embodiment contains the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 in excess with respect to the monofunctional (meth)acrylate compound represented by Chemical Formula 1, it is determined by The aromatic ring fraction value calculated by Equation 1 may be -0.015 or greater than -0.015 and -0.011 or less than -0.011.

Since the aromatic ring fraction value calculated by Equation 1 is -0.015 or greater than - 0.015 and -0.011 or less, so the reactivity of the photosensitive resin layer of one embodiment becomes faster and therefore, the time and degree of color development of the dry film resist including the photosensitive resin layer of one embodiment becomes It is excellent, and thus the effect of improving the physical properties of the display device including the dry film photoresist can be achieved.

The aromatic ring fraction parameter is a value obtained by calculating the aromatic ring content of the photopolymerizable compound excluding the content of O and S atoms and dividing this by the average molecular weight of the composition, and the aromatic ring fraction value may be -0.015 or Greater than -0.015 and -0.011 or less than -0.011, -0.015 or greater than -0.015 and -0.012 or less than -0.012, -0.015 or greater than -0.015 and -0.013 or less than -0.013, or -0.014 or greater than -0.014 and is -0.013 or less than -0.013. By using the photopolymerizable compound satisfying the aromatic ring fraction value, the photosensitive resin layer of one embodiment can achieve the effect of having excellent developability and releasability while maintaining good resolution and adhesion.

In addition, when the aromatic ring fraction value is less than -0.015, the polyfunctional (meth)acrylate compound is contained in an excessively small amount, and the inclusion of the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 increases the resistance to the developer. The technical effect of the resistance of the solution is reduced, which may cause technical problems of improving adhesion and resolution. When the value exceeds -0.011, since the monofunctional (meth)acrylate compound represented by Chemical Formula 1 is included, the number of repeating units of ethylene oxide having hydrophilicity in the molecular structure decreases, which may cause an increase in molecular weight and The technical problem of prolonging the peeling time.

Equation 1 may specifically mean the following equation.

In Equation 1, Pcn may mean the number of aromatic rings of the (meth)acrylate compound represented by Chemical Formula _n . That is, Pc ₁ means the number of aromatic rings of the monofunctional (meth)acrylate compound represented by Chemical Formula 1, and Pc ₂ may mean the number of aromatic rings of the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 number.

In Equation 1, Oc _n may mean the number of O atoms and S atoms of the (meth)acrylate compound represented by Chemical Formula n. That is, Oc ₁ means the number of O atoms and S atoms of the monofunctional (meth)acrylate compound represented by Chemical Formula 1, and Oc ₂ may mean the number of the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 The number of O atoms and S atoms.

In Equation 1, Wrn may mean a weight percentage of the (meth)acrylate compound represented by Chemical Formula _n with respect to the total weight of the monofunctional (meth)acrylate compound and the multifunctional (meth)acrylate compound. That is, Wr ₁ means the weight percentage of the monofunctional (meth)acrylate compound represented by Chemical Formula 1 with respect to the total weight of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound, and Wr ₂ may mean the weight percentage of the multifunctional (meth)acrylate compound represented by Chemical Formula 2 with respect to the total weight of the monofunctional (meth)acrylate compound and the multifunctional (meth)acrylate compound.

In Equation 1, Mw _n may mean the weight average molecular weight of the (meth)acrylate compound represented by Chemical Formula n. That is, Mw ₁ means the weight average molecular weight of the monofunctional (meth)acrylate compound represented by Chemical Formula 1, and Mw ₂ may mean the weight average molecular weight of the polyfunctional (meth)acrylate compound represented by Chemical Formula 2.

That is, in one embodiment, the aromatic ring fraction value calculated by Equation 1 can be specifically calculated by Equation 1-1 below.

In Equation 1-1, Pc ₁ is the number of aromatic rings of the monofunctional (meth)acrylate compound represented by Chemical Formula 1, and Pc ₂ is the aromatic ring of the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 Oc ₁ is the number of O atoms and S atoms of the monofunctional (meth)acrylate compound represented by Chemical Formula 1, Oc ₂ is the O atom of the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 and The number of S atoms, Wr ₁ is the weight percent of the monofunctional (meth)acrylate compound represented by Chemical Formula 1 with respect to the total weight of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound, Wr ₂ is the weight percentage of the multifunctional (meth)acrylate compound represented by Chemical Formula 2 with respect to the total weight of the monofunctional (meth)acrylate compound and the multifunctional (meth)acrylate compound, and Mw ₁ is represented by the Chemical Formula 1 is the weight average molecular weight of the monofunctional (meth)acrylate compound, and Mw ₂ is the weight average molecular weight of the polyfunctional (meth)acrylate compound represented by Chemical Formula 2.

In Equation 1, _Pcn represents the number of aromatic rings per (meth)acrylate compound. The number of aromatic rings means the number of monocyclic rings contained in the (meth)acrylate compound, and in the case of condensed rings, it means the number of each condensed monocyclic ring. For example, when the (meth)acrylate compound contains one naphthyl group, two benzene rings (which are monocyclic) are fused, and thus Pc _n is 2. Pc _n is 3 when the (meth)acrylate compound contains one anthracenyl or phenanthrenyl group.

That is, the monofunctional (meth)acrylate compound represented by Chemical Formula 1 may have a Pcn of 0 or more and 10 or less, 0 or more and 2 or less, or ₀ , and is represented by The polyfunctional (meth)acrylate compound represented by Chemical Formula 2 may have a Pcn of 0 or more and 10 or less, 0 or more and 2 or less, or ₀ .

Oc _n is the number of O atoms and S atoms in each (meth)acrylate compound, but does not include the number of "O" contained in the (meth)acrylate.

For example, when the (meth)acrylate compound is dodecanediol dimethacrylate, Oc _n is 0, and if the (meth)acrylate compound is phenylthioethylacrylate, then Ocn _is 1.

_Wrn may be the weight percent of each (meth)acrylate compound relative to the total weight of the monofunctional (meth)acrylate compound and the multifunctional (meth)acrylate compound. For example, if the (meth)acrylate compound used is mixed with 60 kg of dodecanediol dimethacrylate and 40 kg of phenylthioethyl acrylate, then dodecanediol dimethyl acrylate The _Wrn of the phenyl acrylate was (60/100)×100=60, and the _Wrn of the phenylthioethyl acrylate was (40/100)×100=40.

Meanwhile, in Equation 1, the ratio between Oc ₁ of the monofunctional (meth)acrylate compound and Oc ₂ of the polyfunctional (meth)acrylate compound may be 1:0.3 or more than 1:0.3 and 1:0. 0.9 or less than 1: 0.9, 1: 0.5 or more than 1: 0.5 and 1: 0.9 or less than 1: 0.9, 1: 0.5 or more than 1: 0.5 and 1: 0.75 or less than 1: 0.75, 1: 0.5 or more 1:0.5 and 1:0.7 or less than 1:0.7.

Furthermore, in Equation 1, the ratio between the Mw ₁ of the monofunctional (meth)acrylate compound and the Mw ₂ of the multifunctional (meth)acrylate compound may be 1:1.1 or greater than 1:1.1 and 1:1: 1.9 or less than 1:1.9, 1:1.1 or more than 1:1.1 and 1:1.5 or less than 1:1.5, 1:1.1 or more than 1:1.1 and 1:1.4 or less than 1:1.4, 1:1.2 or more 1:1.2 and 1:1.4 or less, 1:1.2 or more and 1:1.3 or less than 1:1.3.

2. Dry film photoresist

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

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

Meanwhile, the photosensitive resin layer may have an aromatic ring fraction value calculated by Equation 1 below, which is -0.015 or more and -0.011 or less than -0.011.

In Equation 1, for the monofunctional (meth)acrylate compound represented by the following Chemical Formula 1 and the polyfunctional (meth)acrylate compound represented by the following Chemical Formula 2, Pc _n is each (meth)acrylate compound The _number of aromatic _rings of the the weight percent of the total weight of the compound and the polyfunctional (meth)acrylate compound, and Mw _n is the weight average molecular weight of the (meth)acrylate compound,

In Chemical Formula 1, R ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₂ is an alkylene group having 1 to 10 carbon atoms, R ₃ is an alkyl group having 1 to 10 carbon atoms, and n1 is an integer from 1 to 20,

In Chemical Formula 2, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₅ is an alkylene group having 1 to 10 carbon atoms, and R ₆ is a central group containing 1 to 20 carbon atoms of p-valent functional groups, n2 is an integer of 1 to 20, and p is the number of functional groups substituted for R6 and is an integer of ₃ to 10.

Details about Equation 1 include everything set forth above in another embodiment.

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

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

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

The protective film prevents damage to the photoresist during handling, and functions as a protective cover that protects the photosensitive resin layer from foreign matter such as dust, and is laminated on the photosensitive resin layer without forming on the backside of the substrate film. The protective film is used to protect the photosensitive resin layer from external influences. When dry film photoresist is applied It needs to be easily detached when post-process, and it needs proper releasability and adhesion to allow it to deform during storage and dispensing.

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

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

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

The step of drying the coated photosensitive resin composition can be performed by heating means 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 more and 100° C. ℃ or less than 100℃.

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 On a substrate, wherein the aromatic ring fraction value calculated by Equation 1 below is -0.015 or greater than -0.015 and -0.011 or less than -0.011.

In Equation 1, for the monofunctional (meth)acrylate compound represented by the following Chemical Formula 1 and the polyfunctional (meth)acrylate compound represented by the following Chemical Formula 2, Pc _n is each (meth)acrylate compound The _number of aromatic _rings of the the weight percent of the total weight of the compound and the polyfunctional (meth)acrylate compound, and Mw _n is the weight average molecular weight of the (meth)acrylate compound,

In Chemical Formula 1, R ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₂ is an alkylene group having 1 to 10 carbon atoms, R ₃ is an alkyl group having 1 to 10 carbon atoms, and n1 is an integer from 1 to 20, [Chemical Formula 2]

In Chemical Formula 2, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₅ is an alkylene group having 1 to 10 carbon atoms, and R ₆ is a central group containing 1 to 20 carbon atoms of p-valent functional groups, n2 is an integer of 1 to 20, and p is the number of functional groups substituted for R6 and is an integer of ₃ to 10.

Details about the photosensitive resin composition include all the content set forth in the one embodiment and the other embodiment.

That is, the photosensitive resin layer includes an alkali-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 compound represented by the following Chemical Formula 2 (Meth)acrylate compound.

In Chemical Formula 1, R ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₂ is an alkylene group having 1 to 10 carbon atoms, R ₃ is an alkyl group having 1 to 10 carbon atoms, and n1 is an integer from 1 to 20,

In Chemical Formula 2, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₅ is an alkylene group having 1 to 10 carbon atoms, and R ₆ is a central group containing 1 to 20 carbon atoms of p-valent functional groups, n2 is an integer of 1 to 20, and p is the number of functional groups substituted for R6 and is an integer of ₃ to 10.

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

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

Polymer substrates are generally manufactured by in-line coating methods, rather than adding anti-blocking agents (which are generally added in consideration of runnability and winding characteristics during manufacturing), and have the advantage of not compromising transparency when used. The organic particle layer of alternative particles.

Here, examples of the organic particles to be used as particles that do not impair transparency while taking into account runnability and winding properties may include, for example, organic particles in which, for example, methyl methacrylate, ethyl methacrylate, methyl methacrylate, methyl methacrylate, and methyl methacrylate are formed. Acrylic, olefinic particles of isobutyl acrylate, n-butyl methacrylate, n-butyl methyl methacrylate, acrylic acid, methacrylic acid copolymer or terpolymer (eg polyethylene, polystyrene or poly) propylene), acrylic and olefin-based copolymers, or multi-layer multi-component particles of homopolymer particles and then coating the layer with another type of monomer.

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

c2+a2+b2定義。顆粒的形狀應為球形，此在走料性方面是較佳的。 Specifically, the organic particles should be spherical and also have a refractive index different from that of the binder resin. Here, "spherical" means that the ratio of the minor axis (a) to the major axis (b) in the ellipse is 0.5<a/b<2, and the relationship to the diagonal (d) in the rectangle is given by d2

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

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

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

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

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

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

Solvents that can be used to prepare coating solutions using binder resins and organic particles The agent is preferably water.

As described above, an unstretched polyester film obtained by melt extrusion of 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 preferably has a thickness of about 30 nm to 200 nm in terms of thickness after final drying. If the coating solution containing the organic particles is applied to a thickness of more than 30 nm on the uniaxially stretched film, there are problems that the organic particles are easily dropped and scratched, and white powder is generated. When coating thicker than 200 nm, coating streaks may be generated in the coating direction in in-line coating with high coating speed due to the increased viscosity of the coating solution.

The polymer substrate obtained by coating with organic particles different from general anti-blocking agents by the in-line coating method as described above maintains feedability and winding characteristics due to the particle layer and since the organic particles have extremely high performance. 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 films including the anti-blocking agent are laminated as before, pit-like defects do not occur. Since particles such as silicon dioxide are not only larger in size than organic particles, but also distributed over the entire substrate film, the effect of silicon dioxide is negligible even in regions adjacent to the photosensitive resin layer.

On the other hand, in the polymer substrate used in the present disclosure, the organic particles have There is 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 compromising other circuit properties.

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

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

4. Circuit board, display device

According to another embodiment of the present disclosure, a circuit board or a display device including the photosensitive resin layer containing the photosensitive resin composition of the one embodiment can be provided. Details about the photosensitive resin layer include all the content set forth above in the 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 type photoresist of another embodiment on a circuit board or a display device manufacturing substrate and then performing exposure and development. In addition, a method of laminating the photosensitive resin of the photosensitive element according to another embodiment on a circuit board or a display device manufacturing substrate and then performing exposure and development can be mentioned.

When the dry film type photoresist or the 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 layer on the circuit board or the display device manufacturing substrate .

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

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

According to the present disclosure, a photosensitive resin layer capable of achieving excellent developing properties, and a dry film type photoresist and a photosensitive element including the photosensitive resin layer can be provided.

The present disclosure will be explained in more detail by 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-necked round bottom flask was equipped with a mechanical stirrer and a reflux device, and then the inside of the flask was purged with nitrogen gas. To the flask purged with nitrogen, 80 grams of methyl ethyl ketone (MEK) and 7.5 grams of methanol (MeOH) were added, and then 0.45 grams of azobisisobutyronitrile (AIBN) was added and dissolve it completely. To this were added 8 g of acrylic acid (AA), 15 g of methacrylic acid (MAA), 15 g of butyl acrylate (BA), 52 g of methyl methacrylate (MMA) ) and a monomer mixture of 10 g of styrene (SM) as monomers, heated to 80° C., and then polymerized for 6 hours to prepare an alkaline developable binder resin 1 .

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

In a specific example of the measurement conditions of the weight average molecular weight, the alkali-developable binder resin is dissolved in tetrahydrofuran, so that the alkali-developable binder resin At a concentration of 1.0 (w/w) % in THF (approximately 0.5 (w/w) % on a solids basis), filtration was performed using a syringe filter with a pore size of 0.45 microns , and then injected into the GPC in an amount of 20 μl, tetrahydrofuran (THF) was used as the mobile phase of the GPC, and the flow rate was 1.0 ml/min. The column consisted of an Agilent PL gel 5 micron guard (7.5 x 50 mm) connected in series with two Agilent PL gel 5 micron mixed D (7.5 x 300 mm) and the measurements were performed at 40°C using an Agilent 1260 Infinity II System RI Detector as a detector.

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

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

Preparation Example 2

The four-necked round bottom flask was equipped with a mechanical stirrer and a reflux device, and then the inside of the flask was purged with nitrogen gas. To the flask purged with nitrogen, 235 grams of methyl ethyl ketone (MEK) and 19 grams of methanol (MeOH) were added, and then 1.9 grams of azobisisobutyronitrile (AIBN) was added and allowed to It dissolves completely. 63.5 grams of methacrylic acid was added to it A monomer mixture of (methacrylic acid, MAA), 120.6 g of methyl methacrylate (MMA), and 69.8 g of styrene (SM) as monomers, heated to 80° C., and then polymerized for 6 hours to prepare Alkaline developable binder resin 2 (weight average molecular weight: 37500 g/mol, glass transition temperature: 128°C, solid content: 49% by weight, acid value: 163 mg potassium hydroxide/g).

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

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

The obtained photosensitive resin composition was coated on a 40-micrometer PET film using a coating bar. The applied photosensitive resin composition layer was dried using a hot air oven. At this time, the drying temperature was 80° C., the drying time was 5 minutes, and the thickness of the photosensitive resin composition layer after drying was 40 μm.

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

The PET film is produced by the following process.

PET is prepared by subjecting ethylene glycol and terephthalic acid to a transesterification reaction and a polycondensation reaction. The PET pellets were dried under reduced pressure at 120°C for 8 hours, then fed to an extruder and melted at 280°C. It was cast by electrostatic application casting method It was wound on a casting drum with a surface temperature of 20°C, and cooled and hardened to form an unstretched film. The thickness of the unstretched film was adjusted to 250 microns by adjusting the discharge of the extruder. Next, the unstretched film was stretched 4 times in the longitudinal direction, and finally a coating solution obtained by mixing 4 g of acrylic resin and 0.1 g of polymethyl methacrylate as organic particles in 95.9 g of water was subjected to was dried, and then the resultant was coated on one surface of the unstretched film using gravure to have a thickness of 50 nm. The polymethyl methacrylate used here is a polymethyl methacrylate whose surface is coated with polystyrene, is spherical, and has a refractive index difference of 0.03 with the acrylic resin.

The longitudinally uniaxially stretched film coated with the coating solution containing organic particles was preheated at 120° C. and stretched 4 times in the transverse direction.

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

<Experimental example>

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

1. Fractional value of aromatic ring

Regarding the photosensitive resin compositions prepared in the examples and comparative examples, according to the following Equation 1 below calculates the aromatic ring fraction value.

In Equation 1, with respect to A040 (which is a monofunctional (meth)acrylate compound) and T063 (which is a trifunctional (meth)acrylate compound contained in the photosensitive resin composition), Pc _n is each ( The number of aromatic rings of the meth)acrylate compound, Oc _n is the number of O atoms and S atoms per (meth)acrylate compound, Wrn is the _number of each (meth)acrylate compound relative to the monofunctional ( The weight percent of the total weight of the meth)acrylate compound A040 and the trifunctional (meth)acrylate compound T063, and Mw _n is the weight average molecular weight of the (meth)acrylate compound.

2. Thin wire adhesion (unit: microns)

The protective film was peeled off from the dry film resists prepared in Examples and Comparative Examples, and the photosensitive resin of the dry film resists was laminated using a Bodong MACH 610i to contact a copper clad laminate with a thickness of 1.6 mm under the following conditions The surface of the copper layer subjected to brush abrasion, whereby a laminate was formed: substrate preheating roll temperature 120°C, laminator roll temperature 115°C, roll pressure 4.0 kilogram force per square centimeter (kgf/cm) ³ ) and the roll speed was 2.0 m/min.

The laminate was irradiated with ultraviolet rays at an exposure dose of 16 mJ/cm 2 by FDi-3 (ORC) using a photomask for circuit evaluation, and then allowed to stand for 15 minutes. Then, the resultant was developed with a 1.0 wt % Na ₂ CO ₃ aqueous solution at 30±1° C. for 1 minute under spray-type developing conditions with a spray pressure of 1.5 kgf/cm 2 .

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

3. Resolution (unit: micron)

The protective film was peeled off from the dry film resists prepared in Examples and Comparative Examples, and the photosensitive resin of the dry film resists was laminated using a Bodong MACH 610i to contact a copper clad laminate with a thickness of 1.6 mm under the following conditions The surface of the copper layer subjected to brush abrasion, whereby a laminate was formed: the substrate preheat roll temperature was 120°C, the laminator roll temperature was 115°C, the roll pressure was 4.0 kgf/cm 2 and the roll speed was 2.0 m/min.

The laminate was irradiated with ultraviolet rays at an exposure dose of 16 mJ/cm 2 for 10 seconds by an LDI exposure machine (FDi-3, ORC, Japan), so that the width of the circuit line and the distance between the circuit line after development The space interval was changed to 1:1 and then allowed to stand for 15 minutes. Then, the resultant was developed with a 1.0 wt % Na ₂ CO ₃ aqueous solution at 30±1° C. for 1 minute under spray-type developing conditions with a spray pressure of 1.5 kgf/cm 2 .

4. Evaluation of Plating Contamination Protection Properties

The dry film photoresists prepared in the examples and comparative examples were cut into a size of 40 centimeters (cm) x 50 centimeters, the protective film was removed, and a step tablet was subjected to an exposure dose of 20 steps/41 steps. exposure, and peeled off the PET film to A cured film is obtained. This cured film was immersed in 1 liter of a copper sulfate/sulfuric acid aqueous plating solution for 3 days. The copper plate was subjected to electrolytic copper plating at a current of 2 amps for 10 minutes using a Halcel test bathtub (manufactured by Jungdo Test Instruments Lab., Korea).

When a plating solution in which the cured film was not immersed was used as a reference sample and plating was performed by means of a coating solution in which the cured film was immersed, the appearance of plating was observed with the naked eye, if there was abnormality in the appearance of plating or If there is a change in gloss, it is rated as X, and if it is the same as the reference sample and therefore there is no abnormality at all, it is rated as O.

5. Peeling rate (unit: second)

The protective film was peeled off from the dry film type photoresists prepared in Examples and Comparative Examples, and the photosensitive resin of the dry film type photoresist was laminated to a copper clad laminate with a thickness of 1.6 mm by Bodong MACH 610i under the following conditions The surface of the copper layer subjected to brush abrasion, thereby forming a laminate: substrate preheat roll temperature 120°C, laminator roll temperature 115°C, roll pressure 4.0 kgf/cm² and roll speed is 2.0 m/min.

The laminate was irradiated with ultraviolet rays at an exposure dose of 16 mJ/cm 2 by FDi-3 (ORC) using a photomask for circuit evaluation for 10 seconds, and then allowed to stand for 15 minutes. Then, the supporting PET film for the dry film type photoresist was peeled off and developed with a 1.0 wt % Na ₂ CO ₃ aqueous solution at 30±1° C. under a spray type developing condition with a spray pressure of 1.5 kgf/cm 2 for up to 1 minute.

Then, using a 3% aqueous sodium hydroxide solution (at a temperature of 50°C), stripped. The peel rate was evaluated by measuring the time required for the release of the photocured layer from the copper plate.

As shown in Table 2, it can be confirmed that since the example has an aromatic ring fraction value of -0.015 or more and -0.011 or less than -0.011, it can be confirmed that compared with Comparative Example 1 in which the aromatic ring fraction value is more than -0.011 In other words, they showed similar levels of fine line adhesion and resolution, and at the same time, the examples exhibited remarkably excellent peel rates. In addition, since the example has an aromatic ring fraction value of -0.015 or more and -0.011 or less than -0.011, it shows a remarkably excellent performance compared to Comparative Example 2 whose aromatic ring fraction value is less than -0.015 Excellent fine line adhesion, resolution and plating contamination prevention properties.

Claims (18)

A photosensitive resin layer comprising: a photopolymerizable compound containing a trifunctional or higher polyfunctional (meth)acrylate compound, a monofunctional (meth)acrylate compound and a bifunctional (meth)acrylate compound; and Alkaline developable binder resin; wherein the monofunctional (meth)acrylate compound includes a compound of the following chemical formula 1, wherein the trifunctional or higher polyfunctional (meth)acrylate compound includes a compound of the following chemical formula 2 A compound wherein the aromatic ring fraction value calculated by Equation 1 below is -0.015 or greater and -0.011 or less:

In Equation 1, Pc _n is the number of aromatic rings per (meth)acrylate compound, Oc _n is the number of O atoms and S atoms in each (meth)acrylate compound, wherein Oc _n Excluding the number of "O" contained in each (meth)acrylate, Wr _n is the number of each (meth)acrylate compound relative to each (meth)acrylate compound weight percent of the total weight, and Mw _n is the weight average molecular weight of each (meth)acrylate compound described,

In Chemical Formula 1, R ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₂ is an alkylene group having 1 to 10 carbon atoms, R ₃ is an alkyl group having 1 to 10 carbon atoms, and n1 is an integer from 1 to 20,

In Chemical Formula 2, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₅ is an alkylene group having 1 to 10 carbon atoms, and R ₆ is a central group containing 1 to 20 carbon atoms of p-valent functional groups, n2 is an integer of 1 to 20, and p is the number of functional groups that replace the R6, 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 has wherein three or more alkylene oxide groups having 1 to 10 carbon atoms and trifunctional One or more (meth)acrylate functional groups are bonded to the structure having a central group of 1 to 20 carbon atoms. The photosensitive resin layer of claim 1, wherein the trifunctional or higher polyfunctional (meth)acrylate compound includes a compound of the following 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 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, and n3 to n5 are each independently an integer of 1 to 3. The photosensitive resin layer of claim 1, wherein the photopolymerizable compound contains 100 parts by weight or more of the trifunctional based on 100 parts by weight of the monofunctional (meth)acrylate compound or higher polyfunctional (meth)acrylate compounds. The photosensitive resin layer according to claim 1, wherein the monofunctional (meth)acrylate compound contains a (meth)acrylate containing an epoxy resin having 1 to 10 carbon atoms alkyl. The photosensitive resin layer according to claim 1, wherein the photopolymerizable compound comprises: the monofunctional (meth)acrylate compound containing (meth)acrylate, the (meth)acrylate containing an alkylene oxide having 1 to 10 carbon atoms; and the trifunctional or higher polyfunctional (meth)acrylate compound having three or more alkylene oxides having 1 to 10 carbon atoms therein and structures in which three or more (meth)acrylate functional groups are bonded to a central group having 1 to 20 carbon atoms. The photosensitive resin layer of claim 1, wherein the alkali-developable binder resin has an amount of 20,000 g/mol or more and 150,000 g/mol or less than 150,000 g/mol Weight average molecular weight. The photosensitive resin layer according to claim 1, wherein in Equation 1, Oc 1 of the monofunctional (meth)acrylate compound and Oc ₁ of the trifunctional or higher polyfunctional (meth)acrylate compound The ratio between Oc ₂ is 1:0.3 or more and 1:0.9 or less than 1:0.9. The photosensitive resin layer according to claim 1, wherein in Equation 1, the Mw 1 of the monofunctional (meth)acrylate compound and the trifunctional or higher polyfunctional (meth)acrylate compound Mw ₁ The ratio between Mw ₂ is 1:1.1 or more and 1:1.9 or less than 1:1.9. The photosensitive resin layer according to claim 1, wherein the trifunctional or higher polyfunctional (meth)acrylate compound is 110 parts by weight based on 100 parts by weight of the monofunctional (meth)acrylate compound part or more and an amount of 500 parts by weight or less than 500 parts by weight is contained. The photosensitive resin layer according to claim 1, wherein the difunctional (meth)acrylate compound is 500 parts by weight or more based on 100 parts by weight of the monofunctional (meth)acrylate compound And it is contained in an amount of 1500 parts by weight or less. The photosensitive resin layer according to claim 1, wherein the difunctional (meth)acrylate compound is 500 parts by weight based on 100 parts by weight of the trifunctional or higher polyfunctional (meth)acrylate compound part or more and an amount of 1000 parts by weight or less than 1000 parts by weight is contained. The photosensitive resin layer of claim 1, wherein the alkali-developable binder resin comprises a first alkali-developable binder resin including a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4 , a repeating unit represented by the following Chemical Formula 5, a repeating unit represented by the following Chemical Formula 6, and a repeating unit represented by the following Chemical Formula 7; and a second alkaline developable binder resin, including the following Chemical formula 4 The repeating unit represented by The repeating unit represented by the following Chemical Formula 5 and the repeating unit represented by the following Chemical Formula 6:

In Chemical Formula 3, R ₃ " is hydrogen,

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

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

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 than 500 parts by weight part and an amount of 1000 parts by weight or less is contained. The photosensitive resin layer of claim 13, wherein the ratio of the glass transition temperature of the first alkali-developable binder resin to the glass transition temperature of the second alkali-developable binder resin is 1:1.5 or Greater than 1:1.5 and 1:5 or less than 1:5. The photosensitive resin layer of claim 13, wherein the ratio of the acid value of the first alkali-developable binder resin to the acid value of the second alkali-developable binder resin is 1:1.01 or more than 1 : 1.01 and 1:1.5 or less than 1:1.5. A dry film type light comprising the photosensitive resin layer as claimed in claim 1 resistance. A photosensitive element, comprising: a polymer substrate; and the photosensitive resin layer according to claim 1, formed on the polymer substrate.