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

Abstract

The present disclosure relates to a photosensitive resin layer including a photopolymerizable compound including a tri- or higher functional polyfunctional (meth)acrylate compound; and a base-developable binder resin, and having an aromatic ring fraction value of -0.015 or more and -0.011 or less, a dry film photoresist using the same, and a photosensitive element.

Description

TECHNICAL FIELD

[0001] This application claims the benefit of Korean Patent Application No. 10-2019-0179944, filed December 31, 2019, and Korean Patent Application No. 10-2020-0095386, filed July 30, 2020, in the Korean Intellectual Property Office, which are incorporated by reference herein in their entirety.

[0002] The present disclosure relates to a photosensitive resin layer and a dry film photoresist and a photosensitive element using the same. BACKGROUND

[0003] The photosensitive resin composition is used in the form of a dry film photoresist (DFR), a liquid photoresist ink, etc. (which are used for a printed circuit board (PCB) or a lead frame).

[0004] At present, the dry film photoresist is widely used not only for the manufacture of a printed circuit board (PCB) and a lead frame, but also for the manufacture of a barrier rib of a plasma display panel (PDP), an ITO electrode of other displays, a bus address electrode, a black matrix, etc.

[0005] Generally, this type of dry film photoresist is often used for lamination on a copper-clad laminate. In this regard, as one example of a manufacturing process of a printed circuit board (PCB), a pre-treatment process is first performed in order to laminate a copper-clad laminate as an initial board material of the PCB. The pre-treatment process is performed in the order of drilling, deburring, and surface finishing, etc. in an outer layer process, and surface finishing or pickling is performed in an inner layer process. In the surface finishing, a bristle brush and a jet pumice process are mainly used, and the pickling can be performed through soft etching and 5 wt% sulfuric acid pickling.

[0006] In order to form a circuit on the copper-clad laminate which has undergone the pre-treatment process, a dry film photoresist (hereinafter referred to as DFR) is generally laminated on a copper layer of the copper-clad laminate. In this process, a laminator is used to laminate a photoresist layer of the DFR on a copper surface while peeling a protective film of the DFR. Generally, the lamination is performed at a speed of 0.5 m / min to 3.5 m / min, a temperature of 100°C to 130°C, and a heating roll pressure of 10 psi to 90 psi.

[0007] The printed circuit board subjected to the lamination process is left for 15 minutes or more to stabilize the circuit board, and then the photoresist of the DFR on which the desired circuit pattern is formed is exposed through a photomask. When the photomask is irradiated with ultraviolet rays in this process, the photoresist irradiated with ultraviolet rays starts to polymerize through the photoinitiator contained in the irradiated portion. First, the oxygen in the photoresist is consumed first, and then the activated monomer polymerizes to cause a crosslinking reaction. Thereafter, the polymerization reaction continues while a large amount of monomer is consumed. At the same time, the unexposed portion exists in a state in which the crosslinking reaction is not performed.

[0008] Next, a developing process of removing the unexposed portion of the photoresist is performed. In the case of the DFR which is alkali-developable, an aqueous solution of 0.8 to 1.2 wt% of potassium carbonate and sodium carbonate is used as a developing solution. In this process, the photoresist in the unexposed portion is washed away through a saponification reaction between the carboxylic acid of the binder polymer and the developing solution in the developing solution, and the cured photoresist remains on the copper surface.

[0009] Next, according to the inner layer process and the outer layer process, the circuit is formed through different processes. However, in the inner layer process, the circuit is formed on the circuit board through an etching and stripping process, and in the outer layer process, a plating and tenting process are performed, and then etching and solder stripping are performed to form a predetermined circuit.

[0010] Recently, in a photosensitive resin composition, there is a need to develop a photosensitive resin composition which has high sensitivity to an ultrahigh pressure mercury lamp or a laser direct exposure, increases resistance to a developing solution, thereby being able to form a high-density circuit in a developing process, has an excellent color development degree, can be used as a UV mark for setting a substrate exposure position, and shortens a stripping time of a cured film, has a small stripping sample, and thus does not clog a filter. SUMMARY

[0011] TECHNICAL PROBLEM

[0012] An object of the present disclosure is to provide a photosensitive resin layer which can achieve excellent fine line adhesion and resolution, and improve the alignment recognition rate of a product in an exposure process, thereby shortening the production time of a final product, reducing the defect rate, and thus improving reliability.

[0013] Another object of the present disclosure is to provide a dry film photoresist and a photosensitive element including the photosensitive resin layer.

[0014] TECHNICAL SOLUTION

[0015] To achieve the above object, the present specification provides a photosensitive resin layer including: a photopolymerizable compound including a tri- or higher functional polyfunctional (meth)acrylate compound; and a base-developable adhesive resin;

[0016] wherein an aromatic ring fraction value calculated from Equation 1 below is -0.015 or more and -0.011 or less.

[0017] [Equation 1]

[0018]

[0019] In Equation 1,

[0020] Pc n is the number of aromatic rings of each (meth)acrylate compound,

[0021] Oc n is the number of O atoms and S atoms in each (meth)acrylate compound,

[0022] Wr n is the weight percentage of each (meth)acrylate compound with respect to the total weight of the (meth)acrylate compound, and

[0023] Mw n is the weight average molecular weight of the (meth)acrylate compound.

[0024] In the present disclosure, the tri- or higher functional polyfunctional (meth)acrylate compound can have a structure in which three or more alkyleneoxy groups 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.

[0025] The tri- or higher functional polyfunctional (meth)acrylate compound can include a compound of Chemical Formula 2.

[0026] The tri- or higher functional polyfunctional (meth)acrylate compound can include a compound of Chemical Formula 2-1. The compound of Chemical Formula 2-1 is described below.

[0027] The photopolymerizable compound can further include a mono-functional (meth)acrylate compound.

[0028] The photopolymerizable compound can include 100 parts by weight or more of the polyfunctional (meth)acrylate compound based on 100 parts by weight of the mono-functional (meth)acrylate compound.

[0029] The monofunctional (meth)acrylate compound can include a (meth)acrylate including an alkyleneoxy group having 1 to 10 carbon atoms.

[0030] The monofunctional (meth)acrylate compound can include a compound of Chemical Formula 1.

[0031] The photopolymerizable compound can include a monofunctional (meth)acrylate compound including a (meth)acrylate including an alkyleneoxy group having 1 to 10 carbon atoms, and a trifunctional or higher functional polyfunctional (meth)acrylate compound having a structure in which three or more alkyleneoxy groups 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.

[0032] The weight average molecular weight of the alkali-developable adhesive resin can be 20,000 g / mol or more and 150,000 g / mol or less.

[0033] In Equation 1, the ratio between Oc1 of the monofunctional (meth)acrylate compound and Oc2 of the polyfunctional (meth)acrylate compound can be 1:0.3 or more and 1:0.9 or less.

[0034] In Equation 1, the ratio between Mw1 of the monofunctional (meth)acrylate compound and Mw2 of the polyfunctional (meth)acrylate compound can be 1:1.1 or more and 1:1.9 or less.

[0035] The content of the polyfunctional (meth)acrylate compound can be 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.

[0036] The photopolymerizable compound can further include a difunctional (meth)acrylate compound.

[0037] The content of the difunctional (meth)acrylate compound can be 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.

[0038] The content of the difunctional (meth)acrylate compound can be 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.

[0039] The alkali-developable adhesive resin can include a first alkali-developable adhesive 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, and a repeating unit represented by Chemical Formula 7, and a second alkali-developable adhesive resin including a repeating unit represented by Chemical Formula 4, a repeating unit represented by Chemical Formula 5, and a repeating unit represented by Chemical Formula 6. Chemical Formulas 3 to 7 are described below.

[0040] The content of the second alkali-developable adhesive resin can be 500 parts by weight or more and 1000 parts by weight or less, based on 100 parts by weight of the first alkali-developable adhesive resin.

[0041] The ratio of the glass transition temperatures of the first alkali-developable adhesive resin and the second alkali-developable adhesive resin can be 1:1.5 or more and 1:5 or less.

[0042] The ratio of the acid values of the first alkali-developable adhesive resin and the second alkali-developable adhesive resin can be 1:1.01 or more and 1:1.5 or less.

[0043] The present specification also provides a dry film photoresist including the photosensitive resin layer.

[0044] The present specification also provides a photosensitive element including the photosensitive resin layer.

[0045] Hereinafter, the photosensitive resin layer according to the specific embodiments of the present disclosure and the dry film photoresist, the photosensitive element using the same will be described in more detail.

[0046] The technical terms used in the present specification are used only to refer to specific embodiments, and are not intended to limit the present disclosure, unless otherwise specified throughout the specification.

[0047] The singular forms "1", "one", and "the" used in the present specification include plural referents unless the context clearly dictates otherwise.

[0048] The term "include" or "comprise" used in the present specification designates a specific feature, region, integer, step, operation, element, and / or component, but does not exclude the presence or addition of different specific features, regions, integers, steps, operations, elements, components, and / or groups.

[0049] In addition, the terms including ordinal numbers such as "first", "second", etc. are used only for the purpose of distinguishing one component from another component, and are not limited to the ordinal numbers. For example, without departing from the scope of the present disclosure, the first component can be referred to as the second component, or similarly, the second component can be referred to as the first component.

[0050] In the present specification, examples of the substituent are as described below, but are not limited thereto.

[0051] In the present specification, the term "substituted" means that a hydrogen atom in the substituent is bonded to another functional group, and there is no limitation on the position to be substituted, as long as the position is a position where a hydrogen atom is substituted, i.e., a position which can be substituted by a substituent, and when two or more are substituted, the two or more substituents can be the same as or different from each other.

[0052] In the present specification, the term "substituted or unsubstituted" means substituted or unsubstituted by one or more substituents selected from deuterium; a halogen group; a cyano group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amide group; a primary amino group; a carboxyl group; a sulfonic acid group; a sulfonamide group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an alkoxy silyl alkyl group; an aryl phosphine group; or a heterocyclic group containing at least one of N, O and S atoms, or the term "substituted or unsubstituted" means substituted or unsubstituted by a substituent having two or more substituents exemplified above bonded thereto. For example, the "substituent having two or more substituents bonded thereto" can be a biphenyl group. That is, the biphenyl group can also be an aryl group, and can be understood as a substituent having two phenyl groups bonded thereto.

[0053] In the present specification, the symbol or means a bond to another substituent, and a direct bond means that there is no other atom in the moiety represented by L.

[0054] In the present specification, the (meth)acryloyl group is intended to include both an acryloyl group and a methacryloyl group. For example, the (meth)acrylate is intended to include both an acrylate and a methacrylate.

[0055] In this specification, alkyl groups are monovalent functional groups derived from alkanes and can be straight-chain or branched. There is no particular limitation on the number of carbon atoms in straight-chain alkyl groups, but 1 to 20 is preferred. Furthermore, branched alkyl groups have 3 to 20 carbon atoms. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptane-4-yl, etc. Alkyl groups may be substituted or unsubstituted, and when substituted, the examples of substituents are the same as described above.

[0056] In this specification, aryl is a monovalent functional group derived from aromatic hydrocarbons and is not particularly limited, but preferably has 6 to 20 carbon atoms, and can be monocyclic or polycyclic aryl. Specific examples of monocyclic aryl groups include phenyl, biphenyl, terphenyl, etc., but are not limited thereto. Specific examples of polycyclic aryl groups include naphthyl, anthraceneyl, phenanthryl, pyrene, perylene, etc. Aryl, fluorene, etc., but not limited to these. The aryl group can be substituted or unsubstituted, and when it is substituted, the examples of substituents are the same as described above.

[0057] In this specification, alkylene is a divalent functional group derived from an alkane, and the description of alkyl as defined above can be applied in addition to the fact that alkylene is a divalent functional group. For example, it can be straight-chain or branched, such as methylene, ethylene, propylene, isobutylene, sec-butylene, tert-butylene, pentylene, hexylene, etc. Alkylene can be substituted or unsubstituted.

[0058] In this specification, a multivalent functional group is a residue to which multiple hydrogen atoms have been removed from the bond of any compound; for example, it can be a divalent, trivalent, or tetravalent functional group. As an example, a tetravalent functional group from cyclobutane refers to a residue to which any four hydrogen atoms have been removed from the bond of cyclobutane.

[0059] In this specification, a direct bond or single bond refers to a bond line in which no atom or group of atoms exists at the corresponding position. Specifically, a direct bond or single bond refers to a bond formed by R in a chemical formula. a or L bin the case where no other atoms are present in the moiety represented by (where a and b are each an integer of 1 to 20).

[0060] In the present specification, the term "(photo)cured product" or "(photo) cured" is intended to include not only the case where a component having a curable or crosslinkable unsaturated group in a chemical structure is completely cured, crosslinked, or polymerized, but also the case where such a component is partially cured, crosslinked, or polymerized.

[0061] Hereinafter, the present disclosure will be described in more detail.

[0062] 1. Photosensitive resin composition

[0063] According to one embodiment of the present disclosure, a photosensitive resin layer can be provided, comprising: a photopolymerizable compound including a tri- or higher functional polyfunctional (meth)acrylate compound; and a base-developable adhesive resin;

[0064] wherein the aromatic ring fraction value calculated from the following Equation 1 is -0.015 or more and -0.011 or less.

[0065] [Equation 1]

[0066]

[0067] In Equation 1,

[0068] Pc n is the number of aromatic rings of each (meth)acrylate compound,

[0069] Oc n is the number of O atoms and S atoms in each (meth)acrylate compound,

[0070] Wr n is the weight percentage of each (meth)acrylate compound with respect to the total weight of the (meth)acrylate compound,

[0071] Mw n is the weight average molecular weight of the (meth)acrylate compound.

[0072] The present inventors have found through experiments that, since the aromatic ring fraction value calculated from Equation 1 of the photosensitive resin layer of one embodiment is -0.015 or more and -0.011 or less, it is possible to ensure technical effects of having excellent developing performance and peeling performance while maintaining good resolution and adhesion.

[0073] (1). Base-developable adhesive resin

[0074] The photosensitive resin layer of the present disclosure can include a base-developable adhesive resin.

[0075] Specifically, the alkali-developable adhesive resin can include at least two or more alkali-developable adhesive resins. The at least two or more alkali-developable adhesive resins can refer to a mixture of two or more alkali-developable adhesive resins.

[0076] The at least two or more alkali-developable adhesive resins can include: a first alkali-developable adhesive resin including a repeating unit represented by Chemical Formula 3 below, a repeating unit represented by Chemical Formula 4 below, a repeating unit represented by Chemical Formula 5 below, a repeating unit represented by Chemical Formula 6 below, and a repeating unit represented by Chemical Formula 7 below; and a second alkali-developable adhesive resin including a repeating unit represented by Chemical Formula 4 below, a repeating unit represented by Chemical Formula 5 below, and a repeating unit represented by Chemical Formula 6 below.

[0077] Specifically, the alkali-developable adhesive resin can include a random copolymer of a repeating unit represented by Chemical Formula 3 below, a repeating unit represented by Chemical Formula 4 below, a repeating unit represented by Chemical Formula 5 below, a repeating unit represented by Chemical Formula 6 below, and a repeating unit represented by Chemical Formula 7 below.

[0078] [Chemical Formula 3]

[0079]

[0080] In Chemical Formula 3, R3” is hydrogen,

[0081] [Chemical Formula 4]

[0082]

[0083] In Chemical Formula 4, R3’ is an alkyl group having 1 to 10 carbon atoms,

[0084] [Chemical Formula 5]

[0085]

[0086] In Chemical Formula 5, R4” is an alkyl group having 1 to 10 carbon atoms, and R5” is an alkyl group having 1 to 10 carbon atoms,

[0087] [Chemical Formula 6]

[0088]

[0089] In Chemical Formula 6, Ar is an aryl group having 6 to 20 carbon atoms,

[0090] [Chemical Formula 7]

[0091]

[0092] In Chemical Formula 7, R4' is hydrogen, and R5' is an alkyl group having 1 to 10 carbon atoms.

[0093] In Chemical Formula 3 to Chemical Formula 7, a specific example of the alkyl group having 1 to 10 carbon atoms can include a methyl group.

[0094] Ar is an aryl group having 6 to 20 carbon atoms, and a specific example of the aryl group having 6 to 20 carbon atoms can include a phenyl group.

[0095] The repeating unit represented by Chemical Formula 4 can be a repeating unit from a monomer represented by the following Chemical Formula 4-1.

[0096] [Chemical Formula 4-1]

[0097]

[0098] In Chemical Formula 4-1, R3' is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 4-1, the definition of R3' is the same as described above in Chemical Formula 4. A specific example of the monomer represented by Chemical Formula 4-1 can include methacrylic acid (MAA).

[0099] The repeating unit represented by Chemical Formula 5 can be a repeating unit from a monomer represented by the following Chemical Formula 5-1.

[0100] [Chemical Formula 5-1]

[0101]

[0102] In Chemical Formula 5-1, R4" is an alkyl group having 1 to 10 carbon atoms, and R5" is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 5-1, the definitions of R4" and R5" are the same as described above in Chemical Formula 5. A specific example of the monomer represented by Chemical Formula 5-1 can include methyl methacrylate (MMA).

[0103] The repeating unit represented by Chemical Formula 6 can be a repeating unit from a monomer represented by the following Chemical Formula 6-1.

[0104] [Chemical Formula 6-1]

[0105]

[0106] 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 described above in Chemical Formula 6. A specific example of the monomer represented by Chemical Formula 6-1 can include styrene (SM).

[0107] The weight average molecular weight of the first alkali-developable binder resin and the second alkali-developable binder resin can be 30,000 g / mol or more and 150,000 g / mol or less, and the glass transition temperature can be 20°C or more and 150°C or less. Thereby, the coating properties and flowability of the dry film photoresist, and the mechanical strength of the resist itself after circuit formation can be improved. In front or rear, the weight average molecular weight is measured using Waters 450 GPC, in which polystyrene is used as a standard, and the chromatographic column is Shodex 105, 104, 103. The glass transition temperature is measured using Perkin Elmer DSC 7.

[0108] The acid value of the first alkali-developable binder resin can be 140 mg KOH / g or more and 160 mg KOH / g or less. Further, the acid value of the second alkali-developable binder resin can be 160 mg KOH / g or more and 200 mg KOH / g or less.

[0109] Specifically, the ratio of the glass transition temperature of the first alkali-developable binder resin to the second alkali-developable binder resin can be 1:1.5 or more and 1:5 or less, 1:1.5 or more and 1:3 or less, 1:1.5 or more and 1:2 or less, 1:1.5 or more and 1:1.8 or less, 1:1.5 or more and 1:75 or less, or 1:1.6 or more and 1:7 or less.

[0110] Further, the ratio of the acid value of the first alkali-developable binder resin to the second alkali-developable binder resin can be 1:1.01 or more and 1:1.5 or less, 1:1.1 or more and 1:1.5 or less, 1:1.25 or more and 1:1.5 or less, or 1:1.4 or more and 1:1.5 or less.

[0111] Meanwhile, the first alkali-developable binder resin included in the photosensitive resin composition of one embodiment can include 1.2 moles or more and 3 moles or less, 1.2 moles or more and 2 moles or less, 1.5 moles or more and 2 moles or less, or 1.5 moles or more and 1.6 moles or less of the repeating unit represented by Chemical Formula 4, based on 1 mole of the repeating unit represented by Chemical Formula 3.

[0112] Further, the second alkali-developable binder resin included in the photosensitive resin composition of one embodiment can include 2 moles or more and 10 moles or less, 3 moles or more and 10 moles or less, 3 moles or more and 5 moles or less, or 4 moles or more and 5 moles or less of the repeating unit represented by Chemical Formula 5, based on 1 mole of the repeating unit represented by Chemical Formula 7.

[0113] Meanwhile, the second alkali-developable binder resin can include a random copolymer of 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.

[0114] [Chemical Formula 4]

[0115]

[0116] In Chemical Formula 4, R3' is an alkyl group having 1 to 10 carbon atoms.

[0117] [Chemical Formula 5]

[0118]

[0119] In Chemical Formula 5, R4" is an alkyl group having 1 to 10 carbon atoms, and R5" is an alkyl group having 1 to 10 carbon atoms,

[0120] [Chemical Formula 6]

[0121]

[0122] In Chemical Formula 6, Ar is an aryl group having 6 to 20 carbon atoms.

[0123] The repeating unit represented by Chemical Formula 4 can be a repeating unit from a monomer represented by Chemical Formula 4-1 below.

[0124] [Chemical Formula 4-1]

[0125]

[0126] In Chemical Formula 4-1, R3' is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 4-1, the definition of R3' is the same as described for Chemical Formula 4. Specific examples of the monomer represented by Chemical Formula 4-1 can include methacrylic acid (MAA).

[0127] The repeating unit represented by Chemical Formula 5 can be a repeating unit from a monomer represented by Chemical Formula 5-1 below.

[0128] [Chemical Formula 5-1]

[0129]

[0130] In Chemical Formula 5-1, R4" is an alkyl group having 1 to 10 carbon atoms, and R5" is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 5-1, the definitions of R4" and R5" are the same as described for Chemical Formula 5. Specific examples of the monomer represented by Chemical Formula 5-1 can include methyl methacrylate (MMA).

[0131] The repeating unit represented by Chemical Formula 6 can be a repeating unit from a monomer represented by Chemical Formula 6-1 below.

[0132] [Chemical Formula 6-1]

[0133]

[0134] 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 described for Chemical Formula 6. Specific examples of the monomer represented by Chemical Formula 6-1 can include styrene (SM).

[0135] Specifically, the first alkali-developable binder resin can include the repeating unit represented by Chemical Formula 4: the repeating unit represented by Chemical Formula 5: the repeating unit represented by Chemical Formula 6 in a ratio of 1: (2 or more and 5 or less): (0.2 or more and 0.9 or less), 1: (2 or more and 3 or less): (0.5 or more and 0.9 or less), 1: (2.5 or more and 3 or less): (0.6 or more and 0.9 or less), or 1: (2.75 or more and 3 or less): (0.6 or more and 0.75 or less).

[0136] In addition, the second alkali-developable binder resin can include the repeating unit represented by Chemical Formula 4: the repeating unit represented by Chemical Formula 5: the repeating unit represented by Chemical Formula 6 in a ratio of 1: (1.1 or more and 2 or less): (0.2 or more and 0.99 or less), 1: (1.5 or more and 2 or less): (0.5 or more and 0.99 or less), or 1: (1.5 or more and 1.75 or less): (0.75 or more and 0.99 or less).

[0137] Meanwhile, based on 100 parts by weight of the first alkali-developable binder resin, the photosensitive resin composition of one embodiment of the present disclosure can include 500 parts by weight or more and 1000 parts by weight or less, 600 parts by weight or more and 800 parts by weight or less, 700 parts by weight or more and 800 parts by weight or less of the second alkali-developable binder resin.

[0138] As used herein, the weight average molecular weight refers to a polystyrene-conversion weight average molecular weight measured by gel permeation chromatography (GPC). In the process of measuring the polystyrene-conversion weight average molecular weight by GPC, a detector and an analysis column such as a well-known analysis device and a differential refractive index detector can be used, and temperature conditions, a solvent, and a flow rate commonly applied can be used.

[0139] Specific examples of the measurement conditions are as follows: The alkali-developable binder resin, which was dissolved in tetrahydrofuran so that the concentration in THF was 1.0 (w / w) % (about 0.5 (w / w) % based on the solid content), was filtered using a syringe filter with a pore size of 0.45 μm, and then injected into the GPC in an amount of 20 μl, using tetrahydrofuran (THF) as the mobile phase of the GPC, and the flow rate was 1.0 mL / min. The column configuration was one Agilent PLgel 5 μm Guard (7.5 x 50 mm) and two Agilent PLgel 5 μm Mixed D (7.5 x 300 mm) connected in series, and the measurement was performed at 40°C using an Agilent 1260 Infinity II system, an RI detector as the detector.

[0140] Polystyrene standard samples (STD A, B, C, D) having various molecular weights of polystyrene dissolved in tetrahydrofuran at a concentration of 0.1 (w / w) % were filtered through a syringe filter with a pore size of 0.45 μm, and then injected into the GPC, and the weight average molecular weight (Mw) value of the alkali-developable binder resin was determined using a calibration curve.

[0141] STD A (Mp): 791,000 / 27,810 / 945

[0142] STD B (Mp): 282,000 / 10,700 / 580

[0143] STD C (Mp): 126,000 / 4,430 / 370

[0144] STD D (Mp): 51,200 / 1,920 / 162

[0145] The glass transition temperature of the reference and the binder polymer was compared by DSC (differential scanning calorimeter) (Perkin-Elmer, DSC-7). The measurement can be performed by keeping the temperature at 20°C for 15 minutes, and then increasing the temperature to 200°C at a rate of 1°C / min.

[0146] The acid value of the alkali-developable binder resin was measured by the following method: About 1 g of the alkali-developable binder resin was taken, dissolved in 50 ml of a mixed solvent (20% MeOH, 80% acetone), two drops of 1% phenolphthalein indicator were added thereto, and then titrated with 0.1 N-KOH to measure the acid value.

[0147] The content of the alkali-developable adhesive resin is 20% by weight or more and 80% by weight or less, based on the solid content, relative to the total weight of the photosensitive resin composition. When the content of the alkali-developable adhesive resin is within the above range, an effect of enhancing fine line adhesion after circuit formation can be obtained. The solid content as a weight basis refers to the remaining components excluding the solvent from the photosensitive resin composition.

[0148] The content of the alkali-developable adhesive resin of the present disclosure can be 40% by weight or more and 70% by weight or less, relative to the total weight of the photosensitive resin composition for forming a photosensitive resin layer. When the content of the alkali-developable adhesive resin is less than 40% by weight relative to the total photosensitive resin composition, there is a disadvantage that defects such as short circuiting due to contamination in development occur, and when the content of the alkali-developable adhesive resin exceeds 70% by weight, there is a problem that circuit performance such as adhesion and resolution deteriorate.

[0149] (2) Photopolymerization initiator

[0150] The photopolymerization initiator included in the photosensitive resin layer according to the present disclosure is a substance that initiates chain reaction of a photopolymerizable monomer by ultraviolet rays and other rays, and plays an important role in curing a dry film photoresist.

[0151] The compound that can be used as the photopolymerization initiator can include anthraquinone derivatives such as 2-methylanthraquinone and 2-ethylanthraquinone, and benzoin derivatives such as benzoin methyl ether, benzophenone, phenanthraquinone, and 4,4'-bis-(dimethylamino)benzophenone.

[0152] In addition, a compound selected from the group consisting of 2,2'-bis(2- chlorophenyl)-4,4',5,5'-tetraphenyl-2H-benzotriazole, 2,2-dimethoxy-1,2- diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-[4-morpholinophenyl]-1-butanone, 2-hydroxy-2- methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1- [4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 3,3-dimethyl-4- methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone, 1-(4- isopropylphenyl)-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-dodecylphenyl)-2- hydroxy-2-methyl-1-propan-1-one, 4-benzoyl-4'-methyl-1,3-dioxane, 4- dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl ester, 4- dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid butyl ester, 4- dimethylaminobenzoic acid 2-ethylhexyl ester, 4-dimethylaminobenzoic acid 2- isopentyl ester, 2,2-diethoxyacetophenone, benzyl ketone dimethyl acetal, benzyl ketone β-methoxy diethyl acetal, 1-phenyl-1,2-propyldioxime-o,o'-(2- carbonyl)ethoxy ether, methyl o-benzoylbenzoate, bis[4-dimethylaminophenyl) ketone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, isobutoxybenzoin, t-butoxybenzoin, p-dimethylaminobenzophenone, p-t-butyltrichloroacetophenone, p-t- butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2- isopropylthioxanthone, dibenzosuberone, α,α-dichloro-4-phenoxyacetophenone, and 4-dimethylaminobenzoic acid pentyl ester can be used as the photopolymerization initiator, but are not limited thereto.

[0153] The content of the photopolymerization initiator is 0.1% by weight or more and 10% by weight or less, based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer, with respect to the solid content. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity can be obtained. The solid content as a weight basis refers to the remaining components excluding the solvent from the photosensitive resin composition.

[0154] 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 used, thus, there is a disadvantage that the production efficiency is extremely reduced. When the content of the photopolymerization initiator exceeds 10% by weight, there is a problem that the film becomes brittle and the contamination of the developer increases, resulting in defects such as short circuit.

[0155] (3) Photopolymerizable compound

[0156] The photopolymerizable compound of the present disclosure has resistance to a developer after UV exposure and thus is capable of forming a pattern.

[0157] The photopolymerizable compound of the present disclosure can include a tri- or higher functional multifunctional (meth)acrylate compound.

[0158] Specifically, the tri- or higher functional multifunctional (meth)acrylate compound can have a structure in which three or more alkyleneoxy groups 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.

[0159] More specifically, the tri- or higher functional multifunctional (meth)acrylate compound can include a compound of the following Chemical Formula 2.

[0160] [Chemical Formula 2]

[0161]

[0162] In Chemical Formula 2, R4 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R5 is an alkylene group having 1 to 10 carbon atoms, R6 is a p-valent functional group including a central group having 1 to 20 carbon atoms, n2 is an integer of 1 to 20, p is the number of functional groups substituting R6, and is an integer of 3 to 10.

[0163] 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 refers to the number of functional groups substituting R6, and can be an integer of 3 to 10, an integer of 3 to 5, or an integer of 3 to 4.

[0164] That is, in Chemical Formula 2, since p, which represents the number of functional groups substituted for R6, is an integer of 3 to 10, the tri- or higher functional polyfunctional (meth)acrylate compound represented by Chemical Formula 2 can be a tri- or higher functional polyfunctional (meth)acrylate compound.

[0165] Specifically, the polyfunctional (meth)acrylate compound can be represented by the following Chemical Formula 2-1.

[0166] [Chemical Formula 2-1]

[0167]

[0168] In Chemical Formula 2-1, R6' is a trivalent functional group having 1 to 10 carbon atoms, R7 to R9 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, n3 to n5 are each independently an integer of 1 to 20.

[0169] In Chemical Formula 2-1, n3 to n5 can be an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to 5.

[0170] Examples of the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 are not particularly limited, but can be, for example, T063 (trimethylolpropane [EO]6 triacrylate) represented by the following Chemical Formula B.

[0171] [Chemical Formula B]

[0172]

[0173] 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 has more reactive groups and increased crosslinking during photocuring, compared to a monofunctional (meth)acrylate compound. For these technical reasons, a decrease in circuit performance that can be problematic 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 change can be achieved.

[0174] Meanwhile, the photopolymerizable compound can further include a monofunctional (meth)acrylate compound.

[0175] Specifically, the monofunctional (meth)acrylate compound can include a (meth)acrylate including an alkylene oxy group having 1 to 10 carbon atoms.

[0176] That is, the photopolymerizable compound can include a monofunctional (meth)acrylate compound including a (meth)acrylate including an alkyleneoxy group having 1 to 10 carbon atoms; and a trifunctional or higher functional multifunctional (meth)acrylate compound having a structure in which three or more alkyleneoxy groups 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.

[0177] More specifically, the monofunctional (meth)acrylate compound can include a monofunctional (meth)acrylate compound represented by the following Chemical Formula 1.

[0178] [Chemical Formula 1]

[0179]

[0180] In Chemical Formula 1, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R2 is an alkylene group having 1 to 10 carbon atoms, R3 is an alkyl group having 1 to 10 carbon atoms, and n1 is an integer of 1 to 20.

[0181] That is, the photosensitive resin layer according to one embodiment of the disclosure can include a mixture of a monofunctional (meth)acrylate compound and a multifunctional (meth)acrylate compound.

[0182] Meanwhile, the photosensitive resin for forming the photosensitive resin layer of one embodiment can include 110 parts by weight or more 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 or less, or 150 parts by weight or more and 200 parts by weight or less of the multifunctional (meth)acrylate compound, based on 100 parts by weight of the monofunctional (meth)acrylate compound.

[0183] Since the photosensitive resin layer of one embodiment includes the multifunctional (meth)acrylate compound in excess with respect to the monofunctional (meth)acrylate compound, it is possible to simultaneously achieve the effect of shortening the peeling time of the monofunctional (meth)acrylate compound represented by Chemical Formula 1 and the effect of improving the resistance to a developer of the multifunctional (meth)acrylate compound represented by Chemical Formula 2, thereby improving the adhesion and the resolution, thereby satisfying the aromatic ring fraction value calculated from Equation 1 of -0.015 or more and -0.011 or less, and finally ensuring excellent development performance.

[0184] When the photosensitive resin layer of one embodiment includes less than 100 parts by weight of the multifunctional (meth)acrylate compound, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the resistance to a developer is weakened, which can cause a technical problem in achieving good adhesion and resolution.

[0185] Meanwhile, the photopolymerizable compound can include a difunctional (meth)acrylate compound including an alkylene glycol-based di(meth)acrylate and a urethane-based di(meth)acrylate.

[0186] That is, the photosensitive resin layer of one embodiment includes a photopolymerizable compound, which can include a monofunctional (meth)acrylate compound; a polyfunctional (meth)acrylate compound; and a difunctional (meth)acrylate compound including an alkylene glycol-based di(meth)acrylate and a urethane-based di(meth)acrylate.

[0187] The alkylene glycol-based di(meth)acrylate can include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate; commercially available products such as Miramer M244 (BPA(EO)3DA, bisphenol A(EO)3 diacrylate), Miramer M240 (BPA(EO)4DA, bisphenol A(EO)4 diacrylate), Miramer M241 (bisphenol A(EO)4 dimethacrylate), Miramer M2100 (BPA(EO) 10 DA, bisphenol A(EO) 10 DA, bisphenol A(EO) 20 DA, bisphenol A(EO) 20 DA, bisphenol A(EO) 10 dimethacrylate) manufactured by Miwon Specialty Chemical Co., Ltd.

[0188] Further, KUA-1330h or the like can be used as the urethane-based di(meth)acrylate.

[0189] The urethane-based di(meth)acrylate has a larger molecular weight than existing simple alkylene oxides and has a linear structure, thereby imparting flexibility. This is the reason for improving the hole sealing performance required for a dry film resist (DFR) for an outer layer and the hydrophobicity of a polyol which is one of components of urethane acrylate, and improving the resistance to a plating solution which is a strong acid so as not to contaminate the plating solution.

[0190] 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 reacting the obtained urethane compound with a compound having both a hydroxyl group and an ethylenically unsaturated group.

[0191] The polyether compound having a hydroxyl group is a polyether diol, and diols 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 with 1,4-butanediol is used.

[0192] The diisocyanate compound can include aliphatic diisocyanate compounds having a divalent aliphatic group such as an alkylene group; alicyclic diisocyanate compounds having a divalent alicyclic group such as a cycloalkylene group; aromatic diisocyanate compounds; and isocyanurate-modified components, carbodiimidize-modified components, biuret-modified components, and the like thereof.

[0193] At this time, examples of the aliphatic diisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and the like.

[0194] The alicyclic diisocyanate compound can include isophorone diisocyanate, methylenebis(cyclohexyl)diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, and the like.

[0195] The aromatic diisocyanate compound can include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, a dimeric polymer of 2,4-toluene diisocyanate or 2,6-toluene diisocyanate, (ortho-, para-, or meta-)xylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, and the like.

[0196] They are used alone or in combination of two or more. In addition, they can include isocyanate compounds having two or more isocyanate groups, such as triphenylmethane triisocyanate and tris(isocyanatophenyl) thiophosphate. Among them, the alicyclic diisocyanate compound is preferred from the viewpoint of improving the flexibility and toughness of the photocured product and thereby improving the adhesion to the substrate.

[0197] The polyether compound or polyester compound having a hydroxyl group is reacted with a diisocyanate compound to produce 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 1.1 to 2.0, relative to 1 mole of the polyether compound or polyester compound having a hydroxyl group. If the content of the diisocyanate compound is less than 1.01 mole or more than 2.0 mole, a urethane compound having isocyanate groups at both ends cannot be stably obtained.

[0198] In addition, in the reaction for synthesizing the urethane compound, dibutyl tin dilaurate is preferably added as a catalyst.

[0199] The reaction temperature is preferably 60°C to 120°C. When the reaction temperature is less than 60°C, there is a tendency that the reaction does not proceed sufficiently, and when the reaction temperature exceeds 120°C, the reaction operation can be dangerous due to sudden heat generation.

[0200] The compound having both a hydroxyl group and an ethylenically unsaturated group used for reaction with the urethane compound thus produced can include a compound having a hydroxyl group and a (meth)acryloyl group in the molecule. These compounds include: a (meth)acrylic acid hydroxyl ester; a (meth)acrylic acid hydroxyl ester-caprolactone adduct or an alkylene oxide adduct; an ester compound produced by reacting a polyhydric alcohol such as glycerol with a (meth)acrylic acid; and a glycidyl (meth)acrylate-acrylic acid adduct.

[0201] The (meth)acrylic acid hydroxyl ester can include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate.

[0202] The (meth)acrylic acid hydroxyl ester-caprolactone adduct can include: a hydroxyethyl (meth)acrylate-caprolactone adduct, a hydroxypropyl (meth)acrylate-caprolactone adduct, a hydroxybutyl (meth)acrylate-caprolactone adduct, and the alkylene oxide adduct can include: a hydroxyethyl (meth)acrylate-alkylene oxide adduct, a hydroxypropyl (meth)acrylate-propylene oxide adduct, a hydroxybutyl (meth)acrylate-butylene oxide adduct.

[0203] The ester compound can include, for example, glyceryl mono(meth)acrylate, glyceryl di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane mono(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, di(meth)acrylate of trimethylolpropane-ethylene oxide adduct, di(meth)acrylate of trimethylolpropane-propylene oxide adduct. These substances are used alone or in combination of two or more.

[0204] The urethane-based di(meth)acrylate is a compound obtained by an addition reaction of a urethane compound with a compound having both a hydroxyl group and an ethylenically unsaturated group, which can be obtained by adding the compound having both a hydroxyl group and an ethylenically unsaturated group in a molar ratio of 2.0 to 2.4 with respect to 1 mole of the urethane compound, and then allowing it to undergo an addition reaction at 60°C to 90°C.

[0205] Preferably, the weight average molecular weight of the urethane-based di(meth)acrylate is 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 improve flexibility and toughness, and thus adhesion to a substrate cannot be improved, and when the weight average molecular weight exceeds 60,000 g / mol, there is a problem in that development performance is deteriorated and development time is slowed down. Therefore, preferably, the weight average molecular weight of the urethane-based di(meth)acrylate according to the present disclosure is 1,000 g / mol to 60,000 g / mol.

[0206] In the present disclosure, in a photosensitive resin composition for forming the photosensitive resin layer, 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 1% by weight to 20% by weight, and preferably 1.5% by weight to 15% by weight. 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 effect thereof is insufficient, and when the content exceeds 20% by weight, there is a disadvantage in that development time is rapidly increased and a large amount of scum and sludge is generated during development after exposure.

[0207] The content of the urethane-based di(meth)acrylate of one embodiment can be 1 part by weight or more and 50 parts by weight or less, 1 part by weight or more and 30 parts by weight or less, 1 part by weight or more and 10 parts by weight or less, or 1 part by weight or more and 5 parts by weight or less, based on 100 parts by weight of the alkylene glycol-based di(meth)acrylate.

[0208] Specifically, the photosensitive resin composition for forming a photosensitive resin layer of one embodiment can include 500 parts by weight or more and 1500 parts by weight or less, 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 and 900 parts by weight or less of a bifunctional (meth)acrylate compound, based on 100 parts by weight of a monofunctional (meth)acrylate compound.

[0209] That is, the photosensitive resin layer of one embodiment can include 110 parts by weight or more of the multifunctional (meth)acrylate compound and 500 parts by weight or more and 1500 parts by weight or less of the bifunctional (meth)acrylate compound, based on 100 parts by weight of the monofunctional (meth)acrylate compound.

[0210] In addition, the photosensitive resin layer of one embodiment can include 500 parts by weight or more and 1000 parts by weight or less, 500 parts by weight or more and 800 parts by weight or less, 500 parts by weight or more and 750 parts by weight or less, 500 parts by weight or more and 700 parts by weight or less, or 500 parts by weight or more and 600 parts by weight or less of the bifunctional (meth)acrylate compound, based on 100 parts by weight of the multifunctional (meth)acrylate compound.

[0211] In the present disclosure, the content of the monofunctional photopolymerizable compound can be 0.1 % by weight or more and 2.5 % by weight or less, based on the total weight of the photosensitive resin composition used for forming the photosensitive resin layer.

[0212] In addition, in the present disclosure, the content of the multifunctional photopolymerizable compound can be 2.6 % by weight or more and 5.0 % by weight or less, based on the total weight of the photosensitive resin composition used for forming the photosensitive resin layer.

[0213] That is, the photosensitive resin composition used for forming the photosensitive resin layer can include 0.1 % by weight or more and 2.5 % by weight or less of the monofunctional photopolymerizable compound and 2.6 % by weight or more and 5.0 % by weight or less of the multifunctional photopolymerizable compound, based on the total weight of the photosensitive resin composition.

[0214] When the content of the monofunctional photopolymerizable compound is less than 0.1 % by weight or the content of the multifunctional photopolymerizable compound is less than 2.6 % by weight, based on the total weight of the photosensitive resin composition used for forming the photosensitive resin layer, the effect resulting from the addition of the compound represented by Chemical Formula 1 and Chemical Formula 2 is insufficient, and when the content of the monofunctional photopolymerizable compound is greater than 2.5 % by weight or the content of the multifunctional photopolymerizable compound is greater than 5.0 % by weight, there can be a problem in that the hydrophobicity increases and thus the development time rapidly increases after exposure in the development process.

[0215] The photosensitive resin composition used to form the photosensitive resin layer of one embodiment is another photopolymerizable compound, and can include: ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, glycerol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentamethacrylate, 2,2-bis(4-methacryloyloxyl diethoxyphenyl)propane, 2,2-bis(4-methacryloyloxyl polyethoxyphenyl)propane, 2-hydroxy-3-methacryloyloxypropyl methacrylate, ethylene glycol diglycidyl ether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate, diglycidyl phthalate dimethacrylate, glycerol polyglycidyl ether polymethacrylate, a multifunctional (meth)acrylate containing a urethane group, and the like.

[0216] The content of the photopolymerizable compound can be 10% by weight or more and 70% by weight or less, based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer, based on the solid content. When the content of the photopolymerizable compound is within the above range, effects of improving photosensitivity, resolution, adhesion, and the like can be obtained.

[0217] (4) Photosensitive resin composition

[0218] The photosensitive resin composition used to form the photosensitive resin layer can contain, based on the solid content, 20% by weight or more and 80% by weight or less of a base-developable binder resin, 0.1% by weight or more and 10% by weight or less of a photopolymerization initiator, and 10% by weight or more and 70% by weight or less of a photopolymerizable compound. The solid content as a weight basis refers to the remaining components excluding the solvent from the photosensitive resin composition.

[0219] The photosensitive resin composition can further contain a solvent. The solvent is generally selected from the group consisting of methyl ethyl ketone (MEK), methanol, THF, toluene, and acetone, and is not particularly limited thereto, and the content thereof can also be adjusted in accordance with the contents of the photopolymerization initiator, the base-developable binder resin, and the photopolymerizable compound.

[0220] In addition, the photosensitive resin composition can further include other additives as needed. The other additives are plasticizers, and can include: dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate in the form of phthalic acid esters; triethylene glycol diacetate, tetraethylene glycol diacetate in the form of glycol esters; p-toluenesulfonamide, benzene sulfonamide, n-butyl benzene sulfonamide in the form of amides; triphenyl phosphate; and the like.

[0221] In the present disclosure, in order to improve the handling properties of the photosensitive resin composition, a leuco dye or a coloring material can be added. Examples of the leuco dye include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2-methylphenyl)methane, and fluoran dye. Among them, when leuco crystal violet is used, the contrast is good, which is preferred. When the leuco dye is included, the content in the photosensitive resin composition can be 0.1% by weight or more and 10% by weight or less. From the viewpoint of exhibiting contrast, 0.1% by weight or more is preferred, and from the viewpoint of maintaining storage stability, 10% by weight or less is preferred.

[0222] Examples of the coloring material can include: toluenesulfonic acid monohydrate, fuchsin, phthalocyanine green, auramine base, pararosaniline, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite green, diamond green, basic blue 20, and the like. When the coloring material is included, the amount added can be 0.001% by weight or more and 1% by weight or less based on the photosensitive resin composition. When the content is 0.001% by weight or more, there is an effect of improving operability, and when the content is 1% by weight or less, there is an effect of maintaining storage stability.

[0223] In addition, the other additives can further include a thermal polymerization inhibitor, a dye, a decoloring agent, an adhesion promoter.

[0224] Meanwhile, the aromatic ring fraction value of the photosensitive resin layer of one embodiment, calculated from Equation 1 below, can be -0.015 or more and -0.011 or less.

[0225] [Equation 1]

[0226]

[0227] In Equation 1, for the monofunctional (meth)acrylate compound represented by Chemical Formula 1, and the multifunctional (meth)acrylate compound represented by Chemical Formula 2, Pc n is the number of aromatic rings of each (meth)acrylate compound, Oc n is the number of O atoms and S atoms in each (meth)acrylate compound, Wr nis the weight percentage of each (meth)acrylate compound with respect to the total weight of monofunctional (meth)acrylate compounds and polyfunctional (meth)acrylate compounds, and Mw n is the weight average molecular weight of the (meth)acrylate compound.

[0228] Specifically, since the photosensitive resin composition of one embodiment includes the monofunctional (meth)acrylate compound represented by Chemical Formula 1 and the polyfunctional (meth)acrylate compound represented by Chemical Formula 2, the aromatic ring fraction value calculated from Equation 1 can be -0.015 or more and -0.011 or less.

[0229] More specifically, since the photosensitive resin layer of one embodiment includes an excess of the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 with respect to the monofunctional (meth)acrylate compound represented by Chemical Formula 1, the aromatic ring fraction value calculated from Equation 1 can be -0.015 or more and -0.011 or less.

[0230] Since the aromatic ring fraction value calculated from Equation 1 is -0.015 or more and -0.011 or less, the reactivity of the photosensitive resin layer of one embodiment becomes faster, whereby the color development time and degree of the dry film photoresist including the photosensitive resin layer of one embodiment become excellent, and thus an effect of improving the physical properties of a display device including the dry film photoresist can be achieved.

[0231] The aromatic ring fraction parameter is a value obtained by calculating the content of the aromatic ring of the photopolymerizable compound excluding the contents of O atoms and S atoms and dividing it by the average molecular weight of the composition, and the aromatic ring fraction value can be -0.015 or more and -0.011 or less, -0.015 or more and -0.012 or less, -0.015 or more and -0.013 or less, or -0.014 or more and -0.013 or less. By using the photopolymerizable compound satisfying the aromatic ring fraction value, the photosensitive resin layer of one embodiment can achieve an effect of having excellent development performance and peeling performance while maintaining good resolution and adhesion.

[0232] In addition, when the aromatic ring fraction value is less than -0.015, the content of the polyfunctional (meth)acrylate compound is too small, the technical effect of improving the resistance to a developing solution generated by including the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 is reduced, which can cause technical problems in improving adhesion and resolution. When the value exceeds -0.011, the number of repeating units of oxirane in the molecular structure having hydrophilicity generated by including the monofunctional (meth)acrylate compound represented by Chemical Formula 1 is reduced, which can cause technical problems of increasing the molecular weight and prolonging the peeling time.

[0233] Equation 1 can specifically refer to the following equation.

[0234]

[0235] In Equation 1, Pc n may refer to the number of aromatic rings of the (meth)acrylate compound represented by Chemical Formula n. That is, Pc1 refers to the number of aromatic rings of the monofunctional (meth)acrylate compound represented by Chemical Formula 1, and Pc2 can refer to the number of aromatic rings of the multifunctional (meth)acrylate compound represented by Chemical Formula 2.

[0236] In Equation 1, Oc n may refer to the number of O atoms and S atoms of the (meth)acrylate compound represented by Chemical Formula n. That is, Oc1 refers to the number of O atoms and S atoms of the monofunctional (meth)acrylate compound represented by Chemical Formula 1, and Oc2 can refer to the number of O atoms and S atoms of the multifunctional (meth)acrylate compound represented by Chemical Formula 2.

[0237] In Equation 1, Wr n may refer to the 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, Wr1 refers to 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 multifunctional (meth)acrylate compound, and Wr2 can refer to 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.

[0238] In Equation 1, Mw n may refer to the weight average molecular weight of the (meth)acrylate compound represented by Chemical Formula n. That is, Mw1 refers to the weight average molecular weight of the monofunctional (meth)acrylate compound represented by Chemical Formula 1, and Mw2 can refer to the weight average molecular weight of the multifunctional (meth)acrylate compound represented by Chemical Formula 2.

[0239] That is, in one embodiment, the aromatic ring fraction value calculated from Equation 1 can be specifically calculated from the following Equation 1-1.

[0240] [Equation 1-1]

[0241]

[0242] In Equation 1-1, Pc1 is the number of aromatic rings of the monofunctional (meth)acrylate compound represented by Chemical Formula 1, Pc2 is the number of aromatic rings of the multifunctional (meth)acrylate compound represented by Chemical Formula 2, Oc1 is the number of O atoms and S atoms of the monofunctional (meth)acrylate compound represented by Chemical Formula 1, Oc2 is the number of O atoms and S atoms of the multifunctional (meth)acrylate compound represented by Chemical Formula 2, Wr1 is 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 multifunctional (meth)acrylate compound, Wr2 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, Mw1 is the weight average molecular weight of the monofunctional (meth)acrylate compound represented by Chemical Formula 1, and Mw2 is the weight average molecular weight of the multifunctional (meth)acrylate compound represented by Chemical Formula 2.

[0243] In Equation 1, Pc n represents the number of aromatic rings of each (meth)acrylate compound. The number of aromatic rings refers to the number of monocyclic rings included in the (meth)acrylate compound, and in the case of fused rings, refers to the number of each fused monocyclic ring. For example, when the (meth)acrylate compound includes one naphthyl group, two benzene rings as monocyclic rings are fused, and thus, Pc n is 2. When the (meth)acrylate compound includes one anthryl group or phenanthryl group, Pc n is 3.

[0244] That is, Pc n of the monofunctional (meth)acrylate compound represented by Chemical Formula 1 can be 0 or more and 10 or less, 0 or more and 2 or less, or 0, and Pc n of the multifunctional (meth)acrylate compound represented by Chemical Formula 2 can be 0 or more and 10 or less, 0 or more and 2 or less, or 0.

[0245] Oc n is the number of O atoms and S atoms of each (meth)acrylate compound, but does not include the number of "O" included in the (meth)acrylate.

[0246] For example, when the (meth)acrylate compound is dodecanediol dimethacrylate, Oc n is 0, and if the (meth)acrylate compound is phenylthioethyl acrylate, Oc n is 1.

[0247] Wr nmay be a weight percentage of each (meth)acrylate compound with respect to the total weight of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound. For example, if the (meth)acrylate compound to be used is mixed with 60 kg of dodecanediol dimethacrylate and 40 kg of phenylthioethanol acrylate, the Wr n of dodecanediol dimethacrylate is (60 / 100) x 100 = 60, and the Wr n of phenylthioethanol acrylate is (40 / 100) x 100 = 40.

[0248] Meanwhile, in Equation 1, the ratio between Oc1 of the monofunctional (meth)acrylate compound and Oc2 of the polyfunctional (meth)acrylate compound can be 1:0.3 or more and 1:0.9 or less, 1:0.5 or more and 1:0.9 or less, 1:0.5 or more and 1:0.75 or less, 1:0.5 or more and 1:0.7 or less.

[0249] In addition, the ratio between Mw1 of the monofunctional (meth)acrylate compound and Mw2 of the polyfunctional (meth)acrylate compound in Equation 1 can be 1:1.1 or more and 1:1.9 or less, 1:1.1 or more and 1:1.5 or less, 1:1.1 or more and 1:1.4 or less, 1:1.2 or more and 1:1.4 or less, 1:1.2 or more and 1:1.3 or less.

[0250] 2. Dry film photoresist

[0251] According to another embodiment of the present disclosure, a dry film photoresist including the photosensitive resin layer of one embodiment can be provided. The detailed content regarding the photosensitive resin layer includes all of the above described in one embodiment.

[0252] Specifically, the photosensitive resin layer can include a dry product or a cured product of the photosensitive resin composition of one embodiment. The dry product refers to a material obtained through a drying process of the photosensitive resin composition of one embodiment. The cured product refers to a material obtained through a curing process of the photosensitive resin composition of one embodiment.

[0253] Meanwhile, the aromatic ring fraction value calculated from Equation 1 below of the photosensitive resin layer can be -0.015 or more and -0.011 or less.

[0254] [Equation 1]

[0255]

[0256] In Equation 1, for a monofunctional (meth)acrylate compound represented by the following Chemical Formula 1 and a multifunctional (meth)acrylate compound represented by the following Chemical Formula 2, Pc n is the number of aromatic rings of each (meth)acrylate compound, Oc n is the number of O atoms and S atoms in each (meth)acrylate compound, Wr n is the weight percentage of each (meth)acrylate compound with respect to the total weight of the monofunctional (meth)acrylate compound and the multifunctional (meth)acrylate compound, and Mw n is the weight average molecular weight of the (meth)acrylate compound.

[0257] [Chemical Formula 1]

[0258]

[0259] In Chemical Formula 1, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R2 is an alkylene group having 1 to 10 carbon atoms, R3 is an alkyl group having 1 to 10 carbon atoms, and n1 is an integer of 1 to 20.

[0260] [Chemical Formula 2]

[0261]

[0262] In Chemical Formula 2, R4 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R5 is an alkylene group having 1 to 10 carbon atoms, R6 is a p-valent functional group including a central group having 1 to 20 carbon atoms, n2 is an integer of 1 to 20, p is the number of functional groups substituted with R6, and is an integer of 3 to 10.

[0263] The details regarding Equation 1 include all of the above described in another embodiment.

[0264] The thickness of the dry film photoresist is not particularly limited, but, for example, can be freely adjusted in the range of 0.01 μm to 1 mm. When the thickness of the dry film photoresist is increased or decreased by a specific value, the physical properties measured in the dry film photoresist also change by a certain value.

[0265] The dry film photoresist can further include a base film and a protective film. The base film functions as a support for the photosensitive resin layer during the manufacturing process of the dry film photoresist, and facilitates handling during the exposure process of the photosensitive resin layer having adhesive strength.

[0266] Various plastic films can be used as the base film, examples of which can include at least one plastic film selected from the group consisting of an acrylic film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a polynorbornene (PNB) film, a cyclic olefin polymer (COP) film, and a polycarbonate (PC) film. The thickness of the base film is not particularly limited, and for example, can be freely adjusted within a range of 0.01 μm to 1 mm.

[0267] The protective film prevents damage to the resist during the operation, and functions as a protective layer that protects the photosensitive resin layer from foreign impurities such as dust, and is laminated on the back surface of the photosensitive resin layer on which the base film is not formed. The protective film is used to protect the photosensitive resin layer from external influences. When the dry film photoresist is applied to the subsequent process, it needs to be easily detached, and needs proper release and adhesion properties so that it does not deform during storage and dispensing.

[0268] Various plastic films can be used as the protective film, examples of which can include at least one plastic film selected from the group consisting of an acrylic film, a polyethylene (PE) film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) 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, can be freely adjusted within a range of 0.01 μm to 1 mm.

[0269] Examples of the method of manufacturing the dry film photoresist are not particularly limited, and for example, the photosensitive resin composition of one embodiment is coated on a conventional base film such as polyethylene terephthalate using a conventional coating method, and then dried, and the upper surface of the photosensitive resin layer after drying is laminated with a conventional protective film such as a polyethylene film to manufacture a dry film.

[0270] The coating method of the photosensitive resin composition of one embodiment is not particularly limited, and a method such as using a coating bar can be used.

[0271] The step of drying the coated photosensitive resin composition can be performed by a heating means such as a hot air oven, a hot plate, a hot air circulation oven, and an infrared oven, and can be performed at a temperature higher than or equal to 50 °C and lower than or equal to 100 °C.

[0272] 3. Photosensitive element

[0273] According to another embodiment of the present disclosure, a photosensitive element can be provided, including: a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, wherein the photosensitive resin layer has an aromatic ring fraction value calculated from the following Equation 1 of -0.015 or more and -0.011 or less.

[0274] [Equation 1]

[0275]

[0276] In Equation 1, for a monofunctional (meth)acrylate compound represented by the following Chemical Formula 1 and a multifunctional (meth)acrylate compound represented by the following Chemical Formula 2, Pc n is the number of aromatic rings of each (meth)acrylate compound, Oc n is the number of O atoms and S atoms in each (meth)acrylate compound, Wr n is the weight percentage of each (meth)acrylate compound with respect to the total weight of the monofunctional (meth)acrylate compound and the multifunctional (meth)acrylate compound, and Mw n is the weight average molecular weight of the (meth)acrylate compound.

[0277] [Chemical Formula 1]

[0278]

[0279] In Chemical Formula 1, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R2 is an alkylene group having 1 to 10 carbon atoms, R3 is an alkyl group having 1 to 10 carbon atoms, and n1 is an integer of 1 to 20.

[0280] [Chemical Formula 2]

[0281]

[0282] In Chemical Formula 2, R4 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R5 is an alkylene group having 1 to 10 carbon atoms, R6 is a p-valent functional group including a central group having 1 to 20 carbon atoms, n2 is an integer of 1 to 20, p is the number of functional groups substituted with R6, and is an integer of 3 to 10.

[0283] The detailed contents regarding the photosensitive resin composition include all of the above described in one embodiment and another embodiment.

[0284] That is, the photosensitive resin layer contains an alkali-developable binder resin and a photopolymerizable compound, and the photopolymerizable compound can contain a monofunctional (meth)acrylate compound represented by the following Chemical Formula 1 and a multifunctional (meth)acrylate compound represented by the following Chemical Formula 2.

[0285] [Chemical Formula 1]

[0286]

[0287] In Chemical Formula 1, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R2 is an alkylene group having 1 to 10 carbon atoms, R3 is an alkyl group having 1 to 10 carbon atoms, n1 is an integer of 1 to 20,

[0288] [Chemical Formula 2]

[0289]

[0290] In Chemical Formula 2, R4 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R5 is an alkylene group having 1 to 10 carbon atoms, R6 is a p-valent functional group including a central group having 1 to 20 carbon atoms, n2 is an integer of 1 to 20, p is the number of functional groups substituted with R6, and is an integer of 3 to 10.

[0291] Various plastic films can be used as the base film, examples of which can include at least one plastic film selected from the group consisting of an acrylic film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a poly norbornene (PNB) film, a cyclic olefin polymer (COP) film, and a polycarbonate (PC) film. The thickness of the base film is not particularly limited, and for example, can be freely adjusted within a range of 0.01 μm to 1 mm.

[0292] A specific example of the polymer substrate can be a polyester film in which the anti-blocking layer is formed by an in-line coating method in which an unstretched polyester film is uniaxially stretched, a coating solution including a binder resin and organic particles is coated on one surface thereof, and the remaining portion is uniaxially stretched.

[0293] The polymer substrate is generally manufactured by a linear coating method rather than adding an anti-blocking agent, the anti-blocking agent is generally added in consideration of runnability and winding properties in the manufacturing process, and the polymer substrate has an organic particle layer using alternative particles that do not impair transparency.

[0294] Here, examples of the organic particles used as the particles that do not impair transparency while considering runnability and winding properties can include organic particles such as multilayer multi-component particles in which an acrylic particle such as methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, n-butyl methyl methacrylate, acrylic acid, a methacrylic acid copolymer, or a terpolymer; an olefinic particle such as polyethylene, polystyrene, or polypropylene; an acrylic and olefinic copolymer; or a homopolymer particle is formed, and then another type of monomer is coated on the layer.

[0295] The organic particles should specifically be spherical and also have a different refractive index from the binder resin. Here, "spherical" means that the ratio of the minor axis (a) to the major axis (b) in an ellipse is 0.5 < a / b < 2, and the relationship with the diagonal (d) in a rectangle is defined as d2 < a2 + b2. Further, the relationship between the axis (f) having the longest distance between the vertices of a hexahedron and the c-axis other than the a-axis and b-axis is defined as f2 < c2 + a2 + b2. The shape of the particles should be spherical, which is preferable in terms of runnability.

[0296] Further, 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 lot of scattered light, and when there is a lot of such scattered light, the sidewall smoothing effect decreases. This also depends on the size and amount of the organic particles. Preferably, the average particle diameter of the organic particles is about 0.5 μm to 5 μm. When less than this value, the runnability and winding properties deteriorate, and when greater than 5 μm, the haze increases, which is not preferable in view of the problem of dripping. The content of the organic particles is preferably 1 to 10% by weight based on the total amount of the binder resin.

[0297] When the content of the organic particles is less than 1% by weight based on the total amount of the binder resin, the anti-blocking effect is insufficient and easy to scratch, and the runnability and winding properties deteriorate, and when it exceeds 10% by weight, there is a problem of increased haze and deteriorated transparency.

[0298] Meanwhile, in addition to the above organic particles, inorganic particles can also be added. At this time, it is not preferable to add a generally used inorganic anti-blocking agent, and it is preferable to add colloidal silica having a particle diameter of 100 nm or less. The content is preferably 10 parts by weight or less based on 100 parts by weight of the binder resin. When the particle diameter and content as described above are satisfied, it is possible to prevent the occurrence of sidewall defects or grooves (such as pits) caused by the anti-blocking layer when a dry film photoresist is used to form a pattern.

[0299] As the binder resin that functions as a binder that coats such organic particles onto an unstretched polyester film, a binder resin having excellent compatibility with the organic particles can be used. Examples of such a resin can include: acrylic resins such as unsaturated polyester, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, n-butyl methacrylate, acrylic acid, a methacrylic acid copolymer, or a terpolymer; urethane resins; epoxy resins; or melamine resins, etc., and an acrylic resin is preferable.

[0300] A solvent that can be used when preparing a coating solution using a binder resin and organic particles is preferably water.

[0301] As described above, the unstretched polyester film obtained by melt extrusion of the PET pellets is uniaxially stretched, and then the coating solution containing the organic particles in the adhesive resin is applied to the uniaxially stretched film. The application can be performed on at least one side of the uniaxially stretched film, and the thickness thereof is preferably about 30 nm to 200 nm based on the thickness after final drying. If the coating solution containing the organic particles is applied to the uniaxially stretched film to be thinner than 30 nm, there is a problem that the organic particles easily fall off and are easily scratched, and white powder is generated. When applied to be thicker than 200 nm, since the viscosity of the coating solution increases, coating streaks are generated in the application direction in on-line application with a high application speed.

[0302] The polymer substrate obtained by application using the organic particles instead of the conventional anti-blocking agent by the on-line application method as described above is a substrate film that maintains the running property and the winding property due to the particle layer, and has excellent transparency due to the organic particles having excellent light transmission.

[0303] Since the lamination of the photosensitive resin layer is performed on the reverse side of the layer containing the organic particles in the polymer substrate, the photosensitive resin layer is formed on the reverse side of the layer containing the organic particles in this way. Therefore, the dimple-shaped defect that occurs when the substrate film containing the anti-blocking agent is laminated as before does not occur. Since the particles such as silica are not only larger in size than the organic particles, but also distributed throughout the substrate film, the influence of the silica is not significant even in the region adjacent to the photosensitive resin layer.

[0304] On the other hand, in the polymer substrate used in the present disclosure, the size of the organic particles is 0.5 μm to 5 μm, and the organic particle layer is not adjacent to the photosensitive resin layer, and therefore the physical effect of the organic particles is not affected. In addition, by using the organic particles having excellent light transmittance, the side wall defect can be reduced, and other circuit properties are not impaired.

[0305] The photosensitive element can further include a protective film formed on the photosensitive resin layer. The protective film prevents damage to the photosensitive resin layer during the operation, and functions as a protective layer to protect the photosensitive resin layer from foreign impurities such as dust. The protective film is laminated on the back surface of the photosensitive resin layer which does not form the polymer substrate. The protective film is used to protect the photosensitive resin layer from external influences. When a dry film photoresist is applied to the post-treatment, easy peeling is required, and proper release properties and adhesion are required so that it does not deform during storage and distribution.

[0306] Various plastic films can be used as the protective film, examples of which can include at least one plastic film selected from the group consisting of an acrylic film, a polyethylene (PE) film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a poly norbornene (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, can be freely adjusted within a range of 0.01 μm to 1 mm.

[0307] 4. Circuit board, display device

[0308] According to another embodiment of the present disclosure, a circuit board or a display device including a photosensitive resin layer of the photosensitive resin composition of one embodiment can be provided. The detailed content regarding the photosensitive resin layer includes all of the above described in one embodiment.

[0309] The specific details of the circuit board or the display device are not particularly limited, and various publicly known technical configurations can be applied without limitation.

[0310] The photosensitive resin layer included in the circuit board or the display device can be in the form of a film without an opening or in the form of a pattern with an opening.

[0311] Examples of the method of forming the photosensitive resin in the form of a pattern layer include a method of laminating the photosensitive resin layer of the dry film 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 layer 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 proposed.

[0312] When the dry film photoresist or the photosensitive element of another embodiment has a protective film on the photosensitive resin layer, a process of removing the protective film can be performed before the process of laminating the photosensitive resin layer on a circuit board or a display device manufacturing substrate.

[0313] In addition, when the dry film photoresist or the photosensitive element of another embodiment has a polymer substrate or a substrate film laminated on one side of the photosensitive resin layer, a process of immediately removing the polymer substrate or the substrate film can be further performed after the exposure process.

[0314] Accordingly, the photosensitive resin layer included in the dry film photoresist or the photosensitive element of another embodiment can be included in a circuit board or a display device.

[0315] Advantageous effects

[0316] According to the present disclosure, a photosensitive resin layer in which excellent development performance can be achieved, and a dry film photoresist and a photosensitive element including the same can be provided. DETAILED DESCRIPTION

[0317] The present disclosure will be described in greater detail by the following examples. However, these examples are given for illustration only and are not intended to limit the scope of the present disclosure thereto.

[0318] <Preparation Example: Preparation of alkali-developable adhesive resin>

[0319] Preparation Example 1

[0320] A 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. 80 g of methyl ethyl ketone (MEK) and 7.5 g of methanol (MeOH) were added to the flask purged with nitrogen, and then 0.45 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. To this, a monomer mixture of 8 g of acrylic acid (AA), 15 g of methacrylic acid (MAA), 15 g of butyl acrylate (BA), 52 g of methyl methacrylate (MMA), and 10 g of styrene (SM) were added as monomers, heated to 80°C, and then polymerized for 6 hours to prepare an alkali-developable adhesive resin 1.

[0321] The alkali-developable adhesive resin 1 was measured to have a weight average molecular weight of 71538 g / mol, a glass transition temperature of 79°C, a solid content of 51.4 wt%, and an acid value of 156.3 mgKOH / g.

[0322] In a specific example of the measurement condition of the weight average molecular weight, the alkali-developable adhesive resin was dissolved in tetrahydrofuran so that the concentration thereof in THF was 1.0 (w / w) % (about 0.5 (w / w) % based on the solid content), filtered using a syringe filter having a pore size of 0.45 μm, and then injected into the GPC in an amount of 20 μl, using tetrahydrofuran (THF) as the mobile phase of the GPC, and a flow rate of 1.0 mL / min. The chromatographic column was configured in series connection of one Agilent PLgel 5 μm Guard (7.5 x 50 mm) and two Agilent PLgel 5 μm Mixed D (7.5 x 300 mm), and the measurement was performed at 40°C using an Agilent 1260 Infinity II System, RI Detector as a detector.

[0323] The acid value was measured by dissolving 1 g of the alkali-developable adhesive resin in 50 ml of a mixed solvent (20% MeOH, 80% acetone), adding two drops of 1% phenolphthalein indicator thereto, and then measuring the acid value by titration with 0.1N-KOH.

[0324] The solid content is based on the weight of the alkali-developable binder resin prepared in the above Preparation Example, and the weight percentage of the solid content remaining after heating in an oven at 150°C for 120 minutes is measured.

[0325] Preparation Example 2

[0326] A 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. 235 g of methyl ethyl ketone (MEK) and 19 g of methanol (MeOH) were added to the flask purged with nitrogen, and then 1.9 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. To this, a monomer mixture of 63.5 g of methacrylic acid (MAA), 120.6 g of methyl methacrylate (MMA), and 69.8 g of styrene (SM) was added as a monomer, heated to 80°C, and then polymerized for 6 hours to prepare an alkali-developable binder resin 2 (weight average molecular weight: 37500 g / mol, glass transition temperature: 128°C, solid content: 49 wt%, acid value: 163 mgKOH / g).

[0327] [Examples and Comparative Examples: Preparation of photosensitive resin composition and dry film photoresist]

[0328] A photopolymerization initiator was dissolved in methyl ethyl ketone (MEK) as a solvent according to the composition shown in Table 1 below, and then a photopolymerizable compound and an alkali-developable binder resin were added, and mixed for about 1 hour using a mechanical stirrer to prepare a photosensitive resin composition.

[0329] The resulting photosensitive resin composition was coated on a 40 μm PET film using a coating bar. The coated photosensitive resin composition layer was dried using a hot air oven. At this time, the drying temperature was 80°C, the drying time was 5 minutes, and the thickness of the photosensitive resin composition layer after drying was 40 μm.

[0330] A protective film (polyethylene) was laminated on the dried photosensitive resin composition layer to prepare a dry film photoresist.

[0331] The PET film was manufactured by the following process.

[0332] PET was prepared by ester exchange and polycondensation reactions of ethylene glycol and terephthalic acid. The PET pellets were dried at 120°C under reduced pressure for 8 hours, then fed into an extruder and melted at 280°C. Using an electrostatic coating casting method, it was wound on a casting drum with a surface temperature of 20°C, cooled and solidified to form an unstretched film. The thickness of the unstretched film was adjusted to 250 μm by adjusting the discharge amount of the extruder. Next, the unstretched film was stretched 4 times in the longitudinal direction, a coating solution obtained by mixing 4 g of an acrylic resin and 0.1 g of polymethyl methacrylate as an organic particle in 95.9 g of water was lastly dried, then coated onto one surface thereof using a gravure to have a thickness of 50 nm. The polymethyl methacrylate used here is polymethyl methacrylate on the surface of which polystyrene is coated, is spherical, and has a refractive index difference of 0.03 from the acrylic resin.

[0333] The uniaxially stretched film coated with the coating solution containing the organic particle was preheated at 120°C, and stretched 4 times in the transverse direction.

[0334] 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 having a total thickness of 20 μm and a coating layer thickness of 50 nm.

[0335] [Table 1]

[0336]

[0337]

[0338] [Experimental Example]

[0339] The physical properties of the dry films photoresists prepared in the examples and comparative examples were measured by the following methods, and the results are shown in Table 2 below.

[0340] 1. Aromatic ring fraction

[0341] For the photosensitive resin compositions prepared in the examples and comparative examples, the aromatic ring fraction value was calculated according to the following Equation 1.

[0342] [Equation 1]

[0343]

[0344] In Equation 1, for A040 included in the photosensitive resin composition as a monofunctional (meth)acrylate compound and T063 as a trifunctional (meth)acrylate compound, Pc n is the number of aromatic rings of each (meth)acrylate compound, Oc n is the number of O atoms and S atoms of each (meth)acrylate compound, Wrn is the weight percentage of each (meth)acrylate compound relative to the total weight of monofunctional (meth)acrylate compound A040 and trifunctional (meth)acrylate compound T063, Mw n is the weight average molecular weight of the (meth)acrylate compound.

[0345] 2. Fine line adhesion (unit: μm)

[0346] The protective film was peeled off from the dry film photoresist prepared in the examples and comparative examples, and the photosensitive resin layer of the dry film photoresist was laminated using HAKUTO MACH 610i under the conditions of a substrate preheating roll temperature of 120°C, a laminator roll temperature of 115°C, a roll pressure of 4.0 kgf / cm 2 and a roll speed of 2.0 min / m so as to contact the copper layer surface of the copper-clad laminate having a brushed thickness of 1.6 mm, thereby forming a laminate.

[0347] The laminate was irradiated with ultraviolet rays at an exposure amount of 16 mJ / cm 2 using a photomask for circuit evaluation by FDI-3 (ORC), and then left for 15 minutes. Then, development was performed using a 1.0 wt% Na2CO3 aqueous solution under a spray-type development condition of a spray pressure of 1.5 kgf / cm 2 and 30 ± 1°C for 1 minute.

[0348] In the laminate on which development was completed, the minimum line width of the photosensitive resin layer was measured using a ZEISS AXIOPHOT microscope, and evaluated as fine line adhesion. It can be evaluated that the smaller the value, the better the fine line adhesion.

[0349] 3. Resolution (unit: μm)

[0350] The protective film was peeled off from the dry film photoresist prepared in the examples and comparative examples, and the photosensitive resin layer of the dry film photoresist was laminated using HAKUTO MACH 610i under the conditions of a substrate preheating roll temperature of 120°C, a laminator roll temperature of 115°C, a roll pressure of 4.0 kgf / cm 2 and a roll speed of 2.0 min / m so as to contact the copper layer surface of the copper-clad laminate having a brushed thickness of 1.6 mm, thereby forming a laminate.

[0351] The laminate was irradiated with ultraviolet rays at an exposure amount of 16 mJ / cm 2 using a photomask for circuit evaluation by LDI exposure machine (FDI-3, Japan ORC) for 10 seconds so that the width of the circuit line and the interval between the circuit lines became 1:1 after development, and then left for 15 minutes. Then, development was performed using a 1.0 wt% Na2CO3 aqueous solution under a spray-type development condition of a spray pressure of 1.5 kgf / cm 2and developed for 1 minute under spray pressure of 1.5 kgf / cm

[0352] 4. Evaluation of plating anti-stain performance

[0353] The dry film photoresist prepared in the examples and comparative examples was cut to a size of 40 cm x 50 cm, the protective film was removed, and a stage exposure table was exposed with an exposure amount of 20 stages / 41 stages, and the PET film was peeled off to obtain a cured film. The cured film was immersed in a plating solution of 1 L of a copper sulfate / sulfuric acid aqueous solution for 3 days. A copper plate was electrolytic copper plated for 10 minutes using a Halcel test bath (manufactured by Jungdo Test Instruments Lab., Korea) at a current of 2 A.

[0354] When a plating solution in which the cured film was not immersed was used as a reference sample and plating was performed using a coating solution in which the cured film was immersed, the appearance of the plated layer was observed with the naked eye, and if there was an abnormality in the appearance of the plated layer or the gloss was changed, X was judged, and if it was the same as the reference sample and thus completely free of abnormality, O was judged.

[0355] 5. Peeling rate (unit: seconds)

[0356] The protective film was peeled off from the dry film photoresist prepared in the examples and comparative examples, and the photosensitive resin layer of the dry film photoresist was laminated by HAKUTO MACH 610i under conditions of a substrate preheating roll temperature of 120°C, a laminator roll temperature of 115°C, a roll pressure of 4.0 kgf / cm 2 and a roll speed of 2.0 min / m so as to contact the copper layer surface of a copper-clad laminate whose brushed thickness was 1.6 mm, thereby forming a laminate.

[0357] The laminate was irradiated with ultraviolet rays for 10 seconds at an exposure amount of 16 mJ / cm 2 using a photomask for circuit evaluation by FDI-3 (ORC), and then left to stand for 15 minutes. Then, the supporting PET film of the dry film photoresist was peeled off, and developed for 1 minute under spray pressure of 1.5 kgf / cm 2 and a development temperature of 30±1°C using a 1.0 wt% Na2CO3 aqueous solution.

[0358] Then, peeling was performed using a 3% sodium hydroxide aqueous solution (temperature of 50°C). The peeling rate was evaluated by measuring the time required for the photocured layer to be peeled off from the copper plate.

[0359] [Table 2]

[0360]

[0361] As shown in Table 2, it can be confirmed that since the aromatic ring fraction values of the examples are -0.015 or more and -0.011 or less, they exhibit fine line adhesion and resolution at a similar level to Comparative Example 1 having an aromatic ring fraction value greater than -0.011, and at the same time, the examples exhibit significantly superior peeling rate. In addition, since the aromatic ring fraction values of the examples are -0.015 or more and -0.011 or less, they exhibit significantly superior fine line adhesion, resolution, and stain resistance compared to Comparative Example 2 having an aromatic ring fraction value less than -0.015.

Claims

1. A photosensitive resin layer comprising: a photopolymerizable compound including a tri- or higher functional polyfunctional (meth)acrylate compound; and a base-developable binder resin; wherein the photopolymerizable compound further includes a mono-functional (meth)acrylate compound, wherein the mono-functional (meth)acrylate compound includes a compound of the following Chemical Formula 1, wherein the tri- or higher functional polyfunctional (meth)acrylate compound includes a compound of the following Chemical Formula 2, and wherein an aromatic ring fraction value calculated from the following Equation 1 is -0.015 or more and -0.011 or less: [Equation 1] In Equation 1, Pc n is the number of aromatic rings of the respective (meth)acrylate compound, Oc n is the number of O atoms and S atoms in each (meth)acrylate compound, Wr n is the weight percentage of each (meth)acrylate compound relative to the total weight of the (meth)acrylate compounds, and Mw n is the weight average molecular weight of each (meth)acrylate compound, [Chemical Formula 1] In Chemical Formula 1, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R2 is an alkylene group having 1 to 10 carbon atoms, R3 is an alkyl group having 1 to 10 carbon atoms, n1 is an integer of 1 to 20, [Chemical Formula 2] In Chemical Formula 2, R4 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R5 is an alkylene group having 1 to 10 carbon atoms, R6 is a p-valent functional group including a central group having 1 to 20 carbon atoms, n2 is an integer of 1 to 20, and p is the number of functional groups substituted with R6, and is an integer of 3 to 10.

2. The photosensitive resin layer according to claim 1, wherein, the tri- or higher functional polyfunctional (meth)acrylate compound has a structure in which three or more alkyleneoxy groups 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.

3. The photosensitive resin layer according to claim 1, wherein the tri- or higher functional polyfunctional (meth)acrylate compound includes a compound of the following Chemical Formula 2-1: [Chemical Formula 2-1] In Chemical Formula 2-1, R6' is a trivalent functional group having 1 to 10 carbon atoms, R7 to R9 are each independently an alkylene group having 1 to 10 carbon atoms, R 10 to R 12 each independently is hydrogen or alkyl having 1 to 10 carbon atoms, n3 to n5 are each independently an integer of 1 to 3.

4. The photosensitive resin layer according to claim 1, wherein the photopolymerizable compound includes 100 parts by weight or more of the polyfunctional (meth)acrylate compound based on 100 parts by weight of the mono-functional (meth)acrylate compound.

5. The photosensitive resin layer according to claim 1, wherein the mono-functional (meth)acrylate compound includes a (meth)acrylate including an alkyleneoxy group having 1 to 10 carbon atoms.

6. The photosensitive resin layer according to claim 1, wherein the photopolymerizable compound includes: a mono-functional (meth)acrylate compound including a (meth)acrylate including an alkyleneoxy group having 1 to 10 carbon atoms; and a tri- or higher functional polyfunctional (meth)acrylate compound having a structure in which three or more alkyleneoxy groups 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.

7. The photosensitive resin layer according to claim 1, wherein, The alkali-developable adhesive resin has a weight average molecular weight of 20,000 g / mol or more and 150,000 g / mol or less.

8. The photosensitive resin layer according to claim 1, wherein, In Equation 1, The ratio between Oc1 of the monofunctional (meth)acrylate compound and Oc2 of the multifunctional (meth)acrylate compound is 1:0.3 or more and 1:0.9 or less.

9. The photosensitive resin layer according to claim 1, wherein In Equation 1, The ratio between Mw1 of the monofunctional (meth)acrylate compound and Mw2 of the multifunctional (meth)acrylate compound is 1:1.1 or more and 1:1.9 or less.

10. The photosensitive resin layer according to claim 1, wherein The content of the multifunctional (meth)acrylate compound is 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.

11. The photosensitive resin layer according to claim 1, wherein, The photopolymerizable compound further includes a difunctional (meth)acrylate compound.

12. The photosensitive resin layer according to claim 11, wherein The content of the difunctional (meth)acrylate compound is 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.

13. The photosensitive resin layer according to claim 11, wherein The content of the difunctional (meth)acrylate compound is 500 parts by weight or more and 1000 parts by weight or less, based on 100 parts by weight of the multifunctional (meth)acrylate compound.

14. The photosensitive resin layer according to claim 1, wherein The alkali-developable adhesive resin includes: a first alkali-developable adhesive 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 alkali-developable adhesive resin including a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5, and a repeating unit represented by the following Chemical Formula 6: [Chemical Formula 3] In Chemical Formula 3, R3” is hydrogen, [Chemical Formula 4] In Chemical Formula 4, R3’ is an alkyl group having 1 to 10 carbon atoms, [Chemical Formula 5] In Chemical Formula 5, R4” is an alkyl group having 1 to 10 carbon atoms, and R5” is an alkyl group having 1 to 10 carbon atoms, [Chemical Formula 6] In Chemical Formula 6, Ar is an aryl group having 6 to 20 carbon atoms, [Chemical Formula 7] In Chemical Formula 7, R4’ is hydrogen, R5’ is an alkyl group having 1 to 10 carbon atoms.

15. The photosensitive resin layer according to claim 14, wherein The content of the second alkali-developable adhesive resin is 500 parts by weight or more and 1000 parts by weight or less, based on 100 parts by weight of the first alkali-developable adhesive resin.

16. The photosensitive resin layer according to claim 14, wherein The ratio of the glass transition temperatures of the first alkali-developable adhesive resin and the second alkali-developable adhesive resin is 1:1.5 or more and 1:5 or less.

17. The photosensitive resin layer according to claim 14, wherein, The ratio of the acid values of the first alkali-developable adhesive resin and the second alkali-developable adhesive resin is 1:1.01 or more and 1:1.5 or less.

18. A dry film photoresist comprising the photosensitive resin layer according to claim 1.

19. A photosensitive element comprising: a polymer substrate; and the photosensitive resin layer according to claim 1 formed on the polymer substrate.

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