CN114761874A

CN114761874A - Photosensitive resin layer, dry film photoresist using the same, and photosensitive element

Info

Publication number: CN114761874A
Application number: CN202080084590.4A
Authority: CN
Inventors: 沈相和
Original assignee: Kolon Industries Inc
Current assignee: Kolon Industries Inc
Priority date: 2019-12-31
Filing date: 2020-12-11
Publication date: 2022-07-15
Also published as: WO2021137466A1; JP2023509861A; TWI826758B; JP7387900B2; TW202136325A

Abstract

The present invention relates to a photosensitive resin layer, and a dry film photoresist and a photosensitive element using the same, the photosensitive resin layer comprising: a photopolymerizable compound comprising a trifunctional or higher polyfunctional (meth) acrylate compound, wherein a change in a color coordinate (b) value with time calculated according to formula 1 in the photosensitive resin layer satisfies a specific range, and an alkali-developable binder resin.

Description

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

Technical Field

Cross reference to related applications

The present application claims the rights of korean patent application No.10-2019-0179942, filed by 12/31/2019 from the korean intellectual property office, korean patent application No.10-2019-0179943, filed by 12/31/2019 from 2020, korean patent application No.10-2020-0095384, filed by 30/7/2020, and korean patent application No.10-2020-0095385, filed by 30/7/2020, each of which is incorporated herein by reference in its entirety.

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

Background

The photosensitive resin composition is used in the form of a dry film photoresist (DFR) or a liquid photoresist ink, etc. for use in a Printed Circuit Board (PCB) or a lead frame.

Currently, the dry film photoresist is widely used not only in the manufacture of Printed Circuit Boards (PCBs) and lead frames, but also in the manufacture of barrier ribs (rib barriers) of Plasma Display Panels (PDPs), ITO electrodes of other displays, bus address electrodes (bus address electrodes), black matrices, and the like.

Typically, this type of dry film photoresist is often used in applications where it is laminated to a copper clad laminate. In connection with this, as an example of a Printed Circuit Board (PCB) manufacturing process, a pretreatment process is first performed to laminate a copper clad laminate as an initial board for a PCB. The pretreatment process is performed in the order of drilling, deburring, surface dressing, etc. in the outer process, and surface dressing or acid washing is performed in the inner process. In the surface finishing, a bristle brush and jet pumice grinding process (jet pumice process) is mainly used, and acid washing may be performed by soft etching and 5 wt% sulfuric acid washing.

In order to form a circuit on the copper clad laminate subjected to the pretreatment process, a dry film photoresist (hereinafter, referred to as DFR) may be generally laminated on the copper layer of the copper clad laminate. In this process, a laminator was used to laminate the photoresist layer of the DFR on the copper surface while peeling the protective film of the DFR. Typically, lamination is carried out at a rate of 0.5m/min to 3.5m/min, at a temperature of 100 ℃ to 130 ℃, and at a heated roll pressure of 10psi to 90 psi.

The printed circuit board subjected to the lamination process is left for 15 minutes or more to stabilize the printed circuit board, and then the photoresist of DFR is exposed through a photomask having a desired circuit pattern formed thereon. In this process, when the photomask is irradiated with ultraviolet rays, the photoresist irradiated with ultraviolet rays starts polymerization by the photoinitiator contained in the irradiated portion. First, oxygen in the photoresist begins to be consumed, and then the activated monomer is polymerized to cause a crosslinking reaction. Thereafter, when a large amount of the monomer is consumed, the polymerization reaction proceeds. Meanwhile, the unexposed portion exists in a state where the crosslinking reaction does not proceed.

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

Next, a circuit is formed through different processes according to the inner layer process and the outer layer process. However, in the inner layer process, circuits are formed on the circuit board through an etching and stripping process, and in the outer layer process, a plating process and a dry film trepanning process (stretching process) are performed, followed by etching and solder stripping to form predetermined circuits.

Recently, among photosensitive resin compositions, there is a demand for development of a photosensitive resin composition which has high sensitivity to direct exposure to an ultra-high pressure mercury lamp or laser, improves resistance to a developer solution, and thus enables formation of a high-density circuit in a developing process; the photosensitive resin composition has excellent color development for use as a UV mark for setting an exposure position of a substrate; and the photosensitive resin composition shortens the peeling time of the cured film, has a small peeled sample, and thus does not clog a filter.

Disclosure of Invention

[ problem ] to

An object of the present disclosure is to provide a photosensitive resin layer capable of realizing excellent fine line adhesiveness and resolution, and improving the alignment recognition rate of a product during exposure to shorten the manufacturing time of a final product, reducing the defect rate to improve reliability.

It is another object of the present disclosure to provide a dry film photoresist, a photosensitive element, a circuit board and a display device including the above photosensitive resin layer.

[ solution ]

In order to achieve the above object, the present invention provides a photosensitive resin layer comprising: a photopolymerizable compound comprising a trifunctional or higher multifunctional (meth) acrylate compound; and an alkali developable binder resin, wherein the amount of the alkali developable binder resin is 10mJ/cm²Above and 30mJ/cm²The time (t) from the time point when the exposure was started to the time point when the amount of change in the color coordinate b x value calculated by the following formula 1 was 5.0 was 5 minutes or less,

[ equation 1]

The amount of change in the color coordinates b ([ Delta ] b) during the exposure time (t)^* ₁)＝(b^* ₀-b^* ₁)

In the formula 1, the first and second groups of the compound,

b^* ₁is at 10mJ/cm²Above and 30mJ/cm²The value of the color coordinate (b) of the photosensitive resin layer after exposure for t minutes at the following exposure dose, and

b^* ₀is a value of color coordinates (b) of the photosensitive resin layer before exposure.

Further, there may be provided a photosensitive resin layer in which a variation amount of a color coordinate b calculated according to the following formula 2 is 0.6 or more and 14.0 or less,

[ equation 2]

Amount of change in color coordinates b ([ Delta ] b) during an exposure time of 1 minute^* ₁)＝(b^* ₀-b^* ₁)

In the case of the formula 2, the,

b^* ₁is at 10mJ/cm²Above and 30mJ/cm²The value of color coordinate (b) of the photosensitive resin layer after exposure for 1 minute at the following exposure dose, and

The trifunctional or higher polyfunctional (meth) acrylate compound may 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.

The trifunctional or higher multifunctional (meth) acrylate compound may include a compound of chemical formula 2.

The multifunctional (meth) acrylate compound having three or more functions may include the compound of chemical formula 2-1. The compound of chemical formula 2-1 is described below.

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

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

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

The monofunctional (meth) acrylate compound may include a compound of chemical formula 1.

The photopolymerizable compound may comprise: a monofunctional (meth) acrylate compound including a (meth) acrylate ester including an alkyleneoxy group containing 1 to 10 carbon atoms; and a trifunctional or higher 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.

The weight average molecular weight of the alkali-developable binder resin may be 20000g/mol or more and 150000g/mol or less.

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

The content of the second alkali-developable binder resin may 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 binder resin.

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

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

The present invention also provides a dry film photoresist comprising the above photosensitive resin layer.

The present invention also provides a photosensitive element comprising: a polymeric substrate; and the above photosensitive resin layer formed on the polymer substrate.

The invention also provides a circuit board and a display device comprising the dry film photoresist.

The invention also provides a circuit board comprising the photosensitive resin layer.

The invention also provides a display device comprising the photosensitive resin layer.

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

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

As used herein, the singular forms "1," "an," and "the" include plural references unless the context clearly dictates otherwise.

The terms "comprises" or "comprising," as used herein, specify the presence of stated features, regions, integers, steps, acts, elements, and/or components, but do not preclude the presence or addition of different specified features, regions, integers, steps, acts, elements, components, and/or groups thereof.

Furthermore, the use of terms including ordinal numbers such as "first," "second," etc., is used for the purpose of distinguishing one component from another component without limitation to the ordinal number. For example, a first component can be termed a second component, or, similarly, a second component can be termed a first component, without departing from the scope of the present disclosure.

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

In the present specification, the term "substituted" means that other functional groups are bonded to substitute a hydrogen atom in a compound, and a position to be substituted is not limited as long as the position is a position at which the hydrogen atom is substituted, that is, a position which may be substituted by a substituent, and when substituted by two or more, the two or more substituents may be the same as or different from each other.

In the present specification, the term "substituted or unsubstituted" means substituted or unsubstituted with one or more substituents selected from the group consisting of: 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; alkylthio (alkylthio group); arylthio (arylthio group); alkyl sulfoxide groups (alkyl sulfonyl groups); an aryl sulfoxide group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; aralkyl group; an aralkenyl group; an alkylaryl group; an alkoxysilylalkyl group; an arylphosphine group; or a heterocyclic group containing at least one of N, O and the S atom, or the term "substituted or unsubstituted" means substituted or unsubstituted with a substituent that is linked to two or more of the substituents exemplified above. For example, "a substituent in which two or more substituents are linked" may be a biphenyl group. That is, biphenyl can also be an aryl group, and is understood to be a substituent with two phenyl groups attached.

In this specification, the symbols

Or-means a bond to another substituent, andan attachment means that no other atoms are present in the moiety denoted L.

In the present specification, (meth) acryloyl is intended to include both acryloyl and methacryloyl. For example, (meth) acrylates are intended to include both acrylates and methacrylates.

In this specification, an alkyl group is a monovalent functional group derived from an alkane, and may be linear or branched. The number of carbon atoms of the linear alkyl group is not particularly limited, but is preferably 1 to 20. In addition, the branched alkyl group has 3 to 20 carbon atoms. Specific examples of the alkyl group include 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-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 2-methylpentyl, methyl-pentyl, ethyl-butyl, hexyl, 2-methylpentyl, and the like, 4-methylhexyl, 5-methylhexyl, and 2, 6-dimethylheptan-4-yl, and the like, but are not limited thereto. The alkyl group may be substituted or unsubstituted, and when the alkyl group is substituted, examples of the substituent are the same as described above.

In the present specification, the aryl group is a monovalent functional group derived from aromatic hydrocarbon, and is not particularly limited, but preferably has 6 to 20 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. Specific examples of the monocyclic aryl group may include, but are not limited to, phenyl, biphenyl, terphenyl, and the like. Specific examples of the polycyclic aromatic group may include naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, perylene, etc,

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

In the present specification, alkylene is a divalent functional group derived from alkane, and the description of alkyl as defined above may be applied except that alkylene is a divalent functional group. For example, it may be linear or branched, methylene, ethylene, propylene, isobutylene, sec-butylene, tert-butylene, pentylene, hexylene, and the like. The alkylene group may be substituted or unsubstituted.

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

In the present specification, a direct bond or a single bond means that it is connected to a bonding wire in which no atom or atomic group exists at the corresponding position. Specifically, a direct bond or a single bond means R in the formula_aOr L_b(wherein a and b are each an integer of 1 to 20) in the moiety.

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 the chemical structure is completely cured, crosslinked or polymerized, but also the case where such a component is partially cured, crosslinked or polymerized.

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

According to an embodiment of the present disclosure, there may be provided a photosensitive resin layer including: a photopolymerizable compound comprising a trifunctional or higher multifunctional (meth) acrylate compound; and an alkali developable binder resin, wherein the amount of the alkali developable binder resin is 10mJ/cm²Above and 30mJ/cm²The time (t) from the time point when the exposure dose is started to the time point when the change amount of the color coordinate b calculated by the formula 1 is 5.0 is 5 minutes or less.

The present inventors have found through experiments that when the photosensitive resin layer of one embodiment has a characteristic that the time (t) until the time point when the variation amount of the color coordinate b calculated according to formula 1 is 5.0 is 5 minutes or less, the circuit performance is the same as that of the existing product, but the photocuring speed is increased, and thus, the time required to change the contrast is improved due to the technical reasons of accelerating the time required to express color development in the film and increasing the variation amount of color development, thereby securing excellent development performance, and completed the present disclosure.

1. Alkali developable binder resins

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

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

The at least two or more alkali developable binder resins may comprise: a first alkali-developable binder resin including a repeating unit represented by the following chemical formula 3, a repeating unit represented by the following chemical formula 4, a repeating unit represented by the following chemical formula 5, a repeating unit represented by the following chemical formula 6, and a repeating unit represented by the following chemical formula 7; and a second alkali-developable binder resin including a repeating unit represented by the following chemical formula 4, a repeating unit represented by the following chemical formula 5, and a repeating unit represented by the following chemical formula 6,

[ chemical formula 3]

In chemical formula 3, R₃"is a hydrogen atom or a hydrogen atom,

[ 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 containing 1 to 10 carbon atoms, and R₅"is an alkyl group containing 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, and R₅' is an alkyl group having 1 to 10 carbon atoms.

Specifically, the alkali-developable binder resin may include a random copolymer of a repeating unit represented by the following chemical formula 3, a repeating unit represented by the following chemical formula 4, a repeating unit represented by the following chemical formula 5, a repeating unit represented by the following chemical formula 6, and a repeating unit represented by the following chemical formula 7.

[ chemical formula 3]

In chemical formula 3, R₃"is a hydrogen atom or a hydrogen atom,

[ 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 containing 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 formulas 3 to 7, specific examples of the alkyl group having 1 to 10 carbon atoms may include a methyl group.

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

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

[ chemical formula 4-1]

In chemical formula 4-1, R₃' is an alkyl group having 1 to 10 carbon atoms. In the chemical formula 4-1, R₃Definition and proofreading of `R described in chemical formula 4₃' is as defined. Specific examples of the monomer represented by chemical formula 4-1 may include methacrylic acid (MAA).

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

[ chemical formula 5-1]

In chemical formula 5-1, R₄"is an alkyl group having 1 to 10 carbon atoms, and R₅"is an alkyl group containing 1 to 10 carbon atoms. In chemical formula 5-1, R₄"and R₅"is defined as described for chemical formula 5. Specific examples of the monomer represented by chemical formula 5-1 may include Methyl Methacrylate (MMA).

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

[ chemical formula 6-1]

In chemical formula 6-1, Ar is an aryl group having 6 to 20 carbon atoms. In chemical formula 6-1, Ar is defined as described for chemical formula 6. Specific examples of the monomer represented by chemical formula 6-1 may include Styrene (SM).

The alkali-developable binder resin may have a weight average molecular weight of 30000g/mol or more and 150000g/mol or less, and a glass transition temperature of 20 ℃ or more and 150 ℃ or less. Thus, the coatability and flowability of the dry film photoresist, as well as the mechanical strength of the resist itself after circuit formation, can be improved. Further, the acid value of the alkali developable binder resin may be 140mg KOH/g or more and 160mg KOH/g or less.

Further, the alkali developable binder resin may have a weight average molecular weight of 20000g/mol or more and 130000g/mol or less, and a glass transition temperature of 30 ℃ or more and 160 ℃ or less. Thus, the coatability and flowability of the dry film photoresist, as well as the mechanical strength of the resist itself after circuit formation, can be improved. In addition to this, the present invention is,

as used herein, the weight average molecular weight refers to a polystyrene-equivalent weight average molecular weight measured by Gel Permeation Chromatography (GPC). In measuring the polystyrene-reduced weight average molecular weight measured by GPC, a detector and an analytical column such as a well-known analytical apparatus and a differential refractive index detector can be used, and the temperature conditions, solvent and flow rate that are generally applied can be employed.

Specific examples of the measurement conditions are as follows: the alkali developable binder resin was dissolved in tetrahydrofuran, filtered at a concentration of 1.0 (w/w)% (about 0.5 (w/w)%, based on the solid content), in THF using a syringe filter with a pore size of 0.45 μm, and then injected into GPC in an amount of 20 μ l, Tetrahydrofuran (THF) was used as a mobile phase of GPC and the flow rate was 1.0 mL/min. The columns were configured with 1 Agilent PLgel 5 μm Guard (7.5X 50mm) and 2 Agilent PLgel 5 μm Mixed D (7.5X 300mm) connected in series, and measured at 40 ℃ by using an Agilent 1260Infinity II System, RI Detector as the Detector.

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

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

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

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

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

The glass transition temperatures of the reference and the binder polymer were compared using DSC (differential scanning calorimeter) (Perkin-Elmer, DSC-7). The measurement can be made by keeping the temperature at 20 ℃ for 15 minutes, then increasing the temperature to 200 ℃ at a rate of 1 ℃/min.

The acid value of the alkali developable binder resin was measured by the following method: about 1g of the alkali developable binder resin was sampled, dissolved in 50ml of a mixed solvent (MeOH 20%, acetone 80%), to which 2 drops of 1% -phenolphthalein indicator were added, followed by titration with 0.1N-KOH to measure the acid value.

The first alkali-developable binder resin may have an acid value of 140mg KOH/g or more and 160mg KOH/g or less. Further, the acid value of the second alkali-developable binder resin may be 160mg KOH/g or more and 200mg KOH/g or less.

Specifically, the ratio of the glass transition temperatures of the first alkali developable binder resin and the second alkali developable binder resin may be 1:1.5 or greater than 1.5 and 1:5 or less than 5, 1:1.5 or greater than 1.5 and 1:3 or less than 3, 1:1.5 or greater than 1.5 and 1:2 or less than 2, 1:1.5 or greater than 1.5 and 1:1.8 or less than 1.8, 1:1.5 or greater than 1.5 and 1:75 or less than 75, or 1:1.5 or greater than 1.5 and 1:6 or less than 6.

Further, the ratio of the acid numbers of the first and second alkali-developable binder resins may be 1:1.01 or greater than 1.01 and 1:1.5 or less than 1.5, 1:1.01 or greater than 1.01 and 1:1.25 or less than 1.25, 1:1.01 or greater than 1.01 and 1:1.2 or less than 1.2, or 1:1.01 or greater than 1.01 and 1:1.1 or less than 1.1.

Meanwhile, the first alkali-developable binder resin included in the photosensitive resin layer of one embodiment may include the repeating unit represented by chemical formula 4 of 1.2mol or more and 3mol or less, 1.2mol or more and 2mol or less, 1.5mol or more and 2mol or less, or 1.5mol or more and 1.6mol or less based on 1mol of the repeating unit represented by chemical formula 3.

In addition, the second alkali-developable binder resin included in the photosensitive resin layer of one embodiment may include the repeating unit represented by chemical formula 5 of 2mol or more and 10mol or less, 3mol or more and 5mol or less, or 4mol or more and 5mol or less, based on 1mol of the repeating unit represented by chemical formula 7.

Meanwhile, the second alkali-developable binder resin may include a random copolymer of a repeating unit represented by the following chemical formula 4, a repeating unit represented by the following chemical formula 5, and a repeating unit represented by the following chemical formula 6.

[ chemical formula 4]

In chemical formula 4, R₃' is an alkyl group having 1 to 10 carbon atoms,

[ chemical formula 5]

[ chemical formula 6]

In chemical formula 6, Ar is an aryl group having 6 to 20 carbon atoms.

[ chemical formula 4-1]

In the chemical formula 4-1, R₃' is an alkyl group having 1 to 10 carbon atoms. In the chemical formula 4-1, R₃' and R as described for chemical formula 4₃' are as defined. Specific examples of the monomer represented by chemical formula 4-1 may include methacrylic acid (MAA).

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

[ chemical formula 5-1]

[ chemical formula 6-1]

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

Specifically, the first alkali-developable binder resin may include a repeating unit represented by chemical formula 4 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): a repeating unit represented by chemical formula 5: a repeating unit represented by chemical formula 6.

Further, the second alkali-developable binder resin may include a repeating unit represented by chemical formula 4 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): a repeating unit represented by chemical formula 5: a repeating unit represented by chemical formula 6.

Meanwhile, the photosensitive resin layer of one embodiment of the present disclosure may include the second alkali-developable binder resin of 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, based on 100 parts by weight of the first alkali-developable binder resin.

As described above, when the second alkali-developable binder resin is added in an excess amount of 500 parts by weight or more based on 100 parts by weight of the first alkali-developable binder resin, the technical effects of imparting a hydrophobic function to the photosensitive resin, increasing the resistance to a developer solution, and improving circuit performance can be achieved.

The content of the alkali developable binder resin is 20 wt% or more and 80 wt% or less with respect to the total weight of the photosensitive resin composition on a solid content basis. When the content of the alkali-developable binder resin is within the above range, an effect of enhancing the adhesion of fine lines after the formation of circuits can be obtained. The solid content is based on weight, and means the remaining components excluding the solvent from the photosensitive resin composition for forming the photosensitive resin layer.

The content of the alkali developable binder resin of the present disclosure may be 40 wt% or more and 70 wt% or less with respect to the total weight of the photosensitive resin composition. When the content of the alkali-developable binder resin is less than 40% by weight relative to the total photosensitive resin composition, there is a disadvantage of causing defects such as short circuits due to contamination during development, and when the content of the alkali-developable binder resin exceeds 70% by weight, there is a problem of deterioration in circuit performance (e.g., adhesiveness) and resolution.

(2) Photopolymerization initiator

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

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

In addition, a compound selected from the following may be used as the photopolymerization initiator, but is not limited thereto: 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenyldiimidazole, 1-hydroxycyclohexylphenylketone, 2-dimethoxy-1, 2-diphenyl-1-ethanone (2,2-dimethoxy-1,2-diphenylethan-1-one), 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- [ 4-morpholinophenyl ] -1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2-dimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-propanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and mixtures thereof, 1- [4- (2-Hydroxymethoxy) phenyl ] -2-hydroxy-2-methyl-1-propanone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-propanone, 1- (4-dodecylphenyl) -2-hydroxy-2-methyl-1-propanone, 4-benzoyl-4 '-methyldimethylsulphide, 4-dimethylaminobenzoic acid, 2-dimethylthioxanthone, 2, 4-dimethylthioxanthone, 3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-propanone, 4-benzoyl-4' -dimethylthioxanthone, 4-dimethylthioxanthone, and mixtures thereof, Methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2-diethoxyacetophenone, benzyl ketone dimethyl acetal (benzyl ketone dimethyl acetal), benzyl ketone beta-methoxydiethyl acetal (benzyl ketone beta-methoxy diethyl acetal), 1-phenyl-1,2-propyldioxime-o, o ' - (2-carbonyl) ethoxy ether (1-phenyl-1, 2-propyliodoxime-o, o ' - (2-carbonyl) ethoxyether, methyl o-benzoylbenzoate, bis [ 4-dimethylaminophenyl) methanone, 4' -bis (diethylamino) benzophenone, 4,4' -dichlorobenzophenone, benzylbenzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, isobutoxybenzoin, tert-butoxybenzoin, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, α -dichloro-4-phenoxyacetophenone and pentyl 4-dimethylaminobenzoate.

The content of the photopolymerization initiator is 2 wt% or more and 10 wt% or less, based on the solid content, relative to the total weight of the photosensitive resin composition for forming the photosensitive resin layer. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity can be obtained. The solid content is based on weight and means the remaining components except the solvent from the photosensitive resin composition.

When the content of the photopolymerization initiator is less than 2% by weight, light efficiency is low and a large amount of exposure must be employed, and thus, there is a disadvantage that production efficiency is extremely lowered. When the content of the photopolymerization initiator exceeds 10% by weight, there is a problem in that the film is brittle and contamination of the developer solution increases, resulting in defects such as short circuits.

(3) Photopolymerizable compounds

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

The photopolymerizable compound of the present disclosure may include a photopolymerizable compound including a multifunctional (meth) acrylate compound having three or more functions.

Specifically, the trifunctional or higher polyfunctional (meth) acrylate compound may 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.

More specifically, the trifunctional or higher multifunctional (meth) acrylate compound may include a compound of the following chemical formula 2:

[ chemical formula 2]

In chemical formula 2, R₄Is hydrogen or alkyl having 1 to 10 carbon atoms, R₅Is alkylene having 1 to 10 carbon atoms, R₆Is a p-valent functional group comprising a central radical having from 1 to 20 carbon atoms, n2 is an integer from 1 to 20, and p is R₆Number of functional groups substituted thereon, andan integer of 3 to 10.

Further, in chemical formula 2, n2 is an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to 5, and p represents R₆The number of functional groups substituted thereon, and may be an integer of 3 to 10, an integer of 3 to 5, or an integer of 3 to 4.

That is, in chemical formula 2, since p represents R₆The number of the above-substituted functional groups is an integer of 3 to 10, so that the trifunctional or higher multifunctional (meth) acrylate compound represented by chemical formula 2 may be a trifunctional or higher multifunctional (meth) acrylate compound.

Specifically, the multifunctional (meth) acrylate compound may be represented by the following chemical formula 2-1:

[ chemical formula 2-1]

In chemical formula 2-1, R₆' is a trivalent functional group containing 1 to 10 carbon atoms, R₇To R₉Each independently an alkylene group containing 1 to 10 carbon atoms, R₁₀To R₁₂Each independently hydrogen or an alkyl group containing 1 to 10 carbon atoms, and n3 to n5 each independently is an integer of 1 to 20.

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

Examples of the polyfunctional (meth) acrylate compound represented by chemical formula 2 are not particularly limited, but may be, for example, T063 (trimethylolpropane [ EO ] represented by the following chemical formula B)]₆Triacrylate).

[ chemical formula B ]

When the photosensitive resin layer of an embodiment includes the multifunctional (meth) acrylate compound represented by chemical formula 2, the multifunctional (meth) acrylate compound represented by chemical formula 2 is more cross-linked and has more reactive groups during photo-curing than the monofunctional (meth) acrylate compound. For these technical reasons, it is possible to prevent the circuit performance, which may be a problem when only the multifunctional (meth) acrylate compound represented by chemical formula 2 is added, from being lowered, and to achieve the effect of increasing the amount of change in color development.

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

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

That is, the photopolymerizable compound may comprise: a monofunctional (meth) acrylate compound including a (meth) acrylate ester including an alkyleneoxy group containing 1 to 10 carbon atoms; and a trifunctional or more 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.

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

[ chemical formula 1]

In chemical formula 1, R₁Is hydrogen or alkyl having 1 to 10 carbon atoms, R₂Is alkylene having 1 to 10 carbon atoms, R₃Is an alkyl group having 1 to 10 carbon atoms, and n1 is an integer of 1 to 20.

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

Specifically, in chemical formula 1, n1 may be an integer of 1 to 20, an integer of 1 to 10, or an integer of 5 to 10. Examples of the monofunctional (meth) acrylate compound represented by chemical formula 1 are not particularly limited, but may be, for example, a040 (methoxypropanediol [400] acrylate) represented by chemical formula a below.

[ chemical formula A ]

When the photosensitive resin layer of one embodiment includes the monofunctional (meth) acrylate compound represented by chemical formula 1, an effect of rapidly achieving color change of the film in an exposed portion may be achieved due to a technical reason of increasing a photocuring speed.

Meanwhile, the photosensitive resin layer of an embodiment may include a trifunctional or more multifunctional (meth) acrylate compound in an amount of 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, based on 100 parts by weight of the monofunctional (meth) acrylate compound.

When the photosensitive resin layer of an embodiment includes an excess amount of the polyfunctional (meth) acrylate compound relative to the monofunctional (meth) acrylate compound, the following effects can be simultaneously achieved: increasing a photocuring speed of the monofunctional (meth) acrylate compound represented by chemical formula 1, thereby rapidly achieving color change of the film; and increasing crosslinking during photocuring of the multifunctional (meth) acrylate compound represented by chemical formula 2 to thereby prevent a decrease in circuit performance occurring when only a monofunctional material is added, and increasing the amount of active groups to increase the amount of change in color development, thereby satisfying a time (t) of 5 minutes or less until a point of time at which the amount of change in color coordinate b x calculated according to formula 1 is 5.0, and finally ensuring excellent developing performance.

When the photosensitive resin layer of one embodiment includes less than 100 parts by weight of the polyfunctional (meth) acrylate compound based on 100 parts by weight of the monofunctional (meth) acrylate compound, there may be a technical problem that circuit performance is deteriorated and the amount of change in color development is reduced.

Meanwhile, the photopolymerizable compound may comprise a bifunctional (meth) acrylate compound including alkylene glycol di (meth) acrylates and urethane di (meth) acrylates.

That is, the photosensitive resin layer of one embodiment includes a photopolymerizable compound, which may include: a monofunctional (meth) acrylate compound; a polyfunctional (meth) acrylate compound; difunctional (meth) acrylates including alkylene glycol di (meth) acrylates and urethane di (meth) acrylates.

The alkylene glycol di (meth) acrylate may 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, butanediol 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) manufactured by Miwon Specialty Chemical co₃DA. Bisphenol A (EO)₃Diacrylate), Miramer M240(BPA (EO)₄DA, bisphenol A (EO)₄Diacrylate), Miramer M241 (bisphenol A (EO)₄Dimethacrylate), Miramer M2100(BPA (EO)₁₀DA. Bisphenol A (EO)₁₀Diacrylate), Miramer M2200(BPA (EO)₂₀DA, bisphenol A (EO)₂₀Diacrylate), Miramer M2101 (bisphenol A (EO)₁₀Dimethacrylate).

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

The urethane di (meth) acrylates may have a molecular weight greater than that of the existing single alkylene oxide and have a linear structure, thereby imparting flexibility. This is a reason for improving the coverage property (stretching property) required for a dry film photoresist (DFR) for an outer layer and the hydrophobicity of a polyol, which is one of components of urethane acrylate, and is a reason for improving the resistance to a plating solution, which is a strong acid, and thus not staining the plating solution.

The urethane di (meth) acrylates can be obtained by the following steps: the diisocyanate compound is reacted with a polyether compound having a hydroxyl group or a polyester compound having a hydroxyl group to obtain a urethane compound, and then the obtained urethane compound is reacted with a compound having both a hydroxyl group and an ethylenically unsaturated group.

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

The diisocyanate compound may include: aliphatic diisocyanate compounds having a divalent aliphatic group (e.g., alkylene group), alicyclic diisocyanate compounds having a divalent alicyclic group (e.g., cycloalkylene group), aromatic diisocyanate compounds, and isocyanurate-modified components thereof, carbodiimidized-modified components, butyrylated-modified components thereof, and the like.

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

The alicyclic diisocyanate compound may include isophorone diisocyanate, methylene bis (cyclohexyl) diisocyanate, and 1, 3-or 1, 4-bis (isocyanatomethyl) cyclohexane, etc.

The aromatic diisocyanate compound may include 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, dimeric polymers of 2, 4-toluene diisocyanate or 2, 6-toluene diisocyanate, (o-, p-or m) -xylene diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, and the like.

They are used alone or in a combination of two or more. Further, they may include isocyanate compounds having two or more isocyanate groups, such as triphenylmethane triisocyanate and tris (isocyanatophenyl) thiophosphate. Among them, from the viewpoint of enhancing flexibility and toughness of the photo-cured product and thus improving adhesion to a substrate, the alicyclic diisocyanate compound is preferable.

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

In addition, in the reaction for synthesizing the urethane compound, dibutyltin dilaurate is preferably added as a catalyst.

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

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

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

The hydroxy (meth) acrylate-caprolactone adduct may include a hydroxyethyl (meth) acrylate-caprolactone adduct, a hydroxypropyl (meth) acrylate-caprolactone adduct, and a hydroxybutyl (meth) acrylate-caprolactone adduct, and the alkylene oxide adduct may include a hydroxyethyl (meth) acrylate-alkylene oxide adduct, a hydroxypropyl (meth) acrylate-propylene oxide adduct, and a hydroxybutyl (meth) acrylate-butylene oxide adduct.

The ester compound may include, for example, glycerol mono (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane mono (meth) acrylate, bis (trimethylolpropane) tri (meth) acrylate, di (meth) acrylate of a trimethylolpropane-ethylene oxide adduct, di (meth) acrylate of a trimethylolpropane-propylene oxide adduct. These ester compounds are used alone or in a combination of two or more.

The urethane di (meth) acrylate is a compound obtained by an addition reaction of a urethane compound and a compound having both a hydroxyl group and an ethylenically unsaturated group, and can be obtained by adding a compound having both a hydroxyl group and an ethylenically unsaturated group at a molar ratio of 2.0 to 2.4 with respect to 1 mole of the urethane compound, and then subjecting it to an addition reaction at 60 to 90 ℃.

Preferably, the weight average molecular weight of the urethane di (meth) acrylates is in the range of 1,000g/mol to 60,000 g/mol. When the weight average molecular weight is less than 1,000g/mol, it is difficult to sufficiently improve flexibility and toughness, and thus substrate adhesion cannot be improved, whereas when the weight average molecular weight exceeds 60,000g/mol, there is a problem that development performance may be deteriorated and development time may be slowed. Thus, it is preferred that the weight average molecular weight of the urethane di (meth) acrylates according to the present disclosure is from 1,000g/mol to 60,000 g/mol.

In the present disclosure, in the photosensitive resin composition for forming a photosensitive resin layer, the content of the urethane based di (meth) acrylate having a weight average molecular weight of 1,000g/mol to 60,000g/mol is 1 wt% to 20 wt%, preferably 1.5 wt% to 15 wt%. When the content of the urethane type di (meth) acrylate having a weight average molecular weight of 1,000g/mol to 60,000g/mol is less than 1% by weight, the effect resulting therefrom is insufficient, and when the content exceeds 20% by weight, there may be a disadvantage in that the development time is rapidly increased in the development process after exposure and also a large amount of scum and sludge is generated.

The photosensitive resin layer of an embodiment may include the urethane based di (meth) acrylate in an amount of 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.

When the content of the urethane based di (meth) acrylate is 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the alkylene glycol based di (meth) acrylate, the photosensitive resin composition of one embodiment can achieve technical effects such as prevention of deterioration of circuit performance, peeling and development time variation.

Specifically, the photosensitive resin layer of an embodiment may include the bifunctional (meth) acrylate compound in an amount of 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, based on 100 parts by weight of the monofunctional (meth) acrylate compound.

That is, the photosensitive resin layer of an embodiment may 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 difunctional (meth) acrylate compound, based on 100 parts by weight of the monofunctional (meth) acrylate compound.

Further, the photosensitive resin layer of an embodiment may include the bifunctional (meth) acrylate compound in an amount of 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, 500 parts by weight or more and 600 parts by weight or less, based on 100 parts by weight of the polyfunctional (meth) acrylate compound.

As described above, when the monofunctional (meth) acrylate compound, the polyfunctional (meth) acrylate compound, and the bifunctional (meth) acrylate compound are contained and, at the same time, they are contained to satisfy the above weight ranges, the photosensitive resin layer of one embodiment may exhibit suitable circuit properties and when 10mJ/cm is applied²Or greater light intensity, a technical effect of enabling rapid color development and color change of the exposed portion can be achieved.

In the present disclosure, the monofunctional photopolymerizable compound may be contained in an amount of 0.1 wt% or more and 2.5 wt% or less based on the total weight of the photosensitive resin composition for forming the photosensitive resin layer.

In addition, in the present disclosure, the content of the multifunctional photopolymerizable compound may be 2.6 wt% or more and 5.0 wt% or less based on the total weight of the photosensitive resin composition for forming the photosensitive resin layer.

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

When the photosensitive resin layer is formed such that the content of the monofunctional photopolymerizable compound is less than 0.1 wt% or the content of the multifunctional photopolymerizable compound is less than 2.6 wt% based on the total weight of the photosensitive resin composition for forming the photosensitive resin layer, the effects brought about by the addition of the compound represented by chemical formula 1 and the compound represented by chemical formula 2 are insufficient, whereas when the content of the monofunctional photopolymerizable compound is more than 2.5 wt% or the content of the multifunctional photopolymerizable compound is more than 5.0 wt%, there may be a problem that hydrophobicity increases, whereby the development time during development after exposure rapidly increases.

The photosensitive resin layer of an embodiment may include an additional photopolymerizable compound, and may 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 trimethacrylate, dipentaerythritol pentamethacrylate, 2-bis (4-methacryloxydiethoxyphenyl) propane, 2-bis (4-methacryloxypolyethoxyphenyl) propane, a, 2-hydroxy-3-methacryloxypropyl methacrylate (2-hydroxy-3-methacryloxypropyl methacrylate), ethylene glycol diglycidyl ether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate, phthalic acid diglycidyl ester dimethacrylate, glycerol polyglycidyl ether polymethacrylate, polyfunctional (meth) acrylate containing a urethane group, and the like.

The content of the photopolymerizable compound may be 10 wt% or more and 70 wt% or less with respect to the total weight of the photosensitive resin composition for forming 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 may be obtained.

The photosensitive resin composition for forming the photosensitive resin layer may include 20 wt% or more and 80 wt% or less of an alkali developable binder resin, 0.1 wt% or more and 10 wt% or less of a photopolymerization initiator, and 10 wt% or more and 70 wt% or less of a photopolymerizable compound, based on the solid content. The solid content is based on weight and means the remaining components except the solvent from the photosensitive resin composition.

The photosensitive resin composition may further include a solvent. The solvent is generally selected from Methyl Ethyl Ketone (MEK), methanol, THF, toluene, and acetone, and is not particularly limited thereto, and the content thereof may also be adjusted according to the contents of the photopolymerization initiator, the alkali-developable binder resin, and the photopolymerizable compound.

In addition, the photosensitive resin composition may further include other additives, as needed. Other additives are plasticizers and may include: dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate in the form of phthalate esters; triethylene glycol diacetate in the form of ethylene glycol esters, tetraethylene glycol diacetate; para-toluenesulfonamide, benzenesulfonamide, n-butylbenzenesulfonamide in the amide form; triphenyl phosphate, and the like.

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

Examples of the coloring material may include toluenesulfonic acid monohydrate, fuchsin, phthalocyanine green, auramine base (auramine base), parafuchsin, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite green, diamond green, and basic blue 20, and the like. When the coloring material is included, the addition amount may be 0.001 wt% or more and 1 wt% or less based on the photosensitive resin composition. When the content is 0.001 wt% or more, there is an effect of improving workability, and when the content is 1 wt% or less, there is an effect of maintaining storage stability.

In addition, other additives may also include thermal polymerization inhibitors, dyes, decolorants, adhesion promoters.

Meanwhile, for the photosensitive resin layer of one embodiment, the thickness is from 10mJ/cm²Above and 30mJ/cm²The time (t) from the time point when the exposure dose below starts to the time point when the amount of change in the color coordinate b x value calculated according to the following formula 1 is 5.0 may be 5 minutes or less, 3 minutes or less, 30 seconds or more and 3 minutes or less, or 30 seconds or more and 2 minutes or less.

[ equation 1]

In the formula 1, the first and second groups of the compound,

b^* ₀is a value of color coordinates (b ×) of the photosensitive resin layer before exposure.

This can be achieved by including the above-described photopolymerizable compound in the photosensitive resin layer in one embodiment.

Specifically, when the photosensitive resin layer of an embodiment includes the monofunctional (meth) acrylate compound represented by chemical formula 1 and the multifunctional (meth) acrylate compound represented by chemical formula 2, and the content of the multifunctional (meth) acrylate compound is 100 parts by weight or more based on 100 parts by weight of the monofunctional (meth) acrylate compound, the time (t) to the point of time at which the change amount of the color coordinate b' value calculated according to chemical formula 1 is 5.0 may be 5 minutes or less.

When the concentration is 10mJ/cm²Above and 30mJ/cm²When the time (t) from the time point when the following exposure dose starts exposure to the time point when the variation amount of the color coordinate b calculated according to formula 1 is 5.0 is 5 minutes or less, the reactivity of the photosensitive resin layer of one embodiment becomes faster, and thus, the color development time and the color development degree of the dry film photoresist including the photosensitive resin layer of one embodiment become excellent. Thus, when the dry film photoresist is exposed, not only is the alignment recognition rate for the product increased, and the production time shortened and the defect rate reduced, but also improvement in including the dry film photoresist can be achievedResist shows the effect of physical properties of the device.

Meanwhile, the change amount of the color coordinate b of the photosensitive resin layer calculated according to the following formula 2 may be 0.6 or more and 14.0 or less,

[ formula 2]

In the formula 2, b^* ₁Is at 10mJ/cm²Above and 30mJ/cm²Value of color coordinate (b x) of the photosensitive resin layer after exposure for 1 minute at the following exposure dose, and b^* ₀Is a value of color coordinates (b) of the photosensitive resin layer before exposure.

The present inventors have found through experiments that when the variation amount of the color coordinate b calculated according to formula 2 is 0.6 or more and 14.0 or less, excellent developing performance can be ensured, and completed the present disclosure.

Meanwhile, the change amount of the color coordinate b of the photosensitive resin layer of one embodiment calculated according to formula 2 may be 0.6 or more and 14.0 or less, 3.1 or more and 13.5 or less, 4 or more and 8 or less, or 4.1 or more and 7.5 or less. This can be achieved by including the above-described photopolymerizable compound in the photosensitive resin layer in one embodiment.

[ formula 2]

In the formula 2, b^* ₁Is at 10mJ/cm²Above and 30mJ/cm²Value of color coordinate (b x) of the photosensitive resin layer after exposure for 1 minute at the following exposure dose, and b^* ₀Is a value of color coordinates (b ×) of the photosensitive resin layer before exposure.

Specifically, when the photosensitive resin layer of an embodiment includes the monofunctional (meth) acrylate compound represented by chemical formula 1 and the multifunctional (meth) acrylate compound represented by chemical formula 2, the amount of change in the color coordinate b calculated according to chemical formula 2 may be 0.6 or more and 14.0 or less.

When the variation amount of the color coordinate b calculated according to formula 2 may be 0.6 or more and 14.0 or less, the reactivity of the photosensitive resin layer of an embodiment becomes faster, and thus, the development time and the development degree of the dry film photoresist including the photosensitive resin layer of an embodiment become excellent. Thus, when the dry film photoresist is exposed, not only the alignment recognition rate for the product is increased and the production time is shortened and the defect rate is reduced, but also an effect of improving the physical properties of the display device including the dry film photoresist can be achieved.

The thickness of the photosensitive resin layer to be measured for the color coordinate (b ″) value may be 15 μm or more and 50 μm or less, 15 μm or more and 45 μm or less, 15 μm or more and 40 μm or less, or 20 μm or more and 40 μm or less, or 25 μm or more and 40 μm or less.

Further, the photosensitive resin layer as a measurement object of the color coordinate (b ×) value may have 0.10cm²Above and 5.00cm²Below or 2.00cm²Above and 4.00cm²The following cross-sectional area parallel to the ground. The thickness or cross-sectional area of the photosensitive resin layer can be measured by an optical microscope.

B in equation 2^* ₀And b^* ₁The measurement of (2) can be performed using a colorimeter. In particular, b^* ₀And b^* ₁B-values that can represent color coordinates (a, b) that are values indicating coordinate axes of unique colors, respectively, have positive (+) and negative (-) values based on 0, and if b is positive (+), it displays yellow; if b is negative (-), it shows blue.

B in equation 2^* ₀And b^* ₁Can be measured according to ASTM method E313 using a Konica Minolta CM-2600d colorimeter.

Specifically, the color coordinates of equation 2, i.e., b^* ₀And b^* ₁Can be measured according to ASTM E313-96 (index: D65/10 degrees) using a Konica Minolta CM-2600D color difference meter.

In addition, the color coordinates of equation 2, i.e., b^* ₀And b^* ₁Can be measured in SCI (including specular reflection) mode or SCE (excluding specular reflection) mode using a Konica Minolta CM-2600d colorimeter or the like.

SCI (including specular reflection light) mode refers to a mode for measuring the color coordinates of the entire reflected light including not only diffuse reflection light but also specular reflection light.

The SCE (specular reflection excluded) mode is a mode in which specular reflection light is removed and the color coordinates of diffuse reflection light are measured.

That is, in one embodiment, the amount of change in the color coordinate b calculated according to formula 2 may be one of the amount of change in the color coordinate b measured in the SCI (including specular reflection light) mode using a color difference meter such as Konica Minolta CM-2600d or the amount of change in the color coordinate b measured in the SCE (excluding specular reflection light) mode using a color difference meter such as Konica Minolta CM-2600 d.

In the formula 2, b^* ₁May be at 10mJ/cm²Above and 30mJ/cm²Value of color coordinate (b;), b, of the photosensitive resin layer after exposure for 1 minute with the following exposure dose^* ₀May be a value of color coordinates (b) of the photosensitive resin layer before exposure.

In formula 2, when b^* ₁Is at 10mJ/cm²Above and 30mJ/cm²The amount of change (Δ b) of the color coordinate b calculated according to formula 2 when the value of the color coordinate b of the photosensitive resin layer is obtained after exposure for 1 minute at the following exposure dose^* ₁) May refer to the amount of change in the initial color coordinate b after exposure of the photosensitive resin layer of one embodiment.

That is, when the change amount of the color coordinate b calculated according to formula 2 of the photosensitive resin layer of one embodiment is 0.6 or more and 14.0 or less, the change amount of the initial color coordinate b after the exposure of the photosensitive resin layer of one embodiment is 0.6 or more and 14.0 or less.

The amount of change (Δ b) in the color coordinates b calculated according to equation 2^* ₁) Is 0.6 or more and 14.0In the following cases, when the polyfunctional (meth) acrylate compound is contained in an excess amount relative to the monofunctional (meth) acrylate compound of one embodiment, the following effects can be simultaneously achieved: increasing a photocuring speed of the monofunctional (meth) acrylate compound represented by chemical formula 1, thereby rapidly achieving color change of the film; and increasing crosslinking during photocuring of the multifunctional (meth) acrylate compound represented by chemical formula 2 to thus prevent degradation of circuit properties occurring when only a monofunctional material is added, and increasing the amount of active groups to increase the amount of change in color development, thereby ensuring excellent developing properties.

Meanwhile, the photosensitive resin layer of an embodiment may have a variation amount of the color coordinate b calculated according to the following formula 3 of 2.2 or more and 14.0 or less.

[ equation 3]

The amount of change in the color coordinates b ([ delta ] b) during an exposure time of 3 minutes^* ₃)＝(b^* ₀-b^* ₃)

In the formula 3, the first and second groups,

b^* ₃is at 10mJ/cm²Above and 30mJ/cm²Value of color coordinate (b x) of the photosensitive resin layer after exposure for 3 minutes at the following exposure dose, and b^* ₀Is a value of color coordinates (b) of the photosensitive resin layer before exposure.

The amount of change (Δ b) in the color coordinates b calculated according to equation 3^* ₃) In the case of 2.2 or more and 14.0 or less, the polyfunctional (meth) acrylate compound is contained in an excess amount relative to the monofunctional (meth) acrylate compound of one embodiment, so that the following effects can be simultaneously achieved: increasing a photocuring speed of the monofunctional (meth) acrylate compound represented by chemical formula 1, thereby rapidly achieving color change of the film; and increasing crosslinking during photocuring of the multifunctional (meth) acrylate compound represented by chemical formula 2 to thus prevent degradation of circuit properties occurring when only a monofunctional material is added, and increasing the amount of active groups to increase the amount of change in color development to ensure excellent developmentAnd (4) performance.

In addition, the change amount of the color coordinate b of the photosensitive resin layer according to the following formula 4 is 4.0 or more and 14.3 or less, or 7.0 or more and 13.0 or less.

[ formula 4]

The amount of change in the color coordinates b ([ delta ] b) during an exposure time of 5 minutes^* ₅)＝(b^* ₀-b^* ₅)

In the formula 4, b^* ₅Is at 10mJ/cm²Above and 30mJ/cm²Value of color coordinate (b x) of the photosensitive resin layer after exposure for 5 minutes at the following exposure dose, and b^* ₀Is a value of color coordinates (b) of the photosensitive resin layer before exposure.

The change amount (Δ b) of the color coordinate b calculated according to formula 4 in the photosensitive resin layer^* ₅) In the case of 4.0 or more and 14.3 or less, the polyfunctional (meth) acrylate compound is contained in an excess amount relative to the monofunctional (meth) acrylate compound of one embodiment, so that the following effects can be simultaneously achieved: increasing the photocuring speed of the monofunctional (meth) acrylate compound represented by chemical formula 1, thereby rapidly achieving color change of the film; and increasing crosslinking during photocuring of the multifunctional (meth) acrylate compound represented by chemical formula 2 to thus prevent degradation of circuit properties occurring when only a monofunctional material is added, and increasing the amount of active groups to increase the amount of change in color development, thereby ensuring excellent developing properties.

2. Dry film photoresist

According to another embodiment of the present disclosure, there may be provided a dry film photoresist including the photosensitive resin layer of one embodiment. Details regarding the photosensitive resin layer include all that is described above in one embodiment.

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

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

The dry film photoresist may 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 is convenient to handle during the exposure of the photosensitive resin layer having adhesive strength.

Various plastic films may be used as the base film, and examples thereof may 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 may be freely adjusted in the range of 0.01 μm to 1mm, for example.

The protective film prevents damage to the resist during processing, and serves as a protective cover for protecting the photosensitive resin layer from foreign substances 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 serves to protect the photosensitive resin layer from the outside. When the dry film photoresist is applied to a subsequent process, it needs to be easily released and requires appropriate peelability and adhesiveness so that it is not deformed during storage and dispensing.

Various plastic films may be used as the protective film, and examples thereof may include at least one plastic film selected from the group consisting of 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 may be freely adjusted within a range of 0.01 μm to 1mm, for example.

Examples of the method of manufacturing the dry film photoresist are not particularly limited, and for example, the photosensitive resin composition 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 dried photosensitive resin layer is laminated with a conventional protective film such as polyethylene to manufacture a dry film.

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

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

Meanwhile, the dry film photoresist of one embodiment may have the following features: from at 10mJ/cm²Above and 30mJ/cm²The time (t) from the time point when the exposure of the photosensitive resin layer is started to the time point when the change amount of the color coordinate b calculated by the following formula 1 is 5.0 is 5 minutes or less, 3 minutes or less, 30 seconds or more and 3 minutes or less, or 30 seconds or more and 2 minutes or less.

[ equation 1]

In the formula 1, b^* ₁Is at 10mJ/cm²Above and 30mJ/cm²The value of color coordinate (b x) of the photosensitive resin layer after exposure for t minutes at the following exposure dose, and b^* ₀Is a value of color coordinates (b) of the photosensitive resin layer before exposure.

Specifically, when the photosensitive resin layer of one embodiment includes a monofunctional (meth) acrylate compound represented by chemical formula 1 and a multifunctional (meth) acrylate compound represented by chemical formula 2, and the content of the multifunctional (meth) acrylate compound is 1 based on 100 parts by weight of the monofunctional (meth) acrylate compoundAbove 00 parts by weight, the dry film photoresist of one embodiment may have the following characteristics: from the bottom to the top at 10mJ/cm²Above and 30mJ/cm²The time (t) from the time point when the exposure of the photosensitive resin layer was started to the time point when the amount of change in the color coordinate b x calculated by formula 1 was 5.0 was 5 minutes or less.

When the concentration is 10mJ/cm²Above and 30mJ/cm²When the time (t) from the time point when the following exposure dose starts to expose the photosensitive resin layer to the time point when the amount of change in the color coordinate b x calculated according to formula 1 is 5.0 is 5 minutes, the development time and the degree of development of the dry film photoresist including the photosensitive resin layer of the embodiment become excellent. Thus, when the dry film photoresist is exposed, not only the alignment recognition rate for the product is increased and the production time is shortened and the defect rate is reduced, but also an effect of improving the physical properties of the display device including the dry film photoresist can be achieved.

Meanwhile, the dry film photoresist of one embodiment may have the following features: the amount of change in the color coordinate b of the photosensitive resin layer, which is calculated according to the following formula 2, may be 2.2 or more and 14.0 or less, 3.1 or more and 13.5 or less, 4 or more and 8 or less, or 4.1 or more and 7.5 or less.

[ formula 2]

In the formula 2, b^* ₁Is at 10mJ/cm²Above and 30mJ/cm²Value of color coordinate (b x) of the photosensitive resin layer after exposure for 1 minute at the following exposure dose, and b^* ₀Is a value of color coordinates (b) of the photosensitive resin layer before exposure. This can be achieved by including the above-described photopolymerizable compound in the photosensitive resin layer in one embodiment.

The detailed description about the variation amount of the color coordinate b calculated according to formula 1 includes the entire contents described above.

Specifically, when the photosensitive resin layer of an embodiment includes the monofunctional (meth) acrylate compound represented by chemical formula 1 and the multifunctional (meth) acrylate compound represented by chemical formula 2, the amount of change in the color coordinate b calculated according to chemical formula 2 may be 2.2 or more and 14.0 or less.

When the amount of change in the color coordinate b calculated according to formula 2 is 2.2 or more and 14.0 or less, the development time and the degree of development of the dry film photoresist including the photosensitive resin layer of the embodiment become excellent. Accordingly, an effect of improving physical properties of a display device including the dry film photoresist may be achieved.

3. Photosensitive element

According to another embodiment of the present disclosure, there may be provided a photosensitive element including: a polymeric substrate; and the above photosensitive resin layer formed on the polymer substrate at 10mJ/cm²Above and 30mJ/cm²The time (t) from the time point when the exposure of the photosensitive resin layer is started to the time point when the change amount of the color coordinate b calculated by the following formula 1 is 5.0 is 5 minutes or less, 3 minutes or less, 30 seconds or more and 3 minutes or less, or 30 seconds or more and 2 minutes or less.

[ equation 1]

The amount of change in the color coordinates b x value during the exposure time (t) (Δ b)^* ₁)＝(b^* ₀-b^* ₁)

Further, in the photosensitive element of one embodiment, a change amount of the color coordinate b of the photosensitive resin layer calculated according to the following formula 2 may be 2.2 or more and 14.0 or less, 3.1 or more and 13.5 or less, 4 or more and 8 or less, or 4.1 or more and 7.5 or less.

[ formula 2]

Color coordinate b value during 1 minute exposure timeAmount of change (Δ b)^* ₁)＝(b^* ₀-b^* ₁)

The detailed description about the variation amount of the color coordinate b calculated according to formula 2 includes the entire contents described above.

Specifically, the photosensitive resin layer includes an alkali-developable binder resin and a photopolymerizable compound including a monofunctional (meth) acrylate compound represented by the following chemical formula 1 and a polyfunctional (meth) acrylate compound represented by the following chemical formula 2.

[ chemical formula 1]

In chemical formula 1, R₁Is hydrogen or alkyl having 1 to 10 carbon atoms, R₂Is alkylene having 1 to 10 carbon atoms, R₃Is an alkyl group having 1 to 10 carbon atoms, n1 is an integer of 1 to 20,

[ chemical formula 2]

In chemical formula 2, R₄Is hydrogen or alkyl having 1 to 10 carbon atoms, R₅Is alkylene having 1 to 10 carbon atoms, R₆Is a p-valent functional group comprising a central radical having from 1 to 20 carbon atoms, n2 is an integer from 1 to 20, and p is R₆The number of the functional groups substituted, and is an integer of 3 to 10.

The detailed description about the photosensitive resin layer includes all the contents described above in one embodiment and the other embodiments.

That is, the photosensitive resin layer includes an alkali developable binder resin and a photopolymerizable compound, and the photopolymerizable compound may include a monofunctional (meth) acrylate compound represented by the following chemical formula 1 and a multifunctional (meth) acrylate compound represented by the following chemical formula 2.

[ chemical formula 1]

[ chemical formula 2]

A specific example of the polymer substrate may be a polyester film formed with an anti-blocking layer formed by an in-line coating method as follows: the method includes uniaxially stretching an unstretched polyester film, coating a coating solution containing a binder resin and organic particles on one surface thereof, and uniaxially stretching the remaining portion.

The polymer substrate is generally manufactured by an in-line coating method without adding an anti-blocking agent, which is generally added in consideration of runnability and winding characteristics in the manufacturing process, and has an organic particle layer using substitute particles that do not impair transparency.

Here, examples of the organic particles used as particles that do not impair transparency while taking the runnability and winding characteristics into consideration may include organic particles such as multi-layered multi-component particles in which acrylic particles such as methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methyl methacrylate, acrylic acid, methacrylic acid copolymers or terpolymers are formed; olefin-based particles such as polyethylene, polystyrene or polypropylene; acrylic and olefinic copolymers; or homopolymer particles, and then another type of monomer is coated on the layer.

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

And is characterized in that the difference in refractive index between the organic particles and the binder resin is 0.05 or less. When the refractive index difference is greater than 0.05, haze increases. This means that there is much scattered light, and when there is much such scattered light, the side wall smoothing effect is reduced. This also depends on the size and amount of the organic particles. Preferably, the organic particles have an average particle size of about 0.5 μm to 5 μm. When less than this value, the workability and the winding characteristics deteriorate, and when more than 5 μm, the haze increases, which is not preferable in view of the occurrence of the dripping problem. The content of the organic particles is preferably 1 to 10% by weight based on the total amount of the binder resin.

When the content of the organic particles is less than 1% by weight based on the total amount of the binder resin, the anti-blocking effect is insufficient and easily scratched, and the runnability and the winding characteristics are deteriorated, and when it exceeds 10% by weight, there may be a problem that the haze is increased and the transparency is deteriorated.

Meanwhile, inorganic particles may be added in addition to the above organic particles. At this time, it is not preferable to add an inorganic anti-blocking agent which is generally used, but it is preferable to add colloidal silica having a particle size of 100nm or less. The content thereof is preferably 10 parts by weight or less based on 100 parts by weight of the binder resin. When the particle size and content as described above are satisfied, sidewall defects or grooves (e.g., pits) caused by an anti-blocking layer can be prevented from occurring when patterning using a dry film photoresist.

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

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

As described above, an unstretched polyester film obtained by melt extrusion of PET pellets is uniaxially stretched, and then a coating solution containing organic particles in a binder resin is coated on the uniaxially stretched film. The coating may be performed on at least one side of the uniaxially stretched film, and the thickness thereof is preferably about 30 to 200nm, based on the thickness after final drying. If a coating solution containing organic particles is coated on a uniaxially stretched film to be thinner than 30nm, there is a problem that the organic particles are easily dropped and easily scratched, and white powder is generated. When coated to be thicker than 200nm, coating streaks are generated in the coating direction in on-line coating with a high coating speed due to an increase in the viscosity of the coating solution.

The polymer substrate obtained by coating using organic particles instead of a conventional anti-blocking agent using the in-line coating method as described above is a substrate film that maintains runnability and winding characteristics due to the particle layer, and has excellent transparency due to the organic particles having excellent light transmission.

Since the lamination of the photosensitive resin layer is performed on the opposite surface of the layer containing organic particles in the polymer substrate, the photosensitive resin layer is formed on the opposite surface of the layer containing organic particles in this manner. Therefore, a crater-like defect which occurs when a base film including an antiblocking agent is laminated as before does not occur. Since particles such as silicon dioxide are not only larger in size than organic particles but also distributed throughout the base film, the influence of silicon dioxide appears unimportant even in the region adjacent to the photosensitive resin layer.

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

The photosensitive element may further include a protective film formed on the photosensitive resin layer. The protective film prevents damage to the photosensitive resin layer during processing and serves as a protective cover for protecting the photosensitive resin layer from foreign substances such as dust. The protective film is laminated on the back surface of the photosensitive resin layer on which the polymer substrate is not formed. The protective film serves to protect the photosensitive resin layer from the outside. When the dry film photoresist is applied to a subsequent process, it needs to be easily released and requires appropriate peelability and adhesiveness so that it is not deformed during storage and dispensing.

4. Circuit board and display device

According to another embodiment of the present disclosure, there may be provided a circuit board or a display device including the photosensitive resin layer of one embodiment. The detailed description about the photosensitive resin layer includes all the contents described above in one embodiment.

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

The photosensitive resin layer included in the circuit board or the display device may be in the form of a film having no opening or in the form of a pattern having openings.

Examples of the method of forming the photosensitive resin in the form of a pattern layer include the following methods: the photosensitive resin layer of the dry film photoresist of the further embodiment is laminated on a circuit board or a display device manufacturing substrate, followed by exposure and development. Further, there can be mentioned 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.

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

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

Accordingly, the photosensitive resin layer included in the dry film photoresist or the photosensitive element of the further embodiment may be included in a circuit board or a display device.

[ advantageous effects ]

According to the present disclosure, it is possible to provide a photosensitive resin layer that realizes excellent fine line adhesion and resolution, and improves the alignment recognition rate of a product during exposure to shorten the manufacturing time of a final product, and reduces the defect rate to improve reliability.

Further, according to the present disclosure, there may be provided a dry film photoresist, a photosensitive element, a circuit board, and a display device including the above photosensitive resin layer.

Detailed Description

The present disclosure will be described in more detail by the embodiments shown below. However, these examples are given only for illustrating the present invention and are not intended to limit the scope of the present invention to these examples.

< preparation examples: preparation of alkali developable Binder resin >

Preparation of example 1

A four-necked round bottom flask was equipped with a mechanical stirrer and reflux apparatus, and then the inside of the flask was purged with nitrogen. 80g of Methyl Ethyl Ketone (MEK) and 7.5g of methanol (MeOH) were added to a flask purged with nitrogen, and then 0.45g of Azobisisobutyronitrile (AIBN) was added and completely dissolved. A monomer mixture of 8g of Acrylic Acid (AA), 15g of methacrylic acid (MAA), 15g of Butyl Acrylate (BA), 52g of Methyl Methacrylate (MMA) and 10g of Styrene (SM) was added thereto as a monomer, heated to 80 ℃, and then polymerized for 6 hours to prepare an alkali-developable adhesive resin 1.

The alkali developable binder resin 1 had a weight average molecular weight of 71538g/mol, a glass transition temperature of 79 ℃, a solid content of 51.4 wt%, and an acid value of 156.3 mgKOH/g.

In a specific example of the weight-average molecular weight measurement conditions, the alkali developable binder resin was dissolved in tetrahydrofuran, filtered using a syringe filter with a pore size of 0.45 μm at a concentration of 1.0 (w/w)% (about 0.5 (w/w)%, based on the solid content) in THF, and then injected into GPC in an amount of 20 μ l, Tetrahydrofuran (THF) was used as a mobile phase of GPC and the flow rate was 1.0 mL/min. The columns were configured with 1 Agilent PLgel 5 μm Guard (7.5X 50mm) and 2 Agilent PLgel 5 μm Mixed D (7.5X 300mm) connected in series, and measured at 40 ℃ by using an Agilent 1260Infinity II System, RI Detector as the Detector.

The acid value is measured by the following method: about 1g of the alkali developable binder resin was sampled, dissolved in 50ml of a mixed solvent (MeOH 20%, acetone 80%), to which 2 drops of 1% -phenolphthalein indicator were added, followed by titration with 0.1N-KOH to measure the acid value.

The solid content is based on the weight of the alkali-developable binder resin prepared in the above preparation examples, and the weight percentage of the solid content remaining after heating in an oven at 150 ℃ for 120 minutes was measured.

Preparation of example 2

A four-necked round bottom flask was equipped with a mechanical stirrer and reflux apparatus, and then the inside of the flask was purged with nitrogen. 110g of Methyl Ethyl Ketone (MEK) and 10g of methanol (MeOH) were added to a flask purged with nitrogen, and then 1g of Azobisisobutyronitrile (AIBN) was added and completely dissolved. A monomer mixture of 30g of methacrylic acid (MAA), 100g of Methyl Methacrylate (MMA) and 30g of Styrene (SM) was added thereto as monomers, heated to 80 ℃, and then polymerized for 6 hours to prepare an alkali developable adhesive resin 2. (weight average molecular weight: 49852g/mol, glass transition temperature: 125 ℃, solid content: 48.5% by weight, acid value: 163.17 mgKOH/g).

< examples and comparative examples: preparation of photosensitive resin composition and Dry film Photoresist >

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.

The obtained 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 ℃ and the drying time was 5 minutes, and the thickness of the photosensitive resin composition layer after drying was 40 μm.

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

The above PET film was produced by the following process.

The PET is prepared by carrying out ester exchange reaction and polycondensation reaction on ethylene glycol and terephthalic acid. The PET pellets were dried under reduced pressure at 120 ℃ for 8 hours, then fed to an extruder and melted at 280 ℃. It was wound on a casting drum having a surface temperature of 20 ℃ using an electrostatic coating casting method, 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, and a coating solution obtained by mixing 4g of an acrylic resin and 0.1g of polymethyl methacrylate as organic particles in 95.9g of water was applied to one surface thereof using gravure printing, and then finally dried to have a thickness of 50 nm. The polymethyl methacrylate used here is a spherical polymethyl methacrylate coated with polystyrene on the surface thereof, and the difference in refractive index from the acrylic resin is 0.03.

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

The above film was heat-set at a maximum temperature of 230 ℃ 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 thickness of 50 nm.

[ Table 1]

< test examples >

The physical properties of the dry film photoresists prepared in examples and comparative examples were measured by the following methods, and the results are shown in the following tables 2 to 4, respectively.

1. Amount of change in color coordinate b value with respect to exposure time

The protective film was peeled off from the dry film photoresists prepared in examples and comparative examples under the following conditions: the substrate preheating roller temperature was 120 ℃, the laminator roller temperature was 115 ℃ and the roller pressure was 4.0kgf/cm²And a roller speed of 2.0min/m, the photosensitive resin layer of the dry film photoresist was laminated by a HAKUTO MACH 610i to contact the copper layer surface of the brushed copper clad laminate having a thickness of 0.4mm, thereby forming a laminate.

The supporting PET film for the dry film photoresist was peeled off from the laminate and then laminated to a thickness of 29 μm and a cross-sectional area of 3cm²Using a Konica Minolta CM-2600d color difference meter to measure color coordinates (b) in SCI (including specular reflection) mode and SCE (excluding specular reflection) mode, respectively^* ₀)。

Thereafter, using a pattern for circuit evaluation (opening portions increased in width by 1 μm from 4 μm to 50 μm arranged at 2 μm intervals), 19mJ/cm was exposed by an LDI exposure machine (FDI-3, Japan ORC)²The exposure dose of (2) was to remove the dry film photoresist of the PET film by irradiation with ultraviolet rays. Color coordinates (b) were measured after exposure for the samples according to ASTM method E313-96(D65/10degree) using a Konica Minolta CM-2600D colorimeter in SCI (including specular reflectance) mode and SCE (excluding specular reflectance) mode^* _n)。

For the measured values, the color coordinates b are calculated according to the following formula^*The amount of change in the value.

[ formula ]

Amount of change of color coordinates b ([ Delta ] b) during n minutes of exposure time^* _n)＝(b^* ₀-b^* _n)

In the formula, b^* _nAt 19mJ/cm²Exposure dose of (c) the value of the color coordinate (b x) of the photosensitive resin layer after exposure for n minutes, and b^* ₀Is a value of color coordinates (b ×) of the photosensitive resin layer before exposure.

[ Table 2]

As shown in table 2, example 1 shows that the change amount of the color coordinate b value at 1 minute measured in the SCI mode was 6.41, the change amount of the color coordinate b value at 3 minutes was 9.13, and the change amount of the color coordinate b value at 5 minutes was 9.98, confirming that example 1 is remarkably excellent in the degree of color development.

Unlike the examples, for comparative example 1 not including the monofunctional (meth) acrylate compound, the change amount of the color coordinate b value at 1 minute measured in the SCI mode was 0.54, the change amount of the color coordinate b value at 3 minutes was 2.11, and the change amount of the color coordinate b value at 5 minutes was 3.92, confirming that comparative example 1 is significantly inferior in the degree of color development, compared to the examples of the present disclosure.

In addition, as compared with examples of the present disclosure, for comparative example 2 not containing the polyfunctional (meth) acrylate compound, the change amount of the color coordinate b value at 1 minute measured in the SCI mode was 0.49, the change amount of the color coordinate b value at 3 minutes was 2.05, and the change amount of the color coordinate b value at 5 minutes was 3.68, confirming that comparative example 2 is significantly inferior in the degree of color development.

[ Table 3]

As shown in table 3, example 1 shows that the change amount of the color coordinate b value at 1 minute measured in the SCE mode was 5.43, the change amount of the color coordinate b value at 3 minutes was 7.82, and the change amount of the color coordinate b value at 5 minutes was 8.59, confirming that example 1 is remarkably excellent in the degree of color development. Unlike the examples, for comparative example 1 not including the monofunctional (meth) acrylate compound, the amount of change in the b value of the color coordinate at 1 minute measured in the SCE mode was 0.45, the amount of change in the b value of the color coordinate at 3 minutes was 2.01, and the amount of change in the b value of the color coordinate at 5 minutes was 3.82, confirming that comparative example 1 is significantly inferior in the degree of color development, compared to examples of the present disclosure.

In addition, as compared with examples of the present disclosure, in comparative example 2 not containing the polyfunctional (meth) acrylate compound, the change amount of the color coordinate b value at 1 minute measured in the SCE mode was 0.36, the change amount of the color coordinate b value at 3 minutes was 1.93, and the change amount of the color coordinate b value at 5 minutes was 3.54, confirming that comparative example 2 was significantly inferior in the degree of color development.

2. Development time (unit: minute)

The protective film was peeled off from the dry film photoresists prepared in examples and comparative examples under the following conditions: the substrate preheating roller temperature was 120 ℃, the laminator roller temperature was 115 ℃ and the roller pressure was 4.0kgf/cm²And a roller speed of 2.0min/m, a photosensitive resin layer of a dry film photoresist was laminated using a HAKUTO MACH 610i to contact the surface of the copper layer of the brushed copper clad laminate having a thickness of 0.4mm, thereby forming a laminate.

In the laminate, the photoresist had a thickness of 29 μm and a cross-sectional area of 3cm for a dry film²Using a Konica Minolta CM-2600d color difference meter to measure the color coordinates (b) in SCI (including specular reflectance) mode^* ₀)。

Thereafter, using the pattern for evaluating the circuit, it was exposed by an LDI exposure machine (FDI-3, Japan ORC) at 19mJ/cm²The exposure dose of (2) irradiating the dry film photoresist with ultraviolet rays. Color coordinates (b) were measured after exposure for the samples in SCI (including specular reflection) mode according to ASTM E313-96 (index: D65/10degree) using a Konica Minolta CM-2600D colorimeter^* _n)。

For the measured values, the measurement reaches the color coordinate b according to the following formula^*The amount of change was 5.0 at time (t).

[ formula ]

Amount of change of color coordinates b ([ Delta ] b) during t minutes of exposure time^* ₁)＝(b^* ₀-b^* ₁)

In the formula, b^* ₁At 19mJ/cm²Exposure dose of (2) photosensitive resin layer after exposure for t minutesThe value of (b) and b^* ₀Is a value of color coordinates (b ×) of the photosensitive resin layer before exposure.

3. Fine wire adhesiveness (Unit:. mu.m)

In the laminate, using the pattern for circuit evaluation, 19mJ/cm was exposed by an LDI exposure machine (FDI-3, Japan ORC)²The dry film photoresist was irradiated with ultraviolet rays and then allowed to stand for 15 minutes. Thereafter, the dry film photoresist was sprayed at 30. + -. 1 ℃ under a pressure of 1.5kgf/cm²Under the jet-type development conditions of (1.0 wt%) of Na₂CO₃The aqueous solution was developed for 1 minute.

In the completely developed laminate, the minimum line width of the photosensitive resin layer was measured with a ZEISS axiophoto microscope and evaluated as fine line adhesiveness. It can be evaluated that the smaller the value, the better the fine line adhesion.

4. Resolution (Unit: mum)

The protective film was peeled off from the dry film photoresists prepared in examples and comparative examples under the following conditions: the substrate preheating roller temperature was 120 ℃, the laminator roller temperature was 115 ℃ and the roller pressure was 4.0kgf/cm²And a roller speed of 2.0min/m, a photosensitive resin layer of a dry film photoresist was laminated using a HAKUTO MACH 610i to contact the copper layer surface of a brushed copper clad laminate having a thickness of 0.4mm, thereby forming a laminate.

Exposure by LDI Exposure machine (FDI-3, Japan ORC) at 19mJ/cm²The laminate was irradiated with ultraviolet rays so that the width of the circuit lines and the pitch between the circuit lines became 1:1 after development, and then allowed to stand for 15 minutes. Thereafter, the laminate was sprayed at 30. + -. 1 ℃ with a pressure of 1.5kgf/cm²Under the development conditions of the jet type, 1.0wt% of Na₂CO₃The aqueous solution was developed for 1 minute.

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

5. Evaluation of plating antifouling Properties

The dry film photoresists prepared in examples and comparative examples were cut into a size of 40cm × 50cm, the protective film was removed, a step table (step table) was exposed at an exposure dose of 20 steps/41 steps, and the PET film was peeled off to obtain a cured film. The cured film was immersed in 1L of a copper sulfate/sulfuric acid aqueous solution plating solution for 3 days. The copper plate was subjected to electrolytic copper plating using a Halcel Test bath (manufactured by Jungdo Test Instruments lab. korea) at a current of 2A for 10 minutes.

When a plating solution in which the cured film is not impregnated is used as a reference sample and plating is performed by the plating solution in which the cured film is impregnated, the appearance of the plating layer is observed with the naked eye, and if there is an abnormality or a change in glossiness in the appearance of the plating layer, X is judged; if the sample is the same as the reference sample and thus no abnormality is present at all, O is judged.

6. Peeling speed (unit: second)

The protective film was peeled off from the dry film photoresists prepared in examples and comparative examples under the following conditions: the substrate preheating roller temperature was 120 ℃, the laminator roller temperature was 115 ℃ and the roller pressure was 4.0kgf/cm²And a roller speed of 2.0min/m, a photosensitive resin layer of a dry film photoresist was laminated by a HAKUTO MACH 610i to contact the surface of the copper layer of the brushed copper clad laminate having a thickness of 0.4mm, thereby forming a laminate.

Using the pattern for circuit evaluation, 19mJ/cm by an LDI exposure machine (FDI-3, Japan ORC)²The laminated body was irradiated with ultraviolet rays and then allowed to stand for 15 minutes. Thereafter, the pressure of the spray was 1.5kgf/cm at 30. + -. 1 ℃ C²Under the jet-type development conditions of (1.0 wt%) of Na₂CO₃The aqueous solution was developed for 1 minute.

Then, the mixture was peeled off using a 3% aqueous solution of sodium hydroxide (temperature: 50 ℃ C.). The peeling speed was evaluated by measuring the time required for the light cured layer to peel from the copper plate.

[ Table 4]

As shown in Table 4, example 1 exhibited excellent thin line adhesion and resolution, while color coordinate b^*The development time when the amount of change reached 5.0 was within 1 minute, confirming that example 1 exhibited a rapid and remarkably excellent development time.

Unlike the examples, it can be confirmed that, as compared with the examples of the present disclosure, for comparative example 1 not including the monofunctional (meth) acrylate compound, the color coordinate b^*The color development time when the amount of change reached 5.0 was significantly poor.

In addition, it can be confirmed that, as compared with examples of the present disclosure, for comparative example 2 not including the polyfunctional (meth) acrylate compound, the color coordinate b^*The color development time when the amount of change in value reached 5.0 was significantly poor.

Claims

1. A photosensitive resin layer comprising: a photopolymerizable compound comprising a trifunctional or higher multifunctional (meth) acrylate compound; and an alkali-developable binder resin,

wherein the concentration is 10mJ/cm²Above and 30mJ/cm²The time t from the time point when the exposure dose below started to the time point when the amount of change in the color coordinate b x value calculated according to the following formula 1 was 5.0 was 5 minutes or less,

[ equation 1]

Quantity of change Δ b of color coordinates b during exposure time t^* ₁＝(b^* ₀-b^* ₁)

In the formula 1, the first and second groups of the compound,

b^* ₁is at 10mJ/cm²Above and 30mJ/cm²The color coordinate b of the photosensitive resin layer after exposure for t minutes at the following exposure dose, and

b^* ₀is a value of color coordinate b of the photosensitive resin layer before exposure.

2. The photosensitive resin layer according to claim 1, wherein a variation amount of a color coordinate b calculated according to the following formula 2 is 0.6 or more and 14.0 or less during an exposure time of 1 minute,

[ formula 2]

Amount of change Δ b of color coordinates b during an exposure time of 1 minute^* ₁＝(b^* ₀-b^* ₁)

In the formula 2, the first and second groups,

b^* ₁is at 10mJ/cm²Above and 30mJ/cm²The color coordinate b of the photosensitive resin layer after exposure for 1 minute at the following exposure dose, and

b^* ₀is the color coordinate b value of the photosensitive resin layer before exposure.

3. The photosensitive resin layer of claim 1, wherein the trifunctional or more 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.

4. The photosensitive resin layer of claim 1, wherein the trifunctional or higher multifunctional (meth) acrylate compound comprises a compound of the following chemical formula 2:

[ chemical formula 2]

In the chemical formula 2, the first and second organic solvents,

R₄is hydrogen or contains 1 to 10An alkyl group of a carbon atom,

R₅is an alkylene group having 1 to 10 carbon atoms,

R₆is a p-valent functional group comprising a central group containing 1 to 20 carbon atoms,

n2 is an integer from 1 to 20, an

p is R₆The number of the functional groups substituted, and is an integer of 3 to 10.

5. The photosensitive resin layer of claim 1, wherein the trifunctional or higher multifunctional (meth) acrylate compound comprises a compound of the following chemical formula 2-1:

[ chemical formula 2-1]

In the chemical formula 2-1, the,

R₆' is a trivalent functional group containing 1 to 10 carbon atoms,

R₇to R₉Each independently an alkylene group containing 1 to 10 carbon atoms,

R₁₀to R₁₂Each independently hydrogen or alkyl having 1 to 10 carbon atoms, and

n3 to n5 are each independently an integer of 1 to 3.

6. The photosensitive resin layer of claim 1, wherein the photopolymerizable compound further comprises a monofunctional (meth) acrylate compound.

7. The photosensitive resin layer of claim 6, wherein the photopolymerizable compound comprises 100 parts by weight or more of the trifunctional or more multifunctional (meth) acrylate compound based on 100 parts by weight of the monofunctional (meth) acrylate compound.

8. The photosensitive resin layer of claim 6, wherein the monofunctional (meth) acrylate compound comprises a (meth) acrylate comprising an alkyleneoxy group containing 1 to 10 carbon atoms.

9. The photosensitive resin layer of claim 6, wherein the photopolymerizable compound comprises:

a monofunctional (meth) acrylate compound including a (meth) acrylate ester including an alkyleneoxy group containing 1 to 10 carbon atoms; and

a trifunctional or more 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.

10. The photosensitive resin layer of claim 1, wherein the alkali developable binder resin has a weight average molecular weight of 20000g/mol or more and 150000g/mol or less.

11. The photosensitive resin layer of claim 1, wherein the alkali-developable binder resin comprises:

a first alkali-developable binder resin including a repeating unit represented by the following chemical formula 3, a repeating unit represented by the following chemical formula 4, a repeating unit represented by the following chemical formula 5, a repeating unit represented by the following chemical formula 6, and a repeating unit represented by the following chemical formula 7; and

a second alkali-developable binder resin including a repeating unit represented by the following chemical formula 4, a repeating unit represented by the following chemical formula 5, and a repeating unit represented by the following chemical formula 6,

[ chemical formula 3]

In the chemical formula 3, the first and second,

R₃"is a hydrogen atom or a hydrogen atom,

[ chemical formula 4]

In the chemical formula 4, the first and second organic solvents,

R₃' is an alkyl group having 1 to 10 carbon atoms,

[ chemical formula 5]

In the chemical formula 5, the first and second organic solvents,

R₄"is an alkyl group having 1 to 10 carbon atoms, and

R₅"is an alkyl group containing 1 to 10 carbon atoms,

[ chemical formula 6]

In the chemical formula 6, the first and second,

ar is an aryl group having 6 to 20 carbon atoms,

[ chemical formula 7]

In the chemical formula 7, the first and second,

R₄is hydrogen, and

R₅' is an alkyl group having 1 to 10 carbon atoms.

12. The photosensitive resin layer of claim 11, wherein the content of the second alkali-developable binder 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 binder resin.

13. The photosensitive resin layer according to claim 1, wherein the thickness of the photosensitive resin layer is 15 μm or more and 50 μm or less.

14. The photosensitive resin layer of claim 1, wherein the color coordinates are measured according to ASTM E313-96, coefficient: d65/10 degrees.

15. The photosensitive resin layer of claim 2, wherein the color coordinates are measured using a color difference meter in a specular reflection light included SCI mode or a specular reflection light excluded SCE mode.

16. The photosensitive resin layer according to claim 1, wherein a variation amount of a color coordinate b calculated according to the following formula 3 is 2.2 or more and 14.0 or less,

[ formula 3]

Amount of change Δ b of color coordinates b during an exposure time of 3 minutes^* ₃＝(b^* ₀-b^* ₃)

In the formula 3, the first and second groups,

b^* ₃is at 10mJ/cm²Above and 30mJ/cm²The color coordinate b of the photosensitive resin layer after exposure for 3 minutes at the following exposure dose, and

17. The photosensitive resin layer according to claim 1, wherein a change amount of the color coordinates b calculated according to the following formula 4 is 4.0 or more and 14.3 or less,

[ formula 4]

Amount of change Δ b of color coordinates b during an exposure time of 5 minutes^* ₅＝(b^* ₀-b^* ₅)

In the case of the formula 4, the,

b^* ₅is at 10mJ/cm²Above and 30mJ/cm²The color coordinate b of the photosensitive resin layer after exposure for 5 minutes at the following exposure dose, and

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

19. A photosensitive element, comprising:

a polymeric substrate; and

the photosensitive resin layer of claim 1 formed on the polymer substrate.