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

Abstract

The present invention relates to a photosensitive resin composition comprising a monofunctional photopolymerizable compound and a multifunctional photopolymerizable compound of three or more functions, and having excellent substrate adhesion, and a dry film photoresist and a photosensitive element using the same.

Description

Technical Field

[0001] Cross-reference to related applications

[0002] This application claims the benefit of Korean Patent Application No. 10-2019-0179945, filed on December 31, 2019, with the Korean Intellectual Property Office, and Korean Patent Application No. 10-2020-0095387, filed on July 30, 2020, the disclosures of which are incorporated herein by reference in their entirety.

[0003] This disclosure relates to a photosensitive resin layer, a dry film photoresist using the photosensitive resin layer, and a photosensitive element. Background Technology

[0004] Photosensitive resin compositions are used in the form of dry film photoresist (DFR) for printed circuit boards (PCBs) or lead frames, liquid photoresist inks, etc.

[0005] Currently, 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 partitions for plasma display panels (PDPs), ITO electrodes for other displays, bus address electrodes, black matrices, etc.

[0006] Typically, this type of dry film photoresist is frequently used in applications where it is laminated onto copper-clad laminates. Relatedly, as an example of the printed circuit board (PCB) manufacturing process, a pretreatment process is first performed to laminate the copper-clad laminate, which serves as the raw board material for the PCB. The pretreatment process follows a sequence: drilling, deburring, and surface finishing in the outer layer processes, and surface finishing or pickling in the inner layer processes. Surface finishing primarily utilizes brushing and pumice blasting processes, while pickling can involve soft etching and a 5% by weight sulfuric acid pickling solution.

[0007] To form circuits on a pre-processed copper-clad laminate, dry film photoresist (DFR) is typically laminated onto the copper layer of the laminate. In this process, the DFR photoresist layer is laminated onto the copper surface while a laminator is used to peel off the protective film of the DFR. Lamination is typically performed at speeds of 0.5 m / min to 3.5 m / min, temperatures of 100°C to 130°C, and heated roller pressures of 10 psi to 90 psi.

[0008] The laminated printed circuit board is left to stand for at least 15 minutes to stabilize. Then, the DFR photoresist is exposed through a photomask with the desired circuit pattern formed on it. During this process, when the photomask is irradiated with ultraviolet light, the UV-irradiated photoresist begins to polymerize through the photoinitiator contained in the irradiated area. First, the oxygen in the photoresist is consumed, and then the activated monomers polymerize to initiate a cross-linking reaction. Subsequently, the polymerization reaction continues while a large amount of monomer is consumed. Meanwhile, the unexposed areas exist in a state where no cross-linking reaction has occurred.

[0009] Next, a development process is performed to remove the unexposed portions of the photoresist. In the case of alkaline developable DFR, an aqueous solution of potassium carbonate and sodium carbonate at 0.8% to 1.2% by weight is used as the developer. During this process, the unexposed portions of the photoresist are washed away by a saponification reaction between the carboxylic acid of the binder polymer and the developer in the developer, and the cured photoresist remains on the copper surface.

[0010] Then, depending on the inner and outer layer processes, the circuit is formed using different processes. However, in the inner layer process, the circuit is formed on the circuit board through etching and stripping processes, while in the outer layer process, electroplating and masking processes are performed, followed by etching and solder stripping to form the predetermined circuit.

[0011] Recently, there is a need to develop a photosensitive resin composition that exhibits high sensitivity to direct exposure by ultra-high pressure mercury lamps or lasers, increases resistance to developer, thereby enabling the formation of high-density circuits during development, possesses excellent color development, can be used as a UV marker for setting the exposure position of the substrate, and shortens the peeling time of the cured film. The peeled sample is small, so it will not clog the filter. Summary of the Invention

[0012] Technical issues

[0013] One object of this disclosure is to provide a photosensitive resin layer that can achieve excellent substrate adhesion.

[0014] Another object of this disclosure is to provide a dry film photoresist comprising the photosensitive resin layer and a photosensitive element device.

[0015] Technical solution

[0016] To achieve the above objectives, this specification provides a photosensitive resin layer comprising: a photopolymerizable compound containing a multifunctional (meth)acrylate compound with trifunctionality or higher; and an alkaline developing adhesive resin, wherein, during a tape peel test on a film sample laminated with the photosensitive resin layer onto a substrate using a peel tester, the adhesion, as defined by the following formula 1, is 90% or more:

[0017] [Formula 1]

[0018] Adhesion (%) = (Surface area of ​​substrate and photosensitive resin layer after tape peel test / Surface area of ​​photosensitive resin layer in contact with substrate before tape peel test) * 100.

[0019] The trifunctional or higher polyfunctional (meth)acrylate compound may have a structure in which three or more alkoxide 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.

[0020] The trifunctional or higher polyfunctional (meth)acrylate compounds may include compounds of formula 2.

[0021] The trifunctional or higher polyfunctional (meth)acrylate compounds may include compounds of formula 2-1. Compounds of formula 2-1 are described below.

[0022] The photopolymerizable compound may also include a monofunctional (meth)acrylate compound.

[0023] Based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photopolymerizable compound may contain more than 100 parts by weight of the polyfunctional (meth)acrylate compound.

[0024] The monofunctional (meth)acrylate compound may comprise: a (meth)acrylate comprising an alkeneoxy group having 1 to 10 carbon atoms.

[0025] The monofunctional (meth)acrylate compound may include compounds of formula 1.

[0026] The photopolymerizable compound may comprise: a monofunctional (meth)acrylate compound comprising: a (meth)acrylate containing an alkene group having 1 to 10 carbon atoms; and a trifunctional or more polyfunctional (meth)acrylate compound having a structure in which three or more alkene 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.

[0027] The weight-average molecular weight of the alkaline developing adhesive resin can be above 20,000 g / mol and below 150,000 g / mol.

[0028] Based on 100 parts by weight of the monofunctional (meth)acrylate compound, the content of the polyfunctional (meth)acrylate compound may be less than 100 parts by weight.

[0029] Based on 100 parts by weight of the monofunctional (meth)acrylate compound, the content of the polyfunctional (meth)acrylate compound may be more than 30 parts by weight and less than 90 parts by weight.

[0030] The alkaline developer adhesive resin may comprise: a first alkaline developer adhesive resin comprising repeating units represented by chemical formula 3, repeating units represented by chemical formula 4, repeating units represented by chemical formula 5, repeating units represented by chemical formula 6, and repeating units represented by chemical formula 7; and a second alkaline developer adhesive resin comprising repeating units represented by chemical formula 4, repeating units represented by chemical formula 5, and repeating units represented by chemical formula 6. Chemical formulas 3 to 7 are described below.

[0031] Based on 100 parts by weight of the first alkaline developer adhesive resin, the content of the second alkaline developer adhesive resin may be 500 parts by weight or more and 1000 parts by weight or less.

[0032] The ratio of the glass transition temperatures of the first alkaline developer adhesive resin to the second alkaline developer adhesive resin can be from 1:1.5 to 1:5.

[0033] The ratio of the acid values ​​of the first alkaline developer adhesive resin to the second alkaline developer adhesive resin can be from 1:1.01 to 1:1.5.

[0034] The thickness of the photosensitive resin layer can be greater than 1 μm and less than 1000 μm.

[0035] The cross-sectional area of ​​the photosensitive resin layer can be 0.10 cm². 2 Above and 5.00cm 2 the following.

[0036] This specification also provides a dry film photoresist, comprising: a photosensitive resin layer containing the photosensitive resin composition.

[0037] This specification also provides a photosensitive element, comprising: a polymer substrate; and the photosensitive resin layer formed on the polymer substrate.

[0038] This specification also provides a photosensitive element, comprising: a polymer substrate; and the photosensitive resin layer formed on the polymer substrate, wherein, during a tape peel test on a film sample of the photosensitive resin layer laminated on the substrate using a peel tester, the adhesion, as defined by the following formula 1, is 90% or more:

[0039] [Formula 1]

[0040] Adhesion (%) = (Surface area of ​​substrate and photosensitive resin layer after tape peel test / Surface area of ​​photosensitive resin layer in contact with substrate before tape peel test) * 100.

[0041] The photosensitive resin compositions, photosensitive resin layers, and dry film photoresists and photosensitive elements using the present disclosure will be described in more detail below according to specific embodiments of the present disclosure.

[0042] Unless otherwise stated throughout this specification, the technical terms used herein are for reference only in specific implementations and are not intended to limit this disclosure.

[0043] Unless the context clearly specifies otherwise, the singular forms “a,” “an,” and “the” used in this specification include the plural reference.

[0044] As used in this specification, the terms "comprising" or "including" specify a particular feature, region, integer, step, action, element, and / or component, but do not preclude the presence or addition of different particular features, regions, integers, steps, actions, elements, components, and / or combinations.

[0045] Furthermore, terms including ordinal numbers such as "first," "second," etc., are used only for the purpose of distinguishing one component from another and are not limited by ordinal numbers. For example, the first component may be referred to as the second component, or similarly, the second component may be referred to as the first component, without departing from the scope of this disclosure.

[0046] Examples of substituents in this specification are described below, but are not limited thereto.

[0047] In this specification, the term "substitution" means the bonding of other functional groups to replace hydrogen atoms in a compound, and there are no restrictions on the position of substitution, as long as the position is where a hydrogen atom is substituted, that is, the position where the substituent can substitute. When two or more substituents are substituted, the two or more substituents can be the same or different from each other.

[0048] In this specification, the term "substituted or unsubstituted" means unsubstituted or substituted by one or more substituents selected from deuterium; halogen group; cyano; nitro; hydroxyl; carbonyl; ester group; imide group; amide group; primary amino group; carboxyl group; sulfonic acid group; sulfonamide group; phosphine oxide group; alkoxy; aryloxy; alkoxysulfoxy; arylsulfoxide group; alkyl sulfoxide group; aryl sulfoxide group; silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; arylenyl group; alkaryl group; alkoxysilylalkyl group; arylphosphine group; or heterocyclic group containing at least one of N, O, S atoms, or unsubstituted or substituted by substituents linked to two or more substituents exemplified above. For example, "substituents linked to two or more substituents" can be biphenyl. That is, biphenyl can also be aryl and can be understood as substituents linked to two phenyl groups.

[0049] In this specification, symbols Or -* indicates a bond connected to another substituent, and a direct bond refers to the case where no other atoms are present in the part represented by L.

[0050] In this specification, (meth)acrylic acids refer to both acrylic acids and methacrylic acids. For example, (meth)acrylates refer to both acrylic esters and methacrylates.

[0051] In this specification, alkyl groups are monovalent functional groups derived from alkanes and can be straight-chain or branched. There is no specific limitation on the number of carbon atoms in straight-chain alkyl groups, but 1 to 20 is preferred. Conversely, branched alkyl groups have 3 to 20 carbon atoms. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptane-4-yl, etc. Alkyl groups may be substituted or unsubstituted, and when substituted, the examples of substituents are the same as described above.

[0052] In this specification, aryl is a monovalent functional group derived from aromatic hydrocarbons and is not specifically limited, but preferably has 6 to 20 carbon atoms, and can be monocyclic or polycyclic aryl. Specific examples of monocyclic aryl groups include phenyl, biphenyl, terphenyl, etc., but are not limited to these. Specific examples of polycyclic aryl groups include naphthyl, anthraceneyl, phenanthryl, pyrene, perylene, etc. Aryl, fluorene, etc., but not limited to these. The aryl group may be substituted or unsubstituted, and when it is substituted, the examples of substituents are the same as described above.

[0053] In this specification, alkylene is a divalent functional group derived from an alkane. Apart from being divalent, other alkyl groups may be described as alkyl as defined above. For example, it can be straight-chain or branched, such as methylene, ethylene, propylene, isobutylene, sec-butylene, tert-butylene, pentylene, hexylene, etc. Alkylenes may be substituted or unsubstituted.

[0054] In this specification, a multivalent functional group is a residue in which multiple hydrogen atoms bonded to any compound are removed; for example, it can be a divalent, trivalent, or tetravalent functional group. For example, a tetravalent functional group from cyclobutane refers to a residue in which any four hydrogen atoms bonded to cyclobutane are removed.

[0055] In this specification, a direct bond or single bond refers to a bond line connecting an atom or group of atoms that does not exist at the corresponding position. Specifically, it refers to a bond formed by R in a chemical formula. a or L b (a and b are integers from 1 to 20) represent the case where no other atoms exist in the part.

[0056] In this specification, the terms "(photo)cured product" or "(photo)cured" refer not only to the complete curing, crosslinking, or polymerization of a component having curable or crosslinkable unsaturated groups in its chemical structure, but also to the partial curing, crosslinking, or polymerization of that component.

[0057] This disclosure will be described in more detail below.

[0058] 1. Photosensitive resin composition

[0059] According to one embodiment of this disclosure, a photosensitive resin layer can be provided, comprising: a photopolymerizable compound comprising a multifunctional (meth)acrylate compound with three or more functions; and an alkaline developing adhesive resin, wherein, during a tape peel test on a film sample laminated with the photosensitive resin layer onto a substrate using a peel tester, the adhesion as defined by Formula 1 is 90% or more.

[0060] The inventors have discovered through experiments that, since the adhesion of the photosensitive resin layer in one embodiment is more than 90% as defined by Formula 1, excellent physical properties (resolution, fine line adhesion, etc.) can be ensured, and this disclosure has been completed.

[0061] 1. Alkaline developing adhesive resin

[0062] The photosensitive resin layer disclosed herein may comprise an alkaline developing adhesive resin.

[0063] Specifically, the alkaline developer adhesive resin may include at least two or more alkaline developer adhesive resins. At least two or more alkaline developer adhesive resins may refer to a mixture of two or more alkaline developer adhesive resins.

[0064] At least two or more alkaline developer adhesive resins may include: a first alkaline developer adhesive resin comprising repeating units represented by chemical formula 3, repeating units represented by chemical formula 4, repeating units represented by chemical formula 5, repeating units represented by chemical formula 6 and repeating units represented by chemical formula 7; and a second alkaline developer adhesive resin comprising repeating units represented by chemical formula 4, repeating units represented by chemical formula 5 and repeating units represented by chemical formula 6.

[0065] [Chemical Formula 3]

[0066]

[0067] In chemical formula 3, R3" represents hydrogen.

[0068] [Chemical Formula 4]

[0069]

[0070] In chemical formula 4, R3' is an alkyl group having 1 to 10 carbon atoms.

[0071] [Chemical Formula 5]

[0072]

[0073] In chemical formula 5, R4" is an alkyl group having 1 to 10 carbon atoms, and R5" is an alkyl group having 1 to 10 carbon atoms.

[0074] [Chemical Formula 6]

[0075]

[0076] In chemical formula 6, Ar is an aryl group having 6 to 20 carbon atoms.

[0077] [Chemical Formula 7]

[0078]

[0079] In chemical formula 7, R4' is hydrogen and R5' is an alkyl group having 1 to 10 carbon atoms.

[0080] Specifically, the alkaline developing adhesive resin may comprise a random copolymer of repeating units represented by the following chemical formula 3, repeating units represented by the following chemical formula 4, repeating units represented by the following chemical formula 5, repeating units represented by the following chemical formula 6, and repeating units represented by the following chemical formula 7.

[0081] [Chemical Formula 3]

[0082]

[0083] In chemical formula 3, R3" represents hydrogen.

[0084] [Chemical Formula 4]

[0085]

[0086] In chemical formula 4, R3' is an alkyl group having 1 to 10 carbon atoms.

[0087] [Chemical Formula 5]

[0088]

[0089] In chemical formula 5, R4" is an alkyl group having 1 to 10 carbon atoms, and R5" is an alkyl group having 1 to 10 carbon atoms.

[0090] [Chemical Formula 6]

[0091]

[0092] In chemical formula 6, Ar is an aryl group having 6 to 20 carbon atoms.

[0093] [Chemical Formula 7]

[0094]

[0095] In chemical formula 7, R4' is hydrogen and R5' is an alkyl group having 1 to 10 carbon atoms.

[0096] Specific examples of alkyl groups having 1 to 10 carbon atoms in chemical formulas 3 to 7 may include methyl groups.

[0097] Ar is an aryl group having 6 to 20 carbon atoms, and specific examples of an aryl group having 6 to 20 carbon atoms may include phenyl.

[0098] The repeating unit represented by chemical formula 4 can be a repeating unit derived from the monomer represented by the following chemical formula 4-1.

[0099] [Chemical Formula 4-1]

[0100]

[0101] In Formula 4-1, R3' is an alkyl group having 1 to 10 carbon atoms. The definition of R3' in Formula 4-1 is the same as that in Formula 4. Specific examples of monomers represented by Formula 4-1 may include methacrylic acid (MAA).

[0102] The repeating unit represented by chemical formula 5 can be a repeating unit derived from a monomer represented by the following chemical formula 5-1.

[0103] [Chemical Formula 5-1]

[0104]

[0105] In Formula 5-1, R4" is an alkyl group having 1 to 10 carbon atoms, and R5" is an alkyl group having 1 to 10 carbon atoms. The definitions of R4" and R5" in Formula 5-1 are the same as those in Formula 5. Specific examples of monomers represented by Formula 5-1 may include methyl methacrylate (MMA).

[0106] The repeating unit represented by chemical formula 6 can be a repeating unit derived from a monomer represented by chemical formula 6-1 below.

[0107] [Chemical Formula 6-1]

[0108]

[0109] In Formula 6-1, Ar is an aryl group having 6 to 20 carbon atoms. The definition of Ar in Formula 6-1 is the same as that in Formula 6. Specific examples of monomers represented by Formula 6-1 can include styrene (SM).

[0110] The weight-average molecular weight of the alkaline developer binder resin can be above 30,000 g / mol and below 150,000 g / mol, and the glass transition temperature can be above 20°C and below 150°C. This improves the coating performance and followability of the dry film photoresist, and also enhances the mechanical strength of the photoresist itself after circuit formation. Furthermore, the acid value of the alkaline developer binder resin can be above 140 mg KOH / g and below 160 mg KOH / g.

[0111] Furthermore, the weight-average molecular weight of the alkaline developing adhesive resin can be above 20,000 g / mol and below 130,000 g / mol, and the glass transition temperature can be above 30°C and below 160°C. This improves the coating performance and traceability of the dry film photoresist, and also enhances the mechanical strength of the photoresist itself after circuit formation.

[0112] As used in this specification, weight-average molecular weight refers to the weight-average molecular weight of polystyrene as measured by gel permeation chromatography (GPC). In the determination of the weight-average molecular weight of polystyrene by GPC, detectors and analytical columns, such as known analytical devices and differential refractive index detectors, can be used, and commonly used temperature conditions, solvents, and flow rates can be employed.

[0113] Specific examples of measurement conditions are as follows: Basic developer binder resin was dissolved in tetrahydrofuran (THF) to a concentration of 1.0 (w / w)% (approximately 0.5 (w / w)% based on solids content). The solution was filtered using a syringe filter with a pore size of 0.45 μm, and 20 μl was injected into the GPC. Tetrahydrofuran (THF) was used as the mobile phase in the GPC at a flow rate of 1.0 mL / min. The chromatographic column consisted of one Agilent Plagal 5 μm Guard (7.5 x 50 mm) and two Agilent Plagal 5 μm Mixed D (7.5 x 300 mm) columns connected in series. Measurements were performed at 40 °C using an Agilent 1260 Infinity II system with an RIDetector as the detector.

[0114] Polystyrene standard samples (STD A, B, C, D) of different molecular weights dissolved in tetrahydrofuran at a concentration of 0.1% (w / w) were filtered through a syringe filter with a 0.45 μm pore size and then injected into a GPC. The weight-average molecular weight (Mw) of the alkaline developing adhesive resin was determined using a calibration curve.

[0115] STD A(MP):791,000 / 27,810 / 945

[0116] STD B(MP):282,000 / 10,700 / 580

[0117] STD C(MP): 126,000 / 4,430 / 370

[0118] STD D(MP): 51,200 / 1,920 / 162

[0119] The glass transition temperatures of the reference and adhesive polymers were compared using a DSC (Differential Scanning Calorimeter) (Perkin-Elmer, DSC-7). Measurements were taken by holding the temperature at 20°C for 15 minutes and then increasing it to 200°C at a rate of 1°C / min.

[0120] The acid value of alkaline developer adhesive resin is measured by the following method: Take about 1g of alkaline developer adhesive resin, dissolve it in 50ml of mixed solvent (MeOH 20%, acetone 80%) with two drops of 1% phenolphthalein indicator, and measure the acid value by titration with 0.1N-KOH.

[0121] The acid value of the first alkaline developer adhesive resin can be above 140 mg KOH / g and below 160 mg KOH / g. Furthermore, the acid value of the second alkaline developer adhesive resin can be above 160 mg KOH / g and below 200 mg KOH / g.

[0122] Specifically, the ratio of the glass transition temperatures of the first alkaline developer adhesive resin to the second alkaline developer adhesive resin can be 1:1.5 to 1:5, 1:1.5 to 1:3, 1:1.5 to 1:2, 1:1.5 to 1:1.8, 1:1.5 to 1:75, or 1:1.6 to 1:7.

[0123] In addition, the ratio of the acid values ​​of the first alkaline developer adhesive resin to the second alkaline developer adhesive resin can be 1:1.01 to 1:1.5, 1:1.01 to 1:1.25, 1:1.01 to 1:1.2, or 1:1.01 to 1:1.1.

[0124] Meanwhile, based on 1 mol of repeating units represented by chemical formula 3, the first alkaline developing adhesive resin included in the photosensitive resin composition of one embodiment may contain 1.2 mol or more and 3 mol or less, 1.2 mol or more and 2 mol or less, 1.5 mol or more and 2 mol or less, or 1.5 mol or more and 1.6 mol or less of repeating units represented by chemical formula 4.

[0125] Furthermore, based on 1 mol of repeating units represented by Chemical Formula 7, the second alkaline developing adhesive resin included in the photosensitive resin composition of one embodiment may contain 2 mol or more and 10 mol or less, 3 mol or more and 10 mol or less, 3 mol or more and 5 mol or less, or 4 mol or more and 5 mol or less of repeating units represented by Chemical Formula 5.

[0126] Meanwhile, the second alkaline developing adhesive resin may comprise a random copolymer of repeating units represented by the following chemical formula 4, repeating units represented by the following chemical formula 5, and repeating units represented by the following chemical formula 6.

[0127] [Chemical Formula 4]

[0128]

[0129] In chemical formula 4, R3' is an alkyl group having 1 to 10 carbon atoms.

[0130] [Chemical Formula 5]

[0131]

[0132] In chemical formula 5, R4" is an alkyl group having 1 to 10 carbon atoms, and R5" is an alkyl group having 1 to 10 carbon atoms.

[0133] [Chemical Formula 6]

[0134]

[0135] In chemical formula 6, Ar is an aryl group having 6 to 20 carbon atoms.

[0136] The repeating unit represented by chemical formula 4 can be a repeating unit derived from the monomer represented by the following chemical formula 4-1.

[0137] [Chemical Formula 4-1]

[0138]

[0139] In Formula 4-1, R3' is an alkyl group having 1 to 10 carbon atoms. The definition of R3' in Formula 4-1 is the same as that in Formula 4. Specific examples of monomers represented by Formula 4-1 may include methacrylic acid (MAA).

[0140] The repeating unit represented by chemical formula 5 can be a repeating unit derived from a monomer represented by the following chemical formula 5-1.

[0141] [Chemical Formula 5-1]

[0142]

[0143] In Formula 5-1, R4" is an alkyl group having 1 to 10 carbon atoms, and R5" is an alkyl group having 1 to 10 carbon atoms. The definitions of R4" and R5" in Formula 5-1 are the same as those in Formula 5. Specific examples of monomers represented by Formula 5-1 may include methyl methacrylate (MMA).

[0144] The repeating unit represented by chemical formula 6 can be a repeating unit derived from a monomer represented by chemical formula 6-1 below.

[0145] [Chemical Formula 6-1]

[0146]

[0147] In Formula 6-1, Ar is an aryl group having 6 to 20 carbon atoms. The definition of Ar in Formula 6-1 is the same as that described in Formula 6. Specific examples of monomers represented by Formula 6-1 can include styrene (SM).

[0148] Specifically, the first alkaline developing adhesive resin comprises repeating units represented by chemical formula 4: repeating units represented by chemical formula 5: repeating units represented by chemical formula 6 in a ratio of 1:(2 or more and 5 less):(0.2 or more and 0.9 less), 1:(2 or more and 3 less):(0.5 or more and 0.9 less), 1:(2.5 or more and 3 less):(0.6 or more and 0.9 less) or 1:(2.75 or more and 3 less):(0.6 or more and 0.75 less).

[0149] Furthermore, the second alkaline developing adhesive resin comprises repeating units represented by chemical formula 4: repeating units represented by chemical formula 5: repeating units represented by chemical formula 6 in a ratio of 1:(1.1 or more and 2 or less):(0.2 or more and 0.99 or less), 1:(1.5 or more and 2 or less):(0.5 or more and 0.99 or less), or 1:(1.5 or more and 1.75 or less):(0.75 or more and 0.99 or less).

[0150] Meanwhile, based on 100 parts by weight of the first alkaline developing adhesive resin, the photosensitive resin layer of one embodiment of this disclosure may contain 500 or more parts by weight and less than 1,000 parts by weight, 600 or more parts by weight and less than 800 parts by weight, or 700 or more parts by weight and less than 800 parts by weight of the second alkaline developing adhesive resin.

[0151] As described above, by adding an excess of 500 parts by weight or more of the second alkaline developer adhesive resin based on 100 parts by weight of the first alkaline developer adhesive resin, the technical effects of imparting hydrophobic properties to the photosensitive resin, improving its resistance to developer, and enhancing circuit performance can be achieved.

[0152] Based on solids content, the content of alkaline developer adhesive resin is 20% by weight or more and 80% by weight or less relative to the total weight of the photosensitive resin composition. When the content of alkaline developer adhesive resin is within the above range, the effect of enhanced adhesion of fine lines after circuit formation can be obtained. Solids content is based on weight and refers to the remaining components after removing the solvent from the photosensitive resin composition.

[0153] The content of the alkaline developer binder resin disclosed herein can be 40% by weight or more and 70% by weight or less, relative to the total weight of the photosensitive resin composition forming the photosensitive resin layer. When the content of the alkaline developer binder resin is less than 40% by weight relative to the entire photosensitive resin composition, there is a disadvantage of defects such as short circuits caused by contamination during development. When the content of the alkaline developer binder resin exceeds 70% by weight, there are problems with circuit performance such as adhesion and resolution degradation.

[0154] (2) Photopolymerization initiator

[0155] The photopolymerization initiator contained in the photosensitive resin layer of this disclosure is a substance that initiates the chain reaction of photopolymerizable monomers through UV and other radiation, and plays an important role in the curing of dry film photoresist.

[0156] 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.

[0157] In addition, the following can be used: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethyl-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoprop-1-one, 2-benzyl-2-dimethylamino-1-[4-morpholinophenyl]but-1-one, 2-hydroxy-2-methyl-1-phenylprop-1-one, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 1 -[4-(2-hydroxymethoxy)phenyl]-2-hydroxy-2-methylprop-1-one, 2,4-diethylthioxanone, 2-chlorothioxanone, 2,4-dimethylthioxanone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylprop-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylprop-1-one, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethyl... Aminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzyl ketone dimethyl acetal, benzyl ketone β-methoxydiethyl acetal, 1-phenyl-1,2-propyldioxime-o,o'-(2-carbonyl)ethoxy ether, methyl o-benzoylbenzoate, bis[4-dimethylaminophenyl)ketone, 4,4'-bis(diethylamino) Compounds of benzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, isobutoxybenzoin, tert-butoxybenzoin, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, α,α-dichloro-4-phenoxyacetophenone, and 4-dimethylaminobenzoate pentyl ester can be used as photopolymerization initiators, but are not limited to these.

[0158] Based on solids content, the content of the photopolymerization initiator is 2% by weight or more and 10% by weight or less relative to the total weight of the photosensitive resin composition used to form the photosensitive resin layer. Sufficient sensitivity can be obtained when the content of the photopolymerization initiator is within the above range. Solids content is based on weight and refers to the remaining component after removing the solvent from the photosensitive resin composition.

[0159] When the content of the photopolymerization initiator is less than 2% by weight, the light efficiency is low and a large number of exposures are required, resulting in a significant reduction in production efficiency. When the content of the photopolymerization initiator exceeds 10% by weight, problems such as film brittleness and increased developer contamination, leading to defects such as short circuits, occur.

[0160] (3) Photopolymerizable compounds

[0161] The photopolymerizable compounds disclosed herein are resistant to developer after UV exposure, thus enabling the formation of patterns.

[0162] The photopolymerizable compounds disclosed herein may contain polyfunctional (meth)acrylate compounds with more than three functionalities.

[0163] Specifically, a multifunctional (meth)acrylate compound with three or more functions can have a structure in which three or more alkoxide 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.

[0164] More specifically, polyfunctional (meth)acrylate compounds with three or more functions may include polyfunctional (meth)acrylate compounds of the following chemical formula 2:

[0165] [Chemical Formula 2]

[0166]

[0167] In chemical formula 2, R4 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R5 is an alkylene group having 1 to 10 carbon atoms, R6 is a p-valent functional group containing a central group having 1 to 20 carbon atoms, n2 is an integer from 1 to 20, and p is the number of substituted functional groups on R6 and is an integer from 3 to 10.

[0168] In addition, in chemical formula 2, n2 is an integer from 1 to 20, an integer from 1 to 10, or an integer from 1 to 5, and p represents the number of functional groups that substitute for R6, and can be an integer from 3 to 10, an integer from 3 to 5, or an integer from 3 to 4.

[0169] That is, in chemical formula 2, since p, which represents the number of functional groups that substitute for R6, is an integer from 3 to 10, the polyfunctional (meth)acrylate compound represented by chemical formula 2 can be a polyfunctional (meth)acrylate compound with more than three functions.

[0170] Specifically, polyfunctional (meth)acrylate compounds can be represented by the following chemical formula 2-1.

[0171] [Chemical Formula 2-1]

[0172]

[0173] In chemical formula 2-1, R6' is a trivalent functional group having 1 to 10 carbon atoms, and R7 to R9 are each independently an alkylene group having 1 to 10 carbon atoms. 10 To R 12Each is independently hydrogen or an alkyl group having 1 to 10 carbon atoms, and n3 to n5 are independently integers from 1 to 20.

[0174] In chemical formula 2-1, n3 to n5 can be integers from 1 to 20, from 1 to 10, or from 1 to 5.

[0175] There are no specific limitations on the examples of polyfunctional (meth)acrylate compounds represented by chemical formula 2, but it can be, for example, T063 (trimethylolpropane[EO]6 triacrylate) represented by the following chemical formula B.

[0176] [Chemical Formula B]

[0177]

[0178] Since the photosensitive resin composition of one embodiment contains a polyfunctional (meth)acrylate compound represented by chemical formula 2, the photocuring speed and curing degree are improved, contrast can be ensured, and excellent fine line adhesion can be achieved.

[0179] Additionally, the photosensitive resin layer in one embodiment may also contain a monofunctional (meth)acrylate compound.

[0180] Specifically, a monofunctional (meth)acrylate compound may comprise: a (meth)acrylate comprising an alkeneoxy group having 1 to 10 carbon atoms.

[0181] That is, photopolymerizable compounds may include: monofunctional (meth)acrylate compounds comprising: (meth)acrylates containing alkoxides having 1 to 10 carbon atoms; and trifunctional or more polyfunctional (meth)acrylate compounds having a structure in which three or more alkoxides having 1 to 10 carbon atoms and three or more (meth)acrylate functional groups bonded to a central group having 1 to 20 carbon atoms.

[0182] More specifically, monofunctional (meth)acrylate compounds may include monofunctional (meth)acrylate compounds represented by the following chemical formula 1.

[0183] [Chemical Formula 1]

[0184]

[0185] In Formula 1, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R2 is an alkylene group having 1 to 10 carbon atoms, R3 is an alkyl group having 1 to 10 carbon atoms, and n1 is an integer from 1 to 20.

[0186] Specifically, in Formula 1, n1 can be an integer from 1 to 20, an integer from 1 to 10, or an integer from 5 to 10. There are no specific limitations on the examples of monofunctional (meth)acrylate compounds represented by Formula 1, but it can be, for example, A040 (methoxypropylene glycol

[400] acrylate) represented by the following formula A.

[0187] [Chemical Formula A]

[0188]

[0189] As one embodiment, the photosensitive resin layer comprises a monofunctional (meth)acrylate compound represented by Chemical Formula 1. Since the monofunctional (meth)acrylate compound represented by Chemical Formula 1 has a low glass transition temperature, it has relatively high fluidity at the lamination temperature of the dry film photoresist. Therefore, it can achieve the effect of improving physical adhesion to substrates with high surface roughness and inhomogeneity.

[0190] Meanwhile, based on 100 parts by weight of a monofunctional (meth)acrylate compound, the photosensitive resin layer of one embodiment may contain less than 100 parts by weight, more than 30 parts by weight and less than 90 parts by weight, more than 50 parts by weight and less than 90 parts by weight, more than 50 parts by weight and less than 80 parts by weight, or more than 50 parts by weight and less than 75 parts by weight of a polyfunctional (meth)acrylate compound.

[0191] Since the photosensitive resin layer of one embodiment contains a small amount of polyfunctional (meth)acrylate compound relative to the monofunctional (meth)acrylate compound, it simultaneously improves the physical adhesion of the monofunctional (meth)acrylate compound represented by Formula 1 to the substrate, ensures the contrast of the polyfunctional (meth)acrylate compound represented by Formula 2, and improves fine line adhesion, thereby exhibiting excellent development performance, improved adhesion to the substrate, and ensuring excellent physical properties (resolution, fine line adhesion, etc.).

[0192] When the photosensitive resin layer of one embodiment contains more than 100 parts by weight of a polyfunctional (meth)acrylate compound based on 100 parts by weight of a monofunctional (meth)acrylate compound, there is a technical problem of reduced adhesion to the substrate.

[0193] Additionally, photopolymerizable compounds may include bifunctional (meth)acrylate compounds, including alkylene glycol di(meth)acrylates and carbamate di(meth)acrylates.

[0194] That is, the photosensitive resin layer of one embodiment contains a photopolymerizable compound, and the photopolymerizable compound may include monofunctional (meth)acrylate compounds, polyfunctional (meth)acrylate compounds, and difunctional (meth)acrylates including alkylene glycol dimethacrylates and carbamate dimethacrylates.

[0195] Alkyl glycol dimethacrylates may include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butanediol dimethacrylate, ethylene glycol diglycidyl ether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate, and commercially available products such as Miramer M244 (BPA(EO)3DA, bisphenol A(EO)3 dimethacrylate), Miramer M240 (BPA(EO)4DA, bisphenol A(EO)4 dimethacrylate), Miramer M241 (bisphenol A(EO)4 dimethacrylate), and Miramer M2100 (BPA(EO)3) manufactured by MiwonSpecialty Chemical Co., Ltd. 10 DA, bisphenol A (EO) 10 (Diacrylate), Miramer M2200 (BPA(EO)) 20 DA, bisphenol A (EO) 20 (Diacrylate), Miramer M2101 (Bisphenol A(EO)) 10 (dimethacrylate).

[0196] In addition, KUA-1330h and others can be used as carbamate di(meth)acrylates.

[0197] Carbamate di(meth)acrylates can have larger molecular weights and linear structures than existing simple epoxy alkanes, thus imparting flexibility. This is due to the improved masking properties required for the outer dry film photoresist (DFR), the hydrophobicity of the polyols that make up one of the components of carbamate acrylates, and the improved resistance to electroplating solutions, which are strong acids, thus preventing contamination of the electroplating solution.

[0198] Carbamate di(meth)acrylates can be obtained by reacting a diisocyanate compound with a polyether compound or a polyester compound having hydroxyl groups, and then reacting the resulting carbamate compound with a compound having both hydroxyl and olefinic unsaturated groups.

[0199] The polyether compound having hydroxyl groups is a polyether glycol, and glycols such as polybutane glycol, polyoxyethylene, polyoxypropylene, and polyoxytetrahydrofuran are used. As a polyester compound having hydroxyl groups, a compound obtained by condensing adipic acid with 1,4-butanediol is used.

[0200] Diisocyanate compounds (a-2) may include: aliphatic diisocyanate compounds having a divalent aliphatic group such as alkylene; alicyclic diisocyanate compounds having a divalent alicyclic group such as cycloalkylene; aromatic diisocyanate compounds and their isocyanurate modified components, carbodiimide modified components, biuret modified components, etc.

[0201] Examples of aliphatic diisocyanate compounds include hexamethylene isocyanate, trimethylhexamethylene diisocyanate, etc.

[0202] Alicyclic diisocyanate compounds may include isophorone diisocyanate, methylene bis(cyclohexyl) diisocyanate, 1,3- or 1,4-bis(isocyanate methyl)cyclohexane, etc.

[0203] Aromatic diisocyanate compounds may include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, dimers of 2,4-toluene diisocyanate or 2,6-toluene diisocyanate, (ortho, para, or meta)-xylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, etc.

[0204] They can be used alone or in combination of two or more. Furthermore, they can include isocyanate compounds having two or more isocyanate groups, such as triphenylmethane triisocyanate and tris(isocyanate phenyl)thiophosphate. Alicyclic diisocyanate compounds are preferred from the perspective of improving the flexibility and hardness of the photocured product, thereby enhancing adhesion to the substrate.

[0205] A polyether compound or polyester compound having hydroxyl groups 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 relative to 1 mol of the polyether compound or polyester compound having hydroxyl groups, more preferably in a molar ratio of 1.1 to 2.0. If the content of the diisocyanate compound is less than 1.01 mol or greater than 2.0 mol, a urethane compound having isocyanate groups at both ends cannot be stably obtained.

[0206] Furthermore, in the reaction used to synthesize carbamate compounds, dibutyltin dilaurate is preferably added as a catalyst.

[0207] The preferred reaction temperature is between 60°C and 120°C. When the reaction temperature is below 60°C, there is a tendency for the reaction to be incomplete, while when the reaction temperature exceeds 120°C, the reaction operation will be dangerous due to sudden heat generation.

[0208] Compounds having both a hydroxyl and an olefinic unsaturated group that are used to react with the carbamate compounds prepared therefrom can include compounds having both a hydroxyl and a (meth)acryloyl group in the molecule. These compounds include hydroxy(meth)acrylates, hydroxy(meth)acrylate-caprolactone adducts or epoxide adducts, ester compounds prepared by reacting polyols such as glycerol with (meth)acrylic acid, and glycidyl(meth)acrylate-acrylic acid adducts.

[0209] Hydroxy(meth)acrylates may include 2-hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate and hydroxybutyl(meth)acrylate.

[0210] Hydroxy(meth)acrylate-caprolactone adducts may include hydroxyethyl(meth)acrylate·caprolactone adducts, hydroxypropyl(meth)acrylate·caprolactone adducts, and hydroxybutyl(meth)acrylate·caprolactone adducts. Epoxyalkane adducts may include hydroxyethyl(meth)acrylate·epoxyalkane adducts, hydroxypropyl(meth)acrylate·propylene oxide adducts, and hydroxybutyl(meth)acrylate·butoxybutane adducts.

[0211] Ester compounds may include, for example, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane mono(meth)acrylate, bis(trimethylolpropane)tri(meth)acrylate, trimethylolpropane di(meth)acrylate-ethylene oxide adduct, and trimethylolpropane di(meth)acrylate-propylene oxide adduct. These substances may be used alone or in combination of two or more.

[0212] Carbamate di(meth)acrylates are compounds obtained by the addition reaction of a carbamate compound with a compound having both hydroxyl and olefinic unsaturated groups. They can be obtained by adding a compound having both hydroxyl and olefinic unsaturated groups in a molar ratio of 2.0 to 2.4 relative to 1 mol of the carbamate compound, and then carrying out the addition reaction at 60°C to 90°C.

[0213] Preferably, the weight-average molecular weight of the urethane di(meth)acrylate is in the range of 1,000 g / mol to 60,000 g / mol. When the weight-average molecular weight is less than 1,000 g / mol, it is difficult to sufficiently improve flexibility and hardness, and therefore the adhesion to the substrate cannot be improved. When the weight-average molecular weight exceeds 60,000 g / mol, there are problems with deteriorated development performance and slower development time. Therefore, the weight-average molecular weight of the urethane di(meth)acrylate according to this disclosure is preferably from 1,000 g / mol to 60,000 g / mol.

[0214] In this disclosure, the content of urethane di(meth)acrylate with a weight-average molecular weight of 1,000 g / mol to 60,000 g / mol in the photosensitive resin composition is 1% to 20% by weight, preferably 1.5% to 15% by weight. When the content of urethane di(meth)acrylate with a weight-average molecular weight of 1,000 g / mol to 60,000 g / mol is less than 1% by weight, the resulting effect is insufficient. When the content exceeds 20% by weight, there are disadvantages such as a rapid increase in development time during the post-exposure development process and the generation of a large amount of scum and sludge.

[0215] Based on 100 parts by weight of alkylene glycol di(meth)acrylate, the content of the photosensitive resin layer in one embodiment can be more than 1 part by weight and less than 50 parts by weight, more than 1 part by weight and less than 30 parts by weight, more than 1 part by weight and less than 10 parts by weight, or more than 1 part by weight and less than 5 parts by weight.

[0216] Since the content of urethane dimethacrylate is more than 1 part by weight and less than 50 parts by weight relative to 100 parts by weight of alkylene glycol dimethacrylate, the photosensitive resin composition of one embodiment can achieve technical effects such as circuit performance degradation, peeling, and development time variation.

[0217] Specifically, based on 100 parts by weight of a monofunctional (meth)acrylate compound, the photosensitive resin layer of one embodiment may contain 500 parts by weight or more but less than 1500 parts by weight, 500 parts by weight or more but less than 1000 parts by weight, 750 parts by weight or more but less than 1000 parts by weight, or 800 parts by weight or more but less than 900 parts by weight of a difunctional (meth)acrylate compound.

[0218] Furthermore, based on 100 parts by weight of a polyfunctional (meth)acrylate compound, the photosensitive resin layer of one embodiment may contain 500 parts by weight or more and 1000 parts by weight, 500 parts by weight or more and 800 parts by weight, 500 parts by weight or more and 750 parts by weight, 500 parts by weight or more and 700 parts by weight, or 500 parts by weight or more and 600 parts by weight of a difunctional (meth)acrylate compound.

[0219] That is, based on 100 parts by weight of a monofunctional (meth)acrylate compound, the photosensitive resin layer of one embodiment may contain less than 110 parts by weight of a polyfunctional (meth)acrylate compound and more than 500 parts by weight and less than 1500 parts by weight of a difunctional (meth)acrylate compound.

[0220] As described above, as a monofunctional (meth)acrylate compound, simultaneously containing polyfunctional (meth)acrylate compounds and difunctional (meth)acrylate compounds to meet the above weight range, the photosensitive resin composition of one embodiment can not only achieve excellent adhesion to the substrate, but also ensure contrast and achieve excellent fine line adhesion.

[0221] In this disclosure, the content of the monofunctional photopolymerizable compound can be more than 0.1% by weight and less than 2.5% by weight, based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer.

[0222] Furthermore, in this disclosure, based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer, the content of the multifunctional photopolymerizable compound can be 2.6% by weight or more and 5.0% by weight or less.

[0223] That is, based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer, the photosensitive resin composition used to form the photosensitive resin layer may contain more than 0.1% by weight and less than 2.5% by weight of monofunctional photopolymerizable compounds and more than 2.6% by weight and less than 5.0% by weight of polyfunctional photopolymerizable compounds.

[0224] When the content of monofunctional photopolymerizable compounds is less than 0.1% by weight or the content of polyfunctional photopolymerizable compounds is less than 2.6% by weight based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer, the effect produced by the addition of compounds represented by chemical formulas 1 and 2 is insufficient. When the content of monofunctional photopolymerizable compounds is greater than 2.5% by weight or the content of polyfunctional photopolymerizable compounds is greater than 5.0% by weight, the problem of increased hydrophobicity occurs, and therefore, the development time during the post-exposure development process increases rapidly.

[0225] One embodiment of the photosensitive resin layer is another 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 dimethacrylate, pentaerythritol trimethacrylate, etc. Acrylates, pentaerythritol pentamethacrylate, 2,2-bis(4-methacryloyloxydiethoxyphenyl)propane, 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane, 2-hydroxy-3-methacryloyloxypropyl methacrylate, ethylene glycol diglycidyl ether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate, phthalic acid diglycidyl ether dimethacrylate, glycerol polyglycidyl ether polymethacrylate, polyfunctional (meth)acrylates containing urethane groups, etc.

[0226] Based on the solid content, the content of the photopolymerizable compound can be 10% by weight or more and 70% by weight or less relative to the total weight of the photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, effects such as improved photosensitivity, resolution, and adhesion can be obtained.

[0227] (4) Photosensitive resin composition

[0228] Based on solids content, the photosensitive resin composition used to form the photosensitive resin layer may contain 20% by weight or more and 80% by weight of an alkaline developing adhesive resin, 0.1% by weight or more and 10% by weight of a photopolymerization initiator, and 10% by weight or more and 70% by weight of a photopolymerizable compound. Solids content is on a weight basis and refers to the remaining components after removing the solvent from the photosensitive resin composition.

[0229] The photosensitive resin composition may further include a solvent. The solvent is typically selected from methyl ethyl ketone (MEK), methanol, THF, toluene, and acetone, and is not particularly limited thereto. Its content can also be adjusted according to the content of the photopolymerization initiator, the alkaline developer adhesive resin, and the photopolymerizable compound.

[0230] Furthermore, the photosensitive resin composition may further include other additives as needed. These other additives are plasticizers and may include, in the form of phthalates, dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate; in the form of glycol esters, triethylene glycol diacetate, tetraethylene glycol diacetate; in the form of acid amides, p-toluenesulfonamide, benzenesulfonamide, n-butylbenzenesulfonamide; triphenyl phosphate, etc.

[0231] In this disclosure, a colorless dye or coloring substance may be added to improve the processing performance of the photosensitive resin composition. Examples of colorless dyes include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2-methylphenyl)methane, and fluorane dyes. Among these, colorless crystal violet is preferred due to its good contrast. When a colorless dye is included, its content in the photosensitive resin composition can be 0.1% by weight or more and 10% by weight or less. From the perspective of exhibiting contrast, 0.1% by weight or more is preferred, while from the perspective of maintaining storage stability, 10% by weight or less is preferred.

[0232] Examples of coloring substances may include toluenesulfonic acid monohydrate, fuchsin, phthalocyanine green, auramine base, parafuchsin, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, malachite green, diamond green, and Basic Blue 20. When a coloring substance is included, the amount added may be 0.001% by weight or more and 1% by weight or less, based on the photosensitive resin composition. When the content is 0.001% by weight or more, it has the effect of improving handling performance; when the content is 1% by weight or less, it has the effect of maintaining storage stability.

[0233] In addition, other additives may include heat-inhibiting agents, dyes, decolorizing agents, and adhesion promoters.

[0234] Meanwhile, during the tape peel test on the film sample laminated with the photosensitive resin layer on the substrate using a peel tester, the adhesion, as defined by Formula 1, can be 90% or more, 90% or more, less than 100%, or 95% or more and less than 100%. This can be achieved by including the aforementioned photopolymerizable compound in the photosensitive resin layer of one embodiment.

[0235] [Formula 1]

[0236] Adhesion (%) = (Surface area of ​​substrate and photosensitive resin layer after tape peel test / Surface area of ​​photosensitive resin layer in contact with substrate before tape peel test) * 100.

[0237] Specifically, since the photosensitive resin layer of one embodiment contains a monofunctional (meth)acrylate compound represented by chemical formula 1 and a polyfunctional (meth)acrylate compound represented by chemical formula 2, the adhesion defined by formula 1 can be more than 90%.

[0238] Since the adhesion defined by Formula 1 is over 90%, it is possible to improve the substrate adhesion of the dry film photoresist containing the photosensitive resin layer of one embodiment.

[0239] Specifically, in the thin film sample in which the photosensitive resin layer is laminated on the substrate, the substrate can be a reverse-treated foil.

[0240] More specifically, the surface roughness of the substrate can be greater than 1 μm and less than 10 μm, greater than 3 μm and less than 7 μm, or greater than 4 μm and less than 6 μm.

[0241] Meanwhile, the tape peel test of Formula 1 can be performed using a peel tester after the standard tape is bonded to the film sample laminated with the photosensitive resin layer on the substrate.

[0242] When the adhesion is 90% or more as defined by Formula 1, since the photosensitive resin layer of one embodiment contains an excess of monofunctional (meth)acrylate compound relative to the polyfunctional (meth)acrylate compound, and since the monofunctional (meth)acrylate compound represented by Formula 1 has a low glass transition temperature and relatively high fluidity at the lamination temperature of the dry film photoresist, the effect of improving physical adhesion to the substrate with high surface roughness and inhomogeneity can be achieved.

[0243] 2. Dry film photoresist

[0244] According to another embodiment of this disclosure, a dry film photoresist comprising a photosensitive resin layer as described in one embodiment can be provided. Details regarding the photosensitive resin layer are as described in the preceding embodiment.

[0245] Specifically, the photosensitive resin layer may comprise a dried product or a cured product of the photosensitive resin composition of one embodiment. The dried product refers to the material obtained by a drying process of the photosensitive resin composition of one embodiment. The cured product refers to the material obtained by a curing process of the photosensitive resin composition of one embodiment.

[0246] There is no particular limitation on the thickness of the dry film photoresist, but it can be freely adjusted within, for example, the range of 0.01 μm to 1 mm. When the thickness of the dry film photoresist increases or decreases by a certain value, the physical properties measured in the dry film photoresist will also change by a certain value.

[0247] Dry film photoresist may also include a base film and a protective film. The base film serves as a support for the photosensitive resin layer during the manufacturing process of dry film photoresist and facilitates the exposure of the photosensitive resin layer, which has adhesive strength.

[0248] Various plastic films can be used as base films, and examples may include at least one plastic film selected from acrylic films, polyethylene terephthalate (PET) films, triacetyl cellulose (TAC) films, polynorbornene (PNB) films, cyclic olefin polymer (COP) films, and polycarbonate (PC) films. There are no particular limitations on the thickness of the base film; for example, it can be freely adjusted in the range of 0.01 μm to 1 mm.

[0249] The protective film prevents damage to the photoresist during processing and acts as a protective shell to protect the photosensitive resin layer from foreign matter such as dust. It is laminated on the back of the photosensitive resin layer where no base film has formed. The protective film is used to protect the photosensitive resin layer from external influences. When dry film photoresist is applied in post-processing, it needs to be easy to peel off and requires appropriate release properties and adhesion, thus preventing deformation during storage and distribution.

[0250] Various plastic films can be used as protective films, and examples may include at least one plastic film selected from acrylic films, polyethylene (PE) films, polyethylene terephthalate (PET) films, triacetyl cellulose (TAC) films, polynorbornene (PNB) films, cyclic olefin polymer (COP) films, and polycarbonate (PC) films. There is no specific limitation on the thickness of the protective film; for example, it can be freely adjusted in the range of 0.01 μm to 1 mm.

[0251] There are no particular limitations on the examples of methods for manufacturing dry film photoresist. For example, a photosensitive resin composition of one embodiment is coated onto a conventional substrate film, such as polyethylene terephthalate, using a conventional coating method, then dried, and a conventional protective film, such as polyethylene, is laminated onto the upper surface of the dried photosensitive resin layer to manufacture a dry film.

[0252] There are no particular limitations on the coating method of the photosensitive resin composition; for example, a coating bar method can be used.

[0253] The drying step of the coated photosensitive resin composition can be carried out by heating means such as hot air oven, hot plate, hot air circulating furnace and infrared furnace, and can be carried out at a temperature above 50°C and below 100°C.

[0254] Meanwhile, the dry film photoresist of one embodiment may have the following characteristics: during a tape peel test on a thin film sample laminated with the photosensitive resin layer on a substrate using a peel tester, the adhesion, as defined by Formula 2, can be 90% or more, 90% or more, less than 100%, or 95% or more and less than 100%. This can be achieved by including the aforementioned photopolymerizable compound in the photosensitive resin layer of one embodiment.

[0255] [Formula 2]

[0256] Adhesion (%) = (Surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the substrate after the tape peel test / Surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the substrate before the tape peel test) * 100.

[0257] Details regarding adhesion include everything described above.

[0258] Since the adhesion defined by Formula 2 is over 90%, it is possible to improve the substrate adhesion of the dry film photoresist in one embodiment.

[0259] 3. Photosensitive element

[0260] According to another embodiment of this disclosure, a photosensitive element can be provided, comprising: a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, wherein, during a tape peel test on a film sample laminated with the photosensitive resin layer on the substrate using a peel tester, the adhesion, as defined by the following formula 1, is 90% or more:

[0261] [Formula 1]

[0262] Adhesion (%) = (Surface area of ​​substrate and photosensitive resin layer after tape peel test / Surface area of ​​photosensitive resin layer in contact with substrate before tape peel test) * 100.

[0263] Details regarding adhesion include everything described above.

[0264] Since the adhesion defined by Formula 1 is over 90%, a photosensitive element with excellent substrate adhesion can be provided.

[0265] Meanwhile, the photosensitive resin layer contains an alkaline developing adhesive resin and a photopolymerizable compound, and the photopolymerizable compound may include a monofunctional (meth)acrylate compound represented by the following chemical formula 1 and a polyfunctional (meth)acrylate compound represented by the following chemical formula 2.

[0266] [Chemical Formula 1]

[0267]

[0268] In chemical formula 1, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R2 is an alkylene group having 1 to 10 carbon atoms, R3 is an alkyl group having 1 to 10 carbon atoms, and n1 is an integer from 1 to 20.

[0269] [Chemical Formula 2]

[0270]

[0271] In Formula 2, R4 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R5 is an alkylene group having 1 to 10 carbon atoms, R6 is a p-valent functional group containing a central group having 1 to 20 carbon atoms, n2 is an integer from 1 to 20, and p is the number of substituted functional groups on R6, which is an integer from 3 to 10.

[0272] Details regarding the photosensitive resin composition include all that is described above in one embodiment and other embodiments.

[0273] That is, the photosensitive resin layer contains an alkaline developing adhesive resin and a photopolymerizable compound, which may include a monofunctional (meth)acrylate compound represented by the following chemical formula 1 and a polyfunctional (meth)acrylate compound represented by the following chemical formula 2.

[0274] [Chemical Formula 1]

[0275]

[0276] In chemical formula 1, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R2 is an alkylene group having 1 to 10 carbon atoms, R3 is an alkyl group having 1 to 10 carbon atoms, and n1 is an integer from 1 to 20.

[0277] [Chemical Formula 2]

[0278]

[0279] In Formula 2, R4 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R5 is an alkylene group having 1 to 10 carbon atoms, R6 is a p-valent functional group containing a central group having 1 to 20 carbon atoms, n2 is an integer from 1 to 20, and p is the number of substituted functional groups on R6, which is an integer from 3 to 10.

[0280] Various plastic films can be used as protective films, and examples may include at least one plastic film selected from acrylic films, polyethylene (PE) films, polyethylene terephthalate (PET) films, triacetyl cellulose (TAC) films, polynorbornene (PNB) films, cyclic olefin polymer (COP) films, and polycarbonate (PC) films. There are no particular limitations on the thickness of the protective film; for example, it can be freely adjusted in the range of 0.01 μm to 1 mm.

[0281] A specific example of a polymer substrate can be a polyester film, wherein the anti-adhesion layer is formed by uniaxially stretching an unstretched polyester film, coating one surface with a coating solution containing an adhesive resin and organic particles, and uniaxially stretching the remainder in an in-line coating method.

[0282] Polymer substrates are typically manufactured using an online coating method rather than by adding antiblocking agents, which are usually added during manufacturing to take into account operational performance and winding characteristics, and have an organic particle layer using alternative particles that do not compromise transparency.

[0283] Here, examples of organic particles used as particles that do not compromise transparency while taking into account operational performance and winding characteristics can include organic particles such as multilayer, multicomponent particles, wherein acrylic particles such as methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, n-butyl methacrylate, acrylic acid, methacrylic acid copolymers or terpolymers are formed; olefin particles such as polyethylene, polystyrene, or polypropylene; acrylic and olefin copolymers; or homopolymer particles, and then another type of monomer is coated onto the layer.

[0284] These organic particles should specifically be spherical and have a different refractive index than the adhesive resin. Here, "spherical" means that the ratio of the minor axis (a) to the major axis (b) in an ellipse is 0.5.

[0285] Furthermore, the refractive index difference between the organic particles and the binder resin is less than 0.05. When the refractive index difference is greater than 0.05, haze increases. This indicates the presence of a large amount of scattered light, which reduces the sidewall smoothing effect. This also depends on the size and amount of the organic particles. Preferably, the average particle size of the organic particles is about 0.5 μm to 5 μm. When it is smaller than this value, the running performance and winding characteristics deteriorate; when it is greater than 5 μm, haze increases, which is not preferred considering the dropping problem. Based on the total amount of binder resin, the content of organic particles is preferably 1% to 10% by weight.

[0286] When the content of organic particles is less than 1% by weight based on the total amount of adhesive resin, the anti-blocking effect is insufficient, and it is easy to scratch, and the running performance and winding characteristics are deteriorated. When it exceeds 10% by weight, there will be problems of increased haze and deterioration of transparency.

[0287] In addition to the aforementioned organic particles, inorganic particles can also be added. In this case, it is not preferable to add commonly used inorganic anti-blocking agents; rather, it is preferable to add colloidal silica with a particle size of 100 nm or less. Based on 100 parts by weight of adhesive resin, its content is preferably 10 parts by weight or less. When the particle size and content as described above are met, sidewall defects or grooves, such as craters, caused by the anti-blocking layer can be prevented when patterning using dry film photoresist.

[0288] ​As the adhesive resin used to coat such organic particles onto an unstretched polyester film, an adhesive resin with excellent compatibility with the organic particles can be used. Examples of such resins may include acrylic resins such as unsaturated polyesters, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, n-butyl methacrylate, acrylic acid, methacrylic acid copolymers or terpolymers; polyurethane resins; epoxy resins; or melamine resins, etc., preferably acrylic resins.

[0289] Water is the preferred solvent that can be used in the preparation of coating solutions that utilize adhesive resins and organic particles.

[0290] As described above, an unstretched polyester film obtained by melting and extruding PET particles is uniaxially stretched, and then a coating solution containing organic particles in an adhesive resin is applied to the uniaxially stretched film. Coating can be performed on at least one side of the uniaxially stretched film, and the thickness is preferably about 30 nm to 200 nm based on the final dried thickness. If the coating solution containing organic particles is applied to the uniaxially stretched film to a thickness greater than 30 nm, there are problems such as the organic particles easily falling off, causing scratches, and generating white powder. When the coating is thicker than 200 nm, coating streaks are generated in the coating direction in online coating with high coating speeds due to the increased viscosity of the coating solution.

[0291] As described above, the polymer substrate obtained by coating with organic particles other than conventional anti-blocking agents using an online coating method is a base film that maintains operational performance and winding characteristics due to the particle layer, and has excellent transparency due to the excellent light transmittance of the organic particles.

[0292] Because the lamination of the photosensitive resin layer is performed on the opposing surfaces of the organic particle-containing layers within the polymer substrate, the photosensitive resin layer is formed on these opposing surfaces in this manner. Therefore, pitting defects do not occur as previously seen when laminating a base film containing an anti-blocking agent. Since the particles, such as silica, are not only larger than the organic particles but also distributed throughout the base film, the effect of silica is not noticeable even in areas adjacent to the photosensitive resin layer.

[0293] On the other hand, in the polymer substrate used in this disclosure, the size of the organic particles is from 0.5 μm to 5 μm, and the organic particle layer is not adjacent to the photosensitive resin layer, so the physical effects of the organic particles are not affected. Furthermore, by using organic particles with excellent light transmittance, sidewall defects can be reduced without impairing other circuit performance.

[0294] The photosensitive element may also include a protective film formed on the photosensitive resin layer. The protective film prevents damage to the photosensitive resin layer during processing and acts as a protective shell to protect it from foreign matter such as dust. The protective film is laminated onto the back of the photosensitive resin layer where no polymer substrate has been formed. The protective film protects the photosensitive resin layer from external influences. When dry film photoresist is applied in post-processing, it needs to be easy to peel off and requires appropriate release properties and adhesion, thus preventing deformation during storage and distribution.

[0295] Various plastic films can be used as protective films, and examples may include at least one plastic film selected from acrylic films, polyethylene (PE) films, polyethylene terephthalate (PET) films, triacetyl cellulose (TAC) films, polynorbornene (PNB) films, cyclic olefin polymer (COP) films, and polycarbonate (PC) films. There are no particular limitations on the thickness of the protective film; for example, it can be freely adjusted in the range of 0.01 μm to 1 mm.

[0296] 4. Circuit boards and display devices

[0297] According to another embodiment of this disclosure, a circuit board or a display device may be provided, including a photosensitive resin layer comprising a photosensitive resin composition of one embodiment. Details regarding the photosensitive resin layer are included in all the contents described in the above embodiments.

[0298] There are no particular restrictions on the specific details of the circuit board or display device, and various conventionally known technical configurations can be applied without limitation.

[0299] The photosensitive resin layer included in the circuit board or display device can be in the form of a thin film without openings or in the form of a pattern with openings.

[0300] Examples of methods for forming a patterned layer of photosensitive resin include laminating a photosensitive resin layer of a dry film photoresist according to another embodiment onto a circuit board or display device manufacturing substrate, followed by exposure and development. Additionally, methods for laminating a photosensitive resin layer of a photosensitive element according to other embodiments onto a circuit board or display device manufacturing substrate, followed by exposure and development, may also be mentioned.

[0301] When the dry film photoresist or photosensitive element in another embodiment has a protective film on the photosensitive resin layer, the protective film can be removed before the process of laminating the photosensitive resin layer onto the circuit board or display device manufacturing substrate.

[0302] Furthermore, when the dry film photoresist or photosensitive element of other embodiments has a polymer substrate or base film laminated on one side of the photosensitive resin layer, a process of immediately removing the polymer substrate or base film can be performed after the exposure process.

[0303] Therefore, the photosensitive resin layer included in the dry film photoresist or photosensitive element in other embodiments can be included in the circuit board or display device.

[0304] Beneficial effects

[0305] According to this disclosure, a photosensitive resin layer capable of achieving excellent substrate adhesion, a dry film photoresist using the photosensitive resin layer, a circuit board, and a display device can be provided. Attached Figure Description

[0306] Figure 1 An optical microscope image of the adhesion between the substrate and the photosensitive resin layer during a tape peel test measured in the embodiment is shown.

[0307] Figure 2 An optical microscopic image of the adhesion between the substrate and the photosensitive resin layer during the tape peel test measured in Comparative Example 1 is shown.

[0308] Figure 3 An optical microscope image of the adhesion between the substrate and the photosensitive resin layer during the tape peel test measured in Comparative Example 2 is shown. Detailed Implementation

[0309] This disclosure will be described in more detail through the embodiments shown below. However, these embodiments are given for illustrative purposes only and are not intended to limit the scope of the invention thereto.

[0310] <Preparation Example: Preparation of Alkaline Developer Adhesive Resin>

[0311] Preparation Example 1

[0312] Equipped a four-necked round-bottom flask with a mechanical stirrer and reflux device, the flask was then purged with nitrogen. 80 g of methyl ethyl ketone (MEK) and 7.5 g of methanol (MeOH) were added to the nitrogen-purged flask, followed by 0.45 g of azobisisobutyronitrile (AIBN) which was completely dissolved. A monomer mixture of 8 g of acrylic acid (AA), 15 g of methacrylate (MAA), 15 g of butyl acrylate (BA), 52 g of methyl methacrylate (MMA), and 10 g of styrene (SM) was added as monomers, and the mixture was heated to 80°C and polymerized for 6 hours to prepare alkaline developer adhesive resin 1.

[0313] The weight-average molecular weight of alkaline developer adhesive resin 1 was measured to be 71538 g / mol, the glass transition temperature was 79℃, the solid content was 51.4% by weight, and the acid value was 156.3 mg KOH / g.

[0314] In a specific example of the measurement conditions for weight-average molecules, an alkaline developing binder resin was dissolved in tetrahydrofuran (THF) at a concentration of 1.0% (w / w) in THF (approximately 0.5% (w / w) based on solids content). The solution was filtered using a syringe filter with a pore size of 0.45 μm, and 20 μl was injected into a GPC. Tetrahydrofuran (THF) was used as the mobile phase in the GPC at a flow rate of 1.0 mL / min. The chromatographic column consisted of one Agilent PLgel 5 μm Guard column (7.5 x 50 mm) and two Agilent PLgel 5 μm Mixed D columns (7.5 x 300 mm) connected in series. Measurements were performed at 40 °C using an Agilent 1260 Infinity II System with an RI detector.

[0315] The acid value was measured by dissolving approximately 1 g of alkaline developer adhesive resin sample in 50 ml of a mixed solvent (MeOH 20%, acetone 80%) containing two drops of 1% phenolphthalein indicator, and then titrating with 0.1 N-KOH.

[0316] The solids content was based on the weight of the alkaline developing adhesive resin prepared in the above preparation example, and the weight percentage of the solids content remaining after heating in an oven at 150°C for 120 minutes was measured.

[0317] Preparation Example 2

[0318] Equipped a four-necked round-bottom flask with a mechanical stirrer and reflux device, the flask was then purged with nitrogen. 80 g of methyl ethyl ketone (MEK) and 7.5 g of methanol (MeOH) were added to the nitrogen-purged flask, followed by 0.9 g of azobisisobutyronitrile (AIBN) which was completely dissolved. A monomer mixture of 25 g of methacrylic acid (MAA), 47.5 g of methyl methacrylate (MMA), and 27.5 g of styrene (SM) was added as monomers, and the mixture was heated to 80 °C and polymerized for 6 hours to prepare alkaline developer adhesive resin 2 (weight average molecular weight: 39000 g / mol, glass transition temperature: 128 °C, solids content: 45.6 wt%, acid value: 163.1 mg KOH / g).

[0319] <Examples and Comparative Examples: Preparation of Photosensitive Resin Compositions and Dry Film Photoresists>

[0320] The photopolymerization initiator was dissolved in methyl ethyl ketone (MEK) as a solvent according to the composition shown in Table 1 below. Then, the photopolymerizable compound and the basic developing adhesive resin were added, and the mixture was stirred using a mechanical stirrer for about 1 hour to prepare the photosensitive resin composition.

[0321] The obtained photosensitive resin composition was coated onto a 29 μm PET film using a coating rod. The coated photosensitive resin composition layer was then dried in a hot air oven at 80°C for 5 minutes, resulting in a dried photosensitive resin composition layer with a thickness of 29 μm.

[0322] A protective film (polyethylene) is laminated onto a dry photosensitive resin composition layer to prepare a dry film photoresist.

[0323] [Table 1]

[0324]

[0325]

[0326] <Experimental Example>

[0327] The physical properties of the dry film photoresists prepared in the examples and comparative examples were measured by the following methods, and the results are shown in Table 2 below.

[0328] 1. Adhesion of fine threads (unit: μm)

[0329] The protective film was peeled off from the dry film photoresist prepared in the examples and comparative examples, and the photosensitive resin layer of the dry film photoresist was laminated using HAKUTO MACH 610i to contact the copper layer surface of the 1.0 mm thick RTF (reverse processing foil). Soft etching was performed under the following conditions: laminator roll temperature of 110°C and roll pressure of 4.0 kgf / cm². 2 The roller speed is 2.0 min / m, thus forming a laminate.

[0330] In the dry film photoresist laminated on RTF (reverse processing foil), an ORC FDi-3 (laser direct imaging exposure machine) was used at 19 mJ / cm². 2 The fine-line adhesive pattern was irradiated with ultraviolet light at an exposure dose of [missing information - likely a specific exposure dose] (set to a width increasing from 10 μm to 58 μm in 2 μm increments and a pattern spacing of 400 μm), and then allowed to stand for 15 minutes. Next, the supporting PET film for the dry film photoresist was peeled off and then treated with a 1.0 wt% Na₂CO₃ aqueous solution at 30 ± 1 °C and 1.5 kgf / cm². 2 Under jet-type developing conditions with jet pressure, develop for 40 seconds.

[0331] In the developed laminate, the minimum spacing between the photosensitive resin layers was measured using a ZEISS AXIOPHOT microscope and evaluated as resolution. It can be assessed that the smaller this value, the better the resolution.

[0332] 2. Resolution (unit: μm)

[0333] The protective film was peeled off from the dry film photoresist prepared in the examples and comparative examples, and the photosensitive resin layer of the dry film photoresist was laminated using HAKUTO MACH 610i to contact the copper layer surface of the 1.0 mm thick RTF (reverse processing foil). Soft etching was performed under the following conditions: laminator roll temperature of 110°C and roll pressure of 4.0 kgf / cm². 2 The roller speed is 2.0 min / m, thus forming a laminate.

[0334] In the dry film photoresist laminated on RTF (reverse processing foil), an ORC FDi-3 (laser direct imaging exposure machine) was used at 19 mJ / cm². 2 The exposure dose was adjusted by irradiating the resolution pattern with ultraviolet light (set so that the width increases from 10 μm to 58 μm in 2 μm increments and the pattern spacing is 400 μm), and then allowed to stand for 15 minutes. Next, the supporting PET film for the dry film photoresist was peeled off and then treated with a 1.0 wt% Na₂CO₃ aqueous solution at 30 ± 1 °C at 1.5 kgf / cm². 2 Under jet-type developing conditions with jet pressure, develop for 40 seconds.

[0335] In the developed laminate, the minimum spacing between the photosensitive resin layers was measured using a ZEISS AXIOPHOT microscope and evaluated as resolution. It can be assessed that the smaller this value, the better the resolution.

[0336] 3. Peeling speed (unit: seconds)

[0337] The protective film was peeled off from the dry film photoresist prepared in the examples and comparative examples, and a photosensitive resin layer of the dry film photoresist was laminated using HAKUTO MACH 610i to contact the copper layer surface of an RTF (reverse processing foil) with a thickness of 1.0 mm. Soft etching was performed under the following conditions: laminator roll temperature of 110°C and roll pressure of 4.0 kgf / cm². 2 The roller speed is 2.0 min / m, thus forming a laminate.

[0338] In the dry film photoresist laminated on RTF (reverse processing foil), the ORC FDi-3 (Laser Direct Image Exposure Machine) is used at 19 mJ / cm². 2 The stripping pattern (50mm x 50mm square) was irradiated with ultraviolet light at a certain exposure dose and then allowed to stand for 15 minutes. Then, the supporting PET film for the dry film photoresist was peeled off and then treated with a 1.0 wt% Na₂CO₃ aqueous solution at 30±1℃ and 1.5 kgf / cm². 2 Under jet-type developing conditions with jet pressure, develop for 40 seconds.

[0339] Then, a 3% sodium hydroxide aqueous solution (at 50°C) was used for peeling. The peeling speed was evaluated by measuring the time required for the photocured layer to peel off from the copper plate.

[0340] 4. RTF (Reverse-side treated foil) adhesion

[0341] The protective film was peeled off from the dry film photoresist prepared in the examples and comparative examples. A photosensitive resin layer of the dry film photoresist was laminated using HAKUTO MACH 610i to contact the surface of the matte side of an RTF (reverse-side treated foil) with a thickness of 1.0 mm and a surface roughness of about 5 μm. Soft etching was performed under the following conditions: laminator roll temperature of 110°C and roll pressure of 4.0 kgf / cm². 2 The roller speed is 2.0 min / m, thus forming a laminate.

[0342] The supporting PET film for the dry film photoresist was peeled off from the laminate, and then standard 3M#610 tape was bonded to the photosensitive resin layer. The 3M#610 tape was subjected to a tape peel test using a SurTA peel tester (ChemiLab) to evaluate the RTF adhesion. The results are shown in Table 2 below.

[0343] RTF adhesion refers to the percentage of the surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the substrate after the tape peel test to the surface area of ​​the photosensitive resin layer of the dry film photoresist in contact with the substrate before the tape peel test, as shown in Formula 1 below.

[0344] [Formula 1]

[0345] Adhesion (%) = (Surface area of ​​substrate and photosensitive resin layer after tape peel test / Surface area of ​​photosensitive resin layer in contact with substrate before tape peel test) * 100.

[0346] [Table 2]

[0347]

[0348] As shown in Table 2, it can be confirmed that the examples exhibit excellent fine-line adhesion and resolution, while also demonstrating significant RTF adhesion. Unlike the examples, it can be confirmed that Comparative Example 1, which does not contain a monofunctional (meth)acrylate compound, exhibits significantly poorer RTF adhesion compared to the examples of this disclosure.

[0349] Furthermore, it can be confirmed that, in Comparative Example 2, which does not contain a polyfunctional (meth)acrylate compound, the fine line adhesion and resolution are significantly worse compared to the embodiments of this disclosure.

Claims

1. A photosensitive resin layer comprising: a photopolymerizable compound containing a multifunctional (meth)acrylate compound with three or more functionalities; and an alkaline developing adhesive resin. in, During the tape peel test on the film sample with the photosensitive resin layer laminated on the substrate using a peel tester... The alkaline developing adhesive resin comprises a first alkaline developing adhesive resin, which includes repeating units represented by the following chemical formula 3, repeating units represented by the following chemical formula 4, repeating units represented by the following chemical formula 5, repeating units represented by the following chemical formula 6 and repeating units represented by the following chemical formula 7. The second alkaline developing adhesive resin comprises repeating units represented by the following chemical formula 4, repeating units represented by the following chemical formula 5, and repeating units represented by the following chemical formula 6. The adhesion is defined by the following formula 1 as being above 90%: [Formula 1] Adhesion (%) = (Surface area of ​​substrate and photosensitive resin layer after tape peel test / Surface area of ​​photosensitive resin layer in contact with substrate before tape peel test) * 100 [Chemical Formula 3] In chemical formula 3, R3 is hydrogen. [Chemical Formula 4] In chemical formula 4, R3' is an alkyl group having 1 to 10 carbon atoms. [Chemical Formula 5] In chemical formula 5, R4" is an alkyl group having 1 to 10 carbon atoms, and R5" is an alkyl group having 1 to 10 carbon atoms. [Chemical Formula 6] In chemical formula 6, Ar is an aryl group with 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.

2. The photosensitive resin layer according to claim 1, in, The trifunctional or higher polyfunctional (meth)acrylate compounds have a structure in which three or more alkeneoxy groups having 1 to 10 carbon atoms and three or more (meth)acrylate functional groups are bonded to a central group having 1 to 20 carbon atoms.

3. The photosensitive resin layer according to claim 1, in, The trifunctional or higher polyfunctional (meth)acrylate compounds include compounds of the following chemical formula 2: [Chemical Formula 2] In chemical formula 2, R4 is hydrogen or an alkyl group having 1 to 10 carbon atoms. R5 is an alkylene group having 1 to 10 carbon atoms. R6 is a p-valent functional group containing a central group having 1 to 20 carbon atoms. n² is an integer from 1 to 20, and p is the number of functional groups substituted on R6, and is an integer from 3 to 10.

4. The photosensitive resin layer according to claim 1, in, The trifunctional or higher polyfunctional (meth)acrylate compounds include compounds of the following chemical formula 2-1: [Chemical Formula 2-1] In chemical formula 2-1, R6' is a trivalent functional group with 1 to 10 carbon atoms. R7 to R9 are each an alkylene group having 1 to 10 carbon atoms. R 10 To R 12 Each is independently hydrogen or an alkyl group having 1 to 10 carbon atoms, and n3 to n5 are each an independent integer from 1 to 3.

5. The photosensitive resin layer according to claim 1, in, The photopolymerizable compound also includes a monofunctional (meth)acrylate compound.

6. The photosensitive resin layer according to claim 5, in, Based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photopolymerizable compound comprises more than 100 parts by weight of the polyfunctional (meth)acrylate compound.

7. The photosensitive resin layer according to claim 5, in, The monofunctional (meth)acrylate compound comprises: a (meth)acrylate containing an alkeneoxy group having 1 to 10 carbon atoms.

8. The photosensitive resin layer according to claim 5, in, The monofunctional (meth)acrylate compound is a compound comprising the following chemical formula 1: [Chemical Formula 1] In chemical formula 1, R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms. R2 is an alkylene group having 1 to 10 carbon atoms. R3 is an alkyl group having 1 to 10 carbon atoms, and n1 is an integer from 1 to 20.

9. The photosensitive resin layer according to claim 5, in, The photopolymerizable compound comprises: Monofunctional (meth)acrylate compounds comprising: (meth)acrylates containing an alkeneoxy group having 1 to 10 carbon atoms; and A polyfunctional (meth)acrylate compound having three or more alkeneoxy groups having 1 to 10 carbon atoms and three or more (meth)acrylate functional groups bonded to a central group having 1 to 20 carbon atoms.

10. The photosensitive resin layer according to claim 1, in, The weight-average molecular weight of the alkaline developing adhesive resin is above 20,000 g / mol and below 150,000 g / mol.

11. The photosensitive resin layer according to claim 5, in, Based on 100 parts by weight of the monofunctional (meth)acrylate compound, the content of the polyfunctional (meth)acrylate compound is less than 100 parts by weight.

12. The photosensitive resin layer according to claim 5, in, Based on 100 parts by weight of the monofunctional (meth)acrylate compound, the content of the polyfunctional (meth)acrylate compound is 30 parts by weight or more and 90 parts by weight or less.

13. The photosensitive resin layer according to claim 1, in, The content of the second alkaline developer adhesive resin is 500 parts by weight or more and 1000 parts by weight, based on 100 parts by weight of the first alkaline developer adhesive resin.

14. The photosensitive resin layer according to claim 1, in, The ratio of the glass transition temperatures of the first alkaline developer adhesive resin to the second alkaline developer adhesive resin is 1:1.5 to 1:

5.

15. The photosensitive resin layer according to claim 1, in, The ratio of the acid values ​​of the first alkaline developer adhesive resin to the second alkaline developer adhesive resin is from 1:1.01 to 1:1.

5.

16. The photosensitive resin layer according to claim 1, in, The thickness of the photosensitive resin layer is greater than 1 μm and less than 1000 μm.

17. The photosensitive resin layer according to claim 1, in, The cross-sectional area of ​​the photosensitive resin layer is 0.10 cm². 2 Above and 5.00cm 2 the following.

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

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

Images