KR20220151084A - Photosensitive resin composition, and dry film photoresist, photosensitive element, resist pattern, circuit board, display device using the same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition including an alkali developable binder resin, a photopolymerization initiator, a photopolymerizable compound and an aromatic compound having 6 to 30 carbon atoms in which two or more carboxy groups are substituted, and a dry film photoresist, a photosensitive element, a resist pattern, a circuit board and a display device using the same.

Description

Photosensitive resin composition and dry film photoresist using the same, photosensitive element, resist pattern, circuit board, and display device

The present invention relates to a photosensitive resin composition and a dry film photoresist using the same, a photosensitive element, a resist pattern, a circuit board, and a display device.

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

Currently, it not only manufactures printed circuit boards (PCBs) or lead frames, but also manufactures rib barriers for plasma display panels (PDPs), ITO electrodes for other displays, bus address electrodes, and black matrices. Dry film photoresists are also widely used.

These, generally dry film photoresists are widely used for laminating on copper clad laminates. In this regard, as an example of a manufacturing process of a printed circuit board (Printed Circuit Board, PCB), a pretreatment process is first performed in order to laminate a copper clad laminate, which is the original plate material of the PCB. The pretreatment process is drilling, deburring, and fronting in the order of the outer layer process, and fronting or pickling is performed in the inner layer process. In the frontal process, a bristle brush and jet pumice are mainly used, and pickling can go through soft etching and 5wt% sulfuric acid pickling.

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

The printed circuit board that has undergone the lamination process is allowed to stand for 15 minutes or more to stabilize the board, and then exposure is performed on the photoresist of the DFR using a photomask having a desired circuit pattern formed thereon. In this process, when the photomask is irradiated with ultraviolet rays, polymerization of the photoresist irradiated with ultraviolet rays is initiated by a photoinitiator contained in the irradiated portion. First, oxygen in the photoresist is initially consumed, and then an activated monomer is polymerized to cause a crosslinking reaction, and then a polymerization reaction proceeds while a large amount of the monomer is consumed. On the other hand, the unexposed portion exists in a state in which the crosslinking reaction does not proceed.

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

A circuit is formed through different processes according to the next inner layer and outer layer processes. In the inner layer process, a circuit is formed on the board through corrosion and peeling processes, and in the outer layer process, plating and tenting processes are performed, followed by etching and solder peeling to form a predetermined circuit.

The present invention is to provide a photosensitive resin composition capable of implementing an effect of improving adhesion, resolution, and reducing peeling time.

In addition, the present invention is to provide a dry film photoresist, a photosensitive element, a resist pattern, a circuit board, and a display device using the photosensitive resin composition.

In order to solve the above problems, the present specification provides a photosensitive resin composition including an alkali developable binder resin, a photopolymerization initiator, a photopolymerizable compound, and an aromatic compound having 6 to 30 carbon atoms in which two or more carboxy groups are substituted.

In the present specification, a dry film photoresist including a photosensitive resin layer containing the photosensitive resin composition is also provided.

In the present specification, the polymer substrate also; and a photosensitive resin layer including an alkali developable binder resin and an aromatic compound having 6 to 30 carbon atoms substituted with two or more carboxy groups.

In the present specification, a resist pattern including a photosensitive resin pattern containing the photosensitive resin composition is also provided.

In the present specification, a circuit board and a display device including the resist pattern or a metal pattern formed by the resist pattern are also provided.

Hereinafter, a photosensitive resin composition according to specific embodiments of the present invention and a dry film photoresist using the same, a photosensitive element, a resist pattern, a circuit board, and a display device will be described in detail.

Unless explicitly stated herein, terminology is used only to refer to specific embodiments and is not intended to limit the present invention.

As used herein, the singular forms also include the plural forms unless the phrases clearly dictate the contrary.

As used herein, the meaning of 'comprising' specifies a particular property, domain, integer, step, operation, element, and/or component, and other particular property, domain, integer, step, operation, element, component, and/or group. does not exclude the presence or addition of

In this specification, terms including ordinal numbers such as 'first' and 'second' are used for the purpose of distinguishing one component from another component, and are not limited by the ordinal number. For example, within the scope of the present invention, a first element may also be termed a second element, and similarly, a second element may be termed a first element.

In this specification, examples of substituents are described below, but are not limited thereto.

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

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; cyano group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amide group; primary amino group; carboxy group; sulfonic acid group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; Alkyl thioxy group; Arylthioxy group; an alkyl sulfoxy group; aryl sulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl group; an alkoxysilylalkyl group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing at least one of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.

, 또는

는 다른 치환기에 연결되는 결합을 의미하고, 직접결합은 L 로 표시되는 부분에 별도의 원자가 존재하지 않은 경우를 의미한다. In this specification,

, or

means a bond connected to another substituent, and a direct bond means a case where no separate atom exists in the part represented by L.

In the present specification, (meth)acryl is meant to include both acryl and methacryl.

In the present specification, the alkyl group is a monovalent functional group derived from an alkane, and may be straight-chain or branched-chain, and the number of carbon atoms of the straight-chain alkyl group is not particularly limited, but is preferably 1 to 20. In addition, the number of carbon atoms of the branched chain alkyl group is 3 to 20. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-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-dimethylheptan-4-yl, and the like, but is not limited thereto. The alkyl group may be substituted or unsubstituted, and examples of the substituent when substituted are as described above.

In the present specification, the aryl group is a monovalent functional group derived from arene, and is not particularly limited, but preferably has 6 to 20 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto. The aryl group may be substituted or unsubstituted, and examples of substituents in the case of substitution are as described above.

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

According to one embodiment of the present invention, a photosensitive resin composition including an alkali developable binder resin, a photopolymerization initiator, a photopolymerizable compound, and an aromatic compound having 6 to 30 carbon atoms in which two or more carboxy groups are substituted may be provided.

The present inventors confirmed through experiments that the photosensitive resin composition of one embodiment includes an aromatic compound having 6 to 30 carbon atoms substituted with two or more carboxyl groups, thereby improving adhesion, resolution, and reducing peeling time, and completed the invention. did

Specifically, the aromatic compound having 6 to 30 carbon atoms in which two or more carboxyl groups are substituted may include a compound represented by Formula 1 below.

[Formula 1]

In Formula 1, R ₁ is hydrogen, straight or branched chain alkyl having 1 to 20 carbon atoms, linear or branched cycloalkyl having 3 to 20 carbon atoms, or straight or branched chain alkoxy having 1 to 20 carbon atoms, and Ar is It is an aromatic-derived functional group having 6 or more carbon atoms, and n1 is an integer of 2 or more.

Ar may be a divalent or higher functional group derived from an aromatic compound having 6 or more carbon atoms.

Specifically, in Chemical Formula 1, R ₁ is hydrogen, and Ar may be an aromatic-derived functional group having 6 to 12 carbon atoms.

More specifically, the aromatic compound having 6 to 30 carbon atoms in which two or more carboxy groups are substituted may include a compound represented by Formula 1-1 below.

[Formula 1-1]

.

.

The alkali-developable binder resin may include a repeating unit represented by Chemical Formula 2 below, a repeating unit represented by Chemical Formula 3 below, a repeating unit represented by Chemical Formula 4 below, and a repeating unit represented by Chemical Formula 5 below.

[Formula 2]

In Formula 2, R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms, R ₅ is alkyl having 1 to 10 carbon atoms, Ar is aryl having 6 to 20 carbon atoms, n is an integer of 1 to 20,

[Formula 3]

In Formula 3, R ₆ is hydrogen or alkyl having 1 to 10 carbon atoms;

[Formula 4]

In Formula 4, R ₇ is hydrogen or alkyl having 1 to 10 carbon atoms, R ₈ is alkyl having 1 to 10 carbon atoms,

[Formula 5]

In Formula 5, Ar is an aryl having 6 to 20 carbon atoms.

Specifically, the alkali-developable binder resin is a random copolymer of a repeating unit represented by Chemical Formula 2, a repeating unit represented by Chemical Formula 3, a repeating unit represented by Chemical Formula 4, and a repeating unit represented by Chemical Formula 5 can include

By including the repeating unit represented by Formula 2 in the alkali developable binder resin, the degree of hydrophobicity of the alkali developable binder resin is increased through the benzene structure included in the repeating unit represented by Formula 2, thereby increasing the photosensitivity. In the development process of the dry film photoresist using the resin composition, foam generation is suppressed to exhibit excellent developability, and proper physical properties (resolution, thin wire adhesion, etc.) can be secured by improving substrate adhesion.

In Formula 2, R ₄ may be hydrogen or any one of alkyl having 1 to 10 carbon atoms, and a specific example of the alkyl having 1 to 10 carbon atoms is methyl.

In Formula 2, R ₅ is an alkyl having 1 to 10 carbon atoms, and a specific example of the alkyl having 1 to 10 carbon atoms is ethyl.

In Formula 2, Ar is an aryl having 6 to 20 carbon atoms, and a specific example of the aryl having 6 to 20 carbon atoms is phenyl.

The repeating unit represented by Formula 2 may be a repeating unit derived from a monomer represented by Formula 2-1 below.

[Formula 2-1]

In Formula 2-1, R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms, R ₅ is alkyl having 1 to 10 carbon atoms, Ar is aryl having 6 to 20 carbon atoms, and n is an integer of 1 to 20 . In Chemical Formula 2-1, R ₄ , R ₅ , Ar, and n are the same as those described in Chemical Formula 2 above.

Specific examples of the monomer represented by Formula 2-1 include phenoxypolyethyleneoxyacrylate, more specifically 2-phenoxyethylmethacrylate (PHEMA).

The repeating unit represented by Formula 2 is 5 mol% or more and 40 mol% or less, or 5 mol% or more and 30 mol% or less, or 5 mol% or more based on 100 mol% of the total repeating unit molar content contained in the alkali developable binder resin mol% or more and 25 mol% or less, or 10 mol% or more and 25 mol% or less.

In Chemical Formulas 3 to 5, R ₆ and R ₇ are the same as or different from each other, and are each independently hydrogen or alkyl having 1 to 10 carbon atoms, R ₈ is alkyl having 1 to 10 carbon atoms, and Ar is 6 to 20 carbon atoms. is the aryl of

In Chemical Formulas 3 to 5, R ₆ and R ₇ are the same as or different from each other, and each independently may be hydrogen or an alkyl having 1 to 10 carbon atoms, and a specific example of the alkyl having 1 to 10 carbon atoms is methyl can be heard

R ₈ is alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms include methyl.

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

The repeating unit represented by Chemical Formula 3 may be a repeating unit derived from a monomer represented by Chemical Formula 3-1 below.

[Formula 3-1]

In Formula 3-1, R ₆ is hydrogen or alkyl having 1 to 10 carbon atoms. In Chemical Formula 3-1, the contents of R ₆ are the same as those described in Chemical Formula 2 above. A specific example of the monomer represented by Chemical Formula 3-1 is methacrylic acid (MAA).

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

[Formula 4-1]

In Formula 4-1, R ₇ is hydrogen or alkyl having 1 to 10 carbon atoms, and R ₈ is alkyl having 1 to 10 carbon atoms. In Formula 4-1, R ₇ and R ₈ are the same as those described in Formula 4 above. As a specific example of the monomer represented by Chemical Formula 4-1, methylmethacrylate (MMA) may be mentioned.

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

[Formula 5-1]

In Chemical Formula 5-1, Ar is an aryl having 6 to 20 carbon atoms. In Chemical Formula 5-1, Ar is the same as described in Chemical Formula 5 above. A specific example of the monomer represented by Chemical Formula 5-1 is styrene (SM).

The alkali developable binder resin contains 20 mol% or more and 60 mol% or less, or 20 mol% or more of the repeating unit represented by Formula 3 based on 100 mol% of the total repeating unit molar content contained in the alkali developable binder resin. 50 mol% or less, or 30 mol% or more and 40 mol% or less.

In addition, the alkali developable binder resin is 1 mol% or more and 30 mol% or less, or 5 mol% of the repeating unit represented by Formula 4 based on 100 mol% of the total repeating unit mol content contained in the alkali developable binder resin. % or more and 30 mol% or less, and 30 mol% or more and 60 mol% or less of the repeating unit represented by Formula 5, or 30 mol% or more and 50 mol% or less, or 30 mol% or more and 40 mol% or less.

More specifically, the molar ratio of the repeating unit represented by Formula 4 to 100 moles of the repeating unit represented by Formula 5 is 10 mol or more and 99 mol or less, or 15 mol or more and 95 mol or less, or 20 mol or more and 95 mol or more. may be below.

As such, as the content of the hydrophobic repeating unit represented by Chemical Formula 5 increases, the degree of hydrophobicity of the alkali developable binder resin also increases, preventing the generation of foam during the development process of the dry film photoresist using the photosensitive resin composition. can be suppressed

The alkali developable binder resin may have a weight average molecular weight of 30000 g/mol or more and 150000 g/mol or less, and a glass transition temperature of 20 °C or more and 150 °C or less. Accordingly, the coating properties of the dry film photoresist, followability, and mechanical strength of the resist itself after circuit formation may be improved.

In this specification, a weight average molecular weight means the weight average molecular weight of polystyrene conversion measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a conventionally known analyzer and a detector such as a differential refraction detector (Refractive Index Detector) and an analysis column may be used, and a commonly applied temperature Conditions, solvents, and flow rates can be applied.

As a specific example of the above measurement conditions, the alkali developable binder resin is dissolved in tetrahydrofuran to a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on solid content) to form a syringe having a 0.45 μm pore size. After filtration using a filter, 20 μl was injected into GPC, and the mobile phase of GPC was tetrahydrofuran (THF), flowed in at a flow rate of 1.0 mL / min, and the column was Agilent PLgel 5 μm Guard (7.5 x 50 mm) and 2 Agilent PLgel 5㎛ Mixed D (7.5 x 300 mm) were connected in series, and the detector was measured at 40 ° C using an Agilent 1260 Infinity II system and RI Detector.

For this, polystyrene standard samples (STD A, B, C, D) in which polystyrene having various molecular weights were dissolved in tetrahydrofuran at a concentration of 0.1 (w/w)% as follows, filtered through a syringe filter with a 0.45 μm pore size, and then GPC The value of the weight average molecular weight (Mw) of the alkali developable binder resin was obtained using the calibration curve formed by injecting into.

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

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

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

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

The glass transition temperature was compared with the reference and binder polymer in a Differential Scanning Calorimeter (DSC) (Perkin-Elmer, DSC-7). The temperature setting can be measured by maintaining the temperature at 20° C. for 15 minutes and then raising the temperature to 200° C. at a heating rate of 1° C./min.

The alkali developable binder resin may have an acid value of 120 mgKOH/g or more and 200 mgKOH/g or less, or 140 mgKOH/g or more and 160 mgKOH/g or less. The acid value was measured by sampling about 1 g of the alkali developable binder resin, dissolving it in 50 ml of a mixed solvent (MeOH 20%, Acetone 80%), adding two drops of 1%-phenolphthalein indicator, and then titrating with 0.1 N-KOH.

The alkali developable binder resin is included in an amount of 20% by weight or more and 80% by weight or less based on the solid content based on the total weight of the photosensitive resin composition. When the content of the alkaline developable binder resin is within the above range, it is possible to obtain an effect of enhancing adhesion of fine wires after circuit formation. The solid content based on the weight means the remaining components except for the solvent in the photosensitive resin composition.

The alkali developable binder resin is included in an amount of 20% by weight or more and 80% by weight or less based on the solid content based on the total weight of the photosensitive resin composition. When the content of the alkaline developable binder resin is within the above range, it is possible to obtain an effect of enhancing adhesion of fine wires after circuit formation. The solid content based on the weight means the remaining components except for the solvent in the photosensitive resin composition.

The content of the alkali developable binder resin of the present invention may be 40% by weight or more and 70% by weight or less based on the total weight of the photosensitive resin composition. If the content of the alkali developable binder resin is less than 40% by weight of the total photosensitive resin composition, there is a disadvantage in that contamination of the developing stage occurs and defects such as short circuits occur, and if it exceeds 70% by weight, adhesion and resolution, etc. There is a problem of poor circuit properties.

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

Compounds usable as the photopolymerization initiator include anthraquinone derivatives such as 2-methyl anthraquinone and 2-ethyl anthraquinone; and benzoin derivatives such as benzoin methyl ether, benzophenone, phenanthrene quinone, and 4,4'-bis-(dimethylamino)benzophenone.

In addition, 2,2'-bis(2-chlorophenyl)-4,4'-5,5'-tetraphenylbisimidazole, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2- Diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-[4-morph polynophenyl] butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-[4-(2- hydroxymethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 3, 3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone, 1-(4-isopropylphenyl)2-hydroxy-2-methylpropan-1-one, 1 -(4-dodecylphenyl)-2hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4- Dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzylketone dimethylacetal, benzyl Ketone β-methoxy diethylacetal, 1-phenyl-1,2-propyldioxime-o,o'-(2-carbonyl)ethoxyether, methyl o-benzoylbenzoate, bis[4-dimethylaminophenyl ) ketone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-part Toxybenzoin, isobutoxybenzoin, tert-butoxybenzoin, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthio A compound selected from oxanthone, 2-isopropylthioxanthone, dibenzosuberon, α, α-dichloro-4-phenoxyacetophenone, and pentyl 4-dimethylaminobenzoate may be used as a photopolymerization initiator, but is limited thereto. It is not.

The photopolymerization initiator is included in an amount of 1% by weight or more and 10% by weight or less based on the solid content based on the total weight of the photosensitive resin composition. Sufficient sensitivity can be obtained when the amount of the photopolymerization initiator is within the above range. The solid content based on the weight means the remaining components except for the solvent in the photosensitive resin composition.

When the content of the photopolymerization initiator is less than 1% by weight, there is a disadvantage in that the production efficiency is extremely reduced because the light efficiency is low and a large amount of exposure is required. There is a problem of causing defects such as short circuits.

The photopolymerizable compound of the present invention has resistance to a developing solution after UV exposure, allowing pattern formation.

The photopolymerizable compound may include a bifunctional (meth)acrylate compound. The bifunctional (meth)acrylate compound may include an alkylene glycol-based di(meth)acrylate or a bisphenol-based di(meth)acrylate.

As the alkylene glycol-based di(meth)acrylate, a compound represented by Formula 6 may be used.

[Formula 6]

In Formula 6, l+n is an integer of 2 or 3, and m is an integer of 12 to 18.

The compound represented by Formula 6 improves the hydrophobicity of the photosensitive resin composition, remarkably increases resistance to a developing solution and a plating solution, and shortens the peeling time of the cured film.

In the present invention, the amount of the compound represented by Chemical Formula 6 may be 10 wt% or more and 60 wt% or less, or 20 wt% or more and 40 wt% or less, based on the total solid weight of the photosensitive resin composition.

If the content of the compound represented by Formula 6 is less than 10% by weight based on the total weight of the solid content of the photosensitive resin composition, the effect of the addition of the compound represented by Formula 6 is insufficient, and if it exceeds 60% by weight, hydrophobicity This increase may cause a problem in that the development time in the post-exposure development process rapidly increases.

As the bisphenol-based di(meth)acrylate, the bisphenol-based di(meth)acrylate containing ethylene oxide may be used. The bisphenol-based di(meth)acrylate containing ethylene oxide is a bisphenol-based di(meth)acrylate containing 8 moles or less of ethylene oxide per molecule and 8 moles or more and 16 moles or less of ethylene oxide per molecule. Two types of bisphenol-based di(meth)acrylates may be included.

Examples of the bisphenol-based di(meth)acrylate containing 8 moles or less of ethylene oxide include Miramer M244 (BPA(EO)3DA, Bisphenol A (EO) ₃ Diacrylate), Miramer manufactured by Miwon Specialty Chemical Co., Ltd. M240 (BPA(EO) ₄ DA, Bisphenol A (EO) 4 Diacrylate) and Miramer M241 (Bisphenol A (EO) ₄ Dimethacrylate).

Examples of the bisphenol-based di(meth)acrylate containing more than 8 moles of ethylene oxide and less than or equal to 16 moles include Miramer M2100 (BPA(EO) ₁₀ DA, Bisphenol A (EO) ₁₀ manufactured by Miwon Specialty Chemical Co., Ltd.) Diacrylate), Miramer M2200 (BPA(EO) ₂₀ DA, Bisphenol A (EO) ₂₀ Diacrylate), Miramer M2101 (Bisphenol A (EO) ₁₀ Dimethacrylate), etc. can be used.

More specifically, based on 100 parts by weight of the bisphenol-based di(meth)acrylate containing more than 8 moles and 16 moles or less of ethylene oxide per molecule, bisphenol-based di(meth)acrylic acid containing 8 moles or less of ethylene oxide per molecule The rate may be 100 parts by weight or less, 50 parts by weight or less, 1 part by weight or more and 100 parts by weight or less, or 1 part by weight or more and 50 parts by weight or less.

The amount of the photopolymerizable compound may be 10% by weight or more and 70% by weight or less based on the total weight of the photosensitive resin composition on a solid basis. When the content of the photopolymerizable compound is within the above range, an effect of enhancing photosensitivity, resolution, and adhesion may be obtained. The solid content based on the weight means the remaining components except for the solvent in the photosensitive resin composition.

In addition, the photosensitive resin composition may further include other additives as needed. Other additives include dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diallyl phthalate in the form of phthalic acid esters as plasticizers; triethylene glycol diacetate, tetraethylene glycol diacetate in the form of glycol esters; p-toluene sulfonamide, benzenesulfonamide, n-butylbenzenesulfonamide in the form of acid amides; triphenyl phosphate and the like can be used.

In the present invention, in order to improve the handleability of the photosensitive resin composition, a Leuico dye or a coloring material may be added. Examples of the Leuico dye include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, and fluorane dyes. Among them, in the case of using Leuico Crystal Violet, the contrast is good and is preferable. In the case of containing the Leuico dye, the content may be 0.01% by weight or more and 1% by weight or less in the photosensitive resin composition. From the viewpoint of expression of contrast, 0.01% by weight or more is preferable, and from the viewpoint of maintaining storage stability, 1% by weight or less is preferable.

Examples of the coloring material include toluenesulfonic acid monohydrate, fuchsine, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green, Diamond Green, Basic Blue 20, and the like. can be heard In the case of containing the coloring material, the addition amount may be 0.001% by weight or more and 1% by weight or less in the photosensitive resin composition. In the content of 0.001% by weight or more, there is an effect of improving handling properties, and in the content of 1% by weight or less, there is an effect of maintaining storage stability.

In addition, other additives may further include a thermal polymerization inhibitor, a dye, a discoloring agent, an adhesion accelerator, and the like.

In the photosensitive resin composition of the above embodiment, the photosensitive resin composition contains 0.001 wt% or more and 1 wt% or less, 0.01 wt% or more and 1 wt% or less, 0.1 wt% or more and 1 wt% or less, and 0.1 wt% or more of the additive compound, based on solid content. 0.5% by weight or less, or 0.2% by weight or more and 0.3% by weight or less.

The additive compound may include an aromatic compound having 6 to 30 carbon atoms in which two or more carboxy groups are substituted, a plasticizer, a Leuico dye, a coloring material, a thermal polymerization inhibitor, a dye, a discoloring agent, an adhesion promoter, and the like.

In addition, the photosensitive resin composition of the embodiment includes 1 part by weight or more and 50 parts by weight or less, 1 part by weight or more and 30 parts by weight or less, 1 part by weight or more and 30 parts by weight or less, 1 part by weight or more and 20 parts by weight or less, 1 part by weight or more and 15 parts by weight or less, 3 parts by weight or more and 15 parts by weight or less, or 3 parts by weight or more and 12 parts by weight or less.

When less than 1 part by weight of an aromatic compound having 6 to 30 carbon atoms in which two or more carboxy groups are substituted, based on 100 parts by weight of the total additive compound, adhesion may be deteriorated, and the two or more carboxy groups based on the total 100 parts by weight of the additive compound When an aromatic compound having 6 to 30 carbon atoms in which a carboxyl group is substituted is included in an amount of more than 50 parts by weight, technical problems such as deterioration in adhesion and resolution may occur.

The photosensitive resin composition contains, on a solid basis, 20% by weight or more and 80% by weight or less of an alkali developable binder resin, 1% by weight or more and 10% by weight or less of a photopolymerization initiator, 10% by weight or more and 70% by weight or less of a photopolymerizable compound, and 0.001% by weight of an additive compound. It may include more than 1% by weight and less than 1% by weight.

The photosensitive resin composition may further contain a solvent. The solvent is generally selected from methyl ethyl ketone (MEK), methanol, THF, toluene, and acetone, and is not particularly limited to the solvent. It may be contained by adjusting according to the content.

According to another embodiment of the invention, a dry film photoresist including a photosensitive resin layer containing the photosensitive resin composition of one embodiment may be provided. Information about the photosensitive resin composition includes all of the information described above in the embodiment.

Specifically, the photosensitive resin layer may include a dried or cured product of the photosensitive resin composition of one embodiment. The dried material means a material obtained through a drying process of the photosensitive resin composition of the embodiment. The cured product refers to a material obtained through a curing process of the photosensitive resin composition of the embodiment. The thickness of the photosensitive resin layer is not particularly limited, but may be freely adjusted within a range of, for example, 0.01 μm to 1 mm.

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

The dry film photoresist may further include a base film and a protective film. The base film serves as a support for the photosensitive resin layer during manufacturing of the dry film photoresist, and facilitates handling during exposure of the photosensitive resin layer having adhesiveness.

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

The protective film serves as a protective cover to prevent damage to the resist during handling and to protect the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface of the photosensitive resin layer on which the base film is not formed. The protective film serves to protect the photosensitive resin layer from the outside, and requires appropriate release property and adhesiveness so that it is easily released when the dry film photoresist is applied to the post-process and not released during storage and distribution.

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

An example of a method for preparing the dry film photoresist is not particularly limited. For example, the photosensitive resin composition of one embodiment is coated on a conventional base film such as polyethylene terephthalate using a conventional coating method, and then dried. and lamination using a conventional protective film such as polyethylene on the top surface of the dried photosensitive resin layer to prepare a dry film.

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

Drying the coated photosensitive resin composition may be performed by a heating means such as a hot air oven, a hot plate, a hot air circulation furnace, an infrared furnace, or the like, and may be performed at a temperature of 50° C. or more and 120° C. or less.

According to another embodiment of the invention, a polymer substrate; and a photosensitive resin layer including an alkali developable binder resin and an aromatic compound having 6 to 30 carbon atoms in which two or more carboxy groups are substituted.

The alkali developable binder resin and the aromatic compound having 6 to 30 carbon atoms substituted with two or more carboxyl groups include all of the above.

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

A specific example of the polymer substrate is a polyester having an antiblocking layer formed by an in-line coating method in which an unstretched polyester film is uniaxially stretched, a crude liquid containing a binder resin and organic particles is applied to one side of the film, and the remaining uniaxially stretched. film can be taken.

The polymer substrate was selected for an in-line coating method instead of adding an anti-blocking agent, which has been conventionally added in consideration of runability and winding characteristics at the time of manufacture, and is provided with an organic particle layer using alternative particles that do not impair transparency. it did

Here, examples of organic particles used as particles that do not impair transparency while considering runability and winding characteristics include methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, and normal butyl methyl methacrylate. acrylic particles such as copolymers or terpolymers of acrylic acid and methacrylic acid; olefinic particles such as polyethylene, polystyrene, and polypropylene; copolymers of acrylics and olefins; Alternatively, organic particles such as multi-layered multi-component particles obtained by forming homopolymer particles and then coating another type of monomer on the layer thereof may be mentioned.

Specifically, such organic particles should have a spherical shape and have a difference in refractive index from that of the binder resin. Here, 'spherical shape' is defined as the ratio of the minor axis (a) to the major axis (b) of an ellipse being 0.5 < a/b < 2, and the relationship with the diagonal (d) of a rectangle being d2≤a2+b2. In addition, the relationship between the axis (f) with the longest distance between vertices in the hexahedron and the c axis other than the a and b axes is defined as f2≤c2+a2+b2. The shape of the particles should be spherical, which is preferable in terms of drivability.

And, it is characterized in that the refractive index difference between the organic particles and the binder resin is 0.05 or less. Haze increases when the difference in refractive index is greater than 0.05. This means that there is a lot of scattered light, and when there is a lot of such scattered light, the smoothing effect of the sidewall is reduced. It also depends on the size and amount of organic particles. It is preferable that the organic particles have an average particle diameter of about 0.5 μm to 5 μm, and when smaller than this, driving characteristics and winding characteristics are lowered, and when larger than 5 μm, haze increases, and it is not preferable in view of the occurrence of a falling off problem. The content of the organic particles is preferably 1 to 10% by weight based on the total amount of the binder resin.

If the content of the organic particles is less than 1% by weight based on the total amount of the binder resin, the anti-blocking effect is insufficient, making it vulnerable to scratches, and winding characteristics and driving characteristics deteriorate. If it exceeds 10% by weight, the haze increases and the transparent properties There could be a problem with this getting worse.

On the other hand, inorganic particles may be added in addition to the organic particles as described above. At this time, it is not preferable to add a commonly used inorganic antiblocking agent, and it is preferable to add colloidal silica having a particle size of 100 nm or less. Its content is preferably 10 parts by weight or less with respect to 100 parts by weight of the binder resin. When the above particle size and content are satisfied, sidewall defects or grooves such as craters caused by the anti-blocking layer may not be generated in pattern formation using the dry film photoresist.

As a binder resin that serves as an adhesive for applying such organic particles onto an unstretched polyester film, those having good compatibility with organic particles may be used. Examples of such resins include unsaturated polyester, methyl methacrylate, acrylic resins such as ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, normal butyl methyl methacrylate, acrylic acid and copolymers or terpolymers of methacrylic acid; urethane-based resin; Epoxy-based resin; or melamine-based resins and the like, preferably acrylic resins.

A solvent that can be used in preparing a liquid with a binder resin and organic particles is preferably water.

In this way, the crude solution containing organic particles in the binder resin is uniaxially stretched on an unstretched polyester film obtained by volume extrusion of PET pellets, and then applied onto the uniaxially stretched film. The coating may be performed on at least one surface of the uniaxially stretched film, and the thickness is preferably about 30 nm to 200 nm based on the thickness after final drying. If the crude liquid containing organic particles is applied on a uniaxially stretched film with a thickness of less than 30 nm, the organic particles are easily detached, making it vulnerable to scratches and generating white powder. Therefore, in in-line coating with a high coating speed, coating streaks occur in the coating direction.

In this way, the polymer substrate obtained by coating using organic particles rather than a general anti-blocking agent by the in-line coating method has excellent transparency due to organic particles having excellent light transmission while maintaining winding characteristics and running characteristics due to the particle layer. It is a base film.

Lamination of the photosensitive resin layer is performed on the opposite side of the layer containing organic particles in the polymer substrate. As the photosensitive resin layer is formed on the opposite side of the layer containing organic particles, the anti-blocking agent is applied as before. There is no occurrence of crater-shaped flaws that appear as the base film containing is laminated. Particles such as silica have a larger size than organic particles and are distributed over the entire base film, so the effect of silica appears insignificantly even in a portion adjacent to the photosensitive resin layer.

On the other hand, in the polymer substrate used in the present invention, the organic particles have a size of 0.5 μm to 5 μm, and the organic particle layer is not adjacent to the photosensitive resin layer, so the organic particles do not have a physical effect. In addition, by using organic particles having excellent light transmittance, defects in the sidewall can be reduced, and other circuit properties are not impaired.

The photosensitive element may further include a protective film formed on the photosensitive resin layer. The protective film serves as a protective cover to prevent damage to the photosensitive resin layer during handling and to protect the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface of the photosensitive resin layer on which the polymer substrate is not formed. The protective film serves to protect the photosensitive resin layer from the outside, and requires appropriate releasability and adhesiveness so that the photosensitive element is easily released when applied to a post-process and not released during storage and distribution.

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

According to another embodiment of the invention, a resist pattern including a photosensitive resin pattern containing the photosensitive resin composition of one embodiment may be provided. Information about the photosensitive resin composition includes all of the information described above in the embodiment.

The photosensitive resin pattern may be a patterned photosensitive composition having openings.

As an example of a method of forming the photosensitive resin pattern, a method of laminating a photosensitive resin layer of the dry film photoresist according to another embodiment on a substrate, followed by exposure and development. In addition, a method of laminating the photosensitive resin layer of the photosensitive element of the other embodiment on a substrate and then performing exposure and development may be mentioned.

As substrates, copper clad laminates, glass substrates sputtered or deposited with transparent electrodes such as ITO and IZO, film substrates, glass substrates coated with dielectric paste, silicon wafers, glass wafers deposited with amorphous silicon, copper, tantalum, molybdenum, etc. A silicon wafer or the like on which a metal thin film is sputtered can be used.

For the exposure process, it is preferable to use a Laser Direct exposure machine including a light source such as UV, visible light, laser, light having a wavelength of 350 to 410 nm, in particular i-ray (365 nm) or h-ray (405 nm). When using a Laser Direct exposure machine, it is possible to work under the condition of exposure energy of 3 to 15 mJ/cm2 or less, and when using a general lamp exposure machine, exposure energy of 20 mJ/cm2 or less. It is useful for producing images for display devices and the like.

The developing process may be by a dipping method, a shower method, a spray method, a brush method, etc., and as a developing solution, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, or amines may be used. .

In the case where the dry film photoresist or photosensitive element of the other embodiment has a protective film on the photosensitive resin layer, a process of removing the protective film may be further performed prior to the lamination process of the photosensitive resin layer on a circuit board or a substrate for display device manufacturing. have.

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

According to another embodiment of the present invention, a circuit board or display device including the resistor pattern of the other embodiment or a metal pattern formed by the resistor pattern of the other embodiment may be provided. The contents of the register pattern include all of the above-described contents in the other embodiments.

The specific content of the circuit board or display device is not particularly limited, and various technical configurations known in the art can be applied without limitation.

The metal pattern may be formed by the above-described resistor pattern. Specifically, a metal pattern may be formed by performing etching or plating through an opening included in the resist pattern. That is, the metal pattern may include a lower metal remaining after the lower metal of the resist pattern is etched through an opening included in the resist pattern, or a metal plated on an opening included in the resist pattern.

Specifically, for example, a conductor pattern, a printed wiring board, a lead frame, an ITO electrode, a black mattress, a semiconductor bump, and the like can be manufactured by etching or plating the lower substrate exposed by the above-described resist pattern. If necessary, after the etching or plating, the resist pattern may be peeled from the substrate with an aqueous solution having a stronger alkalinity than the developing solution and removed.

Accordingly, by using the dry film photoresist of the present invention, a circuit having a fine line width is formed through a conventional etching/plating process, and a PCB having a fine line width is formed through a known process, as well as lead frames, PDPs, and other displays. Productivity can be maximized in generating an image of a device, a semiconductor device, or the like.

According to the present invention, a photosensitive resin composition capable of improving adhesion, resolution, and reducing peeling time, and a dry film photoresist using the same, a resist pattern, a circuit board, and a display device may be provided.

The invention is explained in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

<Production Example: Production of Alkali Developable Binder Resin>

A mechanical stirrer and a reflux device were installed in a 4-neck reaction flask jacket set, and then the inside of the flask was purged with nitrogen. 90 g of methyl ethyl ketone (MEK) and 10 g of methanol (MeOH) were added to the flask purged with nitrogen, and then 0.9 g of azobisisobutyronitrile (AIBN) was added to completely dissolve . Here, as monomers, methacrylic acid (MAA) 24g, methylmethacrylate (MMA) 6g, styrene (Styrene, SM) 30g, and 2-phenoxyethyl methacrylate (PHEMA) ) 40 g of the monomer mixture was added, the temperature was raised to 80 ° C, and polymerization was performed for 6 hours to prepare an alkali developable binder resin (weight average molecular weight: 50000 g / mol, solid content 50.0% by weight, acid value 155 mgKOH / g). .

As a specific example of the weight average molecular weight measurement conditions, the alkali developable binder resin is dissolved in tetrahydrofuran to a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on solid content) to obtain a 0.45 μm Pore After filtration using a Syringe Filter of size, 20 μl was injected into GPC, and the mobile phase of GPC was tetrahydrofuran (Tetrahydrofuran, THF), introduced at a flow rate of 1.0 mL/min, and the column was Agilent PLgel 5 μm Guard (7.5 x 50 mm) and 2 Agilent PLgel 5㎛ Mixed D (7.5 x 300 mm) were connected in series, and the detector was measured at 40 ° C using an Agilent 1260 Infinity II system and RI Detector.

The acid value was measured by sampling 1 g of alkali developable binder resin, dissolving it in 50 ml of a mixed solvent (MeOH 20%, Acetone 80%), adding two drops of 1%-phenolphthalein indicator, and then titrating with 0.1N-KOH.

The solid content was measured by weight percent ratio of the solid content remaining after heating in an oven at 150 ° C. for 120 minutes based on the weight of the alkali developable binder resin prepared in the above-described Preparation Example.

<Examples and Comparative Examples: Preparation of photosensitive resin composition and dry film photoresist>

According to the composition shown in Table 1 below, after dissolving the photopolymerization initiators in methyl ethyl ketone (MEK) as a solvent, a photopolymerizable compound and an alkali developable binder resin were added and mixed for about 1 hour using a mechanical stirrer to obtain a photosensitive resin A composition was prepared.

The obtained photosensitive resin composition was coated on a 19 μm PET film using a coating bar to form a photosensitive resin layer, and dried using a hot air oven, where the drying temperature was 80 ° C. and the drying time was 5 minutes, and the thickness of the photosensitive resin layer after drying was 40 μm.

A dry film photoresist was prepared by laminating the dried photosensitive resin layer using a protective film (polyethylene).

ingredient Product name (or ingredient name) Content (% by weight) Example 1 Example 2 Example 3 Comparative Example 1 Alkali developable binder resin manufacturing example 65.0 65.0 65.0 65.0 photopolymerizable compound M241 5.0 5.0 5.0 5.0 M2101 20.0 20.0 20.0 20.0 photopolymerization initiator EAB 0.05 0.05 0.05 0.05 BCIM 1.30 1.30 1.30 1.30 additive 1,2-benzenedicarboxylic acid 0.011 0.022 0.033 0 Toluenesulfonic acid monohydrate
(Aldrich Chemical) 0.033 0.022 0.011 0.044 N,N-BDA 0.066 0.066 0.066 0.066 Ruiko Crystal Violet (Hodogaya Co., Japan) 0.170 0.170 0.170 0.170 Diamond Green GH (Hodogaya Co., Japan) 0.015 0.015 0.015 0.015 solvent Methyl ethyl ketone (MEK) 8.355 8.355 8.355 8.355 (1) M241 : Bisphenol A (EO) ₄ dimethacrylate (Miwon Specialty Chemical)
(2) M2101 : Bisphenol A (EO) ₁₀ dimethacrylate (Miwon Specialty Chemical)
(3) EAB: 4,4'-(Bisdiethylamino)benzophenone (Aldrich Chemical)
(4) BCIM: 2,2'-Bis-(2-chlorophenyl-4,5,4',5'-tetraphenylbisimidazole (Aldrich Chemical)
(5) N,N-BDA: N,N-benzyldimethylamide

<Experimental example>

With respect to the dry film photoresists prepared in the above Examples and Comparative Examples, physical properties were measured by the following method, and the results are shown in Table 2.

1. Fine wire adhesion (Unit: ㎛)

Peel off the protective film of the dry film photoresist prepared in Examples and Comparative Examples, and preheat the substrate so that the photosensitive resin layer of the dry film photoresist comes into contact with the surface of the copper layer of the 1.6 mm thick copper-clad laminate that has been brush polished. Roll temperature 120 ℃, laminator roll temperature 115 ℃, roll pressure 4.0kgf / ㎠ And lamination was performed using HAKUTO MACH 610i at a roll speed of 2.0 min/m to form a laminate.

After peeling off the dry film photoresist support PET film from the laminate, using a photomask for circuit evaluation, ultraviolet rays were applied for 4 seconds at an exposure amount of 80 mJ/cm ² through ORC EXM-1201-F (parallel light exposure machine). After irradiation, it was allowed to stand for 15 minutes. After that, development was carried out for 1 minute under a spray-type development condition at a spray pressure of 1.5 kgf/cm 2 with a 1.0 wt% aqueous solution of Na ₂ CO ₃ at 30±1 °C.

In the developed laminate, the minimum line width of the photosensitive resin layer was measured with a ZEISS AXIOPHOT Microscope to evaluate fine line adhesion. It can be evaluated that the fine wire adhesion is excellent, so that this value is small.

2. 1:1 resolution (Unit: ㎛)

Peel off the protective film of the dry film photoresist prepared in Examples and Comparative Examples, and preheat the substrate so that the photosensitive resin layer of the dry film photoresist comes into contact with the surface of the copper layer of the 1.6 mm thick copper-clad laminate that has been brush polished. Roll temperature 120 ℃, laminator roll temperature 115 ℃, roll pressure 4.0kgf / ㎠ And lamination was performed using HAKUTO MACH 610i at a roll speed of 2.0 min/m to form a laminate.

After peeling off the dry film photoresist support PET film from the laminate, a photomask for circuit evaluation is used so that the width of the circuit line and the space between the circuit lines can be 1:1 after development. Then, ultraviolet rays were irradiated for 4 seconds at an exposure amount of 80 mJ/cm ² through an ORC EXM-1201-F (parallel light exposure machine), and then left for 15 minutes. After that, development was carried out for 1 minute under a spray-type development condition at a spray pressure of 1.5 kgf/cm 2 with a 1.0 wt% aqueous solution of Na ₂ CO ₃ at 30±1 °C.

In the developed laminate, the minimum value of the gap between the photosensitive resin layers was measured with a ZEISS AXIOPHOT Microscope and evaluated at a 1:1 resolution. As this value is smaller, it can be evaluated that the 1:1 resolution value is excellent.

3. Peeling speed (unit: sec)

Peel off the protective film of the dry film photoresist prepared in Examples and Comparative Examples, and preheat the substrate so that the photosensitive resin layer of the dry film photoresist comes into contact with the surface of the copper layer of the 1.6 mm thick copper-clad laminate that has been brush polished. Roll temperature 120 ℃, laminator roll temperature 115 ℃, roll pressure 4.0kgf / ㎠ And lamination was performed using HAKUTO MACH 610i at a roll speed of 2.0 min/m to form a laminate.

After peeling off the PET film, which is the support of the dry film photoresist, from the laminate, using a photomask for circuit evaluation, ORC's EXM-1201 (parallel light exposure machine) until an exposure amount of 40mJ/cm ² is reached. After irradiating with ultraviolet rays, it was allowed to stand for 15 minutes. After that, development was carried out for twice the minimum development time under the development conditions of a spray method at a spray pressure of 1.5 kgf/cm 2 with a 1.0 wt% aqueous solution of Na ₂ CO ₃ at 30±1 °C.

And, the photosensitive resin layer was peeled from the copper-clad laminate using a 3% sodium hydroxide aqueous solution (temperature 50 ° C.). At this time, the time required for the photosensitive resin layer to separate from the copper-clad laminate was measured.

division Fine wire adhesion (㎛) 1:1 resolution (μm) Peeling speed (sec) Example 1 21 17 27 Example 2 18 15 26 Example 3 22 18 24 Comparative Example 1 22 18 30

As shown in Table 2, it can be confirmed that the examples are excellent in fine wire adhesion and resolution compared to the comparative examples. In addition, it was found that a faster peeling speed can be obtained during the peeling process.

Claims (14)

A photosensitive resin composition comprising an alkali developable binder resin, a photopolymerization initiator, a photopolymerizable compound, and an aromatic compound having 6 to 30 carbon atoms in which two or more carboxy groups are substituted.
According to claim 1,
The aromatic compound having 6 to 30 carbon atoms in which two or more carboxy groups are substituted includes a compound represented by Formula 1 below, a photosensitive resin composition:
[Formula 1]

In Formula 1,
R ₁ is hydrogen, straight or branched chain alkyl having 1 to 20 carbon atoms, straight or branched cycloalkyl having 3 to 20 carbon atoms, or straight or branched alkoxy having 1 to 20 carbon atoms;
Ar is an aromatic functional group having 6 or more carbon atoms,
n1 is an integer greater than or equal to 2;
According to claim 2,
R ₁ is hydrogen;
Ar is an aromatic-derived functional group having 6 or more and 12 or less carbon atoms, the photosensitive resin composition.
According to claim 1,
The aromatic compound having 6 to 30 carbon atoms in which two or more carboxy groups are substituted includes a compound represented by Formula 1-1 below, a photosensitive resin composition:
[Formula 1-1]

.
According to claim 1,
The alkali developable binder resin comprises a repeating unit represented by the following Chemical Formula 2, a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4, and a repeating unit represented by the following Chemical Formula 5:
[Formula 2]

In Formula 2,
R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms;
R ₅ is an alkyl having 1 to 10 carbon atoms;
Ar is an aryl having 6 to 20 carbon atoms;
n is an integer from 1 to 20;
[Formula 3]

In Formula 3,
R ₆ is hydrogen or alkyl having 1 to 10 carbon atoms;
[Formula 4]

In Formula 4,
R ₇ is hydrogen or alkyl having 1 to 10 carbon atoms;
R ₈ is an alkyl having 1 to 10 carbon atoms;
[Formula 5]

In Formula 5,
Ar is an aryl having 6 to 20 carbon atoms.
According to claim 5,
The photosensitive resin composition in which the repeating unit represented by Formula 2 is contained in an amount of 5 mol% or more and 40 mol% or less based on 100 mol% of the total repeating unit molar content contained in the alkali developable binder resin.
According to claim 5,
The alkali developable binder resin is based on 100 mol% of the total repeating unit molar content contained in the alkali developable binder resin,
A photosensitive resin composition comprising 20 mol% or more and 60 mol% or less of the repeating unit represented by Formula 3.
According to claim 5,
The alkali developable binder resin is based on 100 mol% of the total repeating unit molar content contained in the alkali developable binder resin,
1 mol% or more and 30 mol% or less of the repeating unit represented by Formula 4, and
A photosensitive resin composition comprising 30 mol% or more and 60 mol% or less of the repeating unit represented by Formula 5.
According to claim 1,
The photopolymerizable compound comprises a di (meth) acrylate-based compound having two functional groups, the photosensitive resin composition.
A dry film photoresist comprising a photosensitive resin layer containing the photosensitive resin composition of claim 1.
polymer substrate; and
A photosensitive element comprising: a photosensitive resin layer including an alkali developable binder resin and an aromatic compound having 6 to 30 carbon atoms in which two or more carboxy groups are substituted.
A resist pattern comprising a photosensitive resin pattern containing the photosensitive resin composition of claim 1 .
A circuit board comprising the resist pattern of claim 12 or a metal pattern formed by the resist pattern of claim 12.
A display device comprising the resist pattern of claim 12 or a metal pattern formed by the resist pattern of claim 12 .