WO2021137546A1

WO2021137546A1 - Photosensitive resin composition, and dry film photoresist, photosensitive element, circuit board, and display device, each using same

Info

Publication number: WO2021137546A1
Application number: PCT/KR2020/019182
Authority: WO
Inventors: 봉동훈; 심상화
Original assignee: 코오롱인더스트리 주식회사
Priority date: 2019-12-31
Filing date: 2020-12-28
Publication date: 2021-07-08
Also published as: TWI773059B; TW202132921A; JP7376712B2; WO2021137546A8; JP2023500301A; CN115053182A

Abstract

The present invention relates to a photosensitive resin composition, and a dry film photoresist, a photosensitive element, a circuit board, and a display device, each using same, wherein the photosensitive resin uses an alkali developable binder resin comprising a repeating unit represented by chemical formula 1, a repeating unit represented by chemical formula 2, a repeating unit represented by chemical formula 3, and a repeating unit represented by chemical formula 4.

Description

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

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

The photosensitive resin composition is used in the form of dry film photoresist (DFR), liquid photoresist (Liquid Photoresist Ink), etc. used in printed circuit boards (PCB) or lead frames. .

Currently, in addition to manufacturing printed circuit boards (PCBs) and lead frames, rib barriers for plasma display panels (PDP), ITO electrodes for other displays, bus address electrodes, and black matrices are also manufactured. Dry film photoresist is also widely used for the like.

Such, in general, dry film photoresist is often used for lamination on copper clad laminates. In this regard, as an example of a manufacturing process of a printed circuit board (PCB), a pretreatment process is first performed in order to laminate a copper clad laminate, which is an original material of the PCB. The pretreatment process is in the order of drilling, deburing, and front face in the outer layer process, and undergoes face or pickling in the inner layer process. In the face process, bristle brush and jet pumice processes are mainly used, and soft etching and 5wt% sulfuric acid pickling can be used for pickling.

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

The printed circuit board that has undergone the lamination process is left for at least 15 minutes to stabilize the board, and then is exposed to 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 the photoinitiator contained in the irradiated area. First, oxygen in the photoresist is consumed, then the activated monomer is polymerized to cause a crosslinking reaction, and then a large amount of the monomer is consumed and the polymerization reaction proceeds. On the other hand, the unexposed portion exists in a state where the crosslinking reaction has not progressed.

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

Then, a circuit is formed through different processes according to the inner layer and outer layer processes. In the inner layer process, a circuit is formed on the substrate through corrosion and peeling processes, and in the outer layer process, after plating and tenting processes, etching and solder stripping are performed, and a predetermined circuit is formed.

On the other hand, the dry film goes through a wet process when applied in a printed circuit board manufacturing plant, and is dissolved by an alkali solution by a saponification reaction in a developing process that melts an unexposed area or a peeling process that removes the dry film. When this occurs and the bubbles are excessively generated, there is a problem such as overflowing the chamber.

In order to solve this problem, an antifoaming agent that suppresses foam is used in an alkali solution in a ratio of 0.1 to 3%.

However, when an excessive antifoaming agent is used, the production cost increases and productivity is reduced at the same time. When the antifoaming agent is used excessively, it combines with the components of the dry film to generate scum that does not dissolve in water, resulting in poor etching or poor plating. is causing the Therefore, the need for a dry film that does not require the use of an antifoaming agent has increased due to the small amount of foam generated in the developing and peeling process.

On the other hand, when the dry film photoresist is laminated to the copper-clad laminate when the viscosity of the dry film photoresist is too high, the adhesion of the dry film photoresist to the copper-clad laminate is not sufficient, so it is difficult to ensure durability of the printed circuit board.

Therefore, the need for a dry film photoresist having a sufficiently low viscosity has increased.

The present invention relates to a photosensitive resin composition capable of increasing the efficiency of the process by reducing the generation of bubbles in the development and peeling process through a binder resin having increased hydrophobicity.

The present invention relates to a photosensitive resin composition having a sufficiently low viscosity without being cured near the thermal bonding temperature with a substrate for application to a circuit board or a display device, and having improved adhesion to the substrate.

Another object of the present invention is to provide a dry film photoresist, a photosensitive element, a circuit board, and a display device using the photosensitive resin composition.

In order to solve the above problems, in the present specification, alkali including a repeating unit represented by the following formula 1, a repeating unit represented by the following formula 2, a repeating unit represented by the following formula 3, and a repeating unit represented by the following formula 4 Provided is a photosensitive resin composition containing a developable binder resin, a photoinitiator, and a photopolymerizable compound, satisfying any one of the following (1) or (2).

(1) Put the photosensitive resin layer sample containing the photosensitive resin composition into a container with a cross-sectional diameter of 10 cm or more containing the developer so that the volume ratio of the photosensitive resin layer sample to the developer is 2x10 ^-5 m ³ /L, and When spraying from the top of the container while circulating the developer inside the container at a speed of 1000 cc/min or more and 1200 cc/min or less, the highest point of the bubbles generated in the container after 60 minutes of spraying the developer, and the container immediately after spraying the developer. If the height difference between the highest points of my developer is 80 mm or less,

(2) For the photosensitive resin layer sample containing the photosensitive resin composition and having a thickness of 5 μm or more and 30 μm or less, the absolute viscosity obtained in the temperature range of 50° C. or more and 125° C. or less under the condition that the axial force of the photosensitive resin layer sample is 5 N or less The minimum value is 300 Pa s or less,

[Formula 1]

In Formula 1, R ₁ is hydrogen or alkyl _{having 1 to 10 carbon atoms, R 2} is alkyl having 1 to 10 carbon atoms, Ar is aryl having 6 to 20 carbon atoms, n is an integer from 1 to 20,

[Formula 2]

In Formula 2, R ₃ is hydrogen or alkyl having 1 to 10 carbon atoms,

[Formula 3]

In Formula 3, R ₄ is hydrogen or alkyl _{having 1 to 10 carbon atoms, R 5} is alkyl having 1 to 10 carbon atoms,

[Formula 4]

In Formula 4, Ar is aryl having 6 to 20 carbon atoms.

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

In the present specification, also, a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, satisfying any one of the following (1) or (2), a photosensitive element is provided.

(1) Put the photosensitive resin layer sample into a container with a cross-sectional diameter of 10 cm or more containing the developer so that the volume ratio of the photosensitive resin layer sample to the developer is 2x10 ^-5 m ³ /L, and the developer inside the container is 1000 cc When spraying from the top of the container while circulating at a speed of more than /min and less than 1200cc/min, the highest point of the bubble generated in the container after 60 minutes of spraying the developer and the highest point of the developer in the container immediately after starting spraying the developer If the height difference between them is 80 mm or less,

(2) the photosensitive resin layer has a minimum value of absolute viscosity obtained in a temperature range of 50° C. or more and 125° C. or less under the condition that the axial force of the photosensitive resin layer sample is 5 N or less with respect to the photosensitive resin layer sample having a thickness of 5 μm or more and 30 μm or less 300 Pa·s or less.

The present specification also provides a circuit board and a display device including the photosensitive resin layer containing the photosensitive resin composition.

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

Unless explicitly stated herein, terminology is for the purpose of referring to specific embodiments only, and is not intended to limit the present invention.

As used herein, the singular forms also include the plural forms unless the phrases clearly indicate the opposite.

As used herein, the meaning of 'comprising' specifies a particular characteristic, region, integer, step, operation, element and/or component, and other specific characteristic, region, integer, step, operation, element, component, and/or group. It does not exclude the existence or addition of

And, in the present specification, terms including ordinal numbers such as 'first' and 'second' are used for the purpose of distinguishing one component from other components, and are not limited by the ordinal number. For example, within the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may be referred to as a first component.

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

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

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amide group; primary amino group; carboxyl group; sulfonic acid group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; alkoxysilylalkyl group; an arylphosphine group; or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents . 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.

In this specification,

, or

denotes a bond connected to another substituent, and a direct bond denotes a case in which a separate atom does not exist in the portion 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, and the number of carbon atoms in 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. The alkyl group may be substituted or unsubstituted, and when substituted, examples of the substituent 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 monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto. The aryl group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.

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

1. 감광성 수지 조성물1. Photosensitive resin composition

According to one embodiment of the invention, an alkali developable binder comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3), and a repeating unit represented by the following formula (4) A photosensitive resin composition containing a resin, a photoinitiator, and a photopolymerizable compound, satisfying any one of the following (1) or (2), may be provided.

[Formula 1]

[Formula 2]

In Formula 2, R ₃ is hydrogen or alkyl having 1 to 10 carbon atoms,

[Formula 3]

[Formula 4]

In Formula 4, Ar is aryl having 6 to 20 carbon atoms.

The present inventors have found that the photosensitive resin composition of one embodiment includes the repeating unit represented by Formula 1 in the alkali developable binder resin to increase the hydrophobicity of the alkali developable binder resin, so that the photosensitive resin composition is dried using the photosensitive resin composition. In the development process of film photoresist, it shows excellent developability by suppressing the generation of foam, and it was confirmed through experiments that proper physical properties (resolution, fine wire adhesion, etc.) can be secured by improving the adhesion to the substrate and completed the invention. .

In addition, the present inventors said that the photosensitive resin composition of one embodiment includes the repeating unit represented by Formula 1 in the alkali developable binder resin to improve the heat resistance properties of the alkali developable binder resin, so that the photosensitive resin composition As the thermal curing temperature of the used dry film photoresist increases, the dry film photoresist has a sufficiently low viscosity during heat treatment to near the thermal curing temperature, so that the dry film photoresist is thermally bonded to the substrate for application to a circuit board or a display device. The invention was completed after confirming that adhesion to the substrate could be increased through low viscosity at temperature.

(1) Alkali developable binder resin

The alkali developable binder resin of the present invention may include a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, a repeating unit represented by Formula 3, and a repeating unit represented by Formula 4 .

Specifically, the alkali developable binder resin is a random copolymer of the repeating unit represented by Formula 1, the repeating unit represented by Formula 2, the repeating unit represented by Formula 3, and the repeating unit represented by Formula 4 may include.

By including the repeating unit represented by Formula 1 in the alkali developable binder resin to increase the degree of hydrophobicity of the alkali developable binder resin, foam in the developing process of the dry film photoresist using the photosensitive resin composition ), exhibits excellent developability, and improves substrate adhesion to ensure proper physical properties (resolution, fine wire adhesion, etc.).

In Formula 1, R ₁ may be any one of hydrogen or alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms include methyl.

In Formula 1, R ₂ is alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms include ethyl.

In Formula 1, 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 Formula 1 may be a repeating unit derived from a monomer represented by Formula 1-1.

[Formula 1-1]

In Formula 1-1, R ₁ is hydrogen or alkyl _{having 1 to 10 carbon atoms, R 2} 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 Formula 1-1, R ₁ , R ₂ , Ar, and n are the same as described above in Formula 1 above.

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

The repeating unit represented by Formula 1 is 5 mol% or more and 40 mol% or less, or 5 mol% or more and 30 mol% or less, or 5 based on 100 mol% of the total repeating unit molar content contained in the alkali developable binder resin. It may be contained in mol% or more and 25 mol% or less, or 10 mol% or more and 25 mol% or less.

In Formulas 2 to 4, R ₃ and R ₄ are the same as or different from each other, and each independently represents hydrogen or alkyl _{having 1 to 10 carbon atoms, R 5} is alkyl having 1 to 10 carbon atoms, and Ar is 6 to 20 carbon atoms. is the aryl of

In Formulas 2 to 4, R ₃ and R ₄ are the same as or different from each other, and each independently may be any one of hydrogen or alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms include methyl can be heard

R ₅ 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 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 ₃ is hydrogen or alkyl having 1 to 10 carbon atoms. In Formula 2-1, _{the contents of R 3} are the same as those described above in Formula 2 above. Specific examples of the monomer represented by Formula 2-1 may include methacrylic acid (MAA).

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

[Formula 3-1]

In Formula 3-1, R ₄ is hydrogen or alkyl _{having 1 to 10 carbon atoms, and R 5} is alkyl having 1 to 10 carbon atoms. In Formula 3-1, _{the contents of R 4} and R ₅ are the same as those described above in Formula 3 above. A specific example of the monomer represented by Formula 3-1 may include methylmethacrylate (MMA).

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

[Formula 4-1]

In Formula 4-1, Ar is aryl having 6 to 20 carbon atoms. In Formula 4-1, the contents of Ar are the same as those described above in Formula 4 above. A specific example of the monomer represented by Formula 4-1 may include styrene (Styrene, SM).

The alkali developable binder resin is 20 mol% or more and 60 mol% or more, or 20 mol% or more of the repeating unit represented by Formula 2, 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 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 3, or 1 mol % or more and 20 mol% or less, or 5 mol% or more and 30 mol% or less, and 30 mol% or more and 60 mol% or less of the repeating unit represented by Formula 4 above, or 30 mol% or more and 50 mol% or less, or 30 mol% or more 40 mol% or less.

More specifically, the molar ratio of the repeating unit represented by Formula 3 to 100 moles of the repeating unit represented by Formula 4 is 10 moles or more and 99 moles or less, or 15 moles or more and 95 moles or less, or 20 moles or more and 95 moles. or less, or 10 moles or more and 50 moles or less, or 10 moles or more and 40 moles or less, or 10 moles or more and 30 moles or less.

As such, as the content of the repeating unit represented by Formula 4, which is hydrophobic, is increased, the degree of hydrophobicity of the alkali developable binder resin is also increased, thereby preventing the generation of bubbles in the developing 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, coatability, traceability, and mechanical strength of the resist itself after circuit formation of the dry film photoresist may be improved.

In this specification, the weight average molecular weight means the weight average molecular weight in terms of polystyrene 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 commonly known analyzer and a detector such as a differential refraction detector and a column for analysis may be used, and the temperature generally applied Conditions, solvents, and flow rates can be applied.

As a specific example of the measurement conditions, the alkali developable binder resin is dissolved in tetrahydrofuran so as to have a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on solid content), and a syringe of 0.45㎛ pore size After filtration using a filter, 20 μl was injected into GPC, and tetrahydrofuran (THF) was used as the mobile phase of GPC, and was introduced at a flow rate of 1.0 mL/min, and the column was Agilent PLgel 5㎛ Guard (7.5 x 50 mm) and 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, the polystyrene standard sample (STD A, B, C, D) obtained by dissolving polystyrene having various molecular weights as follows at a concentration of 0.1 (w/w)% in tetrahydrofuran was filtered with a 0.45㎛ pore size Syringe Filter and then GPC The value of the weight average molecular weight (Mw) of the alkali developable binder resin was obtained using a calibration curve formed by injecting into the .

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 the 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 increasing 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. For the acid value, about 1 g of the alkali developable binder resin was sampled, dissolved in 50 ml of a mixed solvent (MeOH 20%, Acetone 80%), two drops of 1%-phenolphthalein indicator were added, and then titrated with 0.1N-KOH to measure the acid value.

The alkali developable binder resin is included in an amount of 20 wt% or more and 80 wt% or less, based on the total weight of the photosensitive resin composition on a solid basis. When the content of the alkali developable binder resin is within the above range, it is possible to obtain an effect of strengthening the fine wire adhesion after circuit formation. The solid content, which is the basis of the weight, refers to the remaining components excluding 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 with respect to the total photosensitive resin composition, there is a disadvantage of causing defects such as short circuit due to contamination of the developing end, and when it exceeds 70% by weight, adhesion and resolution, etc. There is a problem in that the circuit properties are poor.

On the other hand, as the alkali developable binder resin, a repeating unit represented by the following formula 13, a repeating unit represented by the following formula 14, a repeating unit represented by the following formula 15, a repeating unit represented by the following formula 16, and a repeating unit represented by the following formula 17 A first alkali developable binder resin including a repeating unit; and a second alkali developable binder resin including a repeating unit represented by the following Chemical Formula 14, a repeating unit represented by the following Chemical Formula 15, and a repeating unit represented by the following Chemical Formula 16;

[Formula 13]

In the above formula (13),

R ₃ ″ is hydrogen,

[Formula 14]

In the formula (14),

R ₃ ' is an alkyl having 1 to 10 carbon atoms,

[Formula 15]

In the formula (15),

R4″ is alkyl having 1 to 10 carbon atoms, R5″ is alkyl having 1 to 10 carbon atoms,

[Formula 16]

In the formula (16),

Ar is aryl having 6 to 20 carbon atoms,

[Formula 17]

In Formula 17,

R ₄ ' is hydrogen,

R ₅ ′ is alkyl having 1 to 10 carbon atoms.

Specifically, the first alkali developable binder resin may include the repeating unit represented by the formula 13, the repeating unit represented by the formula 14, the repeating unit represented by the formula 15, the repeating unit represented by the formula 16, and the formula It may include a random copolymer of the repeating unit represented by 17.

In Formulas 13 to 17, specific examples of the alkyl having 1 to 10 carbon atoms may include methyl.

The repeating unit represented by Chemical Formula 14 may be a repeating unit derived from a monomer represented by the following Chemical Formula 14-1.

[Formula 14-1]

In Formula 14-1, R ₃ ” is alkyl having 1 to 10 carbon atoms. In Formula 14-1, R ₃ ” is the same as described above in Formula 14. Specific examples of the monomer represented by Formula 14-1 may include methacrylic acid (MAA).

The repeating unit represented by Chemical Formula 15 may be a repeating unit derived from a monomer represented by Chemical Formula 15-1.

[Formula 15-1]

In Formula 15-1, R ₄ ″ is an alkyl having 1 to 10 carbon atoms, and R ₅ ″ is an alkyl having 1 to 10 carbon atoms. In Formula 15-1, R ₄ ″ and R ₅ ″ are the same as those described above in Formula 15. Specific examples of the monomer represented by Formula 15-1 may include methylmethacrylate (MMA).

The repeating unit represented by Chemical Formula 16 may be a repeating unit derived from a monomer represented by Chemical Formula 16-1.

[Formula 16-1]

In Formula 16-1, Ar is aryl having 6 to 20 carbon atoms. In Formula 16-1, the content of Ar is the same as described above in Formula 16. Specific examples of the monomer represented by Formula 16-1 may include styrene (Styrene, SM).

The first 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, coatability, traceability, and mechanical strength of the resist itself after circuit formation of the dry film photoresist may be improved. In addition, the first alkali developable binder resin may have an acid value of 140 mgKOH/g or more and 160 mgKOH/g or less.

In addition, the second alkali developable binder resin may have a weight average molecular weight of 20000 g/mol or more and 130000 g/mol or less, and a glass transition temperature of 30° C. or more and 160° C. or less. Accordingly, coatability, traceability, and mechanical strength of the resist itself after circuit formation of the dry film photoresist may be improved.

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

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 the 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 increasing the temperature to 200 °C at a heating rate of 1 °C/min.

For the acid value of the alkali developable binder resin, sample about 1 g of the alkali developable binder resin, dissolve it in 50 ml of a mixed solvent (MeOH 20%, Acetone 80%), add two drops of 1%-phenolphthalein indicator, and then 0.1N-KOH The acid value was measured by titration.

The first alkali developable binder resin may have an acid value of 140 mgKOH/g or more and 160 mgKOH/g or less. In addition, the second alkali developable binder resin may have an acid value of 160 mgKOH/g or more and 200 mgKOH/g or less.

Specifically, the glass transition temperature ratio of the first alkali-developable binder resin and the second alkali-developable binder resin is 1:1.5 or more and 1:5, 1:1.5 or more and 1:3, 1:1.5 or more, 1:2 It may be 1:1.5 or more and 1:1.8 or less, 1:1.5 or more and 1:75 or less, or 1:1.5 or more and 1:6 or less.

In addition, the acid value ratio of the first alkali developable binder resin and the second alkali developable binder resin is 1:1.01 or more and 1:1.5 or less, 1:1.01 or more and 1:1.25 or less, 1:1.01 or more and 1:1.2 or less, or It may be 1:1.01 or more and 1:1.1 or less.

On the other hand, the first alkali developable binder resin included in the photosensitive resin composition of the embodiment contains 1.2 moles or more and 3 moles or less, 1.2 moles of the repeating unit represented by Formula 4 with respect to 1 mole of the repeating unit represented by Formula 3 It may be included in an amount of 2 moles or more, 1.5 moles or more and 2 moles or less, or 1.5 moles or more and 1.6 moles or less.

In addition, the first alkali developable binder resin included in the photosensitive resin composition of the embodiment contains 2 moles or more and 10 moles or less of the repeating unit represented by Formula 15 with respect to 1 mole of the repeating unit represented by Formula 17, 3 It may contain at least 10 moles, 3 moles or more and 5 moles or less, or 4 moles or more and 5 moles or less.

Meanwhile, the second alkali developable binder resin may include a random copolymer of a repeating unit represented by the following Chemical Formula 14, a repeating unit represented by the following Chemical Formula 15, and a repeating unit represented by the following Chemical Formula 16.

[Formula 14]

In Formula 14, R ₃ ' is an alkyl having 1 to 10 carbon atoms,

[Formula 15]

In Formula 15, R ₄ "is alkyl _{having 1 to 10 carbon atoms, R 5} "is alkyl having 1 to 10 carbon atoms,

[Formula 16]

In Formula 16, Ar is aryl having 6 to 20 carbon atoms.

[Formula 14-1]

[Formula 15-1]

[Formula 16-1]

In Formula 16-1, Ar is aryl having 6 to 20 carbon atoms. In Formula 16-1, the contents of Ar are the same as those described above in Formula 6 above. Specific examples of the monomer represented by Formula 16-1 may include styrene (Styrene, SM).

Specifically, the first alkali developable binder resin is a repeating unit represented by Formula 14: a repeating unit represented by Formula 15: A repeating unit represented by Formula 16 is 1: (2 or more and 5 or less): (0.2 or more and 0.9), 1: (2 or more and 3 or less): (0.5 or more and 0.9), 1: (2.5 or more and 3 or less): (0.6 or more and 0.9 or less) or 1: (2.75 or more and 3 or less): (0.6 or more and 0.75) hereinafter) may be included.

In addition, the second alkali developable binder resin is a repeating unit represented by Formula 14: a repeating unit represented by Formula 15: A repeating unit represented by Formula 16 is 1: (1.1 or more and 2 or less): (0.2 or more) 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).

On the other hand, the photosensitive resin composition of an embodiment of the present invention contains 500 parts by weight or more and 1000 parts by weight or less, 600 parts by weight or more and 800 parts by weight or less, of the second alkali developable binder resin with respect to 100 parts by weight of the first alkali developable binder resin, It may be included in an amount of 700 parts by weight or more and 800 parts by weight or less.

As described above, when the second alkali developable binder resin is added in an excess of 500 parts by weight or more with respect to 100 parts by weight of the first alkali developable binder resin, a hydrophobic function is imparted to the photosensitive resin to increase resistance to the developer, thereby increasing circuit properties. A technical effect of improving can be implemented.

(2) photoinitiator

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 the dry film photoresist.

Examples of the compound 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, benzyl ketone 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-methylthi A compound selected from oxanthone, 2-isopropylthioxanthone, dibenzosuberone, α, α-dichloro-4-phenoxyacetophenone, and pentyl 4-dimethylaminobenzoate may be used as the photopolymerization initiator, but is limited thereto it is not

The content of the photoinitiator is included in an amount of 1 wt% or more and 10 wt% or less based on the total weight of the photosensitive resin composition based on the solid content. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity may be obtained. The solid content, which is the basis of the weight, refers to the remaining components excluding the solvent in the photosensitive resin composition.

When the content of the photopolymerization initiator is less than 1% by weight, there is a disadvantage that the production efficiency is extremely reduced because the light efficiency is low and a large amount of exposure is required, and when it exceeds 10% by weight, the film is brittle and the developer contamination This increases and there is a problem of causing defects such as short circuit.

(3) photopolymerizable compounds

The photopolymerizable compound of the present invention has resistance to a developer after UV exposure to enable 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 the following Chemical Formula 5 may be used.

[Formula 5]

In Formula 5, l+n is an integer of 2 or 3, and m is an integer of 12 to 18.

The compound represented by Chemical Formula 5 may improve the hydrophobicity of the photosensitive resin composition to significantly increase resistance to a developer and a plating solution, and shorten the peeling time of the cured film.

In the present invention, the amount of the compound represented by Formula 5 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 5 is less than 10% by weight based on the total solid weight of the photosensitive resin composition, the effect of the addition of the compound represented by Formula 5 is insufficient, and when it exceeds 60% by weight, hydrophobicity This increase may cause a problem in that the development time in the development process after exposure is rapidly increased.

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 the ethylene oxide may include a bisphenol-based di(meth)acrylate containing more than 8 moles and 16 moles or less of ethylene oxide per molecule.

Examples of the bisphenol-based di(meth)acrylate containing more than 8 moles and not more than 16 moles of ethylene oxide 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.

Meanwhile, the photopolymerizable compound may include a trifunctional or more polyfunctional (meth)acrylate compound.

The trifunctional or more multifunctional (meth)acrylate compound may have a structure in which three or more alkylene oxide groups having 1 to 10 carbon atoms and (meth)acrylate functional groups are bonded to a central group having 1 to 20 carbon atoms.

The trifunctional or higher polyfunctional (meth)acrylate compound may include a compound represented by the following Chemical Formula 12.

[Formula 12]

In Formula 12, R ₁₄ is hydrogen or alkyl _{having 1 to 10 carbon atoms, R 15} is alkylene having 1 to 10 carbon atoms, R ₁₆ is p including a central group having 1 to 20 carbon atoms, and n12 is an integer of 1 to 20, p is the _{number of functional groups substituted for R 16} , and an integer of 3 to 10.

The photopolymerizable compound may further include a monofunctional (meth)acrylate compound. That is, the photosensitive resin composition according to an embodiment of the present invention may include a mixture of a monofunctional (meth)acrylate compound and a trifunctional or more polyfunctional (meth)acrylate compound.

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

More specifically, the monofunctional (meth)acrylate compound may include a compound represented by the following Chemical Formula 11.

[Formula 11]

In Formula 11, R ₁₁ is hydrogen or alkyl having 1 to 10 carbon atoms _{, R 12} _{is alkylene having 1 to 10 carbon atoms, R 13} is alkyl having 1 to 10 carbon atoms, and n11 is an integer from 1 to 20 .

Including the monofunctional (meth) acrylate compound represented by Chemical Formula 11, and the trifunctional or more polyfunctional (meth) acrylate compound represented by Chemical Formula 12, circuit properties are equivalent to those of existing products, but the photocuring rate is lower. As the contrast change time is improved for technical reasons of speeding up the time for color development in the resulting film and increasing the amount of color change, excellent developability can be secured.

Specifically, in Formula 11, n11 may be an integer of 1 to 20, an integer of 1 to 10, or an integer of 5 to 10. Examples of the monofunctional (meth)acrylate compound represented by Formula 11 are not particularly limited, but may be, for example, A040 (Methoxy propylene glycol [400] acrylate) represented by Formula A below.

[Formula A]

As the photosensitive resin composition of one embodiment includes the monofunctional (meth) acrylate compound represented by Chemical Formula 11, the effect of rapidly realizing the film color change of the exposed portion due to the technical cause of speeding up the photocuring rate can be implemented

In addition, in Formula 12, n12 is an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to 5, p is an integer of 3 to 10 _{, and p is the number of functional groups substituted for R 16 , 3} It may be an integer of to 5, or an integer of 3 to 4.

That is, as _{p, which means the number of functional groups substituted with R 16} in Chemical Formula 12, is an integer of 3 to 10, it may be a trifunctional or more multifunctional (meth)acrylate compound represented by Chemical Formula 12.

Specifically, the trifunctional or more polyfunctional (meth)acrylate compound may be represented by the following Chemical Formula 12-1.

[Formula 12-1]

In Formula 12-1, R ₂₀ is a trivalent organic group, R ₂₁ to R ₂₃ are each independently alkylene having 1 to 10 carbon atoms, and R ₂₄ to R ₂₆ are each independently hydrogen or 1 to 10 carbon atoms. of alkyl, and n to n5 are each independently an integer of 1 to 20.

In Formula 12-1, n13 to n15 may be an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to 5.

Examples of the trifunctional or higher polyfunctional (meth)acrylate compound represented by Formula 12 are not particularly limited, but may be, for example, T063 (Trimethylolpropane [EO] ₆ triacrylate) represented by Formula B below.

[Formula B]

As the photosensitive resin composition of one embodiment includes the trifunctional or more polyfunctional (meth)acrylate compound represented by Chemical Formula 12, the trifunctional or more polyfunctional polyfunctionalized compound represented by Chemical Formula 12 compared to the monofunctional (meth)acrylate compound When the functional (meth) acrylate compound is photocured, crosslinking increases and circuit properties are prevented from being deteriorated due to technical causes with many reactive groups, and the effect of increasing the amount of color change can be realized.

On the other hand, the photosensitive resin composition of the embodiment includes 110 parts by weight or more and 500 parts by weight or less, 110 parts by weight or more of the trifunctional or more polyfunctional (meth)acrylate compound with respect to 100 parts by weight of the monofunctional (meth)acrylate compound. 300 parts by weight or less, 110 parts by weight or more and 200 parts by weight or less, or 150 parts by weight or more and 200 parts by weight or less.

As the photosensitive resin composition of one embodiment contains an excess of the trifunctional or more polyfunctional (meth)acrylate compound with respect to the monofunctional (meth)acrylate compound, the monofunctional (meth)acrylate represented by Formula 11 The effect of rapidly realizing the color change of the film by increasing the photocuring rate of the compound, and increasing crosslinking during photocuring of the trifunctional or higher polyfunctional (meth)acrylate compound represented by the above formula (12), when adding only a monofunctional material The effect of increasing the amount of change in color development can be realized at the same time by preventing the deterioration of circuit properties and increasing the amount of the reactor.

When the photosensitive resin composition of one embodiment contains less than 100 parts by weight of the trifunctional or more polyfunctional (meth)acrylate compound with respect to 100 parts by weight of the monofunctional (meth)acrylate compound, the amount of circuit degradation and color change Decreasing technical problems may arise.

In addition, the photopolymerizable compound is a bifunctional (meth) acrylate compound, a monofunctional (meth) acrylate compound represented by Chemical Formula 11, and a trifunctional or more polyfunctional (meth) acrylate compound represented by Chemical Formula 12. may include

That is, the photosensitive resin composition of the embodiment includes a photopolymerizable compound, wherein the photopolymerizable compound is a monofunctional (meth)acrylate compound, a trifunctional or more polyfunctional (meth)acrylate compound, and a bifunctional (meth)acryl It may contain a rate compound.

Specifically, the photosensitive resin composition of one embodiment contains 500 parts by weight or more and 1500 parts by weight or less, 500 parts by weight or more and 1000 parts by weight of the bifunctional (meth)acrylate compound with respect to 100 parts by weight of the monofunctional (meth)acrylate compound. Parts by weight or less, 750 parts by weight or more and 1000 parts by weight or less, 800 parts by weight or more and 900 parts by weight or less.

That is, the photosensitive resin composition of one embodiment contains 110 parts by weight or more of the trifunctional or more polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound, and the bifunctional (meth)acrylate compound ) may include 500 parts by weight or more and 1500 parts by weight or less of the acrylate compound.

In addition, the photosensitive resin composition of the embodiment contains 500 parts by weight or more and 1000 parts by weight or less, 500 parts by weight or more of the bifunctional (meth)acrylate compound with respect to 100 parts by weight of the trifunctional or more polyfunctional (meth)acrylate compound. 800 parts by weight or less, 500 parts by weight or more and 750 parts by weight or less, 500 parts by weight or more and 700 parts by weight or less, 500 parts by weight or more and 600 parts by weight or less.

As described above, the monofunctional (meth) acrylate compound, the trifunctional or more polyfunctional (meth) acrylate compound, and the difunctional (meth) acrylate compound are included, and at the same time, as it includes to satisfy the above weight range, the one The photosensitive resin composition of the embodiment enables the expression of appropriate circuit properties, ^{and when a light amount of 10 mJ/cm 2} or more is given, a technical effect of rapid color development and color change of the exposed portion can be realized.

More specifically, the photosensitive resin composition of the embodiment includes a monofunctional (meth)acrylate compound represented by Chemical Formula 11, and a trifunctional compound represented by Chemical Formula 12 based on 100 parts by weight of the bifunctional (meth)acrylate compound. The above polyfunctional (meth)acrylate compound may be included in an amount of 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 content of the photopolymerizable compound may be included in an amount of 10% by weight or more and 70% by weight or less, based on the total weight of the photosensitive resin composition based on the solid content. 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, which is the basis of the weight, refers to the remaining components excluding the solvent in the photosensitive resin composition.

(4) photosensitive resin composition

The photosensitive resin composition may satisfy any one of the following (1) or (2).

(1) In a container with a cross-sectional diameter of 10 cm or more containing a developer, the photosensitive resin layer sample containing the photosensitive resin composition is ^{put so that the volume ratio of the photosensitive resin layer sample to the developer is 2x10 -5} m ³ /L, and the When spraying from the top of the container while circulating the developer inside the container at a speed of 1000 cc/min or more and 1200 cc/min or less, the highest point of the bubbles generated in the container after 60 minutes of spraying the developer, and the container immediately after spraying the developer. If the height difference between the highest points of my developer is 80 mm or less,

(2) For the photosensitive resin layer sample containing the photosensitive resin composition and having a thickness of 5 μm or more and 30 μm or less, the absolute viscosity obtained in the temperature range of 50° C. or more and 125° C. or less under the condition that the axial force of the photosensitive resin layer sample is 5 N or less The minimum value is 300 Pa·s or less.

Specifically, in the photosensitive resin composition, the volume ratio of the photosensitive resin layer sample containing the photosensitive resin composition to the developer is 2x10 ^-5 m ³ /L in a container with a cross-sectional diameter of 10 cm or more containing the developer. When spraying from the top of the container while circulating the developer in the container at a speed of 1000 cc/min or more and 1200 cc/min or less, the highest point of the bubble generated in the container after 60 minutes of spraying the developer, and the developer Immediately after starting spraying, the height difference between the highest points of the developer in the container is 80 mm or less, or 60 mm or less, or 1 mm or more and 80 mm or less, or 1 mm or more and 60 mm or less, or 10 mm or more and 60 mm or less, or 20 mm or more and 60 mm or less, or 40 mm or more and 60 mm or less.

The highest point of the bubble generated in the container after 60 minutes from the start of spraying the developer and the highest point of the developer in the container immediately after starting spraying the developer are both the same vertical height measured based on the bottom of the container parallel to the ground means

In addition, the height difference interval between the two points means a value obtained by subtracting the highest height of the developer in the container immediately after starting spraying the developer from the maximum height of the bubbles generated in the container after 60 minutes from the start of spraying the developer.

Specifically, as an example of a method for measuring the height difference interval, a bubble measuring device with a ruler as shown in FIG. 1 may be used.

In a container with a cross-sectional diameter of 10 cm or more containing the developer, the photosensitive resin layer sample containing the photosensitive resin composition is ^{put so that the volume ratio of the photosensitive resin layer sample to the developer is 2x10 -5} m ³ /L, and the inside of the container When spraying from the top of the container while circulating the developer at a speed of 1000 cc/min or more and 1200 cc/min or less, the highest point of the bubbles generated in the container after 60 minutes of spraying the developer, and the developer in the container immediately after spraying the developer When the height difference interval between the highest points of the uppermost point is excessively increased to more than 80 mm, it is dissolved by the alkali solution by the saponification reaction in the developing process to melt the unexposed part or the peeling process to remove the dry film. If the bubbles are generated excessively, problems such as overflowing the chamber may occur.

In a container with a cross-sectional diameter of 10 cm or more containing the developer, the photosensitive resin layer sample containing the photosensitive resin composition is ^{put so that the volume ratio of the photosensitive resin layer sample to the developer is 2x10 -5} m ³ /L, and the inside of the container When spraying from the top of the container while circulating the developer at a speed of 1000 cc/min or more and 1200 cc/min or less, the highest point of the bubbles generated in the container after 60 minutes of spraying the developer, and the developer in the container immediately after spraying the developer The decrease in the height difference interval between the highest height points of the photosensitive resin composition to 80 mm or less appears to be due to the use of an alkali developable binder resin having an increased degree of hydrophobicity including the repeating unit represented by Formula 1 above.

The cross-sectional diameter of the container may be 10 cm or more, or 10 cm or more and 20 cm or less, and the cross-sectional diameter may mean a maximum diameter of a cross-section parallel to the ground. More specifically, as the container, a cylindrical container having a cross section parallel to the ground and having a diameter of 10 cm or more may be used. A specific example of the container is described in FIG. 1 below.

The developer may use an aqueous alkali solution having a concentration of 0.1 wt% or more and 5 wt% or less, or 0.9 wt% or more and 1.1 wt% or less. The pH of the aqueous alkali solution may be in the range of 9 or more and 11 or less, and the temperature may be adjusted according to the developability of the photosensitive resin layer. Specific examples of the aqueous alkali solution include sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium hydroxide aqueous solution, and the like.

The developer may be contained in an amount of 5% or more and 50% or less, or 10% or more and 50% or less of the total height of the container. Accordingly, it may be sufficient to measure the bubble height generated above the height of the developer.

Also, the height difference between the upper end of the container to which the developer is sprayed and the highest point of the solution in the container immediately after starting the spraying of the developer may be 30 cm or more and 55 cm or less.

The top point of the container to which the developer is sprayed and the highest point of the solution in the container immediately after starting spraying the developer mean the same vertical height measured with respect to the bottom of the container parallel to the ground.

And, the height difference interval between the two points means a value obtained by subtracting the highest height of the developer in the container immediately after starting spraying the developer from the height of the upper end of the container to which the developer is sprayed.

If the difference in height between the top point of the container where the developer is sprayed and the highest point of the solution in the container immediately after starting spraying the developer is excessively reduced to less than 30 cm, bubbles are excessively generated up to the top of the container, so the sample type depends on the type of sample. It may be difficult to compare the difference in the degree of foaming.

If the difference in height between the top point of the container where the developer is sprayed and the highest point of the solution in the bubble analyzer immediately after starting spraying the developer increases to more than 55 cm, the amount of bubbles generated is not sufficient and the bubbles according to the sample type It can be difficult to compare differences in incidence.

In a container having a cross-sectional diameter of 10 cm or more containing the developer, the photosensitive resin layer sample containing the photosensitive resin composition may be added so that ^{the volume ratio of the photosensitive resin layer sample to the developer is 2x10 -5} m ^{3 /L.}

Under the condition that the volume ratio of the photosensitive resin layer sample to the developer ^{satisfies 2x10 -5} m ³ /L, the volume of the developer and the volume of the photosensitive resin layer sample can be applied by changing without limitation. Specifically, the thickness and cross-sectional area of the photosensitive resin layer sample can be changed and applied without limitation.

As such, the volume of the developer and the volume (thickness, cross-sectional area) of the photosensitive resin layer sample are not limited under the condition that ^{the volume ratio of the photosensitive resin layer sample to the developer satisfies 2x10 -5} m ^{3 /L.} If the developer is, for example, 0.5 liters or more and 1.5 liters or less, or 0.8 liters or more and 1.2 liters or less, or 0.9 liters or more and 1.1 liters or less, can be freely adjusted. In addition, the thickness of the photosensitive resin layer sample can be freely adjusted within, for example, 0.01 µm or more and 1 mm or less, or 1 µm or more and 100 µm or less, or 30 µm or more and 50 µm or less. In addition, the area of the photosensitive resin layer sample is an area of a cross-section parallel to the ground, and can be freely adjusted within, ^{for example, 0.1 m 2} or more and 1 m ² or less, or 0.4 m ² or more and 0.6 m ^{2 or less.}

A developer circulation pump may be used to circulate the developer inside the container at a speed of 1000 cc/min or more and 1200 cc/min or less. That is, the developer inside the container may exit through the nozzle at the lower end of the container when the developer circulation pump is operated, move through the developer circulation pump to the upper end of the container, and be sprayed through the nozzle at the upper end of the container.

When the developer is circulated, the circulation speed of the developer may be 1000 cc/min or more and 1200 cc/min or less. Also, the circulating pressure of the developer may be 1 kgf/cm ² or more and 10 kgf/cm ² or less, or 4 kgf/cm ² or more and 6 kgf/cm ² or less.

Various nozzles can be applied without limitation under the conditions that satisfy the circulation speed and circulation pressure, and the circulation rate and circulation pressure are the highest point of the bubble generated in the container after 60 minutes from the start of spraying the developer and the developer It can be applied to the measurement of the height difference between the highest points of the developer in the container immediately after starting spraying.

The difference in height between the highest point of the bubble generated in the container after 60 minutes from the start of spraying the developer and the highest point of the developer in the container immediately after starting spraying the developer is the shortest distance between the two points with the naked eye using a ruler. can be measured At this time, the maximum height at each of the highest point of the bubble generated in the container after 60 minutes from the start of spraying the developer and the highest point of the developer in the container immediately after starting spraying the developer means the highest height based on the bottom of the container. can do.

On the other hand, with respect to the photosensitive resin layer sample containing the photosensitive resin composition and having a thickness of 5 μm or more and 30 μm or less, under the condition that the axial force of the photosensitive resin layer sample is 5 N or less, the minimum value of the absolute viscosity obtained in the temperature range of 50° C. or more and 125° C. or less 300 Pa s or less, or 100 Pa s or less, or 1 Pa s or less 300 Pa s or less, or 1 Pa s or less 100 Pa s or less, or 5 Pa s or less 280 Pa s or less have.

As an example of a method for measuring the absolute viscosity, a viscosity meter may be used, and an example of the viscosity meter may be DHR-2 (TA Instrument).

Looking at the specific absolute viscosity measurement conditions, the viscosity can be measured at a temperature increase rate of 5 °C/min or more and 15 °C/min or less, or 8 °C/min or more and 12 °C/min or less in the temperature range of 50 °C or more and 125 °C or less. . That is, the viscosity can be measured while increasing the temperature from 50 °C to 125 °C at a temperature increase rate of 5 °C/min or more and 15 °C/min or less, or 8 °C/min or more and 12 °C/min or less. Examples of specific methods for maintaining the temperature increase rate are not particularly limited, and various known methods can be used without limitation.

In addition, the absolute viscosity may be measured under the conditions of injecting nitrogen at a rate of 5 L/min or more and 15 L/min or less, or 8 L/min or more and 12 L/min or less. Examples of the specific method for injecting the nitrogen are not particularly limited, and various known methods can be used without limitation.

In addition, the absolute viscosity may be measured at a shear rate of 1 1/s or more and 3 1/s. If the shear rate is excessively increased to more than 3 1/s, it is difficult to measure because it is difficult to measure the flow-type viscometer.

In addition, the absolute viscosity may be measured when the axial force of the photosensitive resin layer sample is 5N or less, or 3N or less, or -5N or more and 5N or less, or -3N or more and 3N or less, or -1N or more and 1N or less. The axial force refers to a force of a normal component when a force generated in the form of a proof force in an arbitrary vertical cross-section under a load applied to the photosensitive resin layer sample is decomposed into a normal component and a tangent component to the cross-section. . That is, the axial force is one of the sectional forces acting on the cross section of the member, and may mean a force acting on the center of the surface and acting in the axial direction.

The thickness of the photosensitive resin layer sample used for measuring the absolute viscosity may be 5 μm or more and 30 μm or less. The thickness or cross-sectional area of the photosensitive resin layer sample may be measured through an optical microscope.

With respect to the photosensitive resin layer sample containing the photosensitive resin composition and having a thickness of 5 μm or more and 30 μm or less, the minimum value of absolute viscosity obtained in a temperature range of 50° C. or more and 125° C. or less under the condition that the axial force of the photosensitive resin layer sample is 5 N or less is If it is excessively increased to more than 300 Pa·s, when the dry film photoresist is thermally bonded to a substrate for application to a circuit board or a display device, it is difficult to sufficiently lower the viscosity at the thermal bonding temperature, resulting in a problem of reduced adhesion to the substrate. can

For the photosensitive resin layer sample containing the photosensitive resin composition and having a thickness of 5 μm or more and 30 μm or less, the minimum value of absolute viscosity obtained in the temperature range of 50° C. or more and 125° C. or less under the condition that the axial force of the photosensitive resin layer sample is 5 N or less is 300 The sufficiently lowered Pa·s appears to be due to the use of an alkali developable binder resin having an increased degree of hydrophobicity in the photosensitive resin composition including the repeating unit represented by Formula 1 above.

On the other hand, the temperature at which the minimum value of the absolute viscosity is obtained may be 110 °C or more and 123 °C or less, or 110 °C or more and less than 116 °C. The photosensitive resin composition of one embodiment has a minimum value of absolute viscosity near the heat bonding temperature of 110 ° C when thermally bonding the dry film photoresist to the substrate for application to a circuit board or display device before reaching the curing temperature. . Accordingly, when the dry film photoresist is thermally bonded to a substrate for application to a circuit board or a display device, adhesion to the substrate can be increased through low viscosity at the thermal bonding temperature.

Specifically, the curing temperature of the photosensitive resin layer sample may be 115 °C or more and 125 °C or less, or 116 °C or more and 125 °C or less. Accordingly, in the photosensitive resin composition of one embodiment, when the dry film photoresist is thermally bonded to a substrate for application to a circuit board or a display device, curing does not proceed near the thermal bonding temperature of 110 ° C. can

Specifically, with respect to the photosensitive resin layer sample, an absolute viscosity value at a temperature of 110° C. may be 5 Pa·s or more and 400 Pa·s or less.

The photosensitive resin composition may include 20 wt% or more and 80 wt% or less of an alkali developable binder resin, 1 wt% or more and 10 wt% or less of a photopolymerization initiator, and 10 wt% or more and 70 wt% or less of a photopolymerizable compound based on the solid content have.

The photosensitive resin composition may further include a solvent. The solvent is generally selected from methyl ethyl ketone (MEK), methanol, THF, toluene, and acetone, and the solvent is not particularly limited, and the content is also of the photopolymerization initiator, alkali developable binder resin and photopolymerizable compound. It may be contained by adjusting according to the content.

In addition, the photosensitive resin composition may further include other additives as necessary. Examples of the 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 acid amide form; triphenyl phosphate and the like can be used.

In this invention, in order to improve the handleability of the photosensitive resin composition, you may put a leuco dye and a coloring substance. Examples of the leuco dye include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, and fluoran dye. Especially, when leuco crystal violet is used, the contrast is favorable and it is preferable. In the case of containing the leuco dye, the content may be 0.1 wt% or more and 10 wt% or less in the photosensitive resin composition. From a viewpoint of expression of contrast, 0.1 weight% or more is preferable, and 10 weight% or less is preferable from a viewpoint of maintaining storage stability.

As the coloring material, for example, toluenesulfonic acid monohydrate, fucine, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green, Diamond Green, Basic Blue 20, etc. can be heard In the case of containing the coloring material, the added amount may be 0.001% by weight or more and 1% by weight or less in the photosensitive resin composition. At a content of 0.001% by weight or more, there is an effect of improving handling, and at a 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 promoter, and the like.

2. 드라이 필름 포토레지스트2. Dry Film Photoresist

According to another embodiment of the present invention, a dry film photoresist including a photosensitive resin layer containing the photosensitive resin composition of the embodiment may be provided. The content of the photosensitive resin composition includes all of the content described above in the embodiment.

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

The thickness of the dry film photoresist is not particularly limited, but can be freely adjusted within, 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 adhesive force.

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

The protective film prevents damage to the resist during handling and serves as a protective cover for protecting the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface of the photosensitive resin layer on which the base film is not formed. The protective film serves to protect the photosensitive resin layer from the outside, and it is easily detached when the dry film photoresist is applied in a post-process, and requires proper releasability and adhesiveness so that it does not release when stored and distributed.

Various plastic films can be used as the protective film, for example, an acrylic film, a polyethylene (PE) film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a polynorbornene (PNB) film, a 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 can be freely adjusted within, for example, 0.01 μm to 1 mm.

The dry film photoresist may satisfy any one of the following (1) or (2).

Specifically, in the dry film photoresist, the volume ratio of the photosensitive resin layer sample containing the photosensitive resin composition to the developer is 2x10 ^-5 m ³ /L in a container with a cross-sectional diameter of 10 cm or more containing the developer. When spraying from the top of the container while circulating the developer inside the container at a speed of 1000 cc/min or more and 1200 cc/min or less, the highest point of the bubble generated in the container after 60 minutes from the start of spraying the developer, Immediately after starting to spray the developer, the height difference between the highest points of the developer in the container is 80 mm or less, or 60 mm or less, or 1 mm or more and 80 mm or less, or 1 mm or more and 60 mm or less, or 10 mm or more and 60 mm or less; or 20 mm or more and 60 mm or less, or 40 mm or more and 60 mm or less.

Various nozzles can be applied without limitation under the conditions that satisfy the circulation speed and circulation pressure, and the circulation rate and circulation pressure are the highest point of the bubble generated in the container after 60 minutes from the start of spraying the developer and the developer It can be applied to the measurement of the difference in height between the highest points of the developer in the container immediately after starting spraying.

The height difference between the highest point of the bubble generated in the container after 60 minutes from the start of spraying the developer and the highest point of the developer in the container immediately after starting spraying the developer is determined by visually examining the shortest distance between the two points using a ruler. can be measured At this time, the maximum height at each of the highest point of the bubble generated in the container after 60 minutes from the start of spraying the developer and the highest point of the developer in the container immediately after starting spraying the developer means the highest height based on the bottom of the container can do.

On the other hand, the photosensitive resin layer contained in the dry film photoresist with respect to the photosensitive resin layer sample having a thickness of 5 μm or more and 30 μm or less, the axial force of the photosensitive resin layer sample is 5 N or less in a temperature range of 50 ℃ or more and 125 ℃ or less. The minimum value of the obtained absolute viscosity is 300 Pa·s or less, or 100 Pa·s or less, or 1 Pa·s or less 300 Pa·s or less, or 1 Pa·s or less 100 Pa·s or less, or 5 Pa·s or less 280 Pa·s or less.

In addition, the absolute viscosity may be measured under the conditions of injecting nitrogen at a rate of 5 L/min or more and 15 L/min or less, or 8 L/min or more and 12 L/min or less. Examples of the specific method of injecting the nitrogen are not particularly limited, and various known methods can be used without limitation.

In addition, the absolute viscosity may be measured at a shear rate of 1 1/s or more and 3 1/s. If the shear rate is excessively increased to more than 3 1/s, it is difficult to measure the flow-type viscometer because it is difficult.

With respect to the photosensitive resin layer sample in which the photosensitive resin layer contained in the dry film photoresist has a thickness of 5 μm or more and 30 μm or less, the absolute obtained in the temperature range of 50° C. or more and 125° C. or less under the condition that the axial force of the photosensitive resin layer sample is 5 N or less. When the minimum value of the viscosity is excessively increased to more than 300 Pa·s, when the dry film photoresist is thermally bonded to the substrate for application to a circuit board or a display device, it is difficult to sufficiently lower the viscosity at the thermal bonding temperature, so that the adhesion to the substrate is reduced. problems may arise.

With respect to the photosensitive resin layer sample in which the photosensitive resin layer contained in the dry film photoresist has a thickness of 5 μm or more and 30 μm or less, the absolute obtained in the temperature range of 50° C. or more and 125° C. or less under the condition that the axial force of the photosensitive resin layer sample is 5 N or less. The reason that the minimum value of the viscosity is sufficiently lowered to 300 Pa·s or less appears to be due to the use of an alkali developable binder resin having an increased degree of hydrophobicity in the photosensitive resin composition including the repeating unit represented by Formula 1 above.

On the other hand, the temperature at which the minimum value of the absolute viscosity is obtained may be 110 °C or more and 123 °C or less, or 110 °C or more and less than 116 °C. The dry film photoresist of the other embodiment may have a minimum value of absolute viscosity near the heat bonding temperature of 110 ° C when thermally bonding the dry film photoresist to the substrate for application to a circuit board or display device before reaching the curing temperature. have. Accordingly, when the dry film photoresist is thermally bonded to a substrate for application to a circuit board or a display device, adhesion to the substrate can be increased through low viscosity at the thermal bonding temperature.

Specifically, the curing temperature of the photosensitive resin layer sample may be 115 °C or more and 125 °C or less, or 116 °C or more and 125 °C or less. Accordingly, in the dry film photoresist of another embodiment, curing does not proceed near the heat bonding temperature of 110° C. when the dry film photoresist is thermally bonded to the substrate for application to a circuit board or a display device. can be raised

An example of the method for producing the dry film photoresist is not particularly limited, for example, the photosensitive resin composition of one embodiment is coated using a conventional coating method on a conventional base film such as polyethylene terephthalate, and then dried A dry film may be prepared by laminating the dried photosensitive resin layer using a conventional protective film such as polyethylene on the upper surface.

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

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

3. 감광성 엘리먼트3. Photosensitive element

According to another embodiment of the invention, a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, the photosensitive element satisfying any one of the following (1) or (2) may be provided.

Specifically, the photosensitive element is placed in a container with a cross-sectional diameter of 10 cm or more containing a developer, and the volume ratio of the photosensitive resin layer sample to the developer is 2x10 ^-5 m ³ /L, and the inside of the container When spraying from the top of the container while circulating the developer at a speed of 1000 cc/min or more and 1200 cc/min or less, the highest point of the bubbles generated in the container after 60 minutes of spraying the developer, and the developer in the container immediately after spraying the developer 80 mm or less, or 60 mm or less, or 1 mm or more and 80 mm or less, or 1 mm or more and 60 mm or less, or 10 mm or more and 60 mm or less, or 20 mm or more and 60 mm or less, Or it may be 40 mm or more and 60 mm or less.

In a container containing the developer containing a cross-sectional diameter of 10 cm or more, the photosensitive resin layer sample was ^{added so that the volume ratio of the photosensitive resin layer sample to the developer was 2x10 -5} m ³ /L, and the developer inside the container was added at 1000 cc/min When spraying from the top of the container while circulating at a speed of more than 1200cc/min, the height between the highest point of the bubble generated in the container after 60 minutes of spraying the developer and the highest point of the developer in the container immediately after starting spraying the developer The content of the difference interval includes all of the content described above in one embodiment and another embodiment. That is, the photosensitive resin layer may include a repeating unit represented by Formula 1; a repeating unit represented by Formula 2; a repeating unit represented by Formula 3; and a repeating unit represented by Chemical Formula 4; and an alkali developable binder resin including a photopolymerizable compound.

In addition, for the photosensitive resin layer sample having a thickness of 5 μm or more and 30 μm or less, the photosensitive resin layer has an axial force of 5 N or less, and the minimum value of absolute viscosity obtained in a temperature range of 50° C. or more and 125° C. or less is 300 Pa·s or less.

The contents of the photosensitive resin layer and the absolute viscosity include all of the contents described above in the one embodiment and the other embodiments. That is, the photosensitive resin layer may include a repeating unit represented by Formula 1; a repeating unit represented by Formula 2; a repeating unit represented by Formula 3; and a repeating unit represented by Chemical Formula 4; and an alkali developable binder resin including a photopolymerizable compound.

a repeating unit represented by Formula 1; a repeating unit represented by Formula 2; a repeating unit represented by Formula 3; and the repeating unit represented by Chemical Formula 4; the content of the alkali developable binder resin and the photopolymerizable compound including the above includes all the contents described above in the embodiment.

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

As a specific example of the polymer substrate, an anti-blocking layer is 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 on one surface of the polymer substrate, and the rest is uniaxially stretched. film can be mentioned.

In the polymer substrate, an in-line coating method was selected instead of adding an anti-blocking agent, which has been usually added in consideration of running properties and winding characteristics during manufacturing, and an organic particle layer using substitute particles that do not impair transparency. did it

Here, examples of organic particles used as particles that do not impair transparency while considering running properties and winding characteristics include methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, and normal butyl methyl methacrylate. Acrylic particles, such as a copolymer or terpolymer of acrylic acid and methacrylic acid; olefinic particles such as polyethylene, polystyrene, and polypropylene; acrylic and olefinic copolymers; Alternatively, organic particles such as multi-layer multi-component particles in which homopolymer particles are formed and then other types of monomers are coated on the layer may be used.

These organic particles should be specifically spherical and have a difference in refractive index with the binder resin. Here, 'spherical' is defined as a ratio of a minor axis (a) to a major axis (b) of 0.5 < a/b < 2 in an ellipse, and a relationship with the diagonal line d in a rectangle is d2≤a2+b2. And in the cube, the relation between the axis f with the longest distance between vertices 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 running performance.

And, it is characterized in that the difference in refractive index between the organic particles and the binder resin is 0.05 or less. If the difference in refractive index is greater than 0.05, Haze is increased. 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 quantity 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 it is smaller than this, running characteristics and winding characteristics are deteriorated, and when it is larger than 5 μm, haze is increased, and it is undesirable in consideration of the occurrence of a drop-off problem. The content of the organic particles is preferably 1 to 10% by weight based on the total amount with the binder resin.

If the content of organic particles is less than 1% by weight based on the total amount of the binder resin, the anti-blocking effect is insufficient and is weak to scratches, winding characteristics and running characteristics are deteriorated, and if it exceeds 10% by weight, haze increases and transparent characteristics 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. In this case, it is not preferable to add an inorganic anti-blocking agent that has been commonly used, and colloidal silica having a particle size of 100 nm or less is preferably added. The content is preferably included in an amount of 10 parts by weight or less based on 100 parts by weight of the binder resin. When the above particle size and content are satisfied, sidewall defects or crater-like grooves caused by the anti-blocking layer in pattern formation using dry film photoresist may not be generated.

As a binder resin that acts as an adhesive for applying such organic particles to an unstretched polyester film, one 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, a copolymer or terpolymer of methacrylic acid; urethane-based resin; epoxy resin; Or a melamine-type resin etc. are mentioned, Preferably it is an acrylic resin.

The solvent that can be used in the preparation of the binder resin and the organic particles is preferably water.

In this way, a crude liquid containing organic particles in a binder resin is uniaxially stretched on an unstretched polyester film obtained by melt-extrusion of PET pellets, and then is applied on the uniaxially stretched film. The application may be performed on at least one surface of the uniaxially oriented 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 thinner than 30 nm on the uniaxially stretched film, the organic particles are easily removed and are vulnerable to scratches, and there is a problem that white powder is generated. If applied thicker than 200 nm, the viscosity of the crude liquid is increased. Due to this, in-line coating with high coating speed, coating streaks occur in the coating direction.

As described above, by the in-line coating method, the polymer substrate obtained by applying organic particles instead of a general anti-blocking agent has excellent transparency due to organic particles having excellent light transmittance 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 as described above, an anti-blocking agent is included as before. There is no crater-shaped flaw that appears as the base film is laminated. Since the particles such as silica are larger in size than organic particles and their distribution is throughout the base film, the effect of silica appears in a portion adjacent to the photosensitive resin layer, even though it is insignificant.

On the other hand, in the polymer substrate used in the present invention, the size of the organic particles is 0.5 μm to 5 μm, and the organic particle layer is not adjacent to the photosensitive resin layer, so that the organic particles do not have a physical effect. In addition, by using organic particles having excellent light transmittance, sidewall defects 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 prevents damage to the photosensitive resin layer during handling and serves as a protective cover for protecting the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface of the photosensitive resin layer on which the polymer substrate is not formed. The protective film serves to protect the photosensitive resin layer from the outside, and when the photosensitive element is applied to a post-process, it is easily detached, and it requires proper release property and adhesiveness so as not to be released when stored and distributed.

4. 회로 기판, 디스플레이 장치4. Circuit board, display device

According to another embodiment of the present invention, a circuit board or display device including the photosensitive resin layer containing the photosensitive resin composition of the embodiment may be provided. The content of the photosensitive resin composition includes all of the content described above in the embodiment.

Specific details regarding the circuit board or the display device are not particularly limited, and various conventionally known technical configurations are applicable without limitation.

The photosensitive resin layer included in the circuit board or the display device may be in the form of a film without openings or in the form of a pattern having openings.

As an example of a method of forming the pattern-shaped photosensitive resin layer, a method of laminating the photosensitive resin layer of the dry film photoresist of the other embodiment on a substrate, followed by exposure and development. In addition, after laminating the photosensitive resin layer of the photosensitive element of the other embodiment on a substrate, there is a method of performing exposure and development.

As the substrate, a copper clad laminate, a glass substrate sputtered or deposited with transparent electrodes such as ITO and IZO, the same film substrate, a glass substrate coated with dielectric paste, a silicon wafer, a glass wafer deposited with amorphous silicon, copper, tantalum, molybdenum, etc. A silicon wafer 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, particularly light having a wavelength of 350 to 410 nm, particularly i-line (365 nm) or h-line (405 nm). When using a laser direct exposure machine, it is possible to work under conditions of 3 to 15 mJ/cm2 or less of exposure energy, and when using a general lamp exposure machine, it is possible to work under conditions of 20mJ/cm2 or less for PCB, lead frame, PDP, and other It is useful for producing images of display devices and the like.

The developing step can be performed by a dipping method, a shower method, a spraying method, a brush method, or the like. As the developer, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines can be used. .

When 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 before laminating the photosensitive resin layer on a circuit board or a substrate for manufacturing a display device may be further performed. have.

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

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

In addition, 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 through a known process, in addition to a lead frame, a PDP, and other display devices , it is possible to maximize productivity in generating images on semiconductor devices, etc.

Specifically, for example, a conductor pattern, a printed wiring board, a lead frame, an ITO electrode, a black mattress, a semiconductor bump, etc. can be manufactured by etching or plating the lower substrate exposed by the photosensitive resin layer in the above-described pattern form. have. If necessary, after the etching or plating, the pattern-shaped photosensitive resin layer may be removed by peeling it from the substrate with an aqueous solution having a stronger alkalinity than a developer.

According to the present invention, a photosensitive resin composition capable of increasing process efficiency by reducing foaming in the development and peeling process through a binder resin with increased hydrophobicity, and a dry film photoresist using the same, a photosensitive element, a circuit board, and a display device may be provided.

In addition, according to the present invention, the photosensitive resin composition with improved adhesion to the substrate and a dry film using the same can have a sufficiently low viscosity without curing near the heat bonding temperature with the substrate for application to a circuit board or a display device A photoresist, a circuit board, and a display device may be provided.

1 shows an image of the bubble meter used in Experimental Example 1.

Figure 2 shows the absolute viscosity measurement results obtained in Example 1.

The invention is described in more detail in the following examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

<제조예 및 비교제조예: 알칼리 현상성 바인더 수지의 제조><Preparation Example and Comparative Preparation Example: Preparation of alkali developable binder resin>

Preparation Example 1

A mechanical stirrer and a reflux device were installed in a four-necked round-bottom flask, and then the inside of the flask was purged with nitrogen. In the flask purged with nitrogen, 68 g of methyl ethyl ketone (Methyl Ethyl Ketone, MEK) and 5 g of methanol (Methanol, MeOH) were added, and then 0.9 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. . Here, as a monomer, methacrylic acid (MAA) 24 g, methyl methacrylate (MMA) 6 g, styrene (Styrene, SM) 30 g, and 2-phenoxyethyl methacrylate (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 obtain an alkali developable binder resin (weight average molecular weight: 65000 g/mol, glass transition temperature 98 ° C, solid content 47.3 wt%, acid value 157 mgKOH /g) was prepared.

The alkali developable binder resin prepared in the above-mentioned Preparation Example was dissolved in tetrahydrofuran so as to have a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on solid content), and a syringe of 0.45㎛ Pore Size After filtration using a filter, 20 μl was injected into GPC. Tetrahydrofuran (THF) was used as the mobile phase of GPC, and it was introduced at a flow rate of 1.0 mL/min. The column consisted of one Agilent PLgel 5㎛ Guard (7.5 x 50 mm) and Agilent PLgel 5㎛ Mixed D (7.5 x 300 mm) were connected in series. Measurements were made at 40°C using an Agilent 1260 Infinity Ⅱ system, RI Detector.

For the acid value, 1 g of the alkali developable binder resin was sampled, dissolved in 50 ml of a mixed solvent (MeOH 20%, Acetone 80%), two drops of 1%-phenolphthalein indicator were added, and then the acid value was measured by titration with 0.1N-KOH.

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

Preparation Example 2

A mechanical stirrer and a reflux device were installed in a four-necked round-bottom flask, and then the inside of the flask was purged with nitrogen. In the flask purged with nitrogen, 80 g of methyl ethyl ketone (Methyl Ethyl Ketone, MEK) and 7.5 g of methanol (Methanol, MeOH) were added, and then 0.45 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. did it Here, as a monomer, 8 g of acrylic acid (AA), 15 g of methacrylic acid (MAA), 15 g of butyl acrylate (BA), 52 g of methyl methacrylate (MMA), and styrene ( Styrene, SM) 10 g of a 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.

The alkali developable binder resin was measured to have a weight average molecular weight of 71538 g/mol, a glass transition temperature of 79° C., a solid content of 51.4% by weight, and an acid value of 156.3 mgKOH/g.

Preparation 3

A mechanical stirrer and a reflux device were installed in a four-necked round-bottom flask, and then the inside of the flask was purged with nitrogen. 110 g of methyl ethyl ketone (Methyl Ethyl Ketone, MEK) and 10 g of methanol (Methanol, MeOH) were added to the flask purged with nitrogen, and then 1 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. Here, a monomer mixture of 30 g of methacrylic acid (MAA), 100 g of methyl methacrylate, and 30 g of styrene (Styrene, SM) was added as a monomer, and the temperature was raised to 80 °C. An alkali developable binder resin (weight average molecular weight 49852 g/mol, glass transition temperature 125° C., solid content 48.5 wt%, acid value 163.17 mgKOH/g) was prepared by polymerization for the next 6 hours.

Comparative Preparation Example 1

A mechanical stirrer and a reflux device were installed in a four-necked round-bottom flask, and then the inside of the flask was purged with nitrogen. 90 g of Methyl Ethyl Ketone (MEK) and 10 g of Propylene Glycol Monomehtyl Ether Acetate (PGMEA) were added to the nitrogen-purged flask, and then 0.8 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. A monomer mixture of 20 g of methyl methacrylic acid, 70 g of methyl methacrylate, and 10 g of styrene was added thereto, the temperature was raised to 80 ° C, and polymerization was performed for 6 hours to obtain an alkali developable binder resin (weight average molecular weight: 60000 g/mol). prepared.

<실시예 및 비교예 : 감광성 수지 조성물 및 드라이 필름 포토레지스트 제조><Examples and Comparative Examples: Preparation of photosensitive resin composition and dry film photoresist>

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

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

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

The PET film was manufactured through the following process.

PET was prepared by transesterification and polycondensation reaction between ethylene glycol and terephthalic acid. The PET pellets were dried under reduced pressure at 120° C. for 8 hours, then supplied to an extruder and melted at 280° C. This was wound on a casting drum having a surface temperature of 20°C using an electrostatic application casting method to solidify by cooling, thereby making an unstretched film. The thickness of the unstretched film was adjusted to 250 μm by controlling the discharge amount of the extruder. Next, the unstretched film is stretched 4 times in the longitudinal direction, and then, on one surface, 4 g of acrylic resin and 0.1 g of polymethyl methacrylate as organic particles are mixed with 95.9 g of water. It was applied so that it might be 50 nm thick. The polymethyl methacrylate used here has a spherical shape as a surface coated with polystyrene, and has a refractive index difference of 0.03 with the acrylic resin.

The longitudinal uniaxially oriented film coated with the crude liquid containing organic particles was preheated at 120° C. and stretched 4 times in the transverse direction.

This film was heat-set at a maximum temperature of 230° C. for 10 seconds under a predetermined length, and cooled to room temperature to obtain a polyester film having a total thickness of 20 μm and a coating layer thickness of 50 nm.

성 분ingredient	상품명(또는 성분명)Trade name (or ingredient name)	함량(중량%)content (wt%)
성 분ingredient	상품명(또는 성분명)Trade name (or ingredient name)	실시예1Example 1	실시예2Example 2	비교예1Comparative Example 1	비교예2Comparative Example 2
알칼리 현상성 바인더 수지Alkali Developable Binder Resin	제조예1Preparation Example 1	52.052.0	42.042.0	--	--
	제조예2Preparation Example 2	--	1.01.0	--	--
	제조예3Preparation 3	--	9.09.0	--	--
	비교제조예1Comparative Preparation Example 1	--	--	52.052.0	52.052.0
광중합성 화합물photopolymerizable compound	M-2101M-2101	2525	17.017.0	2525	1515
	T063T063	--	5.05.0	--	--
	A040A040	--	3.03.0	--	--
	PHEMAPHEMA	--	--	--	1010
광중합 개시제photopolymerization initiator	EABEAB	0.50.5	0.50.5	0.50.5	0.50.5
광중합 개시제photopolymerization initiator	BCIMBCIM	1.51.5	1.51.5	1.51.5	1.51.5
첨가제additive	톨루엔술폰산1수화물 (Aldrich Chemical)Toluenesulfonic acid monohydrate (Aldrich Chemical)	0.50.5	0.50.5	0.50.5	0.50.5
	루이코 크리스탈 바이올렛 (일본 Hodogaya Co.)Ruiko Crystal Violet (Japan Hodogaya Co.)	0.30.3	0.30.3	0.30.3	0.30.3
	다이아몬드 그린 GH(일본 Hodogaya Co.)Diamond Green GH (Japan Hodogaya Co.)	0.20.2	0.20.2	0.20.2	0.20.2
용 제solvent	MEK(Methyl Ethyl Ketone)MEK (Methyl Ethyl Ketone)	20.020.0	20.020.0	20.020.0	20.020.0
(1) M2101 : Bisphenol A (EO)10 dimethacrylate(미원스페셜티케미칼) (2) PHEMA : 2-페녹시에틸메타크릴레이트 (3) EAB : 4,4'-(Bisdiethylamino)benzophenone(Aldrich Chemical) (4) BCIM : 2,2'-Bis-(2-chlorophenyl-4,5,4',5'-tetraphenylbisimidazole(Aldrich Chemical) (5) T063 : Trimethylolpropane [EO] ₆ triacrylate (6) A040 : Methoxy propylene glycol [400] acrylate(n=9) (1) M2101: Bisphenol A (EO)10 dimethacrylate (Miwon Specialty Chemical) (2) PHEMA: 2-phenoxyethyl methacrylate (3) EAB: 4,4'-(Bisdiethylamino)benzophenone (Aldrich Chemical) (4) BCIM: 2,2'-Bis-(2-chlorophenyl-4,5,4',5'-tetraphenylbisimidazole (Aldrich Chemical) (5) T063: Trimethylolpropane [EO] ₆ triacrylate (6) A040: Methoxy propylene glycol [400] acrylate (n=9)

<실험예><Experimental example>

For the dry film photoresists prepared in Examples and Comparative Examples, physical properties were measured in the following manner, and the results are shown in Table 2.

1. 현상액 과의 비누화 반응성1. Saponification reactivity with developer

A sample ^{having a thickness of 40 μm and an area of 0.50 m 2} was prepared by using a photosensitive resin layer in which a protective film and a PET film as a support were peeled off from the dry film photoresist prepared in Examples and Comparative Examples.

After that, the photosensitive resin layer sample was placed in a cylindrical bubble analyzer (diameter of cross section: 10 cm, height: 60 cm, see Fig. 1 below) containing 1.0 liter _{of Na 2} CO _{3 1 wt% aqueous solution of 30 ± 1 ° C.} , using the developer circulation pump (circulation speed 1000~1200cc/min, circulation pressure 5 kgf/cm ² ) connected to the upper and lower parts of the bubble analyzer through the nozzle, circulate the developer for 60 minutes, sprayed.

Specifically, when the developer circulation pump is operated, the developer inside the bubble analyzer exits through the nozzle at the lower end, passes the developer circulation pump and moves to the upper end of the bubble analyzer, and can be sprayed through the nozzle at the top of the container.

At this time, the height difference between the top point of the bubble analyzer where the developer is sprayed and the highest point of the solution in the container immediately after starting spraying the developer was about 48 cm.

At this time, measure the height difference between "the highest point of the bubble generated in the bubble analyzer after 60 minutes of spraying the developer" and "the highest point of the solution in the bubble analyzer immediately after starting spraying the developer" with a ruler installed on the surface of the bubble analyzer. was measured and obtained as the generated bubble height, and the saponification reactivity with the developer was evaluated using this.

2. 세선 밀착력(단위: ㎛)2. 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 is in 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/cm2Then, a laminate was formed by lamination using a HAKUTO MACH 610i under the condition of a roll speed of 2.0 min/m.

After peeling off the PET film, which is the support of the dry film photoresist, from the laminate, using a photomask for circuit evaluation, using ORC's EXM-1201 (parallel light exposure machine) to reach an exposure dose of ^{40mJ/cm 2} After irradiating with ultraviolet light until After that, development was performed for twice the minimum development time under the 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, and the fine wire adhesion was evaluated. It can be evaluated that the fine wire adhesion is excellent, so that this value is small.

3. 1:1 해상도(단위: ㎛)3. 1:1 resolution (unit: μm)

After peeling off the PET film, which is the support for the dry film photoresist, from the laminate, a photomask for circuit evaluation is applied so that the width of the circuit line and the space between the circuit lines become 1:1 after development. Using ORC's EXM-1201 (parallel light exposure machine), it was left for 15 minutes after irradiating ultraviolet rays until it reached an exposure amount of ^{40 mJ/cm 2 .} After that, development was performed for twice the minimum development time under the 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 1:1 resolution. As this value is smaller, it can be evaluated that the 1:1 resolution value is excellent.

4. 박리속도(단위 : 초)4. Peeling speed (unit: seconds)

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

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

구분division	거품의 높이 (mm)Foam height (mm)	세선밀착력fine wire adhesion	해상도resolution	박리속도peel rate
실시예 1Example 1	4040	2525	2525	5050
실시예 2Example 2	6060	2525	2525	4040
비교예 1Comparative Example 1	140140	3030	3030	4040
비교예 2Comparative Example 2	110110	3535	3030	3232

As shown in Table 2, the Example has a significantly reduced foaming height compared to the Comparative Example, so that the saponification reactivity with the developer is low, and has finer fine wire adhesion and resolution, so that it can have excellent developability. In addition, it was found that the peeling process can have a faster peeling speed.

5. 절대점도5. Absolute Viscosity

For the photosensitive resin layer from which the protective film and the PET film as a support were peeled off from the dry film photoresist prepared in Examples and Comparative Examples, using DHR-2 (TA Instrument) equipment, absolute viscosity according to temperature under the following conditions was measured and shown in FIG. 2, and through this, the minimum value of absolute viscosity, the temperature at the minimum value of the absolute viscosity, and the curing temperature were obtained and described in Table 3 below.

- Test type = Flow type, Temp

- Gas = Nitrogen (10L/min)

- Start Temp. = 50 ℃

- Final Temp. = 125 ℃

- Ramp rate = 10 ℃/min

- Shear rate = 1 (1/s)

- Measure value when Axial Force = 3N or less

구분division	경화온도 (℃)Curing temperature (℃)	절대점도의 최소값 (Pa·s)Minimum value of absolute viscosity (Pa s)	절대점도의 최소값에서의 온도 (℃)Temperature at the minimum value of absolute viscosity (°C)	110℃에서의 절대점도 (Pa·s)Absolute Viscosity at 110℃ (Pa·s)
실시예 1Example 1	116116	8.128.12	115115	9.039.03
실시예 2Example 2	116116	1212	115115	1414
비교예 1Comparative Example 1	113113	517517	113113	558558
비교예 2Comparative Example 2	114114	379379	114114	415415

Claims

Alkali developable binder resin, photopolymerization initiator, and photopolymerization including a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3), and a repeating unit represented by the following formula (4) comprising a compound,

The photosensitive resin composition satisfying any one of the following (1) or (2):

(1) Put the photosensitive resin layer sample containing the photosensitive resin composition into a container with a cross-sectional diameter of 10 cm or more containing the developer so that the volume ratio of the photosensitive resin layer sample to the developer is 2x10 -5 m 3 /L, and When spraying from the top of the container while circulating the developer inside the container at a speed of 1000 cc/min or more and 1200 cc/min or less, the highest point of the bubbles generated in the container after 60 minutes of spraying the developer, and the container immediately after spraying the developer. If the height difference between the highest points of my developer is 80 mm or less,

(2) For the photosensitive resin layer sample containing the photosensitive resin composition and having a thickness of 5 μm or more and 30 μm or less, the absolute viscosity obtained in the temperature range of 50° C. or more and 125° C. or less under the condition that the axial force of the photosensitive resin layer sample is 5 N or less The minimum value is 300 Pa s or less,

[Formula 1]

In Formula 1,

R 1 is hydrogen or alkyl having 1 to 10 carbon atoms,

R 2 is alkyl having 1 to 10 carbon atoms,

Ar is aryl having 6 to 20 carbon atoms,

n is an integer from 1 to 20,

[Formula 2]

In the above formula (2),

R 3 is hydrogen or alkyl having 1 to 10 carbon atoms,

[Formula 3]

In the above formula 3,

R 4 is hydrogen or alkyl having 1 to 10 carbon atoms,

R 5 is alkyl having 1 to 10 carbon atoms,

[Formula 4]

In the above formula (4),

Ar is aryl having 6 to 20 carbon atoms.
According to claim 1,

The repeating unit represented by Formula 1 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 1,

The repeating unit represented by the formula (1) is a repeating unit derived from a monomer represented by the following formula (1-1), the photosensitive resin composition:

[Formula 1-1]

In Formula 1-1,

R 1 is hydrogen or alkyl having 1 to 10 carbon atoms,

R 2 is alkyl having 1 to 10 carbon atoms,

Ar is aryl having 6 to 20 carbon atoms,

n is an integer from 1 to 20;
According to claim 1,

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 the formula (2).
According to claim 1,

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 3, and

A photosensitive resin composition comprising 30 mol% or more and 60 mol% or less of the repeating unit represented by the formula (4).
According to claim 1,

The photosensitive resin composition, wherein the molar ratio of the repeating unit represented by Formula 3 to 100 moles of the repeating unit represented by Formula 4 is 10 mol or more and 99 mol or less.
According to claim 1,

The photopolymerizable compound comprises a bifunctional (meth) acrylate compound, the photosensitive resin composition.
According to claim 1,

The photopolymerizable compound is a photosensitive resin composition comprising a trifunctional or more polyfunctional (meth) acrylate compound.
9. The method of claim 8,

The trifunctional or more polyfunctional (meth)acrylate compound has a structure in which three or more alkylene oxide groups having 1 to 10 carbon atoms and (meth)acrylate functional groups are bonded to a central group having 1 to 20 carbon atoms, the photosensitive resin composition.
9. The method of claim 8,

The trifunctional or higher polyfunctional (meth)acrylate compound is a photosensitive resin composition comprising a compound represented by the following Chemical Formula 12:

[Formula 12]

In the above formula (12),

R 14 is hydrogen or alkyl having 1 to 10 carbon atoms,

R 15 is alkylene having 1 to 10 carbon atoms,

R 16 is a p-valent functional group containing a central group having 1 to 20 carbon atoms,

n12 is an integer from 1 to 20;

p is the number of functional groups substituted for R 16 , and is an integer of 3 to 10.
9. The method of claim 8,

The photopolymerizable compound further comprises a monofunctional (meth) acrylate compound, the photosensitive resin composition.
12. The method of claim 11,

The monofunctional (meth) acrylate compound is a photosensitive resin composition comprising a (meth) acrylate containing an alkylene oxide group having 1 to 10 carbon atoms.
12. The method of claim 11,

The monofunctional (meth) acrylate compound is a photosensitive resin composition comprising a compound represented by the following formula (11):

[Formula 11]

In the above formula (11),

R 11 is hydrogen or alkyl having 1 to 10 carbon atoms,

R 12 is alkylene having 1 to 10 carbon atoms,

R 13 is alkyl having 1 to 10 carbon atoms,

n11 is an integer from 1 to 20;
According to claim 1,

A first alkali phenomenon comprising a repeating unit represented by the following formula 13, a repeating unit represented by the following formula 14, a repeating unit represented by the following formula 15, a repeating unit represented by the following formula 16, and a repeating unit represented by the following formula 17 castle binder resin; and

A second alkali developable binder resin including a repeating unit represented by the following Chemical Formula 14, a repeating unit represented by the following Chemical Formula 15, and a repeating unit represented by the following Chemical Formula 16; A photosensitive resin composition further comprising:

[Formula 13]

In the above formula (13),

R 3 ″ is hydrogen,

[Formula 14]

In the formula (14),

R 3 ' is an alkyl having 1 to 10 carbon atoms,

[Formula 15]

In the formula (15),

R4″ is alkyl having 1 to 10 carbon atoms, R5″ is alkyl having 1 to 10 carbon atoms,

[Formula 16]

In the formula (16),

Ar is aryl having 6 to 20 carbon atoms,

[Formula 17]

In Formula 17,

R 4 ' is hydrogen,

R 5 ′ is alkyl having 1 to 10 carbon atoms.
A dry film photoresist comprising a photosensitive resin layer containing the photosensitive resin composition of claim 1.
16. The method of claim 15,

The dry film photoresist is a dry film photoresist satisfying any one of the following (1) or (2):

(1) In a container with a cross-sectional diameter of 10 cm or more containing a developer, the photosensitive resin layer sample containing the photosensitive resin composition is put so that the volume ratio of the photosensitive resin layer sample to the developer is 2x10 -5 m 3 /L, and the When spraying from the top of the container while circulating the developer inside the container at a speed of 1000 cc/min or more and 1200 cc/min or less, the highest point of the bubbles generated in the container after 60 minutes of spraying the developer, and the container immediately after spraying the developer. If the height difference between the highest points of my developer is 80 mm or less,

(2) the photosensitive resin layer has a minimum value of absolute viscosity obtained in a temperature range of 50° C. or more and 125° C. or less under the condition that the axial force of the photosensitive resin layer sample is 5 N or less with respect to the photosensitive resin layer sample having a thickness of 5 μm or more and 30 μm or less 300 Pa·s or less.
polymer substrate; and a photosensitive resin layer formed on the polymer substrate,

A photosensitive element satisfying any one of the following (1) or (2):

(1) Put the photosensitive resin layer sample into a container with a cross-sectional diameter of 10 cm or more containing the developer so that the volume ratio of the photosensitive resin layer sample to the developer is 2x10 -5 m 3 /L, and the developer inside the container is 1000 cc When spraying from the top of the container while circulating at a speed of more than /min and less than 1200cc/min, the highest point of the bubble generated in the container after 60 minutes of spraying the developer and the highest point of the developer in the container immediately after starting spraying the developer If the height difference between them is 80 mm or less,

(2) the photosensitive resin layer has a minimum value of absolute viscosity obtained in a temperature range of 50° C. or more and 125° C. or less under the condition that the axial force of the photosensitive resin layer sample is 5 N or less with respect to the photosensitive resin layer sample having a thickness of 5 μm or more and 30 μm or less 300 Pa·s or less.
18. The method of claim 17,

The photosensitive resin layer may include a repeating unit represented by the following Chemical Formula 1; a repeating unit represented by the following formula (2); a repeating unit represented by the following formula (3); And a repeating unit represented by Formula 4; A photosensitive element comprising an alkali developable binder resin and a photopolymerizable compound, including:

[Formula 1]

In Formula 1,

R 1 is hydrogen or alkyl having 1 to 10 carbon atoms,

R 2 is alkyl having 1 to 10 carbon atoms,

Ar is aryl having 6 to 20 carbon atoms,

n is an integer from 1 to 20,

[Formula 2]

In the above formula (2),

R 3 is hydrogen or alkyl having 1 to 10 carbon atoms,

[Formula 3]

In the above formula 3,

R 4 is hydrogen or alkyl having 1 to 10 carbon atoms,

R 5 is alkyl having 1 to 10 carbon atoms,

[Formula 4]

In the above formula (4),

Ar is aryl having 6 to 20 carbon atoms
A circuit board comprising a photosensitive resin layer containing the photosensitive resin composition of claim 1 .
A display device comprising a photosensitive resin layer containing the photosensitive resin composition of claim 1 .