KR102242553B1 - Photosensitive resin composition, and dry film photoresist, photosensitive element, circuit board, display device using the same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition which uses an alkali developable binder resin including 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, and a dry film photoresist, a photosensitive element, a circuit board, and a display device using the same.

Description

Photosensitive resin composition and dry film photoresist using the same, photosensitive element, circuit board, and display device {PHOTOSENSITIVE RESIN COMPOSITION, AND DRY FILM PHOTORESIST, PHOTOSENSITIVE ELEMENT, CIRCUIT BOARD, DISPLAY DEVICE USING THE SAME}

The present invention relates to a photosensitive resin composition and 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 ink, etc., which are used for printed circuit boards (PCBs) or lead frames. .

Currently, not only manufacturing printed circuit boards (PCBs) and lead frames, but also manufacturing rib barriers of plasma display panels (PDPs), ITO electrodes, bus address electrodes, and black matrixes of other displays. Dry film photoresist is also widely used in the like.

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

In order to form a circuit on the copper clad laminate that has undergone the pretreatment process, in general, a dry film photoresist (hereinafter referred to as DFR) is 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. Generally, the lamination speed is 0.5~3.5m/min, the temperature is 100~130℃, and the roller pressure is heated at 10~90psi.

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

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

Next, a circuit is formed through different processes depending on the inner 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 peeling are performed, and a predetermined circuit is formed.

On the other hand, when the dry film photoresist is too high in viscosity during lamination of the dry film photoresist to the copper clad laminate, there is a limit in which it is difficult to secure the durability of the printed circuit board because the adhesion of the dry film photoresist to the copper clad laminate is insufficient.

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

The present invention relates to providing a photosensitive resin composition with improved adhesion to a substrate, since it is not cured near a thermal bonding temperature with a substrate for application to a circuit board or a display device and can have a sufficiently low viscosity.

In addition, 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, an 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) For a photosensitive resin layer sample containing a developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, containing a photosensitive resin composition, and having a thickness of 5 µm or more and 30 µm or less, under the condition that the photosensitive resin layer sample has an axial force of 5 N or less, 50 A photosensitive resin composition having a minimum absolute viscosity of 300 Pa·s or less obtained in a temperature range of more than or equal to 125°C is provided.

[Formula 1]

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

In the present specification, there is also provided a dry film photoresist including 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, wherein the photosensitive resin layer has a thickness of 5 µm or more and 30 µm or less, and an axial force of 5 N or less with respect to the photosensitive resin layer sample, obtained in a temperature range of 50° C. or more and 125° C. or less. A photosensitive element is provided in which the minimum value of absolute viscosity is 300 Pa·s or less.

In the present specification, there is also provided a circuit board and a display device including a photosensitive resin layer containing the photosensitive resin composition.

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

Unless expressly stated in the specification, terminology is only intended to refer to specific embodiments and is not intended to limit the present invention.

The singular forms used in the present specification also include plural forms unless the phrases clearly indicate the opposite meaning.

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

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 element may be referred to as a second element, and similarly, a second element may be referred to as a first element.

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

In the present specification, the term "substitution" means that other functional groups are 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 can be substituted, and when two or more are substituted , Two or more substituents may be the same or different from each other.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amide group; Primary amino group; Carboxyl group; Sulfonic acid group; Sulfonamide group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkoxysilylalkyl group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents. . For example, "a substituent to 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 to which two phenyl groups are connected.

, 또는

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

, or

Means a bond connected to another substituent, and a direct bond means a case in which a separate atom does not exist in the portion represented by L.

In the present specification, (meth)acrylic is meant to include both acrylic and methacrylic.

In the present specification, the alkyl group is a monovalent functional group derived from alkane and may be linear or branched, and the number of carbon atoms of the linear alkyl group is not particularly limited, but is preferably 1 to 20. Further, the branched chain alkyl group has 3 to 20 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl- Propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptan-4-yl, and the like, but are not limited thereto. 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, is not particularly limited, but preferably has 6 to 20 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group 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. Photosensitive resin composition

According to an 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) For a photosensitive resin layer sample containing a resin, a photopolymerization initiator, and a photopolymerizable compound, containing a photosensitive resin composition, and having a thickness of 5 µm or more and 30 µm or less, the photosensitive resin layer sample has an axial force of 5 N or less and 50°C or more 125 A photosensitive resin composition having a minimum absolute viscosity of 300 Pa·s or less obtained in a temperature section below °C may be provided.

[Formula 1]

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

The present inventors argue that the photosensitive resin composition of the embodiment includes the repeating unit represented by Formula 1 in the alkali developable binder resin, thereby improving the heat resistance of the alkali developable binder resin, and thus drying using the photosensitive resin composition. As the thermal curing temperature of the film photoresist increases and has a sufficiently low viscosity when heat-treated to the vicinity of the thermal curing temperature, the dry film photoresist is thermally bonded to the substrate at the thermal bonding temperature for application to a circuit board or display device. It was confirmed that the adhesion to the substrate can be increased through a low viscosity, and the invention was completed.

(1) Alkaline 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 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 It may include.

By including the repeating unit represented by Chemical Formula 1 in the alkali developable binder resin, the degree of hydrophobicity of the alkali developable binder resin is increased. ) It shows excellent developability by suppressing the occurrence, and it can secure proper physical properties (resolution, fine wire adhesion, etc.) by improving adhesion to the substrate.

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

In Formula 1, Ar is an aryl having 6 to 20 carbon atoms, and a specific example of the aryl having 6 to 20 carbon atoms is phenyl.

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

[Formula 1-1]

In Formula 1-1, R ₁ is hydrogen or alkyl _{having 1 to 10 carbon atoms, R 2} is alkylene having 1 to 10 carbon atoms, Ar is aryl having 6 to 20 carbon atoms, and n is an integer of 1 to 20 to be. In Formula 1-1, _{the contents of R 1} , R ₂ , Ar, and n are the same as those described 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 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 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 aryl of.

In Formulas 2 to 4, R ₃ and R ₄ are the same as or different from each other, and each independently hydrogen or alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms are methyl Can be mentioned.

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 a C6-C20 aryl, and a specific example of the C6-C20 aryl includes 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 content of R 3} is the same as the content of Formula 2 above. Specific examples of the monomer represented by Formula 2-1 may include methacrylic acid (MAA).

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

[Chemical 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 Chemical Formula 3-1, _{the contents of R 4} and R ₅ are the same as those described in Chemical Formula 3. As a specific example of the monomer represented by Formula 3-1, methylmethacrylate (MMA) may be mentioned.

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

[Chemical Formula 4-1]

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

The alkali developable binder resin is 20 mol% or more and 60 mol% or less, or 20 mol% or more, based on 100 mol% of the total molar content of repeating units contained in the alkali developable binder resin. It may contain 50 mol% or less, or 30 mol% or more and 40 mol% or less.

In addition, the alkali developable binder resin is 1 mol% or more and 30 mol% or less, or 1 mol% of the repeating unit represented by Formula 3 based on 100 mol% of the total molar content of the repeating unit contained in the alkali developable binder resin. % 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, or 30 mol% or more and 50 mol% or less, or 30 mol% or more It may contain 40 mol% or less.

More specifically, with respect to 100 moles of the repeating unit represented by Formula 4, the molar ratio of the repeating unit represented by Formula 3 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 mol or more and 50 mol or less, or 10 mol or more and 40 mol or less, or 10 mol or more and 30 mol or less.

As such, the degree of hydrophobicity of the alkali developable binder resin is also increased as the content of the repeating unit represented by Formula 4 which is hydrophobic is increased, thereby suppressing the occurrence of foam in the developing process of a dry film photoresist using the photosensitive resin composition. can do.

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

In this specification, 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 analysis device, a detector such as a Refractive Index Detector, and a column for analysis can be used. 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 to a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on solid content), and a 0.45 μm pore size syringe After filtration using a filter, 20 µl was injected into GPC, and tetrahydrofuran (THF) was used as the mobile phase of the GPC, and flow rate was 1.0 mL/min, and the column was Agilent PLgel 5µm Guard (7.5 x 50 mm) and two Agilent PLgel 5㎛ Mixed D (7.5 x 300 mm) were connected in series, and measured at 40 ℃ using an Agilent 1260 Infinity II system and RI Detector as a detector.

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

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

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

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

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

The glass transition temperature was compared with a reference and a binder polymer in DSC (Differential Scanning Calorimeter) (Perkin-Elmer, DSC-7). The temperature setting can be measured by maintaining the temperature at 20°C for 15 minutes and then raising the temperature to 200°C at a 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. As for the acid value, about 1 g of the alkali developable binder resin was sampled and dissolved in a 50 ml mixed solvent (MeOH 20%, Acetone 80%), and two drops of 1%-phenolphthalein indicator were added, followed by titration with 0.1N-KOH to measure the acid value.

The alkali developable binder resin is contained in an amount of 20% by weight or more and 80% by weight or less with respect to the total weight of the photosensitive resin composition based on solid content. When the content of the alkali developable binder resin is within the above range, after circuit formation, an effect of enhancing fine wire 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.

Meanwhile, 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 the following formula (17) A first alkali developable binder resin including a repeating unit to be used; And a second alkali developable binder resin including a repeating unit represented by the following Formula 14, a repeating unit represented by the following Formula 15, and a repeating unit represented by the following Formula 16.

[Formula 13]

In Chemical Formula 13,

R ₃ "is hydrogen,

[Formula 14]

In Chemical Formula 14,

R ₃ ′ is alkyl having 1 to 10 carbon atoms,

[Formula 15]

In Chemical Formula 15,

R4" is an alkyl having 1 to 10 carbon atoms, R5" is an alkyl having 1 to 10 carbon atoms,

[Formula 16]

In Chemical Formula 16,

Ar is an aryl having 6 to 20 carbon atoms,

[Formula 17]

In Chemical Formula 17,

R ₄ ′ is hydrogen,

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

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

In Formulas 13 to 17, a specific example of the alkyl having 1 to 10 carbon atoms may be methyl.

Ar is a C6-C20 aryl, and a specific example of the C6-C20 aryl includes phenyl.

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

[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 Formula 15 may be a repeating unit derived from a monomer represented by Formula 15-1 below.

[Chemical Formula 15-1]

In Formula 15-1, R ₄ "is alkyl having 1 to 10 carbon atoms, and R ₅ "is 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. As a specific example of the monomer represented by Formula 15-1, methylmethacrylate (MMA) may be mentioned.

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

[Chemical Formula 16-1]

In Formula 16-1, Ar is an aryl having 6 to 20 carbon atoms. In Chemical Formula 16-1, the contents of Ar are the same as those described in Chemical Formula 16. A specific example of the monomer represented by Formula 16-1 may include 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, the coating properties of the dry film photoresist, followability, and mechanical strength of the resist itself after circuit formation 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, the coating properties of the dry film photoresist, followability, and mechanical strength of the resist itself after circuit formation may be improved.

In this specification, 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 analysis device, a detector such as a Refractive Index Detector, and a column for analysis can be used. 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 to a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on solid content), and a 0.45 μm pore size syringe After filtration using a filter, 20 µl was injected into GPC, and tetrahydrofuran (THF) was used as the mobile phase of the GPC, and flow rate was 1.0 mL/min, and the column was Agilent PLgel 5µm Guard (7.5 x 50 mm) and two Agilent PLgel 5㎛ Mixed D (7.5 x 300 mm) were connected in series and measured at 40 ℃ using an Agilent 1260 Infinity II System, RI Detector as a detector.

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

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

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

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

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

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

The acid value of the alkali developable binder resin was dissolved in 50 ml mixed solvent (MeOH 20%, Acetone 80%) by sampling about 1 g of the alkali developable binder resin, and two drops of 1%-phenolphthalein indicator were added, followed by 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 ratio of the glass transition temperature between the first alkali developable binder resin and the second alkaline developable binder resin is 1:1.5 or more and 1:5 or less, 1:1.5 or more and 1:3 or less, and 1:1.5 or more and 1:2. Hereinafter, 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 alkaline 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.

Meanwhile, the first alkali developable binder resin included in the photosensitive resin composition of the embodiment is 1.2 mol or more and 3 mol or less, and 1.2 mol of the repeating unit represented by Chemical Formula 4 with respect to 1 mol of the repeating unit represented by Chemical Formula 3. It may contain at least 2 mol, 1.5 mol or more and 2 mol or less, or 1.5 mol or more and 1.6 mol or less.

In addition, the first alkali-developable binder resin included in the photosensitive resin composition of the embodiment has 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. It may contain mol or more and 10 mol or less, 3 mol or more and 5 mol or less, or 4 mol or more and 5 mol or less.

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

[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 an aryl having 6 to 20 carbon atoms.

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

[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 Formula 15 may be a repeating unit derived from a monomer represented by Formula 15-1 below.

[Chemical Formula 15-1]

In Formula 15-1, R ₄ "is alkyl having 1 to 10 carbon atoms, and R ₅ "is 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. As a specific example of the monomer represented by Formula 15-1, methylmethacrylate (MMA) may be mentioned.

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

[Chemical Formula 16-1]

In Formula 16-1, Ar is an aryl having 6 to 20 carbon atoms. In Chemical Formula 16-1, the contents of Ar are the same as those described above in Chemical Formula 6. A specific example of the monomer represented by Formula 16-1 may include 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: 1: (2 or more and 5 or less): (0.2 0.9 or less), 1: (2 or more and 3 or less): (0.5 or more and 0.9 or less), 1: (2.5 or more and 3 or less): (0.6 or more and 0.9 or less) or 1: (2.75 or more and 3 or less): (0.6 or more 0.75 It can be included as follows).

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: 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 one 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, It may contain 700 parts by weight or more and 800 parts by weight or less.

As described above, by adding an excess of 500 parts by weight or more of the second alkali developable binder resin to 100 parts by weight of the first alkali developable binder resin, imparting a hydrophobic function to the photosensitive resin to increase resistance to a developer, thereby increasing the circuit properties. The technical effect of improving can be implemented.

The alkali developable binder resin is contained in an amount of 20% by weight or more and 80% by weight or less with respect to the total weight of the photosensitive resin composition based on solid content. When the content of the alkali developable binder resin is within the above range, after circuit formation, an effect of enhancing fine wire 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.

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. When the content of the alkali developable binder resin is less than 40% by weight of the total photosensitive resin composition, contamination of the developing stage may occur, resulting in defects such as short circuits, and when it exceeds 70% by weight, adhesion and resolution There is a problem of poor circuit properties.

(2) photopolymerization initiator

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

Compounds that can be used as the photopolymerization initiator include anthraquinone derivatives such as 2-methyl anthraquinone and 2-ethyl anthraquinone; Benzoin derivatives, such as benzoin methyl ether, benzophenone, phenanthrene quinone, and 4,4'-bis-(dimethylamino)benzophenone, are mentioned.

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-diethyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 3, 3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxyoxanthone, 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 Toxicbenzoin, isobutoxybenzoin, tert-butoxybenzoin, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylti A compound selected from oxantone, 2-isopropylthioxanthone, dibenzosuberone, α, α-dichloro-4-phenoxyacetophenone, and pentyl 4-dimethylaminobenzoate may be used as a photopolymerization initiator, but is limited thereto. It is not.

The content of the photopolymerization initiator is included in an amount of 1% by weight or more and 10% by weight or less based on the total weight of the photosensitive resin composition. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity can 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.

If the content of the photopolymerization initiator is less than 1% by weight, the light efficiency is low, so the amount of exposure must be large, so the production efficiency is extremely deteriorated.If the content of the photopolymerization initiator is more than 10% by weight, the film is brittle and the developer is contaminated. There is a problem that this increases and causes a defect such as a short circuit.

(3) photopolymerizable compound

The photopolymerizable compound of the present invention has resistance to a developer after UV exposure, thereby enabling pattern formation.

The photopolymerizable compound may include a difunctional (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 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, significantly increase resistance to a developer and a plating solution, and shorten the peeling time of the cured film.

In the present invention, the compound represented by Chemical Formula 5 may be 10% by weight or more and 60% by weight or less, or 20% by weight or more and 40% by weight or less based on the total weight of the solid content of the photosensitive resin composition.

If the content of the compound represented by Formula 5 is less than 10% by weight relative to the total solid content 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, it is hydrophobic. As this increases, there may be a problem in that the development time in the developing process after exposure is rapidly increased.

Specific examples of the bisphenol-based di(meth)acrylate include Miramer M244 (BPA(EO)3DA, Bisphenol A (EO) ₃ Diacrylate), Miramer M240 (BPA(EO) _{4 manufactured by Miwon Specialty Chemical Co., Ltd.)} DA, Bisphenol A (EO)4 Diacrylate), Miramer M241 (Bisphenol A (EO) ₄ Dimethacrylate), Miramer M2100 (BPA(EO) ₁₀ DA, Bisphenol A (EO) ₁₀ Diacrylate manufactured by Miwon Specialty Chemical Co., Ltd.) ), 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 higher polyfunctional (meth)acrylate compound may have a structure in which three or more of each of an alkylene oxide group having 1 to 10 carbon atoms and three or more (meth)acrylate functional groups are bonded to a central group having 1 to 20 carbon atoms.

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

[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 a functional group p including a central group having 1 to 20 carbon atoms, n12 Is an integer of 1 to 20, p is the _{number of functional groups substituted for R 16} , and is 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 higher polyfunctional (meth)acrylate compound.

The monofunctional (meth)acrylate compound may include a (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 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 of 1 to 20 .

Including the monofunctional (meth)acrylate compound represented by Formula 11, and the trifunctional or higher polyfunctional (meth)acrylate compound represented by Formula 12, the circuit properties with existing products are the same, but the photocuring speed is reduced. As the contrast change time is improved for a technical reason that speeds up the time to develop color in the film and increases 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. The example of the monofunctional (meth)acrylate compound represented by Formula 11 is not limited, but may be, for example, Methoxy propylene glycol [400] acrylate (A040) represented by Formula A below.

[Formula A]

As the photosensitive resin composition of the embodiment includes the monofunctional (meth)acrylate compound represented by Formula 11, the effect of rapidly implementing the color change of the exposed portion of the film due to the technical cause of speeding up the photocuring speed is achieved. 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, and p refers to the number of functional groups substituted for _{R 16, and an integer of 3 to 10, 3} It may be an integer of to 5, or an integer of 3 to 4.

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

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

[Chemical 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 Is 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.

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

[Formula B]

As the photosensitive resin composition of the embodiment includes a trifunctional or higher polyfunctional (meth)acrylate compound represented by Chemical Formula 12, a polyfunctional or higher trifunctional represented by Chemical Formula 12 compared to a monofunctional (meth)acrylate compound When the functional (meth)acrylate compound is photocured, crosslinking increases, the reactor prevents a decrease in circuit properties due to many technical causes, and increases the amount of color change.

On the other hand, the photosensitive resin composition of the embodiment is 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 based on 100 parts by weight of the monofunctional (meth)acrylate compound. It may be included in an amount of 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 the 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 speeding up the photocuring speed of the compound and increasing crosslinking during photocuring of the trifunctional or higher polyfunctional (meth)acrylate compound represented by the above formula (12) when only monofunctional substances are added The effect of increasing the amount of color development by preventing the occurrence of deterioration in circuit properties and increasing the amount of the reactor can be realized at the same time.

When the photosensitive resin composition of the 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, circuit reduction and color change amount Decreasing technical problems can occur.

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

That is, the photosensitive resin composition of the embodiment includes a photopolymerizable compound, and the photopolymerizable compound is a monofunctional (meth)acrylate compound, a trifunctional or more polyfunctional (meth)acrylate compound, and a difunctional (meth)acrylic Rate compounds.

Specifically, the photosensitive resin composition of the embodiment is 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 difunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound. Parts or less, 750 parts by weight or more and 1000 parts by weight or less, and 800 parts by weight or more and 900 parts by weight or less.

That is, the photosensitive resin composition of the embodiment includes 110 parts by weight or more of the trifunctional or higher polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound, and the bifunctional (meth) ) The acrylate compound may be included in an amount of 500 parts by weight or more and 1500 parts by weight or less.

In addition, the photosensitive resin composition of the embodiment is 500 parts by weight or more and 1000 parts by weight or less, 500 parts by weight or more of the difunctional (meth)acrylate compound based on 100 parts by weight of the trifunctional or higher polyfunctional (meth)acrylate compound. It may include 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, and 500 parts by weight or more and 600 parts by weight or less.

As described above, a monofunctional (meth)acrylate compound, a trifunctional or more polyfunctional (meth)acrylate compound, and a difunctional (meth)acrylate compound are included, and at the same time, the weight range is satisfied. The photosensitive resin composition of the embodiment may express appropriate circuit properties, ^{and when a light amount of 10 mJ/cm 2} or more is given, a technical effect capable of rapid color development and color change of the exposed portion may be implemented.

More specifically, the photosensitive resin composition of the embodiment is a monofunctional (meth)acrylate compound represented by Formula 11, and a trifunctional represented by Formula 12 based on 100 parts by weight of the difunctional (meth)acrylate compound. The 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 with respect to the total weight of the photosensitive resin composition on a solid basis. When the content of the photopolymerizable compound is within the above range, an effect of enhancing photosensitivity, resolution, and adhesion may be obtained. The solid content, which is the basis of the weight, refers to the remaining components excluding the solvent in the photosensitive resin composition.

(4) photosensitive resin composition

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 the absolute viscosity obtained in the temperature range of 50°C to 125°C under the condition that the axial force of the photosensitive resin layer sample is 5N or less 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.

As an example of a method of 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 rise 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 a temperature range of 50°C or more and 125°C or less. . That is, starting from 50° C., the viscosity can be measured while increasing the temperature to 125° C. at a 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. An example of a specific method for maintaining the heating rate is not limited to a large extent, and various methods known in the art may be used without limitation.

In addition, the absolute viscosity may be measured under 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. An example of a specific method of injecting nitrogen is not largely limited, and various previously known methods may be used without limitation.

In addition, the absolute viscosity can 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, the flow-type viscometer is unreasonable, making it difficult to measure.

In addition, the absolute viscosity may be measured when the axial force of the photosensitive resin layer sample is 5N or less, or -5N or more and 5N or less, or -1N or more and 1N or less. The axial force refers to the force of the normal component when the force generated in the form of a proof force in an arbitrary vertical section under a load applied to the photosensitive resin layer sample is decomposed into a normal component and a tangential component for that 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 can be measured through an optical microscope.

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 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 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 display device, the viscosity is not sufficiently lowered at the thermal bonding temperature, resulting in a problem that the adhesion to the substrate is reduced. I 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 the absolute viscosity obtained in the temperature range of 50°C to 125°C under the condition that the axial force of the photosensitive resin layer sample is 5N or less is 300 It seems that the fact that the photosensitive resin composition is sufficiently lowered to Pa·s or less is due to the use of an alkali developable binder resin having an increased degree of hydrophobicity including the repeating unit represented by Chemical Formula 1.

Meanwhile, 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 the embodiment may obtain a minimum value of absolute viscosity in the vicinity of 110° C., which is a thermal bonding temperature, when the dry film photoresist is thermally bonded to a substrate for application to a circuit board or a display device before the curing temperature is reached. . 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 may be increased through a 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, when the dry film photoresist is thermally bonded to a substrate for application to a circuit board or a display device, the photosensitive resin composition of the embodiment does not cure near 110° C., which is a thermal bonding temperature, thereby enhancing adhesion to the substrate. I can.

Specifically, for 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% by weight or more and 80% by weight or less of an alkali developable binder resin, 1% by weight or more and 10% by weight or less of a photopolymerization initiator, and 10% by weight or more and 70% by weight or less of a photopolymerizable compound, based on 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 is not particularly limited as the solvent, and the content is also a photopolymerization initiator, an alkali developable binder resin, and a photopolymerizable compound. It may be contained by adjusting according to the content.

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

In the present invention, in order to improve the handling properties of the photosensitive resin composition, a Leuco dye or a colored substance may be added. Examples of the Leuico dye include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, and fluorane dyes. Among them, in the case of using a Ruiko crystal violet, the contrast is good, which is preferable. In the case of containing a Leuco dye, the content may be 0.1% by weight or more and 10% by weight or less in the photosensitive resin composition. From the viewpoint of expression of contrast, 0.1% by weight or more is preferable, and from the viewpoint of maintaining storage stability, 10% by weight or less is preferable.

As a coloring substance, for example, toluenesulfonic acid monohydrate, fuxine, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, diamond green, basic blue 20, etc. Can be lifted. When the colored material is included, the amount added may be 0.001% by weight or more and 1% by weight or less in the photosensitive resin composition. When the content is 0.001% by weight or more, there is an effect of improving the handling properties, and when the content is less than 1% by weight, there is an effect of maintaining storage stability.

Other additives may further include a thermal polymerization inhibitor, a dye, a discoloring agent, an adhesion promoter, and the like.

2. Dry film photoresist

According to another embodiment of the 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 above-described information 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 refers to a material obtained through a curing process of the photosensitive resin composition of the embodiment. Although the thickness of the photosensitive resin layer is not largely limited, for example, it can be freely adjusted within the range of 0.01 μm to 1 mm.

Although the thickness of the dry film photoresist is not largely limited, for example, it can be freely adjusted within the range of 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 predetermined 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 manufacture of the dry film photoresist, and facilitates handling of the photosensitive resin layer having adhesive strength during exposure.

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

The protective film prevents damage to the resist during handling and serves as a protective covering to protect the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface of the photosensitive resin layer on which the base film is not formed. The protective film serves to protect the photosensitive resin layer from the outside, and requires proper releasability and adhesion so that it is easily released when applying a dry film photoresist to a post process, and is not released 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 triacetylcellulose (TAC) film, a polynorbornene (PNB) film, and 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. Although the thickness of the protective film is not largely limited, for example, it can be freely adjusted within the range of 0.01 μm to 1 mm.

The photosensitive resin layer contained in the dry film photoresist was 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 for a photosensitive resin layer sample having a thickness of 5 μm or more and 30 μm or less. Minimum viscosity of 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 It may be less than or equal to s.

As an example of a method of 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 rise 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 a temperature range of 50°C or more and 125°C or less. . That is, starting from 50° C., the viscosity can be measured while increasing the temperature to 125° C. at a 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. An example of a specific method of maintaining the heating rate is not limited to a large extent, and various methods known in the art may be used without limitation.

In addition, the absolute viscosity may be measured under 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. An example of a specific method for injecting nitrogen is not largely limited, and various previously known methods may be used without limitation.

In addition, the absolute viscosity can 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, the flow-type viscometer is unreasonable, making it difficult to measure.

In addition, the absolute viscosity may be measured when the axial force of the photosensitive resin layer sample is 5N or less, or -5N or more and 5N or less, or -1N or more and 1N or less. The axial force refers to the force of the normal component when the force generated in the form of a proof force in an arbitrary vertical section under a load applied to the photosensitive resin layer sample is decomposed into a normal component and a tangential component for that 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 can be measured through an optical microscope.

For the photosensitive resin layer sample in which the photosensitive resin layer contained in the dry film photoresist is 5 µm or more and 30 µm or less in thickness, 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 5N or less. If the minimum value of the viscosity 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 display device, the viscosity is not sufficiently lowered at the thermal bonding temperature, thereby reducing adhesion to the substrate. Can cause problems.

For the photosensitive resin layer sample in which the photosensitive resin layer contained in the dry film photoresist is 5 µm or more and 30 µm or less in thickness, 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 5N or less. The fact 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 including the repeating unit represented by Chemical Formula 1 in the photosensitive resin composition.

Meanwhile, 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. In the dry film photoresist of the other embodiment, when the dry film photoresist is thermally bonded to a substrate for application to a circuit board or display device before the curing temperature is reached, the minimum value of the absolute viscosity can be obtained in the vicinity of the thermal bonding temperature of 110 °C. 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 may be increased through a 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, 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 110° C., which is a thermal bonding temperature, so that adhesion to the substrate is improved. You can increase it.

Specifically, for 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.

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

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

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

3. Photosensitive element

According to another embodiment of the invention, a polymer substrate; And a photosensitive resin layer formed on the polymer substrate, wherein the photosensitive resin layer has a thickness of 5 µm or more and 30 µm or less, with respect to a photosensitive resin layer sample, 50° C. or more and 125° C. under the condition that the photosensitive resin layer sample has an axial force of 5 N or less. A photosensitive element in which the minimum value of the absolute viscosity obtained in the following temperature range is 300 Pa·s or less may be provided.

The content of the photosensitive resin layer and the absolute viscosity includes all of the above-described information in the embodiment and the other embodiment. That is, the photosensitive resin layer may include 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 photopolymerizable compound and an alkali developable binder resin including a repeating unit represented by Formula 4 above.

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 the repeating unit represented by Chemical Formula 4; the contents of the alkali developable binder resin and the photopolymerizable compound include all the contents described above in the embodiment.

Various plastic films can be used for the polymer substrate, 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 at least one plastic film selected from the group consisting of a polycarbonate (PC) film. Although the thickness of the polymer substrate is not largely limited, for example, it can be freely adjusted within the range of 0.01 μm to 1 mm.

A specific example of the polymer substrate is a polyester in which an anti-blocking layer is formed by uniaxially stretching an unstretched polyester film, applying a crude liquid containing a binder resin and organic particles to one side thereof, and uniaxially stretching the remaining uniaxially. A film is mentioned.

The polymer substrate has an in-line coating method instead of not adding an anti-blocking agent, which has been added in consideration of the running property and winding characteristics at the time of manufacture, and has an organic particle layer using alternative particles that do not impair transparency. I did it.

Here, examples of organic particles used as particles that do not impair transparency while taking into account running properties and winding characteristics are methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, and normal butyl methyl methacrylate , Acrylic particles such as copolymers or terpolymers of acrylic acid and methacrylic acid; Olefin-based particles such as polyethylene, polystyrene, and polypropylene; Acrylic and olefin-based copolymers; Alternatively, organic particles such as multi-layered multi-component particles in which homopolymer particles are formed and then coated with other types of monomers on the layer may be used.

Such organic particles should be specifically spherical and have a difference in refractive index from the binder resin. Here,'spherical' is defined as the ratio of the minor axis (a) and the major axis (b) of the ellipse to 0.5 <a/b <2, and the relationship with the diagonal (d) of the rectangle is d2?a2+b2. And the relationship between the axis (f) with the longest distance between vertices in the cube 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, the 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 inferior. It also depends on the size and quantity of the organic particles. It is preferable that the organic particles have an average particle diameter of about 0.5 µm to 5 µm, and if it is smaller than this, the running characteristics and winding characteristics are deteriorated, and if it is larger than 5 µm, the haze increases, and it is not preferable in consideration of the occurrence of a dropping problem. The content of the organic particles is preferably 1 to 10% by weight based on the total amount of the binder resin.

If the content of organic particles is less than 1% by weight based on the total amount of the binder resin, the anti-blocking effect is insufficient and it is weak against scratches, winding characteristics and running characteristics deteriorate, and if it exceeds 10% by weight, the haze increases and transparent characteristics There may be a problem with this worsening.

Meanwhile, 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 used, and it is preferable to add colloidal silica having a particle size of 100 nm or less. 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 particle size and content as described above are satisfied, defects in the sidewall or grooves such as craters may not be generated due to the anti-blocking layer in pattern formation using the dry film photoresist.

As a binder resin that acts as an adhesive for applying such organic particles onto 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, methacrylic acid copolymer or terpolymer; Urethane resin; Epoxy resin; Or melamine resin etc. are mentioned, Preferably it is an acrylic resin.

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

In this way, a crude liquid containing organic particles in a binder resin is uniaxially stretched and then applied onto the uniaxially stretched film after the unstretched polyester film obtained by elution extrusion of PET pellets. Coating may be performed on at least one side of the uniaxially stretched film, and the thickness is preferably about 30 nm to 200 nm based on the thickness after final drying. If the crude liquid containing organic particles is applied on the uniaxially stretched film to a thickness of less than 30 nm, the organic particles are easily detached and are susceptible to scratches, and there is a problem that white powder is generated. If the crude liquid is applied thicker than 200 nm, the viscosity of the crude liquid increases. Therefore, in in-line coating with a high coating speed, coating streaks are generated in the coating direction.

In this way, the polymer substrate obtained by coating with organic particles other than a general anti-blocking agent by the in-line coating method maintains the winding and running characteristics due to the particle layer, and has excellent transparency due to the organic particles having excellent light transmittance. 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, an anti-blocking agent is included as before. There is no occurrence of a crater-shaped flaw that appears as the base film is laminated. Particles such as silica are not only larger in size than organic particles, but also have a distribution throughout the base film, so that the influence of silica appears insignificantly even at a portion adjacent to the photosensitive resin layer.

On the other hand, in the polymer substrate used in the present invention, the organic particles have a size of 0.5 µm to 5 µm, and the organic particle layer is not adjacent to the photosensitive resin layer, so the physical effect of the organic particles is not affected. In addition, by using organic particles having excellent light transmittance, defects in sidewalls 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 covering to protect the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface of the photosensitive resin layer on which the polymer substrate is not formed. The protective film serves to protect the photosensitive resin layer from the outside, and requires proper release properties and adhesion so that the photosensitive element is easily released when applied to a post-process, and is not released 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 triacetylcellulose (TAC) film, a polynorbornene (PNB) film, and 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. Although the thickness of the protective film is not largely limited, for example, it can be freely adjusted within the range of 0.01 μm to 1 mm.

4. Circuit board, display device

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

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

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

Examples of a method of forming the patterned photosensitive resin layer include a method of performing exposure and development after laminating the photosensitive resin layer of the dry film photoresist of the other embodiment on a circuit board or a substrate for manufacturing a display device. I can. In addition, there may be mentioned a method of performing exposure and development after laminating the photosensitive resin layer of the photosensitive element of the other embodiment on a circuit board or a substrate for manufacturing a display device.

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

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

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

According to the present invention, a photosensitive resin composition having improved adhesion to a substrate and a dry film photoresist using the same, since it is not cured near a thermal bonding temperature with a substrate for application to a circuit board or a display device and can have a sufficiently low viscosity , A circuit board, and a display device may be provided.

1 shows the measurement results of absolute viscosity obtained in Example 1.

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

<Production Example and Comparative Production Example: Preparation of alkali developable binder resin>

Manufacturing Example 1

A mechanical stirrer and a reflux device were attached to a four-necked round bottom flask, and then the inside of the flask was purged with nitrogen. 68 g of methyl ethyl ketone (MEK) and 5 g of methanol (Methanol, MeOH) were added to the flask purged with nitrogen, and then 0.9 g of azobisisobutyronitrile (AIBN) was added to completely dissolve . Here, as a monomer, methacrylic acid (MAA) 24g, methylmethacrylate (MMA) 6g, styrene (SM) 30g, and 2-phenoxyethyl methacrylate (PHEMA) ) 40g of the monomer mixture was added, the temperature was raised to 80 ℃, and then polymerized for 6 hours to polymerize an alkali developable binder resin (weight average molecular weight: 65000 g/mol, glass transition temperature 98 ℃, solid content 47.3% by weight, acid value 157 mgKOH) /g) was prepared.

The alkali developable binder resin prepared in the above preparation example was dissolved in tetrahydrofuran to a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on solid content), After filtration using a filter, 20 µl was injected into the GPC. The mobile phase of GPC was tetrahydrofuran (THF) and flowed at a flow rate of 1.0 mL/min, and the column was 1 Agilent PLgel 5㎛ Guard (7.5 x 50 mm) and Agilent PLgel 5㎛ Mixed D (7.5 x 300 mm) two were connected in series. As a detector, an Agilent 1260 Infinity II system, RI Detector was used to measure at 40°C.

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

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

Manufacturing Example 2

A mechanical stirrer and a reflux device were attached to a four-necked round bottom flask, and then the inside of the flask was purged with nitrogen. 80 g of methyl ethyl ketone (MEK) and 7.5 g of methanol (MeOH) were added to the flask purged with nitrogen, and then 0.45 g of azobisisobutyronitrile (AIBN) was added to completely dissolve. Made it. Here, acrylic acid (AA) 8 g, methacrylic acid (MAA) 15 g, butyl acrylate (BA) 15 g, methyl methacrylate (MMA) 52 g, and styrene ( Styrene, SM) 10 g of a monomer mixture was added, the temperature was raised to 80° C., and then polymerized 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 wt%, and an acid value of 156.3 mgKOH/g.

Manufacturing Example 3

A mechanical stirrer and a reflux device were attached to a four-necked round bottom flask, and then the inside of the flask was purged with nitrogen. To the flask purged with nitrogen, 110 g of methyl ethyl ketone (MEK) and 10 g of methanol (Methanol, MeOH) were added, and then 1 g of azobisisobutyronitrile (AIBN) was added to completely Dissolved. Here, a monomer mixture of 30 g of methacrylic acid (MAA), 100 g of methyl methacrylate (MMA), and 30 g of styrene (SM) was added as a monomer, and the temperature was raised to 80 °C. Alkaline 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 Production Example 1

A mechanical stirrer and a reflux device were attached to 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 flask purged with nitrogen, and then 0.8 g of azobisisobutyronitrile (AIBN) was added to completely dissolve. Here, a monomer mixture of 20 g of methyl methacrylic acid, 70 g of methyl methacrylate and 10 g of styrene was added, the temperature was raised to 80° C., and then polymerized for 6 hours to obtain an alkali developable binder resin (weight average molecular weight: 60000 g/mol). Was prepared.

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

According to the composition shown in Table 1 below, photopolymerization initiators are dissolved in methyl ethyl ketone (MEK) as a solvent, and then a photopolymerizable compound and an alkali developable binder resin are added, followed by mixing for about 1 hour using a mechanical stirrer. The 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, at which time the drying temperature was 80° C., the drying time was 5 minutes, and the thickness of the photosensitive resin composition layer after drying was 25 μm.

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

The PET film was manufactured through the following process.

PET was prepared by performing transesterification reaction and polycondensation reaction from ethylene glycol and terephthalic acid. The PET pellets were dried under reduced pressure at 120°C for 8 hours, and then fed to an extruder and melted at 280°C. This was wound on a casting drum having a surface temperature of 20° C. by using an electrostatic application casting method, and cooled and solidified to form an unstretched film. The thickness of the unstretched film was adjusted to 250 μm by controlling the discharge amount of the extruder. Then, after stretching the unstretched film four times in the longitudinal direction, on one side, a crude solution of 4 g of acrylic resin and 0.1 g of polymethyl methacrylate as organic particles was mixed with 95.9 g of water using gravure after final drying. It was applied so as to have a thickness of 50 nm. The polymethyl methacrylate used here is coated with polystyrene on its surface, has a spherical shape, and has a refractive index difference of 0.03 with an acrylic resin.

The longitudinal uniaxially stretched film to which the crude liquid containing organic particles was applied was preheated at 120° C. and stretched four times in the transverse direction.

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

ingredient Brand name (or ingredient name) Content (% by weight) Example 1 Example 2 Comparative Example 1 Comparative Example 2 Alkali developable binder resin Manufacturing Example 1 52.0 42.0 - - Manufacturing Example 2 - 1.0 - - Manufacturing Example 3 - 9.0 - - Comparative Production Example 1 - - 52.0 52.0 Photopolymerizable compound M-2183 25 17.0 25 15 T063 - 5.0 - - A040 - 3.0 - - PHEMA - - - 10 Photopolymerization initiator EAB 0.5 0.5 0.5 0.5 BCIM 1.5 1.5 1.5 1.5 additive Toluenesulfonic acid monohydrate
(Aldrich Chemical) 0.5 0.5 0.5 0.5 Ruiko Crystal Violet
(Japan Hodogaya Co.) 0.3 0.3 0.3 0.3 Diamond Green GH (Japan Hodogaya Co.) 0.2 0.2 0.2 0.2 Solvent MEK (Methyl Ethyl Ketone) 20.0 20.0 20.0 20.0

(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) M2183: Compound of the following structure (Miwon Specialty Chemicals)

(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)

<Experimental Example>

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

1. Absolute viscosity

For the photosensitive resin layer obtained by peeling off the protective film and the PET film as a support 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. Measured and shown in FIGS. 1 and 2 below, the minimum value of the absolute viscosity, the temperature at the minimum value of the absolute viscosity, and the curing temperature were obtained and are shown in Table 2 below.

<Absolute viscosity measurement conditions>

-Test type = Flow type, Temp

-Gas = Nitrogen(10L/min)

-Start Temp. = 50 ℃

-Final Temp. = 125 ℃

-Ramp rate = 10 ℃/min

-Shear rate = 1 (1/s)

-Value measurement when Axial Force = 3N or less

division Curing temperature (℃) Minimum value of absolute viscosity (Pa·s) Temperature at the minimum value of absolute viscosity (℃) Absolute viscosity at 110℃ (Pa·s) Example 1 116 8.12 115 9.03 Example 2 116 12 115 14 Comparative Example 1 113 517 113 558 Comparative Example 2 114 379 114 415

2. Fine wire adhesion (unit: ㎛)

Preheating the substrate so that the protective film of the dry film photoresist prepared in the above Examples and Comparative Examples is peeled off, and the photosensitive resin layer of the dry film photoresist comes into contact with the copper layer surface of the 0.4 mm thick copper clad laminate subjected to brush polishing treatment. Roll temperature 120 ℃, laminator roll temperature 115 ℃, roll pressure 4.0kgf/㎠ Then, a laminate was formed by lamination using a HAKUTO MACH 610i under the condition of a roll speed of 2.0 min/m.

Using the pattern for circuit evaluation of the dry film photoresist in the laminate, ^{ultraviolet rays were irradiated through FDI-3 (LDI exposure machine, Japan ORC) until the exposure amount of 50 mJ/cm 2} was reached, and then allowed to stand for 15 minutes. . After that, development was carried out for twice the minimum development time under the spray-type development condition at a spray pressure of 1.5kgf/cm2 with a 1.0wt% 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 evaluated by fine wire adhesion. It can be evaluated that the smaller this value is, the better the fine wire adhesion.

3. 1:1 resolution (unit: ㎛)

Preheating the substrate so that the protective film of the dry film photoresist prepared in the above Examples and Comparative Examples is peeled off, and the photosensitive resin layer of the dry film photoresist comes into contact with the copper layer surface of the 0.4 mm thick copper clad laminate subjected to brush polishing treatment. Roll temperature 120 ℃, laminator roll temperature 115 ℃, roll pressure 4.0kgf/㎠ Then, a laminate was formed by lamination using a HAKUTO MACH 610i under the condition of a roll speed of 2.0 min/m.

After development of the dry film photoresist in the laminate, a circuit evaluation pattern is used so that the width of the circuit line and the space between the circuit lines become 1:1. , Japan ORC) through ^{UV irradiation until reaching an exposure dose of 50mJ/cm 2} and then allowed to stand for 15 minutes. After that, development was carried out for twice the minimum development time under the spray-type development condition at a spray pressure of 1.5kgf/cm2 with a 1.0wt% aqueous solution _{of Na 2} CO ₃ at 30±1°C.

division Fine wire adhesion resolution Example 1 22 20 Example 2 25 23 Comparative Example 1 30 30 Comparative Example 2 30 29

As shown in Table 3, the Example was found to be remarkably superior in fine wire adhesion and resolution compared to the Comparative Example.

Claims (23)

Alkaline 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) Containing a compound,
For a photosensitive resin layer sample containing a photosensitive resin composition and having a thickness of 5 μm or more and 30 μm or less, the minimum value of the absolute viscosity obtained in the temperature range of 50°C to 125°C under the condition that the axial force of the photosensitive resin layer sample is 5N or less is 300 Pa·s or less, photosensitive resin composition:
[Formula 1]

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

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

In Chemical Formula 3,
R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms,
R ₅ is alkyl of 1 carbon atom,
[Formula 4]

In Chemical Formula 4,
Ar is an aryl having 6 to 20 carbon atoms.
The method of claim 1,
The temperature at which the minimum value of the absolute viscosity is obtained is 110° C. or more and 123° C. or less.
The method of claim 1,
The photosensitive resin composition, wherein the curing temperature of the photosensitive resin layer sample is 115°C or more and 125°C or less.
The method of claim 1,
The photosensitive resin composition, wherein the photosensitive resin layer sample has an absolute viscosity value of 5 Pa·s or more and 400 Pa·s or less at a temperature of 110°C.
The method of claim 1,
The absolute viscosity is that the shear rate is 1 1 / s or more and 3 1 / s or less is measured under conditions of, photosensitive resin composition.
The method of claim 1,
The repeating unit represented by Chemical Formula 1 is contained in an amount of 5 mol% or more and 40 mol% or less based on 100 mol% of the total molar content of the repeating units contained in the alkali developable binder resin.
The method of claim 1,
The alkali developable binder resin is based on 100 mol% of the total molar content of repeating units contained in the alkali developable binder resin,
A photosensitive resin composition comprising 20 mol% or more and 60 mol% or less of the repeating unit represented by Formula 2.
The method of claim 1,
The alkali developable binder resin is based on 100 mol% of the total molar content of repeating units 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 Chemical Formula 4.
The method of claim 1,
With respect to 100 moles of the repeating unit represented by Formula 4, the molar ratio of the repeating unit represented by Formula 3 is 10 moles or more and 99 moles or less.
The method of claim 1,
The photopolymerizable compound comprises a difunctional (meth)acrylate compound, photosensitive resin composition.
The method of claim 1,
The photopolymerizable compound is a photosensitive resin composition comprising a trifunctional or more polyfunctional (meth)acrylate compound.
The method of claim 11,
The trifunctional or higher polyfunctional (meth)acrylate compound has a structure in which three or more (meth)acrylate functional groups are each bonded to a central group having 1 to 20 carbon atoms and an alkylene oxide group having 1 to 10 carbon atoms. Composition.
The method of claim 11,
The trifunctional or higher polyfunctional (meth)acrylate compound is a photosensitive resin composition comprising a compound represented by the following Formula 12:
[Formula 12]

In Chemical 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 functional group in which p 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.
The method of claim 11,
The photopolymerizable compound further comprises a monofunctional (meth)acrylate compound, photosensitive resin composition.
The method of claim 14,
The monofunctional (meth)acrylate compound comprises a (meth)acrylate containing an alkylene oxide group having 1 to 10 carbon atoms, photosensitive resin composition.
The method of claim 14,
The monofunctional (meth)acrylate compound is a photosensitive resin composition comprising a compound represented by the following formula (11):
[Formula 11]

In Chemical 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.
The method of claim 1,
The first alkali phenomenon including 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 photosensitive resin composition further comprising: a second alkali developable binder resin including a repeating unit represented by the following Formula 14, a repeating unit represented by the following Formula 15, and a repeating unit represented by the following Formula 16:
[Formula 13]

In Chemical Formula 13,
R ₃ "is hydrogen,
[Formula 14]

In Chemical Formula 14,
R ₃ ′ is alkyl having 1 to 10 carbon atoms,
[Formula 15]

In Chemical Formula 15,
R4" is an alkyl having 1 to 10 carbon atoms, R5" is an alkyl having 1 to 10 carbon atoms,
[Formula 16]

In Chemical Formula 16,
Ar is an aryl having 6 to 20 carbon atoms,
[Formula 17]

In Chemical 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.
The method of claim 18,
For the photosensitive resin layer sample having a thickness of 5 μm or more and 30 μm or less in the photosensitive resin layer, the minimum value of 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 is 300 Pa· s or less, dry film photoresist.
Polymer substrate; And a photosensitive resin layer formed on the polymer substrate,
The photosensitive resin layer may include a repeating unit represented by Formula 1 below; A repeating unit represented by the following formula (2); A repeating unit represented by the following formula (3); And a photopolymerizable compound and an alkali developable binder resin including; and a repeating unit represented by the following Chemical Formula 4,
For the photosensitive resin layer sample having a thickness of 5 μm or more and 30 μm or less in the photosensitive resin layer, the minimum value of 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 is 300 Pa· s or less, photosensitive element:
[Formula 1]

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

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

In Chemical Formula 3,
R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms,
R ₅ is alkyl of 1 carbon atom,
[Formula 4]

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

Images