KR102177313B1 - 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 comprising a monofunctional photopolymerizable compound and a trifunctional or higher-functional photopolymerizable compound, and having excellent adhesion to a board, and to a dry film photoresist, 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 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 in 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 photoresists are also widely used for 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 subjected to 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 0.5~3.5 m/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% of 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.

In recent years, photosensitive resin compositions have high sensitivity to ultra-high pressure mercury lamps or laser direct exposure, and resistance to developing solutions in the developing process increases, enabling high-density circuit formation, and as a UV marker for setting substrate exposure positions. For use, there is a need for a photosensitive resin composition capable of providing a dry film photoresist having excellent color development, shortening the peeling time of the cured film, and small peeling specimens, so that the filter is not clogged, and has excellent adhesion to the substrate.

The present invention is to provide a photosensitive resin composition capable of implementing excellent adhesion to a substrate, including a monofunctional photopolymerizable compound and a trifunctional or more multifunctional photopolymerizable compound.

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 problem, in the present specification, an alkali developable binder resin, a photopolymerization initiator, and a photopolymerizable compound are included, and the photopolymerizable compound is a monofunctional (meth)acrylate compound represented by the following Formula 1, and the following Including a polyfunctional (meth)acrylate compound represented by Formula 2, and containing less than 100 parts by weight of the polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound, photosensitive Provides a resin composition.

[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,

R ₃ is alkyl having 1 to 10 carbon atoms,

n1 is an integer from 1 to 20,

[Formula 2]

In Chemical Formula 2,

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

R ₅ is alkylene having 1 to 10 carbon atoms,

R ₆ is a functional group in which p containing a central group having 1 to 20 carbon atoms,

n2 is an integer from 1 to 20,

p is the number of functional groups substituted for R ₆ , and is an integer of 3 to 10.

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

In the present specification, the polymer substrate; And a photosensitive resin layer formed on the polymer substrate, and when a tape peeling test is performed using a peel tester on a film sample in which the photosensitive resin layer is laminated on a substrate, an adhesion degree defined by Equation 1 below is 90% or more. A photosensitive element is provided.

[Equation 1]

Adhesion (%) = (The surface area of the substrate and the photosensitive resin layer after the tape peeling test / The surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test) * 100.

In the present specification, a circuit board and a display device including the dry film photoresist are also provided.

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 invention.

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

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

Further, 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 in place 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, a 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 a substituted or unsubstituted 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 linked with two or more substituents 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. For example, (meth)acrylate is meant to include both acrylate and methacrylate.

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 group are as described above.

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

In the present specification, the polyvalent functional group is a residue in which a plurality of hydrogen atoms bonded to an arbitrary compound has been removed, and examples thereof include a divalent functional group, a trivalent functional group, and a tetravalent functional group. For example, a tetravalent functional group derived from cyclobutane refers to a residue in the form of removal of any 4 hydrogen atoms bonded to cyclobutane.

In the present specification, a direct bond or a single bond means that no atom or group of atoms exists at the corresponding position and is connected by a bonding line. Specifically, it means a case in which no separate atom exists in the portion represented by R _a , or L _b (a and b are each integer of 1 to 20) in the formula.

In this specification, “(photo) cured product” or “(photo) cured” means not only when all constituents having a curable or crosslinkable unsaturated group in the chemical structure are cured, crosslinked, or polymerized, but also partially cured. , Crosslinked or polymerized may be covered.

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

1. Photosensitive resin composition

According to an embodiment of the present invention, an alkali developable binder resin, a photopolymerization initiator, and a photopolymerizable compound are included, and the photopolymerizable compound is a monofunctional (meth)acrylate compound represented by the following Formula 1, and the following Formula 2 A photosensitive resin composition comprising the displayed polyfunctional (meth)acrylate compound, and containing less than 100 parts by weight of the polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound Can 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, R ₃ is alkyl having 1 to 10 carbon atoms, and n1 is an integer of 1 to 20 ,

[Formula 2]

In Formula 2, R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms, R ₅ is alkylene having 1 to 10 carbon atoms, R ₆ is a functional group p including a central group having 1 to 20 carbon atoms, n2 Is an integer of 1 to 20, p is the number of functional groups substituted for R ₆ , and is an integer of 3 to 10.

The present inventors believe that the photosensitive resin composition of the embodiment includes a monofunctional (meth)acrylate compound represented by Formula 1, and a polyfunctional (meth)acrylate compound represented by Formula 2, represented by Formula 1 Improved physical adhesion to the substrate implemented by the monofunctional (meth)acrylate compound and excellent photocuring speed and cure achieved by the multifunctional (meth)acrylate compound represented by Formula 2 above, It was confirmed through an experiment that physical properties (resolution, fine wire adhesion, etc.) could be secured and the invention was completed.

(One) Alkali developable binder resin

The photosensitive resin composition of the present invention may contain an alkali developable binder resin.

Specifically, the alkali developable binder resin may include at least two or more alkali developable binder resins. At least two or more alkali developable binder resins may mean a mixture of two or more alkali developable binder resins.

The at least two or more alkali developable binder resins include a repeating unit represented by the following formula 3, a repeating unit represented by the following formula 4, a repeating unit represented by the following formula 5, a repeating unit represented by the following formula 6, and the following formula 7 A first alkali developable binder resin including a repeating unit represented by; And a second alkali developable binder resin including a repeating unit represented by the following Formula 4, a repeating unit represented by the following Formula 5, and a repeating unit represented by the following Formula 6.

[Formula 3]

In Formula 3, R ₃ "is hydrogen,

[Formula 4]

In Formula 4, R ₃ ′ is an alkyl having 1 to 10 carbon atoms,

[Formula 5]

In Formula 5, R ₄ "is an alkyl having 1 to 10 carbon atoms, and R ₅ "is an alkyl having 1 to 10 carbon atoms,

[Formula 6]

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

[Formula 7]

In Formula 7, R ₄ ′ is hydrogen, and R ₅ ′ is alkyl having 1 to 10 carbon atoms.

Specifically, the first alkali developable binder resin is a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), a repeating unit represented by the following formula (5), a repeating unit represented by the following formula (6), and the following formula: It may include a random copolymer of repeating units represented by 7.

[Formula 3]

In Formula 3, R ₃ "is hydrogen,

[Formula 4]

In Formula 4, R ₃ ′ is an alkyl having 1 to 10 carbon atoms,

[Formula 5]

In Formula 5, R ₄ "is an alkyl having 1 to 10 carbon atoms, and R ₅ "is an alkyl having 1 to 10 carbon atoms,

[Formula 6]

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

[Formula 7]

In Formula 7, R ₄ ′ is hydrogen, and R ₅ ′ is alkyl having 1 to 10 carbon atoms.

In Formulas 3 to 7, specific examples of the alkyl having 1 to 10 carbon atoms include methyl.

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

[Formula 4-1]

In Formula 4-1, R ₃ ′ is alkyl having 1 to 10 carbon atoms. In Formula 4-1, R ₃ ′ is the same as described above in Formula 4. Specific examples of the monomer represented by Formula 4-1 may include methacrylic acid (MAA).

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

[Chemical Formula 5-1]

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

The repeating unit represented by Formula 6 may be a repeating unit derived from a monomer represented by Formula 6-1 below.

[Chemical Formula 6-1]

In Formula 6-1, Ar is an aryl having 6 to 20 carbon atoms. In Formula 6-1, the contents of Ar are the same as those described above in Formula 6. As a specific example of the monomer represented by Formula 6-1, styrene (SM) may be mentioned.

The first alkaline 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 the 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 the mechanical strength of the resist itself after circuit formation may be improved.

In the present specification, the weight average molecular weight refers to 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, and a commonly applied temperature 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 heating 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 glass transition temperature ratio of 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, 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 1:1.6 or more and 1:7 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.

On the other hand, the first alkali developable binder resin included in the photosensitive resin composition of the embodiment is 1.2 moles or more and 3 moles or less, and 1.2 moles of the repeating unit represented by Formula 4 with respect to 1 mole of the repeating unit represented by Formula 3 It may 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 5 with respect to 1 mole of the repeating unit represented by Formula 7 Mole 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 4 below, a repeating unit represented by Formula 5 below, and a repeating unit represented by Formula 6 below.

[Formula 4]

In Formula 4, R ₃ ′ is an alkyl having 1 to 10 carbon atoms,

[Formula 5]

In Formula 5, R ₄ "is an alkyl having 1 to 10 carbon atoms, and R ₅ "is an alkyl having 1 to 10 carbon atoms,

[Formula 6]

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

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

[Formula 4-1]

In Formula 4-1, R ₃ ′ is alkyl having 1 to 10 carbon atoms. In Formula 4-1, R ₃ ′ is the same as described above in Formula 4. Specific examples of the monomer represented by Formula 4-1 may include methacrylic acid (MAA).

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

[Chemical Formula 5-1]

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

The repeating unit represented by Formula 6 may be a repeating unit derived from a monomer represented by Formula 6-1 below.

[Chemical Formula 6-1]

In Formula 6-1, Ar is an aryl having 6 to 20 carbon atoms. In Formula 6-1, the contents of Ar are the same as those described above in Formula 6. As a specific example of the monomer represented by Formula 6-1, styrene (SM) may be mentioned.

Specifically, the first alkali developable binder resin is the repeating unit represented by Formula 4: The repeating unit represented by Formula 5: The repeating unit represented by Formula 6 is 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 4: The repeating unit represented by Formula 5: The repeating unit represented by Formula 6 is 1: (1.1 or more and 2 or less): (0.2 or more 0.99 or less), 1: (1.5 or more and 2 or less): (0.5 or more and 0.99 or less), or 1: (1.5 or more and 1.75 or less): (0.75 or more and 0.99 or less).

On the other hand, the photosensitive resin composition of 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, based on 100 parts by weight of the first alkali developable binder resin, 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, it imparts a hydrophobic function to the photosensitive resin to increase resistance to a developer, thereby increasing the circuit properties. Enhancing technical effects 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 forming the circuit, it is possible to obtain an effect of enhancing fine wire adhesion. 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 beta-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 oxanthone, 2-isopropylthioxanthone, dibenzosuberone, a,a-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 contained in an amount of 2% 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.

When the content of the photopolymerization initiator is less than 2% by weight, the production efficiency is extremely deteriorated because the light efficiency is low and a large exposure amount is required, and when it exceeds 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 and enables pattern formation.

The photopolymerizable compound of the present invention may include a monofunctional (meth)acrylate compound represented by Formula 1 below, and a polyfunctional (meth)acrylate compound represented by Formula 2 below.

[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, R ₃ is alkyl having 1 to 10 carbon atoms, and n1 is an integer of 1 to 20 ,

[Formula 2]

In Formula 2, R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms, R ₅ is alkylene having 1 to 10 carbon atoms, R ₆ is a functional group p including a central group having 1 to 20 carbon atoms, n2 Is an integer of 1 to 20, p is the number of functional groups substituted for R ₆ , and is an integer of 3 to 10

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 polyfunctional (meth)acrylate compound.

Specifically, in Formula 1, n1 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 1 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 contains the monofunctional (meth)acrylate compound represented by Formula 1, due to the low glass transition temperature of the monofunctional (meth)acrylate compound represented by Formula 1, dry It has a relatively large fluidity at the lamination temperature of the film photoresist, and thus the effect of improving physical adhesion to a substrate having high surface roughness and unevenness can be realized.

In addition, in Formula 2, n2 is an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to 5, and p refers to the number of functional groups substituted for R ₆ , and an integer of 3 to 10, 3 It may be an integer of 5, or an integer of 3 to 4.

That is, as p, which means the number of functional groups substituted with R ₆ in Formula 2, is an integer of 3 to 10, the polyfunctional (meth)acrylate compound represented by Formula 2 is a polyfunctional (meth)acryl It may be a rate compound.

Specifically, the polyfunctional (meth)acrylate compound may be represented by the following formula 2-1.

[Formula 2-1]

In Formula 2-1, R ₇ to R ₉ are each independently alkylene having 1 to 10 carbon atoms, R ₁₀ to R ₁₂ are each independently hydrogen or alkyl having 1 to 10 carbon atoms, and n3 to n5 are each It is independently an integer of 1 to 20.

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

The example of the polyfunctional (meth)acrylate compound represented by Formula 2 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 the polyfunctional (meth)acrylate compound represented by Formula 2, the photocuring speed and curing degree are improved, thereby securing contrast and implementing excellent fine wire adhesion.

On the other hand, the photosensitive resin composition of the embodiment is less than 100 parts by weight, 30 parts by weight or more and 90 parts by weight or less, 50 parts by weight of the polyfunctional (meth) acrylate compound based on 100 parts by weight of the monofunctional (meth) acrylate compound. It may be included in an amount of 90 parts by weight or less, 50 parts by weight or more and 80 parts by weight or less, or 50 parts by weight or more and 75 parts by weight or less.

As the photosensitive resin composition of the embodiment contains a small amount of the polyfunctional (meth)acrylate compound with respect to the monofunctional (meth)acrylate compound, the substrate of the monofunctional (meth)acrylate compound represented by Formula 1 Improvement of physical adhesion to the surface, securing the contrast of the multifunctional (meth)acrylate compound represented by Chemical Formula 2, and improvement of fine wire adhesion are realized at the same time, showing excellent developability and improving adhesion to the substrate, resulting in excellent physical properties (resolution, fine wire adhesion Etc.).

When the photosensitive resin composition of one embodiment contains 100 parts by weight or more of the polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound, a technical problem of lowering adhesion to the substrate occurs. I can.

Meanwhile, the photopolymerizable compound may further include a difunctional (meth)acrylate compound including an alkylene glycol-based di(meth)acrylate and a urethane-based di(meth)acrylate.

That is, the photosensitive resin composition of the embodiment includes a photopolymerizable compound, and the photopolymerizable compound is a monofunctional (meth)acrylate compound, a polyfunctional (meth)acrylate compound, an alkylene glycol-based di(meth)acrylate And it may include a difunctional (meth) acrylate compound including a urethane-based di (meth) acrylate.

As the alkylene glycol-based di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, Tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate (polyethylene glycol di(meth)acrylate) meth)acrylate), polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, ethylene glycol diglycidyl ether Di(meth)acrylate (ethylene glycol diglycidyl ether di(meth)acrylate), diethylene glycol diglycidyl ether di(meth)acrylate, Miwon Specialty Chemical Co., Ltd. product Miramer M244 (BPA(EO)3DA, Bisphenol A (EO)3 Diacrylate), Miramer M240 (BPA(EO)4DA, Bisphenol A (EO)4 Diacrylate), Miramer M241 (Bisphenol A (EO)4 Dimethacrylate) ), Miramer M2100 (BPA(EO)10DA, Bisphenol A (EO)10 Diacrylate), Miramer M2200 (BPA(EO)20DA, Bisphenol A (EO)20 Diacrylate), Miramer M2101 manufactured by Miwon Specialty Chemical Co., Ltd. (Bisphenol A (EO)10 Dimethacrylate), etc. I can.

In addition, as the urethane-based di(meth)acrylate, KUA-1330h or the like may be used.

The urethane-based di(meth)acrylate can provide flexibility by having a larger molecular weight and a linear structure than a conventional simple alkylene oxide. This is the cause of improving the tenting property required for the dry film photoresist (DFR) for the outer layer, and the hydrophobicity of polyol, which is one of the constituents of urethane acrylate, improves resistance to a plating solution that is a strong acid, so as not to contaminate the plating solution.

The urethane-based di(meth)acrylate is obtained by reacting a polyether compound having a hydroxy group or a polyester compound having a hydroxy group with a diisocyanate compound to obtain a urethane compound, and the obtained urethane compound and a compound having both a hydroxy group and an ethylenically unsaturated group are obtained. It can be obtained by reacting.

As the polyether compound having a hydroxy group, a glycol such as polytetramethylene glycol, polyoxyethylene, polyoxypropylene, and polyoxytetrahydrofuran is used as a polyether glycol, and as the polyester compound having a hydroxy group, adipic acid and A compound obtained by condensing 1,4-butadiol or the like is used.

As the diisocyanate compound (a-2), an aliphatic diisocyanate compound having a divalent aliphatic group such as an alkylene group, an alicyclic diisocyanate compound having a divalent alicyclic group such as cycloalkylene, an aromatic diisocyanate compound, and their isocyanate A cyanurate modified product, a carbodiimidized modified product, a biuret modified product, etc. are mentioned.

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

Examples of the alicyclic diisocyanate compound include isophorone diisocyanate, methylenebis(cyclohexyl)diisocyanate, 1,3- or 1,4-bis(isocyanatemethyl)cyclohexane, and the like.

As the aromatic diisocyanate compound, a dimerization polymer of 2,4-toloene diisocyanate, 2,6-toloene diisocyanate, 2,4-toloene diisocyanate or 2,6-toloene diisocyanate, (o, p or m) -Xylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, etc. are mentioned.

These are used alone or in combination of two or more. Further, an isocyanate compound having two or more isocyanate groups such as triphenylmethane triisocyanate and tris(isocyanate phenyl)thiophosphate may be contained. Among these, an alicyclic diisocyanate compound is preferable from the viewpoint of enhancing the flexibility and toughness of the photocured product and improving adhesion to the substrate.

A urethane compound is prepared by reacting the polyether compound or polyester compound having a hydroxy group with a diisocyanate compound. In the above reaction, the diisocyanate compound is preferably 1.01 to 2.0 mole ratio, more preferably 1.1 to 2.0 mole ratio, with respect to 1 mole of the polyether compound or polyester compound having a hydroxy group. If the content of the diisocyanate compound is less than 1.01 mol or more than 2.0 mol, a urethane compound having isocyanate groups at both ends cannot be stably obtained.

In addition, in the reaction for synthesizing the urethane compound, it is preferable to add dibutyltin dilaurate as a catalyst.

The reaction temperature is preferably 60 to 120°C. If it is less than 60°C, the reaction tends not to proceed sufficiently, and if it exceeds 120°C, the reaction operation may be dangerous due to rapid heat generation.

Compounds having both a hydroxy group and an ethylenically unsaturated group for reaction with the urethane compound thus prepared include a compound having a hydroxy group and a (meth)acryloyl group in the molecule. Such compounds include hydroxy (meth) acrylate, caprolactone adduct or alkylene oxide adduct of hydroxy (meth) acrylate, ester compound prepared by reacting a polyhydric alcohol such as glycerin with (meth) acrylic acid, And glycidyl (meth) arylate acrylic acid adducts.

Examples of the hydroxy (meth) acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.

Examples of the caprolactone adduct of the hydroxy(meth)acrylate include hydroxyethyl(meth)acrylate·caprolactone adduct, hydroxypropyl(meth)acrylate·caprolactone adduct, and hydroxybutyl(meth)acrylate. -Caprolactone adducts are mentioned. Examples of the alkylene oxide adducts include hydroxyethyl (meth)acrylate-alkylene oxide adducts, hydroxypropyl (meth)acrylate-propylene oxide adducts, and hydroxybutyl ( Meth)acrylate-butylene oxide adducts are mentioned.

As the ester compound, for example, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, penerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylol propane mono ( Meth)acrylate, ditrimethylolpropane tri(meth)acrylate, di(meth)acrylate of an ethylene oxide adduct of trimethyrolpropane, and di(meth)acrylate of a propylene oxide adduct of trimethyrolpropane. I can. These are used alone or in combination of two or more.

The urethane-based di(meth)acrylate is a compound derived by addition reaction of the urethane compound with a compound having both a hydroxyl group and an ethylenically unsaturated group, and a compound having both a hydroxyl group and an ethylenically unsaturated group per 1 mole of the urethane compound is 2.0 to 2.4 It can be obtained by adding at a molar ratio and performing an addition reaction at 60 to 90°C.

The urethane-based di(meth)acrylate preferably has a weight average molecular weight in the range of 1,000 to 60,000 g/mol. When the weight average molecular weight is less than 1,000 g/mol, it is difficult to sufficiently increase the flexibility and toughness, so that adhesion to the substrate cannot be improved, and when it exceeds 60,000 g/mol, the developability deteriorates and the development time is slowed. In this regard, it is preferable that the urethane-based di(meth)acrylate according to the present invention has a weight average molecular weight of 1,000 to 60,000 g/mol.

In the present invention, a urethane-based di(meth)acrylate having a weight average molecular weight of 1,000 to 60,000 g/mol is included in 1 to 20% by weight, preferably 1.5 to 15% by weight in the photosensitive resin composition. When the content of the urethane-based di(meth)acrylate having the weight average molecular weight of 1,000 to 60,000 g/mol is less than 1% by weight, the effect is insufficient, and when it exceeds 20% by weight, the development time in the development process after exposure In addition to the rapid increase, there is a disadvantage that scum and sludge are generated in large quantities.

The photosensitive resin composition of the embodiment includes 1 part by weight or more and 50 parts by weight or less, 1 part by weight or more and 30 parts by weight or less, based on 100 parts by weight of the alkylene glycol-based di(meth)acrylate, It may contain 1 part by weight or more and 10 parts by weight or less or 1 part by weight or more and 5 parts by weight or less.

As the urethane-based di(meth)acrylate is included in an amount of 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the alkylene glycol-based di(meth)acrylate, the photosensitive resin composition of the embodiment has a reduction in circuit properties or The technical effect of changing the peeling and developing time can be realized.

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 polyfunctional (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.

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 and 800 parts by weight of the difunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound. Hereinafter, 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.

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

As described above, a monofunctional (meth)acrylate compound, a polyfunctional (meth)acrylate compound, and a difunctional (meth)acrylate compound are included, and at the same time, as they are included to satisfy the weight range, the photosensitivity of the embodiment In the resin composition, not only excellent adhesion to the substrate may be realized, but also contrast may be secured and excellent fine wire adhesion may be realized.

In the present invention, the monofunctional photopolymerizable compound may be included in an amount of 0.1% by weight or more and 2.5% by weight or less based on the total weight of the photosensitive resin composition.

In addition, in the present invention, the polyfunctional photopolymerizable compound may be included in an amount of 2.6% by weight or more and 5.0% by weight or less based on the total weight of the photosensitive resin composition.

That is, the photosensitive resin composition contains 0.1% by weight or more and 2.5% by weight or less of the monofunctional photopolymerizable compound, and 2.6% by weight or more and 5.0% by weight or less of the polyfunctional photopolymerizable compound, based on the total weight of the photosensitive resin composition. Can be included as.

When the photosensitive resin composition is less than 0.1% by weight of the monofunctional photopolymerizable compound or less than 2.6% by weight of the multifunctional photopolymerizable compound, based on the total weight of the photosensitive resin composition, the compound represented by Formulas 1 and 2 When the effect of the addition is insufficient, and the monofunctional photopolymerizable compound is more than 2.5% by weight or the multifunctional photopolymerizable compound is more than 5.0% by weight, the hydrophobicity increases and the development time in the development process after exposure increases rapidly. Problems may arise.

In addition, the photosensitive resin composition of the embodiment is an additional photopolymerizable compound, ethylene glycol dimethacrylate (ethylene glycol dimethacrylate), diethylene glycol dimethacrylate (diethylene glycol dimethacrylate), tetraethylene glycol dimethacrylate (tetraethylene glycol dimethacrylate). dimethacrylate), propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate (neopentyl) glycol dimethacrylate), 1,6-hexane glycol dimethacrylate, trimethyolpropane trimethacrylate, trimethyolpropane triacrylate, glycerin dimethacrylate Acrylate (glycerin dimethacrylate), pentaerythritol dimethacrylate (pentaerythritol dimethacrylate), pentaerythritol trimethacrylate (pentaerythritol trimethacrylate), dipentaerythritol pentamethacrylate (dipentaerythritol pentamethacrylate), 2,2-bis( 4-methacryloxydiethoxyphenyl)propane (2,2-bis(4-methacryloxydiethoxyphenyl)propane), 2,2-bis(4-methacryloxypolyethoxyphenyl)propane (2,2-bis(4- methacryloxypolyethoxyphenyl)propane), 2-hydroxy-3-methacryloyloxypropyl methacrylate, ethylene glycol diglycidyl ether dimer Methacrylate (ethylene glycol diglycidyl ether dimethacrylate), diethylene glycol diglycidyl ether dimethacrylate, phthalic acid diglycidyl ester dimethacrylate (phthalic acid diglycidyl ester dimethacrylate), glycerin It may further include polyglycidyl ether polymethacrylate (glycerin polyglycidyl ether polymethacrylate) and a polyfunctional (meth) acrylate containing a urethane group.

The content of the photopolymerizable compound may be included in an amount of 10% by weight or more and 70% by weight or less, based on the total weight of the photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, it is possible to obtain an effect of enhancing photosensitivity, resolution, and adhesion.

(4) photosensitive resin composition

The photosensitive resin composition may contain 20% by weight or more and 80% by weight or less of an alkali developable binder resin, 0.1% 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 solid content, which is the basis of the weight, refers to the remaining components excluding the solvent in the photosensitive resin composition.

The photosensitive resin composition may further include a solvent. The solvent is generally selected from methyl ethyl ketone (MEK), methanol, THF, toluene, and acetone, and is not particularly limited 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 Ruiko crystal violet, the contrast is good, which is preferable. In the case of containing the Leuico 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 material, for example, toluenesulfonic acid monohydrate, fuxine, phthalocyanine green, oramine 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, the storage stability is maintained.

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

Meanwhile, in the photosensitive resin composition of the embodiment, when a tape peeling test is performed using a peel tester on a film sample in which the photosensitive resin layer containing the photosensitive resin composition is laminated on a substrate, an adhesion degree defined by Equation 1 below is 90. % Or more, 90% or more, 100% or less, or 95% or more and 100% or less. This may be implemented as the photosensitive resin composition of the embodiment includes the above-described photopolymerizable compound.

[Equation 1]

Adhesion (%) = (The surface area of the substrate and the photosensitive resin layer after the tape peeling test / The surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test) * 100.

Specifically, since the photosensitive resin composition of the embodiment includes a monofunctional (meth)acrylate compound represented by Formula 1, and a polyfunctional (meth)acrylate compound represented by Formula 2, the Equation 1 The degree of adhesion defined as may be 90% or more.

As the adhesion defined by Equation 1 is 90% or more, the effect of improving adhesion to the substrate of the dry film photoresist including the cured product of the photosensitive resin composition of the embodiment may be realized.

Specifically, in the film sample in which the photosensitive resin layer containing the photosensitive resin composition is laminated on the substrate, the substrate may be a Reverse Treated Foil.

More specifically, the surface roughness of the substrate may be 1 μm or more and 10 μm or less, 3 μm or more and 7 μm or less, or 4 μm or more and 6 μm or less.

Meanwhile, the tape peeling test of Equation 1 may be performed using a peel test after attaching a standard tape to a film sample in which a photosensitive resin layer containing the photosensitive resin composition is laminated on the substrate.

The adhesion degree defined by Equation 1 is 90% or more, as the photosensitive resin composition of the embodiment contains an excess of the monofunctional (meth)acrylate compound with respect to the polyfunctional (meth)acrylate compound, the formula Due to the low glass transition temperature of the monofunctional (meth)acrylate compound represented by 1, it has relatively high fluidity at the lamination temperature of the dry film photoresist, thereby improving physical adhesion to uneven substrates with high surface roughness. Can be implemented.

2. Dry film photoresist

According to another embodiment of the present invention, a dry film photoresist including a photosensitive resin layer containing the photosensitive resin composition of the above 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 a drying process of the photosensitive resin composition of the embodiment. The cured product means a material obtained through a curing process of the photosensitive resin composition of the embodiment.

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 for 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 may include one or more plastic films 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 release properties and adhesiveness so as to be easily released when applying a dry film photoresist to a post process, and not to be 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.

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 substrate 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.

Meanwhile, in the dry film photoresist of the embodiment, when a tape peeling test is performed using a peel tester on a film sample in which a photosensitive resin layer containing the photosensitive resin composition is stacked on a substrate, the adhesion is defined by the following equation (2). It may be 90% or more, 90% or more and 100% or less, or 95% or more and 100% or less. This may be implemented as the photosensitive resin composition of the embodiment includes the above-described photopolymerizable compound.

[Equation 2]

Adhesion (%) = (The surface area of the photosensitive resin layer of the dry film photoresist in contact with the substrate after the tape peeling test / The surface area of the photosensitive resin layer of the dry film photoresist in contact with the substrate before the tape peeling test) * 100.

The content of the adhesion includes all of the above.

As the adhesion defined by Equation 2 is 90% or more, an effect of improving adhesion to the substrate of the dry film photoresist of the embodiment may be realized.

3. Photosensitive element

According to another embodiment of the invention, a polymer substrate; And a photosensitive resin layer formed on the polymer substrate, and when a tape peeling test is performed using a peel tester on a film sample in which the photosensitive resin layer is laminated on a substrate, an adhesion degree defined by Equation 1 below is 90% or more. A photosensitive element may be provided.

[Equation 1]

Adhesion (%) = (The surface area of the substrate and the photosensitive resin layer after the tape peeling test / The surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test) * 100.

The content of the adhesion includes all of the above.

As the adhesion defined by Equation 1 is 90% or more, a photosensitive element having excellent adhesion to the substrate may be provided.

On the other hand, the photosensitive resin layer includes an alkali developable binder resin and a photopolymerizable compound, and the photopolymerizable compound is a monofunctional (meth)acrylate compound represented by the following Formula 1, and a polyfunctional ( It may contain a meth)acrylate compound.

[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, R ₃ is alkyl having 1 to 10 carbon atoms, and n1 is an integer of 1 to 20 ,

[Formula 2]

In Formula 2, R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms, R ₅ is alkylene having 1 to 10 carbon atoms, R ₆ is a functional group p including a central group having 1 to 20 carbon atoms, n2 Is an integer of 1 to 20, p is the number of functional groups substituted for R ₆ , and is an integer of 3 to 10.

The content of the photosensitive resin composition includes all of the above-described information in the embodiment and other embodiments.

That is, the photosensitive resin layer includes an alkali developable binder resin and a photopolymerizable compound, and the photopolymerizable compound is a monofunctional (meth)acrylate compound represented by the following Formula 1, and a polyfunctional ( It may contain a meth)acrylate compound.

[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, R ₃ is alkyl having 1 to 10 carbon atoms, and n1 is an integer of 1 to 20 ,

[Formula 2]

In Formula 2, R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms, R ₅ is alkylene having 1 to 10 carbon atoms, R ₆ is a functional group p including a central group having 1 to 20 carbon atoms, n2 Is an integer of 1 to 20, p is the number of functional groups substituted for R ₆ , and is an integer of 3 to 10.

Various plastic films can be used for the polymer substrate, for example, an acrylic film, a polyethylene terephthalate (PET) film, a triacetylcellulose (TAC) film, a polynorbornene (PNB) film, a cycloolefin polymer (COP) film. , And may include one or more plastic films 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 adding an anti-blocking agent, which has been added in consideration of the running property and winding characteristics during production, 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 considering running properties and winding characteristics are methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, normal butyl methyl methacrylate , Acrylic particles such as copolymers of acrylic acid and methacrylic acid or terpolymers; 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 with the binder resin. Here,'spherical' is defined as the ratio of the minor axis (a) and the major axis (b) in the ellipse is 0.5<a/b <2, and the relationship with the diagonal (d) in 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 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 when 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 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 can 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 coated on the uniaxially stretched film after the unstretched polyester film obtained by extruding PET pellets by volume extrusion. Coating may be performed on at least one surface of the uniaxially stretched film, and the thickness is preferably about 30 nm to 200 nm based on the thickness after final drying. If the crude liquid containing organic particles is applied on 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. Therefore, in in-line coating with a high coating speed, coating lines 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 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 crater-shaped flaws that appear 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 effect of silica appears to be insignificant even in a portion adjacent to the photosensitive resin layer.

On the other hand, in the polymer substrate used in the present invention, the organic particles have a size of 0.5 μm to 5 μm, and the organic particle layer is not adjacent to the photosensitive resin layer, so that the physical effect of the organic particles is not affected. In addition, by using organic particles having excellent light transmittance, defects of 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.

Specific details of the circuit board or display device are 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 with 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 display device.

According to the present invention, a photosensitive resin composition capable of implementing excellent adhesion to a substrate, and a dry film photoresist using the same, a circuit board, and a display device may be provided.

1 shows an optical microscope image of the adhesion between a substrate and a photosensitive resin layer during a tape peeling test measured in an example.
FIG. 2 shows an optical microscope image of adhesion between a substrate and a photosensitive resin layer during a tape peeling test measured in Comparative Example 1. FIG.
3 shows an optical microscope image of the adhesion between the substrate and the photosensitive resin layer during the tape peeling test measured in Comparative Example 2.

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: 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. 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 1.

The alkali developable binder resin 1 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.

As a specific example of the conditions for measuring the weight average molecular weight, 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 0.45 μm Pore After filtration using a size syringe filter, 20 µl was injected into the GPC, and the mobile phase of the GPC was tetrahydrofuran (THF), and flow rate was 1.0 mL/min, and the column was Agilent PLgel 5µm Guard. One (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 Systen, RI Detector as a detector.

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

Manufacturing Example 2

A mechanical stirrer and a reflux device were attached to a four-neck 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 0.9 g of azobisisobutyronitrile (AIBN) was added to completely dissolve. Made it. Here, a monomer mixture of 25 g of methacrylic acid (MAA), 47.5 g of methyl methacrylate (MMA), and 27.5 g of styrene (SM) was added as a monomer, and the temperature was raised to 80 °C. Alkaline developable binder resin 2 (weight average molecular weight 39000 g/mol, glass transition temperature of 128° C., solid content 45.6% by weight, acid value 163.1 mgKOH/g) was prepared by polymerization for 6 hours.

<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, and then mixed with a mechanical stirrer for about 1 hour. The composition was prepared.

The obtained photosensitive resin composition was coated on a 29 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 29 μm.

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

ingredient product name
(Or ingredient name) Content (% by weight) Example 1 Comparative Example 1 Comparative Example 2 Alkali developable binder resin Manufacturing Example 1 12 12 12 Manufacturing Example 2 90 90 90 Photopolymerizable compound M-2101 17 17 17 M-280 7 7 7 M-241 3 3 3 T063 3 8 - A040 5 - 8 KUA-1330h One One One Photopolymerization initiator BMPS 1.25 1.25 1.25 N-Phenyl glycine 0.1 0.1 0.1 9-PA 0.5 0.5 0.5 additive N,N-Diethylbutylamine 0.7 0.7 0.7 Ruiko Crystal Violet
(Japan Hodogaya Co.) 0.148 0.148 0.148 Diamond Green GH (Japan Hodogaya Co.) 0.025 0.025 0.025 Solvent MEK (Methyl Ethyl Ketone) 12 12 12 Methanol (MeOH) 3 3 3

(5) A040 : Methoxy propylene glycol [400] acrylate

(n=9)
(6) KUA-1330h : 우레탄계 디(메트)아크릴레이트
(7) BMPS : 트리브로모메틸페닐설폰
(8) BTCA : 5-Benzotriazolecarboxylic Acid
(9) 9-PA : 9-페닐아크리딘(1) M2101: Bisphenol A (EO) ₁₀ dimethacrylate (Miwon Specialty Chemical)
(2) M280: polyethylene glycol diacrylate (Miwon Specialty Chemicals)
(3) M241: Bisphenol A (ethoxylate) ₄ dimethacrylate (Miwon Specialty Chemical)
(4) T063: Trimethylolpropane [EO] ₆ triacrylate

(5) A040: Methoxy propylene glycol [400] acrylate

(n=9)
(6) KUA-1330h: Urethane-based di(meth)acrylate
(7) BMPS: Tribromomethylphenylsulfone
(8) BTCA: 5-Benzotriazolecarboxylic Acid
(9) 9-PA: 9-phenylacridine

<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.

One. Fine wire adhesion (unit: ㎛)

By peeling off the protective film of the dry film photoresist prepared in the above Examples and Comparative Examples, the photosensitive resin layer of the dry film photoresist is in contact with the surface of the copper layer of the 1.0 mm thick Reverse Treated Foil (RTF) soft etched. Roll temperature 110 ℃, roll pressure 4.0kgf/㎠ In addition, a laminate was formed by lamination using a HAKUTO MACH 610i under the condition of a roll speed of 2.0 min/m.

Dry film photoresist laminated on RTF (Reverse Treated Foil) is applied by using ORC FDi-3 (Laser Direct Image Exposure Machine) at 19mJ/cm ² with a fine line adhesion pattern (from 10㎛ to 58㎛ by 2㎛ increments) And the pattern spacing of 400 μm) was irradiated with ultraviolet rays and left for 15 minutes. After that, the PET film, which is a support for the dry film photoresist, was peeled off, and development was performed for 40 seconds in a spray pressure of 1.5 kgf/cm 2 in a spray pressure of 1.5 kgf/cm 2 with a 1.0 wt% aqueous solution of Na ₂ CO ₃ at 30±1° C.

In the developed laminate, the minimum line width of the photosensitive resin layer was measured with a ZEISS AXIOPHOT Microscope and evaluated by fine wire adhesion. It can be evaluated that the smaller this value, the better the fine wire adhesion.

2. Resolution (unit: ㎛)

By peeling off the protective film of the dry film photoresist prepared in the above Examples and Comparative Examples, the photosensitive resin layer of the dry film photoresist is in contact with the surface of the copper layer of the 1.0 mm thick Reverse Treated Foil (RTF) soft etched. Roll temperature 110 ℃, roll pressure 4.0kgf/㎠ In addition, a laminate was formed by lamination using a HAKUTO MACH 610i under the condition of a roll speed of 2.0 min/m.

The 2㎛ by increasing the width to RTF (Reverse Treated Foil) A dry-film photoresist to an exposure amount of 19mJ / cm ² using an ORC FDi-3 (Laser Direct Image exposure device) Resolution pattern (from 10㎛ 58㎛ laminated on and The array with a pattern interval of 400 μm) was irradiated with ultraviolet rays and left for 15 minutes. After that, the PET film, which is a support for the dry film photoresist, was peeled off, and development was performed for 40 seconds in a spray pressure of 1.5 kgf/cm 2 in a spray pressure of 1.5 kgf/cm 2 with a 1.0 wt% aqueous solution of Na ₂ CO ₃ at 30±1° C.

In the developed laminate, the minimum value of the gap between the photosensitive resin layers was measured with a ZEISS AXIOPHOT Microscope and evaluated as a resolution. The smaller this value, the better the resolution value can be evaluated.

3. Peeling speed (unit: second)

By peeling off the protective film of the dry film photoresist prepared in the above Examples and Comparative Examples, the photosensitive resin layer of the dry film photoresist is in contact with the surface of the copper layer of the 1.0 mm thick Reverse Treated Foil (RTF) soft etched. Roll temperature 110 ℃, roll pressure 4.0kgf/㎠ In addition, a laminate was formed by lamination using a HAKUTO MACH 610i under the condition of a roll speed of 2.0 min/m.

The dry film photoresist laminated on RTF (Reverse Treated Foil) was irradiated with ultraviolet rays at an exposure amount of 19mJ/cm ² using ORC FDi-3 (Laser Direct Image Exposure Machine) and then left for 15 minutes. . After that, peel off the PET film, which is the support of the dry film photoresist, and develop the photocured film with a spray pressure of 1.5kgf/㎠ with a 1.0wt% aqueous solution of Na ₂ CO ₃ for 40 seconds under the development conditions of the spray method. Was prepared.

Thereafter, peeling was performed using a 3% aqueous sodium hydroxide solution (a temperature of 50° C.). Evaluation of the peel rate was performed by measuring the time the photocured film fell from the copper plate.

4. RTF (Reverse Treated Foil) adhesion

Matte side of Reverse Treated Foil having a 1.0mm thickness and a surface roughness of about 5㎛ in which the photosensitive resin layer of the dry film photoresist was soft-etched by peeling off the protective film of the dry film photoresist prepared in the above Examples and Comparative Examples. A laminate was formed by lamination using HAKUTO MACH 610i under conditions of a laminator roll temperature of 110° C., a roll pressure of 4.0 kgf/cm 2, and a roll speed of 2.0 min/m so as to contact the surface.

After peeling off the PET film, which is a support for the dry film photoresist, from the laminate, 3M #610 Tape, which is a standard tape, is adhered to the photosensitive resin layer, and 3M #610 Tape is applied using a SurTA peel tester (ChemiLab). The tape peeling test was performed to evaluate the RTF adhesion, and are shown in Table 2 below.

The RTF adhesion refers to the percentage ratio of the surface area of the photosensitive resin layer of the dry film photoresist in contact with the substrate after the tape peeling test to the surface area of the photosensitive resin layer of the dry film photoresist in contact with the substrate before the tape peeling test as shown in Equation 1 below. do.

[Equation 1]

Adhesion (%) = (The surface area of the substrate and the photosensitive resin layer after the tape peeling test / The surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test) * 100.

division Fine wire adhesion resolution Peeling speed RTF adhesion Example 1 20 15 35 100% adhesion (refer to Fig. 1) Comparative Example 1 19 14 35 50% adhesion (refer to Fig. 2) Comparative Example 2 23 17 35 100% adhesion (refer to Fig. 3)

As shown in Table 2 above, it was confirmed that the example exhibited excellent fine wire adhesion and resolution, while remarkably exhibiting RTF adhesion.

Unlike the examples, in the case of Comparative Example 1 that does not contain a monofunctional (meth)acrylate compound, compared to the examples of the present application, it was confirmed that the RTF adhesion was significantly inferior.

In addition, in the case of Comparative Example 2 that does not contain the polyfunctional (meth)acrylate compound, it was confirmed that the fine wire adhesion and resolution were remarkably inferior as compared to the present example.

Claims (24)

Including an alkali developable binder resin, a photoinitiator, and a photopolymerizable compound,
The photopolymerizable compound includes a monofunctional (meth)acrylate compound represented by Formula 1 below, and a polyfunctional (meth)acrylate compound represented by Formula 2 below,
A photosensitive resin composition comprising less than 100 parts by weight of the polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound,
When performing a tape peeling test using a peel tester on a film sample in which a photosensitive resin layer containing the photosensitive resin composition is laminated on a substrate,
A photosensitive resin composition having an adhesion degree of 90% or more defined by the following Equation 1:
[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,
R ₃ is alkyl having 1 to 10 carbon atoms,
n1 is an integer from 1 to 20,
[Formula 2]

In Chemical Formula 2,
R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms,
R ₅ is alkylene having 1 to 10 carbon atoms,
R ₆ is a functional group in which p containing a central group having 1 to 20 carbon atoms,
n2 is an integer from 1 to 20,
p is the number of functional groups substituted for R ₆ , and is an integer of 3 to 10,
[Equation 1]
Adhesion (%) = (The surface area of the substrate and the photosensitive resin layer after the tape peeling test / The surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test) * 100.
The method of claim 1,
A photosensitive resin composition comprising 30 parts by weight or more and 90 parts by weight or less of the polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound.
The method of claim 1,
The polyfunctional (meth)acrylate compound comprises a compound represented by the following formula 2-1, photosensitive resin composition:
[Formula 2-1]

In Formula 2-1,
R ₆ ′ is a trivalent functional group having 1 to 10 carbon atoms,
R ₇ to R ₉ are each independently alkylene having 1 to 10 carbon atoms,
R ₁₀ to R ₁₂ are each independently hydrogen or alkyl having 1 to 10 carbon atoms,
n3 to n5 are each independently an integer of 1 to 3.
The method of claim 1,
The photopolymerizable compound further comprises a difunctional (meth)acrylate compound including alkylene glycol-based di (meth) acrylate and urethane-based di (meth) acrylate, photosensitive resin composition.
The method of claim 4,
A photosensitive resin composition containing 1 part by weight or more and 50 parts by weight or less of urethane-based di(meth)acrylate based on 100 parts by weight of the alkylene glycol-based di(meth)acrylate.
The method of claim 4,
A photosensitive resin composition comprising 500 parts by weight or more and 1500 parts by weight or less based on 100 parts by weight of the polyfunctional (meth) acrylate compound
The method of claim 4,
A photosensitive resin composition comprising 500 parts by weight or more and 1000 parts by weight or less based on 100 parts by weight of the monofunctional (meth) acrylate compound.
The method of claim 1,
The first alkaline phenomenon including a repeating unit represented by the following formula 3, a repeating unit represented by the following formula 4, a repeating unit represented by the following formula 5, a repeating unit represented by the following formula 6, and a repeating unit represented by the following formula 7 Castle binder resin; And
A photosensitive resin composition comprising: a repeating unit represented by Formula 4 below, a repeating unit represented by Formula 5 below, and a second alkaline developable binder resin including a repeating unit represented by Formula 6 below:
[Formula 3]

In Chemical Formula 3,
R ₃ "is hydrogen,
[Formula 4]

In Chemical Formula 4,
R ₃ ′ is an alkyl having 1 to 10 carbon atoms,
[Formula 5]

In Chemical Formula 5,
R ₄ "is alkyl having 1 to 10 carbon atoms,
R ₅ "is alkyl having 1 to 10 carbon atoms,
[Formula 6]

In Formula 6,
Ar is an aryl having 6 to 20 carbon atoms,
[Formula 7]

In Chemical Formula 7,
R ₄ ′ is hydrogen,
R ₅ ′ is alkyl having 1 to 10 carbon atoms.
The method of claim 8,
A photosensitive resin composition comprising 500 parts by weight or more and 1000 parts by weight or less of a second alkali developable binder resin based on 100 parts by weight of the first alkali developable binder resin.
The method of claim 8,
The photosensitive resin composition, wherein a glass transition temperature ratio of the first alkali developable binder resin and the second alkaline developable binder resin is 1:1.5 or more and 1:5 or less.
The method of claim 8,
The photosensitive resin composition, wherein an 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.
The method of claim 8,
The first alkali developable binder resin is
A photosensitive resin composition comprising 1.2 moles or more and 3 moles or less of the repeating unit represented by Formula 4 with respect to 1 mole of the repeating unit represented by Formula 3.
The method of claim 8,
The first alkali developable binder resin is
A photosensitive resin composition comprising 2 moles or more and 10 moles or less of the repeating unit represented by Formula 5 with respect to 1 mole of the repeating unit represented by Formula 7.
delete The method of claim 1,
The photosensitive resin composition is a photosensitive resin comprising 20% by weight or more and 80% by weight or less of an alkali developable binder resin, 0.1% 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. Resin composition.
delete The method of claim 1,
The photosensitive resin composition having a thickness of the photosensitive resin layer containing the photosensitive resin composition is 1 μm or more and 1000 μm or less.
The method of claim 1,
The photosensitive resin composition having a cross-sectional area of 0.10 cm ² or more and 5.00 cm ² or less of the photosensitive resin layer containing the photosensitive resin composition.
A dry film photoresist comprising a photosensitive resin layer containing the photosensitive resin composition of claim 1.
The method of claim 19,
When performing a tape peeling test using a peel tester on a film sample in which a photosensitive resin layer containing the photosensitive resin composition is laminated on a substrate,
Dry film photoresist having an adhesion degree of 90% or more defined by Equation 2 below:
[Equation 2]
Adhesion (%) = (The surface area of the photosensitive resin layer of the dry film photoresist in contact with the substrate after the tape peeling test / The surface area of the photosensitive resin layer of the dry film photoresist in contact with the substrate before the tape peeling test) * 100.
Polymer substrate; And a photosensitive resin layer formed on the polymer substrate,
The photosensitive resin layer includes an alkali developable binder resin and a photopolymerizable compound, and the photopolymerizable compound is a monofunctional (meth)acrylate compound represented by Formula 1 below, and a polyfunctional (meth) represented by Formula 2 below. It contains an acrylate compound,
When performing a tape peeling test using a peel tester for a film sample in which the photosensitive resin layer is laminated on a substrate,
A photosensitive element having an adhesion degree of 90% or more defined by the following Equation 1:
[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,
R ₃ is alkyl having 1 to 10 carbon atoms,
n1 is an integer from 1 to 20,
[Formula 2]

In Chemical Formula 2,
R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms,
R ₅ is alkylene having 1 to 10 carbon atoms,
R ₆ is a functional group in which p containing a central group having 1 to 20 carbon atoms,
n2 is an integer from 1 to 20,
p is the number of functional groups substituted for R ₆ , and is an integer of 3 to 10,
[Equation 1]
Adhesion (%) = (The surface area of the substrate and the photosensitive resin layer after the tape peeling test / The surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test) * 100.
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