TWI773059B - Photosensitive resin composition, and dry film photoresist, photosensitive element, circuit board, and display device using the same - Google Patents

Abstract

The present disclosure relates to a photosensitive resin composition including: an alkaline developable binder resin which includes a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 2, a repeating unit represented by Chemical Formula 3, and a repeating unit represented by Chemical Formula 4, and a dry film photoresist, a photosensitive element, a circuit board, and a display device using the same.

Description

Photosensitive resin composition and dry film photoresist, photosensitive Components, circuit boards and display devices

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

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

Currently, dry film photoresist is widely used not only in the manufacture of printed circuit boards (PCBs) and lead frames, but also in the manufacture of rib barriers for plasma display panels (PDPs), ITO electrodes for other displays, and bus bars. Address electrodes, black matrices, and the like.

In general, dry film photoresists of this type are commonly used in applications where they are laminated to copper clad laminates. In relation to this, as an example of a manufacturing process of a printed circuit board (PCB), a pre-processing process is first performed to laminate a copper clad laminate, which is the original plate material of the PCB. The pretreatment process is performed in the order of drilling, deburring, surface conditioning and the like in the outer layer process, and the surface conditioning or the like is performed in the inner layer process Dip. In surface conditioning, a bristle brush process and a jet pumice process are mainly used and the dip may undergo soft etching and 5 wt% sulfuric acid dip.

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

The printed circuit board that has undergone the lamination process is allowed to stand for 15 minutes or more to stabilize the board, and then the photoresist of the DFR is exposed through a reticle on which the desired circuit pattern is formed. When the photomask is irradiated with UV light in this process, the photoresist irradiated with UV light starts to polymerize by the photoinitiator contained in the irradiated portion. First, the oxygen in the photoresist is consumed, and then the activated monomer is polymerized to cause a crosslinking reaction. Thereafter, the polymerization reaction proceeds while consuming a large amount of monomers. Meanwhile, the unexposed portion exists in a state in which the cross-linking reaction has not yet proceeded.

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

Then, depending on the inner layer process and the outer layer process, circuits are formed through different processes. However, in the inner layer process, an on-board circuit is formed through an etching process and a lift-off process, and in the outer layer process, a plating process and a tenting process are performed, followed by etching and solder stripping to form a predetermined circuit.

Meanwhile, the dry film undergoes a wet process when applied in a printed circuit board manufacturing plant and is dissolved in an alkaline solution by a saponification reaction in a development process for dissolving unexposed parts or a peeling process for removing the dry film. However, there is a problem that foam is generated during the dissolution reaction, and when excess foam is generated, the chamber overflows.

In order to solve these problems, antifoaming agents for suppressing foaming are used at a ratio of 0.1 to 3% in an alkaline solution.

However, when an excessive amount of the defoaming agent is used, there are problems in that the production cost is increased and the productivity is also decreased. When the defoamer is used in excess, it combines with the components of the dry film to produce a water-insoluble scum, which causes etching failure or electroplating failure. Accordingly, there is a continuing need for dry films that produce less foam during development and stripping processes and do not require the use of antifoaming agents.

At the same time, when the viscosity of the dry film photoresist is too high when the dry film photoresist is laminated on the copper clad laminate, the adhesion of the dry film photoresist to the copper clad laminate is insufficient, and thus there is a difficulty in ensuring Printed Circuit Board Durability Limits.

Therefore, there is an increasing demand for dry film photoresists with sufficiently low viscosity.

It is an object of the present disclosure to provide a photosensitive resin composition that can reduce foam generation through a binder resin with increased hydrophobicity in the developing process and the peeling process, and thus improve process efficiency.

Another object of the present disclosure is to provide a photosensitive resin composition that can have a sufficiently low viscosity without being cured near the thermal adhesion temperature to a substrate applied to a circuit board or a display device, and thus improves adhesion to the substrate .

Another object of the present disclosure 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 achieve the above object, a photosensitive resin composition is provided herein, comprising: a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the following Chemical Formula 2, a repeating unit represented by the following Chemical Formula 3 and a repeating unit represented by the following Chemical Formula 4 The alkali-developable binder resin of the unit; a photopolymerization initiator; and a photopolymerizable compound, wherein the photosensitive resin composition satisfies any one of the following (1) or (2).

(1) Add the photosensitive resin layer sample containing the photosensitive resin composition to a container containing the developer solution with a cross-sectional diameter of 10 cm or more, so that the volume ratio of the photosensitive resin layer sample to the developer solution is 2 ×10 ^-5 m³/liter, the developer solution inside the container circulates at a rate of 1000 m³/min or more and 1200 m³/min or less, and the speed of the developer solution in the container is When spraying from the upper end, the interval of the height difference between the highest point of the foam generated in the container after the elapse of 60 minutes from the start of spraying the developer solution and the highest point of the developer solution in the container immediately after the start of spraying the developer solution is 80 mm or less than 80 mm, or (2) for a photosensitive resin layer sample containing a photosensitive resin composition and having a thickness of 5 microns or more and 30 microns or less than 30 microns, the axial force on the photosensitive resin layer sample is 5 N or Under the condition of less than 5 N, the minimum value of absolute viscosity obtained in the temperature range of 50 ℃ or greater than 50 ℃ and 125 ℃ or less than 125 ℃ is 300 Pa. seconds or less than 300 Pa. seconds, [Chem. 1]

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

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

In Chemical Formula 3, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₅ is an alkyl group having 1 to 10 carbon atoms,

And in Chemical Formula 4, Ar is an aryl group having 6 to 20 carbon atoms.

Also provided herein is a dry film photoresist comprising a photosensitive resin layer containing a photosensitive resin composition.

This document further provides a photosensitive element, comprising a polymer substrate and a photosensitive resin layer formed on the polymer substrate, and satisfying any one of the following (1) or (2).

(1) Add the photosensitive resin layer sample containing the photosensitive resin composition to a container containing the developer solution with a cross-sectional diameter of 10 cm or more, so that the volume ratio of the photosensitive resin layer sample to the developer solution is 2 ×10 ^-5 m³/liter, the developer solution inside the container circulates at a rate of 1000 m³/min or more and 1200 m³/min or less, and the speed of the developer solution in the container is When spraying from the upper end, the interval of the height difference between the highest point of the foam generated in the container after the elapse of 60 minutes from the start of spraying the developer solution and the highest point of the developer solution in the container immediately after the start of spraying the developer solution is 80 mm or less than 80 mm, or (2) the photosensitive resin layer is characterized by an axial force of 5 N on the photosensitive resin layer sample for a photosensitive resin layer sample having a thickness of 5 microns or more and 30 microns or less Under the condition of less than 5 N, the minimum value of absolute viscosity obtained in the temperature range of 50 ℃ or greater than 50 ℃ and 125 ℃ or less than 125 ℃ is 300 Pa. seconds or less than 300 Pa. second.

This document further provides a circuit board and a display device, comprising a photosensitive resin layer containing a photosensitive resin composition.

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

Unless otherwise defined throughout this specification, technical terms used herein are for reference only to specific embodiments and are not intended to limit the present disclosure.

As used herein, the singular forms "a/an" and "the (the)" include plural references unless the context clearly dictates otherwise.

The terms "comprising" or "comprising" as used herein specify particular features, regions, integers, steps, acts, elements and/or components, but do not exclude different particular features, regions, integers, steps, acts, elements, groups The presence or addition of fractions and/or groups.

Furthermore, terms including ordinal numbers such as "first", "second", etc. are used only for the purpose of distinguishing one component from another and are not limited by ordinal numbers. For example, a first component could be termed a second component, or, similarly, a second component could be termed a first component, without departing from the scope of the present disclosure.

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

In the present specification, the term "substituted" means other functional groups that replace hydrogen atoms in the bonding compound, and the positions to be substituted are not limited as long as the positions are positions where hydrogen atoms are substituted, that is, the substituents may be substituted. The substituted positions, and when two or more than two substituents are substituted, may be the same or different from each other.

In this specification, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; halo; cyano; nitro; Hydroxyl; Carbonyl; Ester; Imino; Imido; Primary Amino; Carboxyl; Sulfonic Acid; Sulfonamide; Phosphine Oxide; Alkoxy; Aryloxy; Arylthiol; Alkylthiooxy; Arylthiooxy; Silyl; Boron; Alkyl; Cycloalkyl; Alkenyl; Aryl; Aralkyl; Aralkenyl; Alkaryl; Alkyl Oxysilylalkyl; arylphosphino or heterocyclyl containing at least one of N, O and S atoms, or unsubstituted or substituted with two or more of the substituents exemplified above The substituent to which the group is attached is substituted. For example, "a substituent to which two or more substituents are attached" can be biphenyl. That is, a biphenyl group can also be an aryl group, and can be interpreted as a substituent to which two phenyl groups are attached.

或

意謂與另一取代基連接的鍵，且直接鍵意謂其中在表示為L的部分中不存在其他原子的情況。 In this manual, the symbol

or

means a bond to another substituent, and a direct bond means a case where no other atoms are present in the moiety denoted L.

In this specification, a (meth)propenyl group means that both a propenyl group and a methacryl group are included.

In the present specification, an alkyl group is a monovalent functional group derived from an alkane, and may be linear or branched. The number of carbon atoms of the straight-chain alkyl group is not particularly limited, but preferably 1 to 20. In addition, the branched chain alkyl group has 3 to 20 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tertiary butyl, tertiary butyl, 1-methyl-butyl , 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tertiary 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, tertiary 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 not limited thereto. Alkyl groups can be substituted or unsubstituted, and when they are substituted, examples of substituents are the same as described above.

In the present specification, the aryl group is a monovalent functional group derived from an aromatic hydrocarbon, and is not particularly limited, but preferably has 6 to 20 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. Specific examples of monocyclic aryl groups may include phenyl, biphenyl, triphenyl (terphenyl group) and similar groups, but not limited thereto. Specific examples of polycyclic aryl groups may include naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group , fluorenyl group and similar groups, but not limited thereto. The aryl group can be substituted or unsubstituted, and when it is substituted, examples of substituents are the same as described above.

In the following, the present disclosure will be described in more detail.

1. Photosensitive resin composition.

According to one embodiment of the present disclosure, there can be provided a photosensitive resin composition comprising: a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the following Chemical Formula 2, a repeating unit represented by the following Chemical Formula 3, and a repeating unit represented by the following Chemical Formula The alkali-developable binder resin of the repeating unit represented by 4; a photopolymerization initiator; and a photopolymerizable compound, wherein the photosensitive resin composition satisfies any one of the following (1) or (2).

(1) Add the photosensitive resin layer sample containing the photosensitive resin composition to a container containing the developer solution with a cross-sectional diameter of 10 cm or more, so that the volume ratio of the photosensitive resin layer sample to the developer solution is 2 ×10 ^-5 m³/liter, the developer solution inside the container circulates at a rate of 1000 m³/min or more and 1200 m³/min or less, and the speed of the developer solution in the container is When spraying from the upper end, the interval of the height difference between the highest point of the foam generated in the container after the elapse of 60 minutes from the start of spraying the developer solution and the highest point of the developer solution in the container immediately after the start of spraying the developer solution is 80 mm or less than 80 mm, or (2) for a photosensitive resin layer sample containing a photosensitive resin composition and having a thickness of 5 microns or more and 30 microns or less than 30 microns, the axial force on the photosensitive resin layer sample is 5 N or Under the condition of less than 5 N, the minimum value of absolute viscosity obtained in the temperature range of 50 ℃ or greater than 50 ℃ and 125 ℃ or less than 125 ℃ is 300 Pa. seconds or less than 300 Pa. second.

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

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

In Chemical Formula 3, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₅ is an alkyl group having 1 to 10 carbon atoms,

And in Chemical Formula 4, Ar is an aryl group having 6 to 20 carbon atoms.

The inventors found through experiments that since the photosensitive resin composition of one embodiment contains the repeating unit represented by Chemical Formula 1 in the alkali-developable adhesive resin to increase the hydrophobicity of the alkali-developable adhesive resin, it is possible In the development process of the dry film photoresist using the photosensitive resin composition, the generation of foam is suppressed and the development characteristics are excellent, and the adhesion to the substrate is further improved and the proper physical characteristics (resolution, fine line adhesion, etc.) are ensured and Complete this disclosure.

In addition, the present inventors found through experiments that since the photosensitive resin composition of one embodiment contains a repeating unit represented by Chemical Formula 1 in the alkali-developable adhesive resin to improve the heat resistance characteristics of the alkali-developable adhesive resin, therefore The thermal curing temperature of the dry film type photoresist using the photosensitive resin composition is increased, and it has a sufficiently low viscosity during the heat treatment until the vicinity of the thermal curing temperature, thereby thermally adhering the dry film type photoresist to the application circuit board. Or the substrate of the display device increases the adhesion force to the substrate through the low viscosity at the thermal bonding temperature, and the present disclosure is completed.

(1) Alkaline developable binder resin

The alkaline developable binder resin of the present disclosure may include: a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 2, a repeating unit represented by Chemical Formula 3, and a repeating unit represented by Chemical Formula 4.

Specifically, the alkali-developable binder resin may contain a formula represented by Chemical Formula 1 A random copolymer of the repeating unit represented by the chemical formula 2, the repeating unit represented by the chemical formula 3, and the repeating unit represented by the chemical formula 4.

Since the repeating unit represented by Chemical Formula 1 is contained in the alkali-developable binder resin to thereby increase the hydrophobicity of the alkali-developable binder resin, it inhibits the use of a dry film type photoresist using a photosensitive resin composition. Foam is generated during the development process, and exhibits excellent development properties and has the potential to improve substrate adhesion and thus ensure proper physical properties (resolution, fine line adhesion, etc.).

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

In Chemical Formula 1, R ₂ is an alkylene group having 1 to 10 carbon atoms, and specific examples of the alkylene group having 1 to 10 carbon atoms may include an ethylene group.

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

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

In Chemical Formula 1-1, R ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₂ is an alkylene group having 1 to 10 carbon atoms, and Ar is an alkylene group having 6 to 20 carbon atoms , and n is an integer from 1 to 20. In Chemical Formula 1-1, the definitions of R ₁ , R ₂ , Ar and n are the same as those described for Chemical Formula 1.

Specific examples of the monomer represented by Chemical Formula 1-1 may include phenoxypolyoxyethylene acrylate, more specifically, 2-phenoxyethyl methacrylate (PHEMA).

The repeating unit represented by Chemical Formula 1 may be contained in an amount of 5 mol % or more and 40 mol % based on 100 mol % of the total repeating units contained in the alkali-developable binder resin or less than 40 mol%, 5 mol% or more than 5 mol% and 30 mol% or less than 30 mol%, 5 mol% or more than 5 mol% and 25 mol% or less than 25 mol% or 10 mol% or more and 25 mol% or less.

In Chemical Formula 2 to Chemical Formula 4, R ₃ and R ₄ are the same or different from each other and are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₅ is an alkyl group having 1 to 10 carbon atoms And Ar is an aryl group having 6 to 20 carbon atoms.

In Chemical Formula 2 to Chemical Formula 4, R ₃ and R ₄ are the same as or different from each other and may each independently be any one of hydrogen or an alkyl group having 1 to 10 carbon atoms, and having 1 to 10 carbon atoms Particular examples of alkyl groups can include methyl groups.

R ₅ is an alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group having 1 to 10 carbon atoms may include a methyl group.

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

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

[Chemical formula 2-1]

In Chemical Formula 2-1, R ₃ is hydrogen or an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 2-1, R ₃ is the same as described above for Chemical Formula 2. Specific examples of the monomer represented by Chemical Formula 2-1 may include methacrylic acid (MAA).

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

In Chemical Formula 3-1, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms and R ₅ is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 3-1, the contents of R ₄ and R ₅ are the same as described above for Chemical Formula 3. Specific examples of the monomer represented by Chemical Formula 3-1 may include methylmethacrylate (MMA).

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

In Chemical Formula 4-1, Ar is an aryl group having 6 to 20 carbon atoms. In Chemical Formula 4-1, the content of Ar is the same as that described above for Chemical Formula 4. Specific examples of the monomer represented by Chemical Formula 4-1 may include styrene (SM).

The alkaline developable binder resin may contain 20 mol % or more and 60 mol % or less, based on 100 mol % of the total repeating units contained in the alkali developable binder resin %, 20 mol% or greater than 20 mol% and 50 mol% or less than 50 mol% or 30 mol% or greater than 30 mol% and 40 mol% or less than 40 mol% by Chemical formula 2 Represents a repeating unit.

In addition, the alkaline developable binder resin may contain 1 mol % or more and 30 mol % or less based on 100 mol % of the total repeating units contained in the alkali developable binder resin 30 mol%, 1 mol% or greater than 1 mol% and 20 mol% or less than 20 mol% or 5 mol% or greater than 5 mol% and 30 mol% or less than 30 mol% The repeating unit represented by Chemical Formula 3, and 30 mol % or more and 60 mol % or less, 30 mol % or more than 30 mol % and 50 mol % or less than 50 mol % % or 30 mol % or more and 40 mol % or less of the repeating unit represented by Chemical Formula 4.

More specifically, the molar ratio of the repeating unit represented by Chemical Formula 3 to 100 mol of the repeating unit represented by Chemical Formula 4 may be 10 mol or more and 99 mol or less, 15 mol or more. Ear or greater than 15 moles and 95 moles or less than 95 moles, 20 moles or greater than 20 moles and 95 moles or less than 95 moles, 10 moles or greater than 10 moles and 50 moles or less than 50 moles Ear, 10 moles or more and 40 moles or less than 40 moles or 10 moles or more and 30 moles or less.

Thus, due to the hydrophobicity of the repeating unit represented by Chemical Formula 4 The content increases, and the hydrophobicity of the alkali-developable binder resin also increases, thereby suppressing the generation of foam in the development process of the dry film type photoresist using the photosensitive resin composition.

The alkaline developable binder resin may have a weight average molecular weight of 30,000 g/mol or more and 150,000 g/mol or less and 20°C or more and 150°C or less Glass transition temperature of 150°C. Thereby, the coating characteristics and the followability of the dry film type photoresist and the mechanical strength of the resist itself after the circuit formation can be improved.

As used herein, weight average molecular weight refers to polystyrene converted weight average molecular weight as measured by gel permeation chromatography (GPC). In the process of measuring polystyrene-converted weight average molecular weight by GPC, detectors and analytical columns such as commonly known analytical equipment and differential refractive index detectors can be used, and commonly used The temperature conditions, solvents, and flow rates of the application.

Specific examples of measurement conditions are as follows. The alkaline developable binder resin was dissolved in tetrahydrofuran to have a concentration of 1.0 (w/w) % in THF (approximately 0.5 (w/w) % by solids), filtered using a 0.45 micron pore size syringe was filtered and then injected into GPC in an amount of 20 microliters, and tetrahydrofuran (THF) was used as the mobile phase of GPC and the flow rate was 1.0 mL/min. The column was configured with one Agilent Plagal 5-micron guard (7.5 x 50 mm) and two Agilent Plagal 5-micron Mixed D (7.5 x 300 mm) connected in series and stored at 40°C by using an Agilent The 1260 Infinity II system and RI detector perform the measurements.

Polystyrene standard samples (STD A, STD B, STD C, STD D) and then Inject into GPC and use a calibration curve to determine the value of the weight average molecular weight (Mw) of the alkaline developable binder resin.

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

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

STD C(MP): 126,000/4430/370

STD D(MP): 51,200/1920/162

The glass transition temperatures of the reference and binder polymers were compared by a Differential Scanning Calorimeter (DSC) (Perkin-Elmer, DSC-7). Measurements can be performed by maintaining the temperature at 20°C for 15 minutes and then increasing the temperature to 200°C at a rate of 1°C/minute.

Alkaline developable binder resins may have 120 mg KOH/gram or greater than 120 mg KOH/gram and 200 mg KOH/gram or less than 200 mg KOH/gram or 140 mg KOH/gram or greater than 140 mg KOH/gram and 160 mg Acid value of KOH/gram or less than 160 mg KOH/gram. Measure the acid value by the following procedure: sample about 1 gram of alkaline developable binder resin, dissolve it in 50 ml of mixed solvent (MeOH 20%, acetone 80%), add two drops of 1% phenolphthalein indicator to it, and The acid value was then measured by titration with 0.1N-KOH.

The alkali-developable binder resin is contained in an amount of 20 wt % or more and 80 wt % or less with respect to the total weight of the photosensitive resin composition in terms of solid content. When the content of the alkali-developable binder resin is within the above-mentioned range, it is possible to obtain the effect of enhancing the adhesion of fine lines after circuit formation. The solid content by weight means the remaining components excluding the solvent from the photosensitive resin composition.

The content of the alkaline developable binder resin of the present disclosure may be 40 wt % or more and 70 wt % relative to the total weight of the photosensitive resin composition % or less than 70% by weight. When the content of the alkali-developable binder resin is less than 40% by weight with respect to the total photosensitive resin composition, there is a disadvantage that defects such as short circuits are caused due to contamination in development, and when the content of the alkali-developable binder resin is When it exceeds 70 wt%, there are problems that circuit characteristics such as adhesion and resolution deteriorate.

Meanwhile, the alkali-developable binder resin may further include a repeating unit represented by the following Chemical Formula 13, a repeating unit represented by the following Chemical Formula 14, a repeating unit represented by the following Chemical Formula 15, a repeating unit represented by the following Chemical Formula 16, and A first alkali-developable binder resin comprising a repeating unit represented by the following Chemical Formula 17; and a second alkali-developable binder resin comprising a repeating unit represented by the following Chemical Formula 14, a repeating unit represented by the following Chemical Formula 15, and a repeating unit represented by the following Chemical Formula 16 Alkaline developable binder resin.

In Chemical Formula 13, R ₃ " is hydrogen,

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

In Chemical Formula 15, R ₄ " is an alkyl group having 1 to 10 carbon atoms, and R ₅ " is an alkyl group having 1 to 10 carbon atoms,

In Chemical Formula 16, _Ar is an aryl group having 6 to 20 carbon atoms,

And in Chemical Formula 17, R ₄ ' is hydrogen, and R ₅ ' is an alkyl group having 1 to 10 carbon atoms.

Specifically, the first alkali-developable binder resin may comprise the chemical formula A random copolymer of the repeating unit represented by Chemical Formula 13, the repeating unit represented by Chemical Formula 14, the repeating unit represented by Chemical Formula 15, the repeating unit represented by Chemical Formula 16, and the repeating unit represented by Chemical Formula 17.

In Chemical Formula 13 to Chemical Formula 17, specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group.

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

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

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

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

In Chemical Formula 15-1, R ₄ " is an alkyl group having 1 to 10 carbon atoms, and R ₅ " is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 15-1, the definitions of R ₄ " and R ₅ " are the same as described above for Chemical Formula 15. Specific examples of the monomer represented by Chemical Formula 15-1 may include methyl methacrylate (MMA).

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

In Chemical Formula 16-1, Ar is an aryl group having 6 to 20 carbon atoms. In Chemical Formula 16-1, the definition of Ar is the same as that described for Chemical Formula 16. Specific examples of the monomer represented by Chemical Formula 16-1 may include styrene (SM).

The first alkaline developable binder resin may have a weight average molecular weight of 30,000 g/mol or more and 150,000 g/mol or less and 20°C or more and 150°C or a glass transition temperature of less than 150°C. Thereby, the coating characteristics and traceability of the dry film type photoresist and the mechanical strength of the resist itself after circuit formation can be improved. Additionally, the first alkaline developable binder resin may have an acid value of 140 mg potassium hydroxide/gram or greater and 160 mg potassium hydroxide/gram or less.

In addition, the first alkaline developable binder resin may have a weight average molecular weight of 20,000 g/mol or more and 130,000 g/mol or less and 30°C or more and A glass transition temperature of 160°C or less. As a result, the coating characteristics and traceability of the dry film photoresist can be improved to and the mechanical strength of the resist itself after the circuit is formed.

As used herein, weight average molecular weight refers to the polystyrene converted weight average molecular weight as measured by gel permeation chromatography (GPC). In the process of measuring the weight average molecular weight of polystyrene conversion by GPC, detectors and analytical columns, such as commonly known analytical equipment and differential refractive index detectors, can be used, and commonly applied temperature conditions, solvents, and flow rates.

Specific examples of measurement conditions are as follows. The alkaline developable binder resin was dissolved in tetrahydrofuran to have a concentration of 1.0 (w/w) % in THF (approximately 0.5 (w/w) % by solids), filtered using a 0.45 micron pore size syringe was filtered and then injected into GPC in an amount of 20 microliters, and tetrahydrofuran (THF) was used as the mobile phase of the GPC and the flow rate was 1.0 ml/min. The column was configured with one Agilent Plagal 5 micron guard (7.5 x 50 mm) and two Agilent Plagal 5 micron Mixed D (7.5 x 300 mm) connected in series, and was heated at 40°C by using an Agilent 1260 Infinity II The system and the RI detector perform the measurements.

Polystyrene standard samples (STD A, STD B, STD C, STD D) and then injected into GPC, and the value of the weight average molecular weight (Mw) of the alkaline developable binder resin was determined using a calibration curve.

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): 51,200/1920/162

by Differential Scanning Calorimeter (DSC) (PerkinElmer, DSC-7) Compare the glass transition temperature of the reference to the binder polymer. Measurements can be performed by maintaining the temperature at 20°C for 15 minutes and then increasing the temperature to 200°C at a rate of 1°C/minute.

The acid value of the alkali-developable adhesive resin was measured by the following process: sample about 1 gram of the alkali-developable adhesive resin, dissolve it in 50 ml of mixed solvent (MeOH 20%, acetone 80%), add two 1% phenolphthalein indicator was dropped, and then the acid value was measured by titration with 0.1N-KOH.

The first alkaline developable binder resin may have an acid value of 140 mg potassium hydroxide/gram or greater and 160 mg potassium hydroxide/gram or less. Additionally, the second alkaline developable binder resin may have an acid value of 160 mg potassium hydroxide/gram or greater and 200 mg potassium hydroxide/gram or less.

Specifically, the ratio of the glass transition temperature of the first alkaline developable binder resin to the second alkaline developable binder resin may be 1:1.5 or more and 1:5 or less than 1:5, 1 : 1.5 or more than 1: 1.5 and 1: 3 or less than 1: 3, 1: 1.5 or more than 1: 1.5 and 1: 2 or less than 1: 2, 1: 1.5 or more than 1: 1.5 and 1: 1.8 or less than 1 : 1.8, 1:1.5 or greater than 1:1.5 and 1:1.75 or less than 1:1.75 or 1:1.5 or greater than 1:1.5 and 1:1.6 or less than 1:1.6.

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

Meanwhile, the first alkali-developable binder resin contained in the photosensitive resin composition of one embodiment may contain a repeating unit represented by Formula 3 with respect to 1 mole 1.2 moles or greater than 1.2 and 3 moles or less, 1.2 moles or greater than 1.2 moles and 2 moles or less, 1.5 moles or greater than 1.5 moles and 2 moles or less Molar or 1.5 mol or more and 1.6 mol or less of the repeating unit represented by Chemical Formula 4.

In addition, the second alkali-developable binder resin contained in the photosensitive resin composition of one embodiment may be 2 mol or more and 10 mol or more of the repeating unit represented by Chemical Formula 17 with respect to 1 mol. less than 10 moles, 3 moles or greater than 3 moles and 10 moles or less than 10 moles, 3 moles or greater than 3 moles and 5 moles or less than 5 moles or 4 moles or greater than 4 moles and The amount of 5 mol or less includes the repeating unit represented by Chemical Formula 15.

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

In Chemical Formula 14, R ₃ ′ is an alkyl group having 1 to 10 carbon atoms.

In Chemical Formula 15, R ₄ " is an alkyl group having 1 to 10 carbon atoms, and R ₅ " is an alkyl group having 1 to 10 carbon atoms,

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

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

In Chemical Formula 14-1, R ₃ " is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 14-1, the definition of R ₃ " is the same as that described for Chemical Formula 14. Specific examples of the monomer represented by Chemical Formula 14-1 may include methacrylic acid (MAA).

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

In Chemical Formula 15-1, R ₄ " is an alkyl group having 1 to 10 carbon atoms, and R ₅ " is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 15-1, the definitions of R ₄ " and R ₅ " are the same as described for Chemical Formula 15. Specific examples of the monomer represented by Chemical Formula 15-1 may include methyl methacrylate (MMA).

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

In Chemical Formula 16-1, Ar is an aryl group having 6 to 20 carbon atoms. In Chemical Formula 16-1, the definition of Ar is the same as that described for Chemical Formula 16. Specific examples of the monomer represented by Chemical Formula 16-1 may include styrene (SM).

Specifically, the first alkali developable binder resin may be 1:(2 or more and 5 or less than 5):(0.2 or more and 0.9 or less than 0.9), 1:(2 or more and 3 or Less than 3): (0.5 or greater than 0.5 and 0.9 or less than 0.9), 1: (2.5 or greater than 2.5 and 3 or less than 3): (0.6 or greater than 0.6 and 0.9 or less than 0.9) or 1: (2.75 or greater than 2.75 and 3 or less than 3): The ratio of (0.6 or more and 0.75 or less than 0.75) includes the repeating unit represented by Chemical Formula 14: the repeating unit represented by Chemical Formula 15: the repeating unit represented by Chemical Formula 16.

In addition, the second alkali developable binder resin may be 1:(1.1 or more and 2 or less than 2):(0.2 or more and 0.99 or less than 0.99), 1:(1.5 or more and 2 or less than 2 ): (0.5 or more and 0.99 or less than 0.99) or 1: (1.5 or more and 1.75 or less than 1.75): (0.75 or more and 0.99 or less than 0.99) at a ratio including the repeating unit represented by Chemical Formula 14: By Hua Repeating unit represented by Chemical Formula 15: The repeating unit represented by Chemical Formula 16.

Meanwhile, based on 100 parts by weight of the first alkali-developable binder resin, the photosensitive resin composition of one embodiment of the present disclosure may include 500 parts by weight or more and 1000 parts by weight or less than 1000 parts by weight, 600 parts by weight or more and 800 parts by weight or less of the second alkaline developable binder resin.

As described above, since the second alkaline developable binder resin is added in an excessive amount of 500 parts by weight or more based on 100 parts by weight of the first alkaline developable binder resin, it is possible to achieve imparting The hydrophobic function of the photosensitive resin increases the resistance to the developer solution and the technical effect of improving the circuit characteristics.

(2) Photopolymerization initiator

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

Compounds that can be used as photopolymerization initiators can include anthraquinone derivatives such as 2-methylanthraquinone and 2-ethylanthraquinone; and benzoin derivatives such as benzoin methyl ether, benzophenone, phenanthraquinone and 4,4'-bis(dimethylamino)benzophenone.

In addition, from 2,2'-bis(2-chlorophenyl)-4,4'-5,5'-tetraphenylbisimidazole, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy -1,2-Diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-N-morpholinopropan-1-one, 2-benzyl yl-2-dimethylamino-1-[4-N-morpholinophenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4 ,6-Trimethylbenzyldiphenylphosphine oxide, 1-[4-(2-hydroxymethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, 2,4 -Diethylthioxanthone, 2-Chlorothioxanthone, 2,4-Dimethylthioxanthone, 3,3- Dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone, 1-(4-isopropylphenyl)-2-hydroxy-2- Methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-benzyl-4'-methyldimethyl Thioether, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4 -2-ethylhexyl dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzyl ketone dimethyl acetal Aldehyde, benzyl ketone β-methoxydiethyl acetal, 1-phenyl-1,2-propyldioxime-o,o'-(2-carbonyl)ethoxy ether, o-benzyl Methyl benzoate, bis[4-dimethylaminophenyl)ketone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, benzyl , benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, isobutoxybenzoin, tertiary butoxybenzoin, p-dimethylaminoacetophenone, p-tertiary benzoin Butyltrichloroacetophenone, p-tertiary butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, α,α - A compound selected from dichloro-4-phenoxyacetophenone and amyl 4-dimethylaminobenzoate can be used as a photopolymerization initiator, but is not limited thereto.

The photopolymerization initiator is contained in an amount of 1 wt % or more and 10 wt % or less with respect to the total weight of the photosensitive resin composition in terms of solid content. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity can be obtained. The solid content by weight means the remaining components excluding the solvent from the photosensitive resin composition.

When the content of the photopolymerization initiator is less than 1% by weight, light efficiency is low and a large amount of exposure must be applied, and thus there is a disadvantage that production efficiency is extremely lowered. When the content of the photopolymerization initiator exceeds 10% by weight, there is a problem that the film is brittle and the contamination of the developer solution increases, causing short-circuit or the like defects.

(3) Photopolymerizable compounds

The photopolymerizable compounds of the present disclosure have resistance to developer solutions after UV exposure and enable patterning.

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

As the alkylene glycol-based di(meth)acrylate, a compound represented by the following Chemical Formula 5 can be used.

In Chemical Formula 5, 1+n is an integer of 2 or 3, and m is an integer of 12 to 18.

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

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

If the content of the compound represented by Chemical Formula 5 is less than 10% by weight based on the total weight of the solid content of the photosensitive resin composition, the effect due to the addition of the compound represented by Chemical Formula 5 is insufficient, and if the content exceeds 60% by weight , it is possible There are problems that the hydrophobicity increases and the development time of the development process increases rapidly after exposure.

As the bisphenol-based di(meth)acrylate, ethylene oxide-containing bisphenol-based di(meth)acrylate can be used. Ethylene oxide-containing bisphenolic di(meth)acrylates may include bisphenolic di(meth)acrylates containing greater than 8 moles and 16 moles or less than 16 moles of ethylene oxide per molecule .

Examples of bisphenol-based di(meth)acrylates containing more than 8 moles and 16 moles or less of ethylene oxide may include those manufactured by Miwon Specialty Chemical Co., Ltd. Miramer M2100 (BPA(EO) ₁₀ DA, Bisphenol A(EO) ₁₀ Diacrylate), Miramer M2200 (BPA(EO) ₂₀ DA, Bisphenol A(EO) ₂₀ Diacrylate) and Miramer M2101 (Bisphenol A(EO) 20 Diacrylate) A(EO) ₁₀ dimethacrylate).

Meanwhile, the photopolymerizable compound may contain a trifunctional or higher polyfunctional (meth)acrylate compound.

The trifunctional or higher polyfunctional (meth)acrylate compound may have three or more alkylene oxide groups having 1 to 10 carbon atoms therein and three or more (meth)acrylates The functional group is bonded to a structure having a central group of 1 to 20 carbon atoms.

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

[Chemical formula 12]

In Chemical Formula 12, R ₁₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₁₅ is an alkylene group having 1 to 10 carbon atoms, and R ₁₆ is an alkylene group having 1 to 20 carbon atoms The p-valent functional group of the central group, n12 is an integer from 1 to 20 and p is the number of functional groups substituted for _R16 and is an integer from 3 to 10.

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

The monofunctional (meth)acrylate compound may contain a (meth)acrylate containing an alkylene oxide group having 1 to 10 carbon atoms.

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

In Chemical Formula 11, R ₁₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₁₂ is an alkylene group having 1 to 10 carbon atoms, and R ₁₃ is an alkylene group having 1 to 10 carbon atoms The alkyl group and n11 are integers from 1 to 20.

By including the monofunctional (meth)acrylate compound represented by Chemical Formula 11 and the trifunctional or higher polyfunctional (meth)acrylate compound represented by Chemical Formula 12, the circuit characteristics are equivalent to those of the existing product, But the photocuring speed is increased so that, for technical reasons of accelerating the color development time of the resulting film and increasing the amount of color change, the time required to change the contrast is increased, thereby ensuring excellent development characteristics.

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

Since the photosensitive resin composition of one embodiment contains the monofunctional (meth)acrylate compound represented by Chemical Formula 11, it is possible to realize a method of rapidly implementing the color change of the film in the exposed portion due to the technical reason of increasing the photocuring speed. Effect.

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

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

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

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

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

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

Since the photosensitive resin composition of one embodiment includes the trifunctional or higher polyfunctional (meth)acrylate compound represented by Chemical Formula 12, the trifunctional or higher polyfunctional (meth)acrylate compound represented by Chemical Formula 12 has a functional or higher polyfunctional The (meth)acrylate compound has increased crosslinking during photocuring, and the reactive group prevents the reduction of circuit characteristics due to various technical reasons and can achieve the effect of increasing the amount of color development change.

Meanwhile, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photosensitive resin composition of one embodiment may be 110 parts by weight or more and 500 parts by weight or less, 110 parts by weight or more 110 parts by weight and 300 parts by weight or less, 110 parts by weight or more and 200 parts by weight or less or 150 parts by weight or more and 200 parts by weight or less Contains trifunctional or higher polyfunctional (meth)acrylate compounds.

Since the photosensitive resin composition of one embodiment contains the trifunctional or higher polyfunctional (meth)acrylate compound in excess relative to the monofunctional (meth)acrylate compound, it is possible to simultaneously achieve an increase in the amount represented by Chemical Formula 11. The photo-curing speed of the monofunctional (meth)acrylate compound and thus the effect of rapidly implementing the color change of the film and the increase in cross-linking during photocuring of the trifunctional or higher polyfunctional (meth)acrylate compound represented by Chemical Formula 12 The effect of increasing the amount of color development change by increasing the amount of reactive groups can be combined and thus prevent the reduction in circuit characteristics that occurs when only the monofunctional material is added.

When the photosensitive resin composition of one embodiment contains less than 100 parts by weight of a trifunctional or higher polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound, there may be a circuit The technical problem is that the characteristics are deteriorated and the amount of color development change is reduced.

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

That is, the photosensitive resin composition of one embodiment includes a photopolymerizable compound, and the photopolymerizable compound may include a monofunctional (meth)acrylate compound, a trifunctional or higher polyfunctional (meth)acrylate compound, and a difunctional (meth)acrylate compound. Functional (meth)acrylate compounds.

Specifically, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photosensitive resin composition of one embodiment may be 500 parts by weight or more and 1500 parts by weight or less, 500 parts by weight or more than 500 parts by weight and 1000 parts by weight or less than 1000 parts by weight, 750 parts by weight or more than 750 parts by weight and 1000 parts by weight or less than 1000 parts by weight or 800 parts by weight or more than 800 parts by weight and 900 parts by weight or less than 900 parts by weight contains a difunctional (meth)acrylate compound.

That is, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photosensitive resin composition of one embodiment may contain 110 parts by weight or more of trifunctional or higher polyfunctional (meth)acrylic acid An ester compound and 500 parts by weight or more and 1500 parts by weight or less of a bifunctional (meth)acrylate compound.

In addition, the photosensitive resin composition of one embodiment may be 500 parts by weight or more and 1000 parts by weight or less, or 500 parts by weight or more and 800 parts by weight or less, 500 parts by weight or more and 750 parts by weight or less, 500 parts by weight or more and 700 parts by weight or less Difunctional (methyl) is contained in an amount of 700 parts by weight or 500 parts by weight or more and 600 parts by weight or less Acrylate compound.

As described above, since a monofunctional (meth)acrylate compound, a trifunctional or higher polyfunctional (meth)acrylate compound, and a bifunctional (meth)acrylate compound are contained while satisfying the above weight range, a The photosensitive resin composition of the embodiment can exhibit appropriate circuit characteristics, and when a light intensity of 10 mJ/cm 2 or more is applied, a technology capable of rapid color development and color change of an exposed portion can be realized Effect.

More specifically, based on 100 parts by weight of the bifunctional (meth)acrylate compound, the photosensitive resin composition of one embodiment may be 100 parts by weight or less, 50 parts by weight or less, 1 part by weight part by weight or more and 50 parts by weight or less or 1 part by weight or more and 100 parts by weight or less containing the monofunctional (meth)acrylate compound represented by Chemical Formula 11 and a trifunctional or higher polyfunctional (meth)acrylate compound represented by Chemical Formula 12.

The content of the photopolymerizable compound may be 10 wt % or more and 70 wt % or less with respect to the total weight of the photosensitive resin composition in terms of solid content. When the content of the photopolymerizable compound is within the above range, it is possible to obtain effects of enhancing photosensitivity, resolution, adhesion, and the like. The solid content by weight means the remaining components excluding the solvent from the photosensitive resin composition.

(4) Photosensitive resin composition

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

(1) Add the photosensitive resin layer sample containing the photosensitive resin composition to a container containing the developer solution with a cross-sectional diameter of 10 cm or more, so that the volume ratio of the photosensitive resin layer sample to the developer solution is 2 ×10 ^-5 m³/liter, the developer solution inside the container circulates at a rate of 1000 m³/min or more and 1200 m³/min or less, and the speed of the developer solution in the container is When spraying from the upper end, the interval of the height difference between the highest point of the foam generated in the container after the elapse of 60 minutes from the start of spraying the developer solution and the highest point of the developer solution in the container immediately after the start of spraying the developer solution is 80 mm or less than 80 mm, or (2) for a photosensitive resin layer sample containing a photosensitive resin composition and having a thickness of 5 microns or more and 30 microns or less than 30 microns, the axial force on the photosensitive resin layer sample is 5 N or Under the condition of less than 5 N, the minimum value of absolute viscosity obtained in the temperature range of 50 ℃ or greater than 50 ℃ and 125 ℃ or less than 125 ℃ is 300 Pa. seconds or less than 300 Pa. second.

Specifically, the photosensitive resin composition may have the following characteristics: a photosensitive resin layer sample containing the photosensitive resin composition is added to a container containing a developer solution having a cross-sectional diameter of 10 cm or more, so that the photosensitive resin layer sample is The volume ratio relative to the developer solution is 2×10 ^-5 cubic meters/liter, and the developer solution inside the container is 1000 cubic centimeters/min or more than 1000 cubic centimeters/min and 1200 cubic centimeters/min or less than 1200 cubic centimeters /min rate cycle, and when spraying at the upper end of the container, the highest point of the foam generated in the container after 60 minutes elapsed since the start of spraying the developer solution and the highest point of the developer solution in the container immediately after the start of spraying the developer solution The height difference between 80mm or less, 60mm or less than 60mm, 1mm or more than 1mm and 80mm or less than 80mm, 1mm or more than 1mm and 60mm or less, 10 mm or more than 10 mm and 60 mm or less than 60 mm, 20 mm or more than 20 mm and 60 mm or less than 60 mm or 40 mm or more than 40 mm and 60 mm or less than 60 mm.

Both the highest point of the foam generated in the container after 60 minutes elapsed since the start of spraying the developer solution and the highest point of the developer solution in the container just after the start of spraying the developer solution mean the vertical measured in the bottom of the container height, which is equal and parallel to the ground.

And, the interval of the height difference between the two points means subtracting the maximum height of the foam generated in the container after 60 minutes have elapsed since the start of spraying the developer solution minus the height of the developer solution in the container immediately after the start of spraying the developer solution. The value obtained for the maximum height.

Specifically, as an example of a method of measuring the interval of the height difference, a foam measuring device marked by a ruler as shown in FIG. 1 below can be used.

Add the photosensitive resin layer sample containing the photosensitive resin composition to the container containing the developer solution with a cross-sectional diameter of 10 cm or more, so that the volume ratio of the photosensitive resin layer sample to the developer solution is 2×10 ^-5 cubic meters/liter, the developer solution inside the container is circulated at a rate of 1000 cubic centimeters/min or more and 1200 cubic centimeters/min or less, and sprayed at the upper end of the container When 60 minutes elapsed since the start of spraying the developer solution, the interval of the height difference between the highest point of the foam generated in the container and the highest point of the developer solution in the container just after the start of spraying the developer solution excessively increased to more than 80 mm In the case of , it is dissolved in an alkaline solution by a saponification reaction in the developing process of dissolving the unexposed part. However, there is a problem that foam is generated during the dissolution reaction, and when excess foam is generated, the chamber overflows.

"Add the photosensitive resin layer sample containing the photosensitive resin composition to a container containing the developer solution with a cross-sectional diameter of 10 cm or more, so that the volume ratio of the photosensitive resin layer sample to the developer solution is 2 × 10 ^-5 cubic meters/liter, the developer solution inside the container is circulated at a rate of 1000 cubic centimeters/min or more and 1200 cubic centimeters/min or less, and sprayed at the upper end of the container When the height difference between the highest point of the foam generated in the container after the elapse of 60 minutes from the start of spraying the developer solution and the highest point of the developer solution in the container immediately after the start of spraying the developer solution is 80 mm or less mm" is considered to be because the photosensitive resin composition contains the repeating unit represented by Chemical Formula 1 and thus uses an alkali developable binder resin having an increased degree of hydrophobicity.

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

As the developer solution, an alkaline aqueous solution having a concentration of 0.1 wt % or more and 5 wt % or less than 5 wt % or 0.9 wt % or more and 1.1 wt % or less can be used. The pH of the alkaline aqueous solution may be in the range of 9 or more and 11 or less, and the temperature thereof may be adjusted according to the developing characteristics of the photosensitive resin layer. Specific examples of the alkaline aqueous solution may include an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, and an aqueous sodium hydroxide solution.

The developer solution may be contained in an amount of 5% or more and 50% or less or 10% or more and 50% or less of the total height of the container. Therefore, it may be sufficient to measure the height of the generated foam to be greater than the height of the developer solution.

In addition, the upper end point of the container for spraying the developer solution is different from the The interval of the height difference between the highest points of the solution in the container after the developer solution may be 30 cm or more and 55 cm or less.

Both the upper end point of the container where the developer solution is sprayed and the highest point of the solution in the container immediately after the start of spraying the developer solution mean the vertical height measured from the bottom of the container, which is equal parallel to the ground.

And, the interval of the height difference between the two points means a value obtained by subtracting the maximum height of the developer solution in the container immediately after the start of spraying the developer solution from the height of the upper end point of the container where the developer solution is sprayed.

Specifically, as an example of a method of measuring the interval of the height difference, a foam measuring device marked by a ruler as shown in FIG. 1 below can be used.

When the interval of the height difference between the upper end point of the container where the developer solution is sprayed and the highest point of the solution in the container just after the developer solution is started is excessively reduced to less than 30 cm, foam is excessively generated up to the upper end portion of the container, and Therefore, it can be difficult to compare differences in the degree of foam generation depending on the sample type.

When the interval of the height difference between the highest point of the container where the developer solution is sprayed and the highest point of the solution in the container just after the developer solution is started is excessively increased to more than 55 cm, the amount of foam generation is not sufficient, and thus it may be possible to It is difficult to compare differences in the degree of foam generation by sample type.

The photosensitive resin layer sample containing the photosensitive resin composition can be added to the container containing the developer solution with a cross-sectional diameter of 10 cm or more, so that the volume ratio of the photosensitive resin layer sample to the developer solution is 2×10 ^-5 m3/liter.

Under the condition that the volume ratio of the photosensitive resin layer sample to the developer solution satisfies 2×10 ⁻⁵ cubic meters/liter, the volume of the developer solution and the volume of the photosensitive resin layer sample can be changed and applied without limitation. Specifically, the thickness and cross-sectional area of the photosensitive resin layer sample can be changed and applied without limitation.

As described above, under the condition that the volume ratio of the photosensitive resin layer sample to the developer solution satisfies 2×10 ⁻⁵ cubic meters per liter, the volume of the developer solution and the volume of the photosensitive resin layer sample (thickness, cross-section area) is not limited. However, for example, the developer solution may be at, eg, 0.5 liters or more and 1.5 liters or less than 1.5 liters, 0.8 liters or more and 1.2 liters or less than 1.2 liters or 0.9 liters or more than 0.9 liters and 1.1 liters or Adjust freely within the range of less than 1.1 liters. In addition, the thickness of the photosensitive resin layer sample can be, for example, 0.01 microns or more and 1 mm or less, 1 micron or more and 100 microns or less than 100 microns or 30 microns or more than 30 microns and 50 microns or less freely adjustable within a range of 50 microns. In addition, the area of the photosensitive resin layer sample is the area of the cross section parallel to the ground, and may be, for example, 0.1 square meter or more and 1 square meter or less than 1 square meter or 0.4 square meter or more Adjust freely within the range of 0.4 square meters and 0.6 square meters or less than 0.6 square meters.

The developer circulation pump can be used to circulate the developer solution inside the container at a rate of 1000 cm3/min or more and 1200 cm3/min or less. That is, the developer solution inside the container is discharged through the nozzle of the lower end portion of the container during the operation of the developer circulation pump, passes through the developer circulation pump, moves to the upper end portion of the container and can be sprayed through the nozzle of the upper end portion of the container.

When circulating the developer solution, the circulating speed of the developer solution may be 1000 cm3/min or more and 1200 cm3/min or less. In addition, the circulating pressure of the developer solution may be 1 kgf/cm2 or more than 1kgf/cm2 and 10kgf/cm2 or less than 10kgf/cm2 or 4kgf/cm2 or more than 4kgf/cm2 and 6kgf/cm2 or less than 6 kgf/cm².

Various nozzles can be used without limitation under the condition that the circulation speed and circulation pressure are satisfied, and the circulation speed and circulation pressure can be applied to measure the highest point of foaming in the container after 60 minutes elapse from the start of spraying the developer solution The interval of the height difference between the highest points of the developer solution in the container after the start of spraying the developer solution.

The interval of the height difference between the highest point of the foam generated in the container after the elapse of 60 minutes from the start of spraying the developer solution and the highest point of the developer solution in the container immediately after the start of spraying the developer solution can be determined by visual inspection using a ruler To measure the shortest distance between two points. At this time, the maximum height at each of the highest point of the foam generated in the container after the elapse of 60 minutes from the start of spraying the developer solution and the highest point of the developer solution in the container immediately after the start of spraying the developer solution can mean The maximum height measured from the bottom of the container.

Meanwhile, for a photosensitive resin layer sample containing a photosensitive resin composition and having a thickness of 5 μm or more and 30 μm or less, under the condition that the axial force of the photosensitive resin layer sample is 5 N or less , the minimum value of the absolute viscosity obtained in the temperature range of 50 ℃ or greater than 50 ℃ and 125 ℃ or less than 125 ℃ may be 300 Pa. seconds or less than 300 Pa. seconds, 100 Pa. seconds or less than 100 Pa. seconds, 1 Pa. seconds or greater than 1 Pa. seconds and 300 Pa. seconds or less than 300 Pa. seconds, 1 Pa. seconds or greater than 1 Pa. seconds and 100 Pa. seconds or less than 100 Pa. seconds or 5 Pa. seconds or greater than 5 Pa. Seconds and 280 Pa. seconds or less than 280 Pa. second.

An example of a method of measuring absolute viscosity may be a viscometric device, and the viscosity An example of a measurement device may be the DHR-2 (TA Instruments).

Observe the specific absolute viscosity measurement conditions, the viscosity can be 5°C/min or more than 5°C/min and 15°C/min or less than 15°C/min in the temperature range of 50°C or more and 125°C or less than 125°C. min or 8°C/min or more than 8°C/min and 12°C/min or less than 12°C/min heating rate measurement. That is, at 5°C/min or more than 5°C/min and 15°C/min or less than 15°C/min or 8°C/min or more than 8°C/min and 12°C/min or less than 12°C/min The heating rate increases the temperature from 50°C to 125°C while measuring the viscosity. An example of a specific method for maintaining the temperature rising rate is not particularly limited, and various methods known in the art can be used without limitation.

In addition, in which 5 liters/min or more and 15 liters/min or less than 15 liters/min or 8 liters/min or more than 8 liters/min and 12 liters/min or less Absolute viscosity was measured under the condition of rate of nitrogen injection. An example of a specific method for injecting nitrogen gas is not particularly limited, and various methods known in the art can be used without limitation.

Additionally, absolute viscosity can be measured at shear rates of 1 1/sec or greater and 3 1/sec or less. If the shear rate is excessively increased to more than 3 1/sec, there is a limit for forcing the use of a flow type viscometer and it is difficult to measure the viscosity.

In addition, when the axial force of the photosensitive resin layer sample is 5N or less, 3N or less than 3N, -5N or more than -5N and 5N or less than 5N, -3N or more than -3N And 3N or less than 3N or -1N or more than -1N and 1N or less than 1N, the absolute viscosity can be measured. Axial force refers to the normal when the force in the form of proof stress in any vertical part is decomposed into the normal component and the tangential component of the cross section under the load applied to the photosensitive resin layer sample Quantity of force. That is, the axial force is one of the cross-sectional forces acting on the cross-section of the component, and can mean acting on the surface The center of the face and the force acting in the axial direction.

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

For a photosensitive resin layer sample containing a photosensitive resin composition and having a thickness of 5 μm or more and 30 μm or less than 30 μm, under the condition that the axial force of the photosensitive resin layer sample is 5 N or less, The minimum value of absolute viscosity obtained in the temperature range of 50 ℃ or more and 125 ℃ or less than 125 ℃ excessively increased to more than 300 Pa. seconds or less than 300 Pa. In the case of seconds, it becomes difficult to sufficiently reduce the viscosity at the thermal adhesion temperature when thermally adhering the dry film photoresist to a substrate applied to a circuit board or a display device, which may cause a problem of reduced adhesion to the substrate.

"For a photosensitive resin layer sample containing a photosensitive resin composition and having a thickness of 5 μm or more and 30 μm or less The minimum value of the absolute viscosity obtained in the temperature range of 50°C or more and 125°C or less under the condition of And therefore an alkali developable binder resin with an increased degree of hydrophobicity is used.

Meanwhile, the temperature at which the minimum value of the absolute viscosity is obtained may be 110°C or more and 123°C or less than 123°C or 110°C or more than 110°C and less than 116°C. For the photosensitive resin composition of one embodiment, the minimum value of absolute viscosity can be obtained around 110°C, which is the temperature for thermally adhering the dry film type photoresist to a circuit board or display device applied to a circuit board or a display device before reaching the curing temperature. Thermal bonding temperature of the substrate. Thus, it is possible to thermally adhere the dry film type photoresist to a substrate applied to a circuit board or a display device via The low viscosity at the thermal bonding temperature increases the adhesion to the substrate.

Specifically, the curing temperature of the photosensitive resin layer sample may be 115°C or more and 125°C or less or 116°C or more and 125°C or less. Therefore, the photosensitive resin composition of one embodiment does not continue to be cured at around 110° C., which is the thermal adhesion temperature when the dry film photoresist is thermally adhered to a substrate applied to a circuit board or a display device , thereby increasing the adhesion to the substrate.

Specifically, for the photosensitive resin layer sample, the absolute viscosity value at a temperature of 110 ° C can be 5 Pa. seconds or greater than 5 Pa. seconds and 400 Pa. seconds or less than 400 Pa. second.

In terms of solid content, the photosensitive resin composition may comprise 20 wt % or more and 80 wt % or less of an alkali developable binder resin, 1 wt % or more and 10 wt % or Less than 10% by weight of the photopolymerization initiator and 10% by weight or more and 70% by weight or less of the photopolymerizable compound.

The photosensitive resin composition may further contain a solvent. The solvent is generally selected from methyl ethyl ketone (MEK), methanol, THF, toluene and acetone and is not particularly limited, and its content can also be determined according to the photopolymerization initiator, alkaline developable adhesive The content of the resin and the photopolymerizable compound is adjusted.

In addition, the photosensitive resin composition may further contain other additives as necessary. Other additives are plasticizers and may contain dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diallyl phthalate in the form of phthalates ; triethylene glycol diacetate and tetraethylene glycol diacetate in the form of glycol esters; p-toluenesulfonamide, benzenesulfonamide and n-butylbenzenesulfonamide in the form of acid amides; Triphenyl phosphate, etc.

In the present disclosure, leuco dyes or coloring materials may be added to improve the handling characteristics of the photosensitive resin composition. Examples of leuco dyes include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, and fluorane dyes. Among them, when leuco crystal violet is used, the contrast ratio is good, which is preferable. When the leuco dye is contained, the content based on the photosensitive resin composition may be 0.1% by weight or more and 10% by weight or less. From the viewpoint of exhibiting contrast, 0.1% by weight or more is preferable, and from the viewpoint of maintaining storage stability, 10% by weight or less is preferable.

Examples of the coloring material may include toluenesulfonic acid monohydrate, magenta, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile blue 2B, victoria blue blue), malachite green, diamond green, basic blue 20 and the like. When the coloring material is included, the added amount may be 0.001 wt % or more and 1 wt % or less based on the photosensitive resin composition. When the content is 0.001% by weight or more, it has the effect of improving handleability, and when the content is 1% by weight or less, it has the effect of maintaining storage stability.

In addition, other additives may further include thermal polymerization inhibitors, dyes, discoloration agents and adhesion accelerators.

2. Dry film photoresist

According to another embodiment of the present disclosure, a dry film photoresist can be provided, including a photosensitive resin layer including the photosensitive resin composition of one embodiment. Details about the photosensitive resin composition include all the content described above in one embodiment.

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

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

The dry film photoresist may further include a substrate film and a protective film. The substrate film acts as a support for the photosensitive resin layer during manufacture of the dry film photoresist and facilitates handling during exposure of the photosensitive resin layer with adhesive strength.

Various plastic films can be used as the substrate film, and examples thereof can include at least one plastic film selected from the group consisting of: acrylic film, polyethylene terephthalate (PET) film, triacetate Cellulose (triacetylcellulose; TAC) film, polynorbornene (polynorbornene; PNB) film, cycloolefin polymer (cycloolefin polymer; COP) film and polycarbonate (polycarbonate; PC) film. The thickness of the substrate film is not particularly limited, and, for example, it can be freely adjusted within a range of 0.01 μm to 1 mm.

The protective film prevents damage to the resist during processing and serves as a protective cover to protect the photosensitive resin layer from foreign substances such as dust, and is laminated on the backside of the photosensitive resin layer on which the substrate film is not formed. The protective film is used to protect the photosensitive resin layer from external influences. When the dry film photoresist is applied to the back end process, it needs to be easily released and it needs to have proper separation and adhesion so that it does not deform during storage and distribution.

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

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

(1) Add the photosensitive resin layer sample containing the photosensitive resin composition to a container containing the developer solution with a cross-sectional diameter of 10 cm or more, so that the volume ratio of the photosensitive resin layer sample to the developer solution is 2 ×10 ^-5 m³/liter, the developer solution inside the container circulates at a rate of 1000 m³/min or more and 1200 m³/min or less, and the speed of the developer solution in the container is When spraying from the upper end, the interval of the height difference between the highest point of the foam generated in the container after the elapse of 60 minutes from the start of spraying the developer solution and the highest point of the developer solution in the container immediately after the start of spraying the developer solution is 80 mm or less than 80 mm, or (2) the photosensitive resin composition layer is characterized in that, for a photosensitive resin layer sample having a thickness of 5 microns or more and 30 microns or less than 30 microns, the axial force in the photosensitive resin layer sample is Under the condition of 5 N or less than 5 N, the minimum value of absolute viscosity obtained in the temperature range of 50 ℃ or greater than 50 ℃ and 125 ℃ or less than 125 ℃ is 300 Pa. seconds or less than 300 Pa. second.

Specifically, the dry film type photoresist may have the following characteristics: adding a photosensitive resin layer sample containing a photosensitive resin composition to a container containing a developer solution with a cross-sectional diameter of 10 cm or more, so that the photosensitive resin layer is The volume ratio of the sample to the developer solution is 2×10 ^-5 cubic meters per liter, and the developer solution inside the container is 1000 cubic centimeters per minute or more and 1200 cubic centimeters per minute or less than 1200 cubic meters per minute. The rate of cm/min is cycled, and when spraying at the upper end of the container, the highest point of the foam generated in the container after 60 minutes elapses since the start of spraying the developer solution and the highest point of the developer solution in the container just after the start of spraying the developer solution The height difference between can be 80mm or less, 60mm or less than 60mm or 1mm or more than 1mm and 80mm or less, 1mm or more than 1mm and 60mm or less than 60mm , 10mm or more and 60mm or less, 20mm or more than 20mm and 60mm or less than 60mm or 40mm or more than 40mm and 60mm or less.

Both the highest point of the foam generated in the container after 60 minutes elapsed since the start of spraying the developer solution and the highest point of the developer solution in the container just after the start of spraying the developer solution mean the vertical measured in the bottom of the container height, which is equal and parallel to the ground.

And, the interval of the height difference between the two points means subtracting the maximum height of the foam generated in the container after 60 minutes have elapsed since the start of spraying the developer solution minus the height of the developer solution in the container immediately after the start of spraying the developer solution. The value obtained for the maximum height.

Specifically, as an example of a method of measuring the interval of the height difference, a foam measuring device marked by a ruler as shown in FIG. 1 below can be used.

Add the photosensitive resin layer sample containing the photosensitive resin composition to the container containing the developer solution with a cross-sectional diameter of 10 cm or more, so that the volume ratio of the photosensitive resin layer sample to the developer solution is 2×10 ^-5 cubic meters/liter, the developer solution inside the container is circulated at a rate of 1000 cubic centimeters/min or more and 1200 cubic centimeters/min or less, and sprayed at the upper end of the container When 60 minutes elapsed since the start of spraying the developer solution, the interval of the height difference between the highest point of the foam generated in the container and the highest point of the developer solution in the container just after the start of spraying the developer solution excessively increased to more than 80 mm In the case of , it is dissolved in an alkaline solution by a saponification reaction in the developing process of dissolving the unexposed part. However, there is a problem that foam is generated during the dissolution reaction, and when excess foam is generated, the chamber overflows.

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

As the developer solution, an alkaline aqueous solution having a concentration of 0.1 wt % or more and 5 wt % or less than 5 wt % or 0.9 wt % or more and 1.1 wt % or less can be used. The pH of the alkaline aqueous solution may be in the range of 9 or more and 11 or less, and the temperature thereof may be adjusted according to the developing characteristics of the photosensitive resin layer. Specific examples of the alkaline aqueous solution may include an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, and an aqueous sodium hydroxide solution.

The developer solution may be contained in an amount of 5% or more and 50% or less or 10% or more and 50% or less of the total height of the container. Therefore, it may be sufficient to measure the height of the generated foam higher than that of the developer solution.

In addition, the interval of the height difference between the upper end point of the container where the developer solution is sprayed and the highest point of the solution in the container immediately after starting to spray the developer solution may be 30 cm or more and 55 cm or less.

The upper end of the container for spraying the developer solution and the beginning of spraying the developer solution The highest point of the solution in the container after the liquid both means the vertical height measured from the bottom of the container, which is equally parallel to the ground.

And, the interval of the height difference between the two points means a value obtained by subtracting the maximum height of the developer solution in the container immediately after the start of spraying the developer solution from the height of the upper end point of the container where the developer solution is sprayed.

Specifically, as an example of a method of measuring the interval of the height difference, a foam measuring device marked by a ruler can be used as shown in FIG. 1 below.

When the interval of the height difference between the upper end point of the container where the developer solution is sprayed and the highest point of the solution in the container just after the developer solution is started is excessively reduced to less than 30 cm, foam is excessively generated up to the upper end portion of the container, and Therefore, it can be difficult to compare differences in the degree of foam generation depending on the sample type.

When the interval of the height difference between the upper end point of the container where the developer solution is sprayed and the highest point of the solution in the container immediately after starting to spray the developer solution is excessively increased to more than 55 cm, the amount of foam generation is not sufficient, and thus it may be possible to It is difficult to compare differences in the degree of foam generation by sample type.

The photosensitive resin layer sample containing the photosensitive resin composition can be added to the container containing the developer solution with a cross-sectional diameter of 10 cm or more, so that the volume ratio of the photosensitive resin layer sample to the developer solution is 2×10 ^-5 m3/liter.

Under the condition that the volume ratio of the photosensitive resin layer sample to the developer solution satisfies 2×10 ⁻⁵ cubic meters/liter, the volume of the developer solution and the volume of the photosensitive resin layer sample can be changed and applied without limitation. Specifically, the thickness and cross-sectional area of the photosensitive resin layer sample can be changed and applied without limitation.

As described above, under the condition that the volume ratio of the photosensitive resin layer sample to the developer solution satisfies 2×10 ⁻⁵ cubic meters per liter, the volume of the developer solution and the volume of the photosensitive resin layer sample (thickness, cross-section area) is not limited. However, for example, the developer solution may be at, eg, 0.5 liters or more and 1.5 liters or less than 1.5 liters, 0.8 liters or more and 1.2 liters or less than 1.2 liters or 0.9 liters or more than 0.9 liters and 1.1 liters or Adjust freely within the range of less than 1.1 liters. In addition, the thickness of the photosensitive resin layer sample can be, for example, 0.01 microns or more and 1 mm or less, 1 micron or more and 100 microns or less than 100 microns or 30 microns or more than 30 microns and 50 microns or less freely adjustable within a range of 50 microns. In addition, the area of the photosensitive resin layer sample is the area of the cross section parallel to the ground, and may be, for example, 0.1 square meter or more and 1 square meter or less than 1 square meter or 0.4 square meter or more Adjust freely within the range of 0.4 square meters and 0.6 square meters or less than 0.6 square meters.

The developer circulation pump can be used to circulate the developer solution inside the container at a rate of 1000 cm3/min or more and 1200 cm3/min or less. That is, the developer solution inside the container is discharged through the nozzle of the lower end portion of the container during the operation of the developer circulation pump, passes through the developer circulation pump, moves to the upper end portion of the container and can be sprayed through the nozzle of the upper end portion of the container.

When circulating the developer solution, the circulating speed of the developer solution may be 1000 cm3/min or more and 1200 cm3/min or less. In addition, the circulating pressure of the developer solution may be 1 kgf/cm2 or more and 10 kgf/cm2 or less or 4 kgf/cm2 or more force/cm² and 6kgf/cm² or less.

Various nozzles can be used without limitation under the condition that the circulation speed and circulation pressure are satisfied, and the circulation speed and circulation pressure can be applied to measure the highest point of foaming in the container after 60 minutes elapse from the start of spraying the developer solution The interval of the height difference between the highest points of the developer solution in the container after the start of spraying the developer solution.

The interval of the height difference between the highest point of the foam generated in the container after the elapse of 60 minutes from the start of spraying the developer solution and the highest point of the developer solution in the container immediately after the start of spraying the developer solution can be determined by visual inspection using a ruler To measure the shortest distance between two points. At this time, the maximum height at each of the highest point of the foam generated in the container after the elapse of 60 minutes from the start of spraying the developer solution and the highest point of the developer solution in the container immediately after the start of spraying the developer solution can mean The maximum height measured from the bottom of the container.

Meanwhile, the photosensitive resin layer contained in the dry film photoresist may have the following characteristics: for a photosensitive resin layer sample having a thickness of 5 μm or more and 30 μm or less than 30 μm, the axial force in the photosensitive resin layer sample Under the condition of 5 N or less than 5 N, the minimum value of absolute viscosity obtained in the temperature range of 50 ℃ or greater than 50 ℃ and 125 ℃ or less than 125 ℃ is 300 Pa. seconds or less than 300 Pa. seconds, 100 Pa. seconds or less than 100 Pa. seconds, 1 Pa. seconds or greater than 1 Pa. seconds and 300 Pa. seconds or less than 300 Pa. seconds, 1 Pa. seconds or greater than 1 Pa. seconds and 100 Pa. seconds or less than 100 Pa. seconds or 5 Pa. seconds or greater than 5 Pa. Seconds and 280 Pa. seconds or less than 280 Pa. second.

An example of a method of measuring absolute viscosity can be a viscometric device, and an example of a viscometric device can be the DHR-2 (TA Instruments).

Observe the specific absolute viscosity measurement conditions, the viscosity can be 5°C/min or more than 5°C/min and 15°C/min or less than 15°C/min or 8°C/min or more than 8°C/min and 12°C/min or less than 12°C/min heating rate measurement. That is, at 5°C/min or more than 5°C/min and 15°C/min or less than 15°C/min or 8°C/min or more than 8°C/min and 12°C/min or less than 12°C/min The heating rate increases the temperature from 50°C to 125°C while measuring the viscosity. An example of a specific method for maintaining the temperature rising rate is not particularly limited, and various methods known in the art can be used without limitation.

In addition, at a rate of 5 liters/min or greater than 5 liters/min and 15 liters/min or less than 15 liters/min or 8 liters/min or greater than 8 liters/min and 12 liters/min or less Absolute viscosity was measured under nitrogen injection. An example of a specific method for injecting nitrogen gas is not particularly limited, and various methods known in the art can be used without limitation.

Additionally, absolute viscosity can be measured at shear rates of 1 1/sec or greater and 3 1/sec or less. If the shear rate is excessively increased to more than 3 1/sec, it is difficult to measure on a flow viscometer and thus there is a limitation that it is difficult to measure the viscosity.

In addition, when the axial force of the photosensitive resin layer sample is 5N or less, 3N or less than 3N, -5N or more than -5N and 5N or less than 5N, -3N or more than -3N And 3N or less than 3N or -1N or more than -1N and 1N or less than 1N, the absolute viscosity can be measured. Axial force refers to the force of the normal component when the force generated in the form of yield stress in any vertical part is decomposed into the normal component and the tangential component of the cross section under the load applied to the photosensitive resin layer sample . That is, the axial force is one of the cross-sectional forces acting on the cross-section of the component, and can mean the force acting in the center of the surface and acting in the axial direction.

The thickness of the photosensitive resin layer sample for measuring absolute viscosity may be 5 microns or more and 30 microns or less. Thickness of photosensitive resin layer sample Or the cross-sectional area can be measured via optical microscopy.

In the case where the photosensitive resin layer contained in the dry film type photoresist is under the following conditions: For a photosensitive resin layer sample having a thickness of 5 μm or more and 30 μm or less, on the axis of the photosensitive resin layer sample Under the condition that the force is 5 N or less, the minimum value of absolute viscosity obtained in the temperature range of 50 ℃ or more and 125 ℃ or less than 125 ℃ excessively increased to more than 300 Pa. seconds or less than 300 Pa. In seconds, it becomes difficult to sufficiently reduce the viscosity at the thermal adhesion temperature when thermally adhering the dry film photoresist to a substrate applied to a circuit board or a display device, which may cause a problem of reduced adhesion to the substrate.

"The photosensitive resin layer contained in the dry film photoresist is sufficiently reduced to 300 Pa in the axial force of the photosensitive resin layer sample for the photosensitive resin layer sample having a thickness of 5 microns or more and 30 microns or less than 30 microns. .sec or less than 300 Pa.sec, under the condition of the minimum value of the absolute viscosity obtained in the temperature range of 50°C or more and 125°C or less than 125°C” is deemed to be due to the composition of the photosensitive resin The compound contains the repeating unit represented by Chemical Formula 1 and thus uses an alkali developable binder resin having an increased degree of hydrophobicity.

Meanwhile, the temperature at which the minimum value of the absolute viscosity is obtained may be 110°C or more and 123°C or less than 123°C or 110°C or more than 110°C and less than 116°C. For the photosensitive resin composition of one embodiment, the minimum value of absolute viscosity can be obtained around 110°C, which is the temperature for thermally adhering the dry film type photoresist to a circuit board or display device applied to a circuit board or a display device before reaching the curing temperature. Thermal bonding temperature of the substrate. Thus, it is possible to increase the adhesion to the substrate through the low viscosity at the thermal adhesion temperature when thermally adhering the dry film photoresist to the substrate applied to a circuit board or a display device.

Specifically, the curing temperature of the photosensitive resin layer sample may be 115° C. or more 115°C and 125°C or less than 125°C or 116°C or greater than 116°C and 125°C or less. Therefore, the photosensitive resin composition of one embodiment does not continue to be cured at around 110° C., which is the thermal adhesion temperature when the dry film photoresist is thermally adhered to a substrate applied to a circuit board or a display device , thereby increasing the adhesion to the substrate.

Specifically, for the photosensitive resin layer sample, the absolute viscosity value at a temperature of 110 ° C can be 5 Pa. seconds or greater than 5 Pa. seconds and 400 Pa. seconds or less than 400 Pa. second.

An example of a method of manufacturing a dry film type photoresist is not particularly limited, and for example, the photosensitive resin composition of one embodiment is coated on a conventional substrate film such as polyethylene terephthalate using a conventional coating method And then dried, and the upper surface of the dried photosensitive resin layer is laminated with a conventional protective film such as polyethylene to produce a dry film.

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

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

3. Photosensitive element

According to another embodiment of the present disclosure, a photosensitive element can be provided, which includes a polymer substrate and a photosensitive resin layer formed on the polymer substrate; and satisfies any one of the following (1) or (2).

(1) Add the photosensitive resin layer sample to a container containing the developer solution with a cross-sectional diameter of 10 cm or more, so that the volume ratio of the photosensitive resin layer sample to the developer solution is 2×10 ^-5 cubic cm Feet/liter, the developer solution inside the container circulates at a rate of 1000 cubic centimeters/min or more and 1200 cubic centimeters/min or less than 1200 cubic centimeters/min, and when sprayed at the upper end of the container, from the start The interval of the height difference between the highest point of the foam generated in the container after the elapse of 60 minutes from spraying the developer solution and the highest point of the developer solution in the container immediately after the start of spraying the developer solution is 80 mm or less, or ( 2) The photosensitive resin layer is characterized in that, for a photosensitive resin layer sample having a thickness of 5 μm or more and 30 μm or less, under the condition that the axial force of the photosensitive resin layer sample is 5 N or less Under 50 ℃ or more than 50 ℃ and 125 ℃ or less than the temperature range of 125 ℃, the minimum value of the absolute viscosity obtained is 300 Pa. seconds or less than 300 Pa. second.

Specifically, the dry film type photoresist may have the following characteristics: adding a photosensitive resin layer sample to a container containing a developer solution with a cross-sectional diameter of 10 cm or more, so that the photosensitive resin layer sample is relative to the developer solution The volume ratio is 2× ^10-5 m3/L, and the developer solution inside the container is circulated at a rate of 1000 m3/min or more and 1200 m3/min or less than 1200 m3/min , and when spraying at the upper end of the container, the height difference between the highest point of the foam generated in the container after the elapse of 60 minutes since the start of spraying the developer solution and the highest point of the developer solution in the container just after the start of spraying the developer solution Spacing may be 80mm or less, 60mm or less, 1mm or more and 80mm or less, 1mm or more and 60mm or less, 10mm or more than 10mm mm and 60 mm or less than 60 mm, 20 mm or more than 20 mm and 60 mm or less than 60 mm or 40 mm or more than 40 mm and 60 mm or less than 60 mm.

Regarding "Add the photosensitive resin layer sample containing the photosensitive resin composition to the container containing the developer solution with a cross-sectional diameter of 10 cm or more, so that the volume ratio of the photosensitive resin layer sample to the developer solution is 2× 10 ^-5 cubic meters per liter, the developer solution inside the container circulates at a rate of 1000 cubic centimeters per minute or more and 1200 cubic centimeters per minute or less, and at the upper end of the container When spraying, the interval of the height difference between the highest point of the foam generated in the container after the elapse of 60 minutes from the start of spraying the developer solution and the highest point of the developer solution in the container immediately after the start of spraying the developer solution" details include the above Everything described herein in one embodiment and another. That is, the photosensitive resin layer may include: an alkali developable binder resin including a repeating unit represented by Chemical Formula 1; a repeating unit represented by Chemical Formula 2; a repeating unit represented by Chemical Formula 3; and a repeating unit represented by Chemical Formula 4 unit; and a photopolymerizable compound.

The thickness of the photosensitive resin layer may have the following characteristics: for a photosensitive resin layer having a thickness of 5 microns or more and 30 microns or less than 30 microns, the axial force of the photosensitive resin layer sample is 5 N or less under the condition of 5 N The minimum value of the absolute viscosity obtained in the temperature range of 50 ℃ or more and 125 ℃ or less than 125 ℃ may be 300 Pa. seconds or less than 300 Pa. second.

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

Regarding the inclusion of the repeating unit represented by the chemical formula 1; represented by the chemical formula 2 The repeating unit of ; the repeating unit represented by Chemical Formula 3; and the alkali developable binder resin of the repeating unit represented by Chemical Formula 4;

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

A specific example of the polymer substrate may be a polyester film, wherein the release layer is a surface of which is coated with a coating solution containing a binder resin and organic particles by uniaxially stretching an unstretched polyester film Formed by a tandem coating method that stretches the remainder uniaxially.

Polymer substrates are typically fabricated by an inline coating method instead of adding a release agent (generally added to take into account flowability and winding properties during fabrication), and have a layer of organic particles using alternative particles that do not compromise transparency.

Here, examples of organic particles used as particles that do not impair transparency while considering fluidity and winding properties may include organic particles such as multilayer multicomponent particles, which are formed such as methyl methacrylate, methacrylic acid Acrylic particles of ethyl ester, isobutyl methacrylate, n-butyl methacrylate, n-butyl methacrylate, acrylic acid, methacrylic acid copolymer or terpolymer; such as polyethylene, polystyrene Or olefinic particles of polypropylene; acrylic and olefinic copolymers; or homopolymer particles and then another type of monomer is coated on the layer.

a2+b2定義。且，六面體中的頂點之間具有最長距離的軸(f)與除a軸及b軸以外的c軸之間的關係由f2

c2+a2+b2定義。粒子的形狀應為球形的，其關於流動性為較佳的。 These organic particles should be specifically spherical and also have a difference in refractive index from the binder resin. Here, "spherical" means that the ratio of the short axis (a) to the long axis (b) in the ellipse is 0.5<a/b<2, and the relationship with the diagonal (d) in the rectangle is given by d2

a2+b2 definition. Also, the relationship between the axis (f) having the longest distance between the vertices of the hexahedron and the c-axis other than the a-axis and the b-axis is given by f2

c2+a2+b2 definition. The shape of the particles should be spherical, which is preferable with regard to flowability.

And, it is characterized in that the difference in refractive index between the organic particles and the binder resin is 0.05 or less. When the difference in refractive index is greater than 0.05, the haze increases. This means that there is a large amount of scattered light, and when there is a large amount of such scattered light, the sidewall smoothing effect is reduced. This also depends on the size and amount of organic particles. Preferably, the organic particles have an average particle size of about 0.5 microns to 5 microns. When it is smaller than this particle size, fluidity and winding characteristics are deteriorated, and when it is larger than 5 micrometers, haze increases, which is unfavorable in view of the occurrence of drop problems. The content of the organic particles is preferably 1 wt % to 10 wt % based on the total amount of the binder resin.

When the content of the organic particles is less than 1% by weight based on the total amount of the binder resin, the anti-blocking effect is insufficient and easily affected by scratches, and the fluidity and winding properties are deteriorated, and when it exceeds 10% by weight, there may be There are problems of increased haze and cracked transparency properties.

Meanwhile, in addition to the above-mentioned organic particles, inorganic particles may also be added. At this time, it is not inclined to increase the common inorganic anti-blocking agent, and it is preferable to increase the colloidal silica with a particle size of 100 nm or less. Based on 100 parts by weight of the binder resin, its content is preferably 10 parts by weight or less. When the particle sizes and contents as described above are satisfied, it is possible to prevent sidewall defects or grooves, such as pits caused by the release layer, from occurring when patterning using a dry film type photoresist.

As a function for coating such organic particles on unstretched polyester film The binder resin of the adhesive, so it is possible to use a binder resin with excellent compatibility with organic particles. Examples of such resins may include acrylic resins such as unsaturated polyester, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, n-butyl methacrylate Ester, acrylic, methacrylic copolymers or terpolymers; urethane-based resins; epoxy-based resins; or melamine-based resins and the like, and acrylic resins are preferred.

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

As described above, an unstretched polyester film obtained by melt-extruding PET pellets was uniaxially stretched, and then a coating solution containing organic particles in a binder resin was coated on the uniaxially stretched on the stretched membrane. Coating can be performed on at least one side of the uniaxially stretched film, and preferably has a thickness of about 30 nm to 200 nm in terms of thickness after final drying. If a coating solution containing organic particles is applied to a uniaxially stretched film with a thickness of more than 30 nm, there are problems that the organic particles are easily detached and easily affected by scratches and white powder is generated. When the coating thickness is greater than 200 nm, coating streaks are generated in the coating direction in the tandem coating with high coating speed due to the increased viscosity of the coating solution.

The polymer substrate obtained by coating with organic particles other than the general release agent by the tandem coating method as described above is a substrate film that maintains fluidity and winding characteristics due to the particle layer, and has excellent The light transmittance of organic particles has excellent transparency.

Since the lamination of the photosensitive resin layer is performed on the opposite surface of the organic particle-containing layer in the polymer substrate, the photosensitive resin layer is formed on the opposite surface of the organic particle-containing layer in this way. Therefore, there is no presence in the substrate film containing the release agent Pit-like defects during lamination as previously described. Since particles such as silica are not only larger in size than organic particles, but are also distributed throughout the substrate film, the effect of silica does not seem to be significant even in regions adjacent to the photosensitive resin layer.

On the other hand, in the polymer substrate used in the present disclosure, the organic particles have a size of 0.5 micrometers to 5 micrometers, and the organic particle layer is not adjacent to the photosensitive resin layer, so that the physical function of the organic particles is not affected. In addition, by using organic particles with excellent light transmittance, sidewall defects can be reduced without impairing other circuit characteristics.

The photosensitive element may further include a protective film formed on the photosensitive resin layer. The protective film prevents damage to the photosensitive resin layer during handling, and serves as a protective cover to protect the photosensitive resin layer from foreign substances such as dust. A protective film is laminated on the back side of the photosensitive resin layer on which the polymer substrate is not formed. The protective film is used to protect the photosensitive resin layer from external influences. When the dry film photoresist is applied to the back end process, it needs to be easily released and it needs to have proper separation and adhesion so that it does not deform during storage and distribution.

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

4. Circuit board, display device

According to another embodiment of the present disclosure, a circuit board or a display device can be provided, including a photosensitive resin layer including the photosensitive resin composition of one embodiment. Details about the photosensitive resin composition include all of the above described in one embodiment Allow.

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

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

Examples of the method of forming the patterned photosensitive resin layer include a method of laminating the photosensitive resin layer of the dry film photoresist of another embodiment on a substrate and then performing exposure and development. In addition, a method of laminating a photosensitive resin layer of a photosensitive element according to another embodiment to a substrate and then performing exposure and development can be mentioned.

As substrates, copper clad laminates, glass substrates on which transparent electrodes such as ITO and IZO are sputtered or deposited, similar film substrates, glass substrates coated with dielectric paste, silicon wafers, on which non-contact electrodes are deposited Glass wafers of crystalline silicon, silicon wafers sputtered with metal films such as copper, tantalum, molybdenum, and the like.

For the exposure process, UV, visible light, lasers are preferably used, and especially lasers containing light with a wavelength of 350 nm to 410 nm, specifically i-line (365 nm) or h-line (405 nm) Direct exposure machine. In the case of using a laser direct exposure machine, when using a normal lamp exposure machine with an exposure energy of 3 mJ/cm2 to 15 mJ/cm2, there is a possibility that the exposure energy is 20 mJ/cm2. /cm² or less than 20mJ/cm². Therefore, it is suitable for generating images of PCBs, leadframes, PDPs and other display devices.

The developing process can be performed by a dipping method, a showering method, a spraying method, a brushing method, or the like. As the developer solution, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines can be used.

When the dry film photoresist or photosensitive element of another embodiment is on the photosensitive resin layer With the protective film, the process of removing the protective film may be performed before the process of laminating the photosensitive resin layer on the circuit board or the substrate for manufacturing the display device.

In addition, when the dry film type photoresist or photosensitive element of another embodiment has a polymer substrate or a substrate film laminated on one side of the photosensitive resin layer, it may be further performed to remove the polymer substrate immediately after the exposure process or Process of substrate film.

Therefore, the photosensitive resin layer contained in the dry film photoresist or the photosensitive element of another embodiment can be included in a circuit board or a display device.

In addition, by using the dry film photoresist of the present disclosure, a circuit with a fine line width is formed through a conventional etching/plating process, and a PCB with a fine line width, as well as a lead frame, a PDP, and other display devices are formed through a known process. and maximizes yield when creating images on semiconductor devices.

Specifically, for example, by etching or plating the lower substrate exposed from the patterned photosensitive resin layer, conductor patterns, printed wiring boards, lead frames, ITO electrodes, black pads, semiconductor bumps, and the like can be manufactured. If necessary, after etching or electroplating, the patterned photosensitive resin layer may be peeled off from the substrate by an aqueous solution having a stronger alkalinity than the developer solution to be removed.

According to the present disclosure, it is possible to provide a photosensitive resin composition that can increase process efficiency by reducing the occurrence of foam in the developing process and the peeling process through the adhesive resin with increased hydrophobicity, and a dry film type photoresist, photosensitive resin composition using the same. Components, circuit boards and display devices.

Furthermore, according to the present disclosure, there can be provided a photosensitive resin composition having improved adhesion to substrates because it can have a sufficiently low viscosity so as not to be cured together with substrates applied to circuit boards or display devices near the thermal adhesion temperature and use Its dry film photoresist, circuit board and display device.

FIG. 1 shows an image of the foam measuring device used in Experimental Example 1. FIG.

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

The present disclosure will be described in more detail with the aid of the examples shown below. However, these examples are only given to illustrate the invention and are not intended to limit the scope of the invention thereto.

<Preparation Example and Comparative Preparation Example: Preparation of Alkaline Developable Binder Resin>

Preparation Example 1

The four-necked round bottom flask was equipped with a mechanical stirrer and a reflux device, and then the interior of the flask was purged with nitrogen. 68 grams of methyl ethyl ketone (MEK) and 5 grams of methanol (MeOH) were added to a nitrogen purged flask, and then 0.9 grams of azobisisobutyronitrile (AIBN) was added and dissolved completely. To this was added a monomer mixture of 24 grams of methacrylic acid (MAA), 6 grams of methyl methacrylate (MMA), 30 grams of styrene (SM), and 40 grams of 2-phenoxyethyl methacrylate (PHEMA) As a monomer, heated up to 80°C, and then polymerized for 6 hours to prepare an alkaline developable binder resin (weight average molecular weight: 65,000 g/mol, glass transition temperature: 98°C, solid content: 47.3 wt%, acid value : 157 mg potassium hydroxide/g).

Dissolving the alkaline developable binder resin prepared in the above preparation example in tetrahydrofuran to have a concentration of 1.0 (w/w) % in THF (approximately 0.5 (w/w) % based on solids), and filtered using a 0.45 micron pore size syringe filter, followed by 20 micron A liter volume was injected into the GPC. Tetrahydrofuran (THF) was used as the mobile phase for GPC and the flow rate was 1.0 mL/min. The column was configured with one Agilent Plagal 5 micron guard (7.5 x 50 mm) and two Agilent Plagal 5 micron Mixed D (7.5 x 300 mm) connected in series, and was heated at 40°C by using an Agilent 1260 Infinity II The system and the RI detector perform the measurements.

Measure by sampling 1 g of alkaline developable binder resin, dissolving it in 50 ml of mixed solvent (MeOH 20%, acetone 80%), adding two drops of 1% phenolphthalein indicator and titrating with 0.1N-KOH acid value.

The solids content is based on the weight of the alkaline developable binder resin prepared in the above preparation example and heated in an oven at 150°C for 120 minutes, and then the weight percent ratio of remaining solids is measured.

Preparation Example 2

The four-necked round bottom flask was equipped with a mechanical stirrer and a reflux device, and then the interior of the flask was purged with nitrogen. 80 grams of methyl ethyl ketone (MEK) and 7.5 grams of methanol (MeOH) were added to a nitrogen purged flask, and then 0.45 grams of azobisisobutyronitrile (AIBN) was added and dissolved completely. To this were added 8 g of acrylic acid (AA), 15 g of methacrylic acid (MAA), 15 g of butyl acrylate (BA), 52 g of methyl methacrylate (MMA) and 10 g of styrene (SM). The monomer mixture was used as a monomer, heated to 80°C, and then polymerized for 6 hours to prepare an alkaline developable binder resin.

The alkaline developable binder resin was measured to have a weight average molecular weight of 71,538 g/mol, a glass transition temperature of 79°C, a solids content of 51.4% by weight, and a solids content of 156.3 mg of potassium hydroxide/gram of acid value.

Preparation Example 3

The four-necked round bottom flask was equipped with a mechanical stirrer and a reflux device, and then the interior of the flask was purged with nitrogen. 110 grams of methyl ethyl ketone (MEK) and 10 grams of methanol (MeOH) were added to a nitrogen purged flask, and then 1 gram of azobisisobutyronitrile (AIBN) was added and dissolved completely. A monomer mixture of 30 g of methacrylic acid (MAA), 100 g of methyl methacrylate (MMA), and 30 g of styrene (SM) was added thereto as monomers, heated to 80° C., and then polymerized for 6 hours to prepare Alkaline developable binder resin (weight average molecular weight: 49,852 g/mol, glass transition temperature: 125°C, solids content: 48.5 wt% and acid value: 163.17 mg potassium hydroxide/g).

Comparative Preparation Example 1

The four-necked round bottom flask was equipped with a mechanical stirrer and a reflux device, and then the interior of the flask was purged with nitrogen. 90 grams of methyl ethyl ketone (MEK) and 10 grams of propylene glycol monomethyl ether acetate (PGMEA) were added to a nitrogen purged flask, followed by 0.8 grams of azodiisobutylene Nitrile (AIBN) and completely dissolved. A monomer mixture of 20 grams of methacrylic acid (MAA), 70 grams of methyl methacrylate, and 10 grams of styrene was added thereto as monomers, heated up to 80° C., and then polymerized for 6 hours to prepare an alkaline developable adhesive Resin (weight average molecular weight: 60,000 g/mol).

<Example and Comparative Example: Preparation of Photosensitive Resin Composition and Dry Film Photoresist>

According to the composition shown in Table 1 below, the photopolymerization initiator was dissolved in methyl ethyl ketone (MEK) as a solvent, and then the photopolymerizable compound and the alkali-developable binder resin were added, and using Mix with a mechanical mixer for about 1 hour to prepare Photosensitive resin composition.

The obtained photosensitive resin composition was coated on a 40-micrometer PET film using a coating bar. The coated photosensitive resin composition layer was dried using a hot air oven. At this 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 40 μm.

A protective film (polyethylene) was laminated on the dried photosensitive resin composition layer to prepare a dry film type photoresist.

The PET film was produced through the following process.

PET is prepared by performing transesterification and polycondensation using ethylene glycol and terephthalic acid. The PET pellets were dried under reduced pressure at 120°C for 8 hours, then fed into an extruder and melted at 280°C. This was wound on a casting drum with a surface temperature of 20°C using an electrostatic coating casting method, and cooled and solidified to form an unstretched film. The thickness of the unstretched film was adjusted to 250 microns by adjusting the discharge of the extruder. Next, the unstretched film was stretched four times in the longitudinal direction, and finally dried using a concave plate. cloth solution, and then coated on one side thereof to have a thickness of 50 nm. The polymethyl methacrylate used here is polymethyl methacrylate coated with polystyrene on its surface, which is spherical and has a refractive index difference of 0.03 with the acrylic resin.

The longitudinally uniaxially stretched film coated with the organic particle-containing coating solution was preheated at 120° C. and stretched four times in the transverse direction.

The film was heat set at a maximum temperature of 230°C for 10 seconds at a predetermined length and cooled to room temperature to obtain a polyester film with a total thickness of 20 microns and a coating thickness of 50 nm.

<Experimental example>

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

1. Saponification reactivity with developer solution

Samples with a thickness of 40 microns and an area of 0.50 square meters were prepared using the photosensitive resin layer, wherein the protective film and the supporting PET film were peeled off from the dry film photoresist prepared in the Examples and Comparative Examples.

Thereafter, the photosensitive resin layer sample was placed in a cylindrical foam analyzer (cross _- sectional diameter: ₁₀ cm, height: 60 cm, see Figure 1) below, and use a developer circulation pump connected to the upper and lower parts of the foam analyzer (circulation speed: 1000 to 1200 cm3/min, circulation pressure: 5 kgf/cm2) , and the developer solution was circulated for 60 minutes and sprayed into the foam analyzer at the upper portion of the foam analyzer.

Specifically, when the developer circulation pump operates, the developer solution inside the foam analyzer is discharged through the nozzle at the lower end portion, passes through the developer circulation pump, moves to the upper end portion of the foam analyzer, and passes from the upper end of the container through the nozzle injection.

At this time, the interval of the height difference between the upper end point of the foam analyzer in which the developer solution was sprayed and the highest point of the developer solution in the container immediately after the start of spraying the developer solution was about 48 mm.

At this time, "the highest point of foam generated in the foam analyzer after 60 minutes elapsed since the start of spraying the developer solution" and "the foam analysis immediately after the start of spraying the developer solution" were measured via a ruler mounted on the surface of the foam analyzer The height difference interval between the highest points of the developer solution in the instrument, and the height of the resulting foam was measured, and this For evaluating the degree of saponification reactivity with developer solutions.

2. Thin wire adhesion (unit: microns)

The protective film was peeled off from the dry film photoresists prepared in Examples and Comparative Examples, and the photosensitive resin layer of the dry film photoresist was laminated by HAKUTO MACH 610i so as to contact the thick copper laminate with a thickness of 1.6 mm. The surface of the copper layer was brushed under the following conditions: the temperature of the substrate preheating roller was 120°C, the temperature of the laminator roller was 115°C, the roller pressure was 4.0 kgf/cm 2 and the tumble rate was 2.0 min/m, A laminate is thus formed.

The supporting PET film for dry film photoresist was peeled off from the laminate, and then irradiated with ultraviolet rays through a photomask using a parallel exposure machine (EXM-1201, manufactured by ORC Manufacturing Co., Ltd.) to Circuit evaluation was performed until an exposure dose of 40 mJ/cm 2 was reached and then allowed to stand for 15 minutes. Thereafter, development was performed at 30±1° C. with a 1.0 wt % Na ₂ CO ₃ aqueous solution under the jet-type developing condition of a jet pressure of 1.5 kgf/cm 2 for twice the minimum developing time.

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

3.1:1 resolution (unit: microns)

The protective film was peeled off from the dry film photoresist prepared in the Examples and Comparative Examples, and the photosensitive resin layer of the dry film photoresist was laminated by Bodong MACH 610i so as to contact the copper layer of the thick copper clad laminate with a thickness of 1.6 mm. The surface was brushed under the following conditions: the substrate preheating roll temperature was 120°C, the laminator roll temperature was 115°C, the roll pressure was 4.0 kgf/cm 2 and the tumble rate was 2.0 min/m, whereby Form a laminate.

The supporting PET film for dry film type photoresist was peeled off from the laminate, and then irradiated with ultraviolet rays through the photomask using a parallel exposure machine (EXM-1201, manufactured by ORC Manufacturing Co., Ltd.) for circuit evaluation up to 40 millimetres The exposure dose of J/cm2 was such that the width of the circuit lines and the space interval between the circuit lines became 1:1, and then it was allowed to stand for 15 minutes. Thereafter, development was performed at 30±1° C. with a 1.0 wt % Na ₂ CO ₃ aqueous solution under the jet-type developing condition of a jet pressure of 1.5 kgf/cm 2 for twice the minimum developing time.

In the developed laminate, the minimum value of the spacing between the photosensitive resin layers was measured by a ZEISS AXIOPHOT microscope and evaluated as 1:1 resolution. It can be estimated that the smaller the value, the better the 1:1 resolution value.

4. Peeling rate (unit: second)

The protective film was peeled off from the dry film photoresist prepared in Examples and Comparative Examples, and the photosensitive resin layer of the dry film photoresist was laminated by Bodong MACH 610i so as to contact the surface of the copper layer of the copper clad laminate with a thickness of 1.6 mm. , brush grinding under the following conditions: the substrate preheating roller temperature is 120°C, the laminator roller temperature is 115°C, the roller pressure is 4.0 kgf/cm 2 and the tumble rate is 2.0 min/m, thereby forming laminate.

The supporting PET film for dry film type photoresist was peeled off from the laminate, and then irradiated with ultraviolet rays through the photomask using a parallel exposure machine (EXM-1201, manufactured by ORC Manufacturing Co., Ltd.) for circuit evaluation up to 40 millimetres J/cm² exposure dose and then allowed to stand for 15 minutes. Subsequently, development was performed at 30±1° C. with a 1.0 wt % Na ₂ CO ₃ aqueous solution under the jet-type development conditions of a jet pressure of 1.5 kgf/cm 2 for twice the minimum development time.

Next, the photosensitive resin layer was peeled off from the copper-clad laminate using a 3% sodium hydroxide aqueous solution (at a temperature of 50° C.). At this point, measure the amount of time required for the photosensitive resin layer to drop from the copper-clad laminate. time.

As shown in Table 2, compared to the comparative example, the example not only significantly reduces the height of foam generation and thus has a lower degree of saponification reactivity with the developer solution, but also has finer fine line adhesion and resolution and thus Can have excellent developability. Additionally, the examples have been found to have faster peel rates during the peel process.

5. Absolute viscosity

For the photosensitive resin layer in which the dry film type photoresist peeling protective film and the supporting PET film were prepared from Examples and Comparative Examples, the absolute viscosity according to temperature was measured using DHR-2 (TA Instruments, Inc.) equipment under the following conditions , and is shown in Figure 2 below. Via this method, the absolute viscosity minimum, the temperature at the absolute viscosity minimum, and the curing temperature were determined and are shown in Table 3 below.

<Measurement Conditions for Absolute Viscosity>

- test type = flow type, temperature

-Gas = Nitrogen (10 liters/min)

-Start temperature=50℃

- Final temperature = 125°C

- Heating rate = 10°C/min

- Shear rate = 1 (1/sec)

- Axial force = 3N or less

Measured under the above conditions.

Claims (19)

A photosensitive resin composition comprising: an alkali-developable adhesive comprising a repeating unit represented by the following chemical formula 1, a repeating unit represented by the following chemical formula 2, a repeating unit represented by the following chemical formula 3, and a repeating unit represented by the following chemical formula 4 A photopolymerization initiator; and a photopolymerizable compound, wherein the photosensitive resin composition satisfies any one of the following (1) or (2): (1) A photosensitive resin composition containing the photosensitive resin composition is The resin layer sample is added to the container containing the developer solution with a cross-sectional diameter of 10 cm or more, so that the volume ratio of the photosensitive resin layer sample to the developer solution is 2×10 ^-5 cubic meters per liter, the developer solution inside the container circulates at a rate of 1000 cm3/min or more and 1200 cm3/min or less, and at the upper end of the container During spraying, between the highest point of foam generated in the container after 60 minutes elapsed since the start of spraying the developer solution and the highest point of the developer solution in the container immediately after the start of spraying the developer solution The interval of the height difference is 80 mm or less, or (2) for a photosensitive resin layer sample containing the photosensitive resin composition and having a thickness of 5 μm or more and 30 μm or less, in all Under the condition that the axial force of the photosensitive resin layer sample is 5 N or less, the minimum value of the absolute viscosity obtained in the temperature range of 50 ° C or more and 125 ° C or less than 125 ° C is 300 Pa ． seconds or less than 300 Pa. seconds, [Chem. 1]

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

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

In Chemical Formula 3, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₅ is an alkyl group having 1 carbon atom,

And in Chemical Formula 4, Ar is an aryl group having 6 to 20 carbon atoms. The photosensitive resin composition according to claim 1, wherein based on 100 mol% of all the repeating units contained in the alkali-developable binder resin, the contained repeating units represented by Chemical Formula 1 are The amount is 5 mol% or more and 40 mol% or less. The photosensitive resin composition of claim 1, wherein the repeating unit represented by Chemical Formula 1 is a repeating unit derived from a monomer represented by the following Chemical Formula 1-1:

In Chemical Formula 1-1, R ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₂ is an alkylene group having 1 to 10 carbon atoms, and Ar is an alkylene group having 6 to 20 carbon atoms , and n is an integer from 1 to 20. The photosensitive resin composition according to claim 1, Wherein, based on 100 mol % of all repeating units contained in the alkaline developable binder resin, the alkaline developable binder resin contains 20 mol % or more and 60 mol % or less than 60 mol% of the repeating unit represented by Chemical Formula 2. The photosensitive resin composition according to claim 1, wherein based on 100 mol% of all repeating units contained in the alkali-developable adhesive resin, the alkali-developable adhesive resin contains 1 mol% % or more and 30 mol % or less of the repeating unit represented by Chemical Formula 3 and 30 mol % or more and 60 mol % or less than 60 mol % The repeating unit represented by Chemical Formula 4. The photosensitive resin composition according to claim 1, wherein a molar ratio of the repeating unit represented by Chemical Formula 3 to 100 mol of the repeating unit represented by Chemical Formula 4 is 10 mol or more and 99 moles or less. The photosensitive resin composition according to claim 1, wherein the photopolymerizable compound comprises a bifunctional (meth)acrylate compound. The photosensitive resin composition according to claim 1, wherein the photopolymerizable compound contains a trifunctional or higher polyfunctional (meth)acrylate compound. The photosensitive resin composition according to claim 8, wherein the trifunctional or higher polyfunctional (meth)acrylate compound has three or more than three epoxy alkyl groups having 1 to 10 carbon atoms in it group and three or more (meth)acrylate functional groups are bonded to a compound having 1 to 20 carbon atoms The structure of the central group. The photosensitive resin composition according to claim 8, wherein the trifunctional or higher polyfunctional (meth)acrylate compound comprises a compound represented by the following Chemical Formula 12:

In Chemical Formula 12, R ₁₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₁₅ is an alkylene group having 1 to 10 carbon atoms, and R ₁₆ is an alkylene group having 1 to 20 carbon atoms The p-valent functional group of the central group, n12 is an integer from 1 to 20, and p is the number of functional groups substituted for _R16 , and is an integer from 3 to 10. The photosensitive resin composition according to claim 8, wherein the photopolymerizable compound further comprises a monofunctional (meth)acrylate compound. The photosensitive resin composition according to claim 11, wherein the monofunctional (meth)acrylate compound comprises a (meth)acrylate comprising a carbon atom having 1 to 10 carbon atoms alkylene oxide group. The photosensitive resin composition according to claim 11, wherein the monofunctional (meth)acrylate compound comprises a compound represented by the following Chemical Formula 11:

In Chemical Formula 11, R ₁₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₁₂ is an alkylene group having 1 to 10 carbon atoms, and R ₁₃ is an alkylene group having 1 to 10 carbon atoms alkyl, and n11 is an integer from 1 to 20. The photosensitive resin composition as claimed in claim 1, further comprising: a first alkali-developable binder resin comprising a repeating unit represented by the following chemical formula 13, a repeating unit represented by the following chemical formula 14, and a repeating unit represented by the following chemical formula 15 a repeating unit, a repeating unit represented by the following Chemical Formula 16, and a repeating unit represented by the following Chemical Formula 17; and a second alkaline developable binder resin comprising a repeating unit represented by the following Chemical Formula 14, a repeating unit represented by the following Chemical Formula 15 and a repeating unit represented by the following Chemical Formula 16:

In Chemical Formula 13, R ₃ " is hydrogen,

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

In Chemical Formula 15, R ₄ " is an alkyl group having 1 to 10 carbon atoms, and R ₅ " is an alkyl group having 1 to 10 carbon atoms,

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

And in Chemical Formula 17, R ₄ ' is hydrogen, and R ₅ ' is an alkyl group having 1 to 10 carbon atoms. A dry film photoresist comprising a photosensitive resin layer containing the photosensitive resin composition of claim 1. A photosensitive element, comprising a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, and satisfying any one of the following (1) or (2): (1) The photosensitive resin composition will be contained A sample of the photosensitive resin layer is added to a container with a cross-sectional diameter of 10 cm or more containing the developer solution, so that the volume ratio of the photosensitive resin layer sample to the developer solution is 2×10 ^-5 cubic meter/liter, the developer solution inside the container is circulated at a rate of 1000 cm3/min or more and 1200 cm3/min or less, and in the container The highest point of the foam generated in the container after 60 minutes elapsed from the start of spraying the developer solution and the highest point of the developer solution in the container just after the start of spraying the developer solution The interval between the height differences is 80 mm or less, or (2) the photosensitive resin layer is characterized in that, for a photosensitive resin layer sample having a thickness of 5 microns or more and 30 microns or less than 30 microns , under the condition that the axial force of the photosensitive resin layer sample is 5 N or less, the minimum value of the absolute viscosity obtained in the temperature range of 50 ° C or more and 125 ° C or less than 125 ° C is 300 Pa. seconds or less than 300 Pa. second. The photosensitive element as claimed in claim 16, wherein the photosensitive resin layer comprises: a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the following Chemical Formula 2, a repeating unit represented by the following Chemical Formula 3, and a repeating unit represented by the following Chemical Formula 4 Alkali-developable binder resins of repeating units represented; and photopolymerizable compounds,

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

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

In Chemical Formula 3, R ₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₅ is an alkyl group having 1 carbon atom,

And in Chemical Formula 4, Ar is an aryl group having 6 to 20 carbon atoms. A circuit board comprising a photosensitive resin layer containing the photosensitive resin composition of claim 1. A display device comprising a photosensitive resin layer containing the photosensitive resin composition of claim 1.

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