KR102250827B1 - Photosensitive resin layer, and dry film photoresist, photosensitive element, circuit board, display device using the same - Google Patents

Abstract

The present invention relates to a photosensitive resin layer, a dry film photoresist using the same, a circuit board, and a display device. The photosensitive resin layer includes: a photopolymerizable compound including a polyfunctional (meth)acrylate compound and a monofunctional (meth)acrylate compound; and an alkali developable binder resin. The present invention can improve reliability by reducing a defective rate.

Description

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

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

The photosensitive resin composition is used in the form of dry film photoresist (DFR), liquid photoresist ink, etc., which are used for printed circuit boards (PCBs) or lead frames. .

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

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

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

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

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

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

In recent years, photosensitive resin compositions have high sensitivity to ultra-high pressure mercury lamps or laser direct exposure, and resistance to developing solutions in the development process increases, enabling high-density circuit formation, and as a UV marker for setting substrate exposure positions. For use, a photosensitive resin composition having excellent color development, shortening the peeling time of the cured film, and small peeling specimens is required without clogging the filter.

The present invention relates to a photosensitive resin layer capable of improving the reliability by realizing excellent fine wire adhesion and resolution, and increasing the alignment recognition rate for products during exposure to shorten the production time of the final product and reduce the defect rate.

In addition, the present invention is to provide a dry film photoresist including the photosensitive resin layer, a photosensitive element, a circuit board, and a display device.

In order to solve the above problems, in the present specification, an alkali developable binder resin, a photopolymerization initiator, and a photopolymerizable compound are included, and the photopolymerizable compound is a monofunctional (meth)acrylate compound represented by the following Formula 1, and the following It provides a photosensitive resin composition comprising a polyfunctional (meth)acrylate compound represented by Chemical Formula 2 and having an aromatic ring fraction value calculated by the following Equation 1 of -0.015 or more and -0.011 or less.

[Equation 1]

Aromatic ring fraction =

In Equation 1,

With respect to the monofunctional (meth)acrylate compound represented by the following formula (1) and the polyfunctional (meth)acrylate compound represented by the following formula (2),

Pc _n is the number of aromatic rings of each (meth)acrylate compound,

Oc _n is the number of O atoms and S atoms of each (meth)acrylate compound,

Wr _n is the weight% of each (meth)acrylate compound with respect to the total weight of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound,

Mw _n is the weight average molecular weight of the (meth)acrylate compound,

[Formula 1]

In Chemical Formula 1,

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

R ₂ is alkylene having 1 to 10 carbon atoms,

R ₃ is alkyl having 1 to 10 carbon atoms,

n1 is an integer from 1 to 20,

[Formula 2]

In Chemical Formula 2,

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

R ₅ is alkylene having 1 to 10 carbon atoms,

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

n2 is an integer from 1 to 20,

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

In the present specification, a photopolymerizable compound including a polyfunctional (meth)acrylate compound having 33 or more functionalities; And an alkali developable binder resin, wherein the aromatic ring fraction value calculated by Equation 1 is -0.015 or more and -0.011 or less, and a photosensitive resin layer may be provided.

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

The trifunctional or higher polyfunctional (meth)acrylate compound may include the compound of Formula 2.

The trifunctional or higher polyfunctional (meth)acrylate compound may include a compound of Formula 2-1 below. The following Chemical Formula 2-1 is as described below.

The photopolymerizable compound may further include a monofunctional (meth)acrylate compound.

The photopolymerizable compound may contain 100 parts by weight or more of the polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound.

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

The monofunctional (meth)acrylate compound may include the compound of Formula 1.

The photopolymerizable compound is a monofunctional (meth)acrylate compound including a (meth)acrylate containing an alkylene oxide group having 1 to 10 carbon atoms; And a trifunctional or higher polyfunctional (meth)acrylate compound having a structure in which three or more (meth)acrylate functional groups are each bonded to a central group having 1 to 20 carbon atoms and an alkylene oxide group having 1 to 10 carbon atoms. I can.

The alkali developable binder resin may have a weight average molecular weight of 20000 g/mol or more and 150000 g/mol or less.

In Equation 1, the _{ratio of Oc 1} of the monofunctional (meth)acrylate compound and Oc ₂ of the polyfunctional (meth)acrylate compound may be 1:0.3 or more and 1:0.9 or less.

In Equation 1, the _{ratio of Mw 1} of the monofunctional (meth)acrylate compound and Mw ₂ of the polyfunctional (meth)acrylate compound may be 1: 1.1 or more and 1: 1.9 or less.

The polyfunctional (meth)acrylate compound may be included in an amount of 110 parts by weight or more and 500 parts by weight or less based on 100 parts by weight of the monofunctional (meth)acrylate compound.

The photopolymerizable compound may further include a difunctional (meth)acrylate compound.

The difunctional (meth)acrylate compound may be included in an amount of 500 parts by weight or more and 1500 parts by weight or less based on 100 parts by weight of the monofunctional (meth)acrylate compound.

The difunctional (meth)acrylate compound may be included in an amount of 500 parts by weight or more and 1000 parts by weight or less based on 100 parts by weight of the polyfunctional (meth)acrylate compound.

The alkali developable binder resin includes a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), a repeating unit represented by the following formula (5), a repeating unit represented by the following formula (6), and the following formula (7). A first alkali developable binder resin including a repeating unit; And a second alkali developable binder resin including a repeating unit represented by the following formula (4), a repeating unit represented by the following formula (5), and a repeating unit represented by the following formula (6). Chemical Formulas 3 to 7 are as described later.

The second alkali developable binder resin may be included in an amount of 500 parts by weight or more and 1000 parts by weight or less based on 100 parts by weight of the first alkali developable binder resin.

The glass transition temperature ratio of the first alkali developable binder resin and the second alkaline developable binder resin may be 1:1.5 or more and 1:5 or less.

The acid value ratio of the first alkali developable binder resin and the second alkaline developable binder resin may be 1:1.01 or more and 1:1.5 or less.

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

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

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

In the present specification, a circuit board including the photosensitive resin layer is also provided.

In the present specification, a display device including the photosensitive resin layer is also provided.

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

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

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

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

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

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

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

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

, 또는

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

, or

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

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

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

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

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

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

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

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

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

1. Photosensitive resin composition

According to an embodiment of the present invention, an alkali developable binder resin, a photopolymerization initiator, and a photopolymerizable compound are included, and the photopolymerizable compound is a monofunctional (meth)acrylate compound represented by the following Formula 1, and the following Formula 2 A photosensitive resin composition comprising the polyfunctional (meth)acrylate compound and having an aromatic ring fraction value calculated by the following equation (1) of -0.015 or more and -0.011 or less may be provided.

[Equation 1]

Aromatic ring fraction =

In Equation 1, with respect to the monofunctional (meth)acrylate compound represented by the following Formula 1, and the polyfunctional (meth)acrylate compound represented by the following Formula 2, Pc _n represents each (meth)acrylate compound. Is the number of aromatic rings, Oc _n is the number of O atoms and S atoms of each (meth)acrylate compound, Wr _n is the total weight of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound Is the weight% of each (meth)acrylate compound, Mw _n is the weight average molecular weight of the (meth)acrylate compound,

[Formula 1]

In Formula 1, R ₁ is hydrogen or alkyl having 1 to 10 carbon atoms _{, R 2 is alkylene having 1 to 10 carbon atoms, R 3} is alkyl having 1 to 10 carbon atoms, and n1 is an integer of 1 to 20 ,

[Formula 2]

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

The present inventors believe that the photosensitive resin composition of the embodiment includes a monofunctional (meth)acrylate compound represented by Chemical Formula 1, and a polyfunctional (meth)acrylate compound represented by Chemical Formula 2, As the value of the aromatic ring fraction calculated by is -0.015 or more and -0.011 or less, it was confirmed through experiment that the technical effect having excellent developability and peelability can be secured while maintaining good resolution and adhesion. Completed.

(1) Alkaline developable binder resin

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

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

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

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

[Formula 3]

In Formula 3, R ₃ "is hydrogen,

[Formula 4]

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

[Formula 5]

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

[Formula 6]

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

[Formula 7]

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

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

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

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

[Chemical Formula 4-1]

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

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

[Chemical Formula 5-1]

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

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

[Chemical Formula 6-1]

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

The first alkali developable binder resin and the second alkaline developable binder resin may have a weight average molecular weight of 30000 g/mol or more and 150000 g/mol or less, and a glass transition temperature of 20° C. or more and 150° C. or less. Accordingly, the coating properties of the dry film photoresist, followability, and mechanical strength of the resist itself after circuit formation may be improved. Above or below, the weight average molecular weight was measured using Waters 450 GPC as a standard polystyrene, the columns were Shodex 105, 104, 103, and the glass transition temperature was measured using Perkin Elmer's DSC 7.

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

Specifically, the ratio of the glass transition temperature between the first alkali developable binder resin and the second alkaline developable binder resin is 1:1.5 or more and 1:5 or less, 1:1.5 or more and 1:3 or less, and 1:1.5 or more and 1:2. Hereinafter, it may be 1:1.5 or more and 1:1.8 or less, 1:1.5 or more and 1:75 or less, or 1:1.6 or more and 1:7 or less.

In addition, the acid value ratio of the first alkali developable binder resin and the second alkaline developable binder resin is 1:1.01 or more and 1:1.5 or less, 1:1.1 or more and 1:1.5 or less, 1:1.25 or more and 1:1.5 or less, or It may be greater than or equal to 1:1.4 and less than or equal to 1:1.5.

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

In addition, the first alkali-developable binder resin included in the photosensitive resin composition of the embodiment has 2 moles or more and 10 moles or less of the repeating unit represented by Formula 5 with respect to 1 mole of the repeating unit represented by Formula 7 Mole or more and 10 mol or less, 3 mol or more and 5 mol or less, or 4 mol or more and 5 mol or less.

Meanwhile, the second alkali developable binder resin may include a random copolymer of a repeating unit represented by Formula 4 below, a repeating unit represented by Formula 5 below, and a repeating unit represented by Formula 6 below.

[Formula 4]

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

[Formula 5]

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

[Formula 6]

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

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

[Chemical Formula 4-1]

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

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

[Chemical Formula 5-1]

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

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

[Chemical Formula 6-1]

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

Specifically, the first alkali developable binder resin is the repeating unit represented by Formula 4: The repeating unit represented by Formula 5: The repeating unit represented by Formula 6 is 1: (2 or more and 5 or less): (0.2 0.9 or less), 1: (2 or more and 3 or less): (0.5 or more and 0.9 or less), 1: (2.5 or more and 3 or less): (0.6 or more and 0.9 or less) or 1: (2.75 or more and 3 or less): (0.6 or more 0.75 It can be included as follows).

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

On the other hand, the photosensitive resin composition of one embodiment of the present invention contains 500 parts by weight or more and 1000 parts by weight or less, 600 parts by weight or more and 800 parts by weight or less, It may contain 700 parts by weight or more and 800 parts by weight or less.

In this specification, the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a commonly known analysis device, a detector such as a Refractive Index Detector, and a column for analysis may be used. Conditions, solvents, and flow rates can be applied.

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

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

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

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

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

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

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

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

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

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

(2) photopolymerization initiator

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

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

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

The content of the photopolymerization initiator is included in an amount of 0.1% by weight or more and 10% by weight or less based on the total weight of the photosensitive resin composition. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity can be obtained. The solid content, which is the basis of the weight, refers to the remaining components excluding the solvent in the photosensitive resin composition.

If the content of the photopolymerization initiator is less than 0.1% by weight, the light efficiency is low, so the amount of exposure must be large, so the production efficiency is extremely deteriorated.If it exceeds 10% by weight, the film is brittle and the developer is contaminated. There is a problem that this increases and causes a defect such as a short circuit.

(3) photopolymerizable compound

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

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

[Formula 1]

In Formula 1, R ₁ is hydrogen or alkyl having 1 to 10 carbon atoms _{, R 2 is alkylene having 1 to 10 carbon atoms, R 3} is alkyl having 1 to 10 carbon atoms, and n1 is an integer of 1 to 20 ,

[Formula 2]

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

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

Specifically, in Formula 1, n1 may be an integer of 1 to 20, an integer of 1 to 10, or an integer of 5 to 10. The example of the monofunctional (meth)acrylate compound represented by Formula 1 is not limited, but may be, for example, Methoxy propylene glycol [400] acrylate (A040) represented by Formula A below.

[Formula A]

As the photosensitive resin composition of the embodiment includes the monofunctional (meth)acrylate compound represented by Formula 1, there are many repeating units of ethylene oxide in the molecular structure having hydrophilicity and the molecular weight is small, thereby reducing the peeling time. Can be implemented.

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

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

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

[Formula 2-1]

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

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

The example of the polyfunctional (meth)acrylate compound represented by Formula 2 is not limited, but may be, for example, T063 (Trimethylolpropane [EO] ₆ triacrylate) represented by Formula B below.

[Formula B]

As the photosensitive resin composition of the embodiment includes the multifunctional (meth)acrylate compound represented by Formula 2, it is possible to achieve an effect of improving adhesion and resolution by increasing resistance to a developer.

On the other hand, the photosensitive resin composition of the embodiment is 110 parts by weight or more and 500 parts by weight or less, 110 parts by weight or more and 300 parts by weight, based on 100 parts by weight of the monofunctional (meth)acrylate compound. Hereinafter, 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 may be included.

As the photosensitive resin composition of one embodiment contains an excess of the polyfunctional (meth)acrylate compound with respect to the monofunctional (meth)acrylate compound, peeling of the monofunctional (meth)acrylate compound represented by Formula 1 The effect of shortening the time and increasing the resistance of the multifunctional (meth)acrylate compound represented by Formula 2 to the developer to improve adhesion and resolution are simultaneously realized, and the aromatic ring calculated by Equation 1 above The fraction value may satisfy -0.015 or more and -0.011 or less, thereby ensuring excellent developability.

When the photosensitive resin composition of the embodiment contains less than 100 parts by weight of the polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound, resistance to a developer is weakened, and thus good adhesion and Technical problems may arise in implementing the resolution.

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

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

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

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

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

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

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

As the diisocyanate compound, an aliphatic diisocyanate compound having a divalent aliphatic group such as an alkylene group, an alicyclic diisocyanate compound having a divalent alicyclic group such as cycloalkylene, an aromatic diisocyanate compound, and isocyanurate thereof And a modified product, a carbodiimide modified product, a biuret modified product, and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In addition, the photosensitive resin composition of the embodiment is 500 parts by weight or more and 1000 parts by weight or less, 500 parts by weight or more and 800 parts by weight, based on 100 parts by weight of the polyfunctional (meth)acrylate compound. Hereinafter, 500 parts by weight or more and 750 parts by weight or less, 500 parts by weight or more and 700 parts by weight or less, and 500 parts by weight or more and 600 parts by weight or less.

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

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

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

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

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

The content of the photopolymerizable compound may be included in an amount of 10% by weight or more and 70% by weight or less with respect to the total weight of the photosensitive resin composition on a solid basis. When the content of the photopolymerizable compound is within the above range, an effect of enhancing photosensitivity, resolution, and adhesion may be obtained.

(4) photosensitive resin composition

The photosensitive resin composition may contain 20% by weight or more and 80% by weight or less of an alkali developable binder resin, 0.1% by weight or more and 10% by weight or less of a photopolymerization initiator, and 10% by weight or more and 70% by weight or less of a photopolymerizable compound, based on solid content. have. The solid content, which is the basis of the weight, refers to the remaining components excluding the solvent in the photosensitive resin composition.

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

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

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

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

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

Meanwhile, the photosensitive resin composition of the embodiment may have an aromatic ring fraction value calculated by Equation 1 below of -0.015 or more and -0.011 or less. This may be implemented as the photosensitive resin composition of the embodiment includes the above-described photopolymerizable compound.

[Equation 1]

Aromatic ring fraction =

In Equation 1, with respect to the monofunctional (meth)acrylate compound represented by Formula 1, and the polyfunctional (meth)acrylate compound represented by Formula 2, Pc _n represents each (meth)acrylate compound. Is the number of aromatic rings, Oc _n is the number of O atoms and S atoms of each (meth)acrylate compound, Wr _n is the total weight of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound It is the weight% of each (meth)acrylate compound with respect to, and Mw _n is the weight average molecular weight of a (meth)acrylate compound.

Specifically, since the photosensitive resin composition of the embodiment includes a monofunctional (meth)acrylate compound represented by Formula 1, and a polyfunctional (meth)acrylate compound represented by Formula 2, the formula 1 The aromatic ring fraction value calculated by may be -0.015 or more and -0.011 or less.

More specifically, as the photosensitive resin composition of the embodiment contains an excess of the polyfunctional (meth)acrylate compound represented by Formula 2 with respect to the monofunctional (meth)acrylate compound represented by Formula 1, the The aromatic ring fraction value calculated by Equation 1 may be -0.015 or more and -0.011 or less.

As the aromatic ring fraction value calculated by Equation 1 is -0.015 or more and -0.011 or less, the reactivity of the photosensitive resin composition of the embodiment is accelerated, and a dry film including a cured product of the photosensitive resin composition of the embodiment The time and degree of color development of the photoresist are excellent, and accordingly, the effect of improving the physical properties of the display device including the dry film photoresist may be realized.

The aromatic ring fraction parameter is calculated by excluding the content of O and S atoms from the aromatic ring content in the photopolymerizable compound and divided by the average molecular weight of the composition, and the aromatic ring fraction value is -0.015 or more -0.011 or less, -0.015 or more It may be -0.012 or less, -0.015 or more -0.013 or less, or -0.014 or more and -0.013 or less. By using a photopolymerizable compound that satisfies the aromatic ring fraction value, the photosensitive resin composition of the embodiment can achieve an effect having excellent developability and peelability while maintaining good resolution and adhesion.

Moreover, when the aromatic ring fraction is less than -0.015, it contains an excessively small amount of the polyfunctional (meth)acrylate compound, which increases the resistance to the developer by including the polyfunctional (meth)acrylate compound represented by Formula 2 above. The technical effect may be lowered, resulting in a technical problem that improves adhesion and resolution, and when the value exceeds -0.011, it contains an excessively small amount of the monofunctional (meth)acrylate compound, and the monofunctional ( As a result of the inclusion of the meth)acrylate compound, the number of repeating units of ethylene oxide in the molecular structure having hydrophilicity is reduced, and the molecular weight is increased, thereby causing a technical problem in that the peeling time is lengthened.

Specifically, Equation 1 may mean the following equation.

In Equation 1, Pc _n may mean the number of aromatic rings of the (meth)acrylate compound represented by Formula n. That is, Pc ₁ refers to the number of aromatic rings of the monofunctional (meth)acrylate compound represented by Chemical Formula 1, and Pc ₂ is the number of aromatic rings of the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 Can mean.

In Equation 1, Oc _n may mean the number of O atoms and S atoms of the (meth)acrylate compound represented by Formula n. That is, Oc ₁ means the number of O atoms and S atoms of _{the monofunctional (meth)acrylate compound represented by Formula 1, and Oc 2} is O of the polyfunctional (meth)acrylate compound represented by Formula 2 It may mean the number of atoms and S atoms.

In Equation 1, Wr _n may mean weight% with respect to the total weight of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound of the (meth)acrylate compound represented by Formula n. . That is, Wr ₁ means a weight% of the total weight of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound of the monofunctional (meth)acrylate compound represented by Formula 1, and Wr ₂ May mean weight% of the polyfunctional (meth)acrylate compound represented by Formula 2 with respect to the total weight of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound.

In Equation 1, Mw _n may mean a weight average molecular weight of the (meth)acrylate compound represented by Chemical Formula n. That is, Mw ₁ refers to the weight average molecular weight of the monofunctional (meth) acrylate compound represented by Formula 1, and Mw ₂ refers to the weight average molecular weight of the polyfunctional (meth) acrylate compound represented by Formula 2 can do.

That is, in the above embodiment, the aromatic ring fraction value calculated by Equation 1 may be specifically calculated by Equation 1-1 below.

[Equation 1-1]

Aromatic ring fraction =

In Equation 1-1, Pc ₁ is the number of aromatic rings of the monofunctional (meth)acrylate compound represented by Formula 1, and Pc ₂ is the polyfunctional (meth)acrylate compound represented by Formula 2 Is the number of aromatic rings, Oc ₁ is the number of O atoms and S atoms of _{the monofunctional (meth)acrylate compound represented by Formula 1, and Oc 2} is the polyfunctional (meth)acrylate compound represented by Formula 2 Is the number of O atoms and S atoms of, and Wr ₁ is the total weight of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound of the monofunctional (meth)acrylate compound represented by Formula 1 above. % By weight, and Wr ₂ is% by weight based on the total weight of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound of the polyfunctional (meth)acrylate compound represented by Chemical Formula 2, and Mw ₁ Is the weight average molecular weight of the monofunctional (meth)acrylate compound represented by Formula 1, and Mw ₂ is the weight average molecular weight of the polyfunctional (meth)acrylate compound represented by Formula 2 above.

In Equation 1, Pc _n represents the number of aromatic rings of each (meth)acrylate compound. The number of aromatic rings means the number of single rings included in the (meth)acrylate compound, and in the case of a condensed ring, it means the number of each condensed single ring. For example, when the (meth)acrylate compound contains one naphthyl group, two single benzene rings are condensed, so Pc _n is 2, and the (meth)acrylate compound contains one anthracene group or a phenanthrene group. In case Pc _n is 3.

That is, the monofunctional (meth)acrylate compound represented by Formula 1 is Pc _n 0 or more and 10 or less, 0 or more and 2 or less, or 0, and the polyfunctional (meth)acrylate compound represented by Formula 2 is Pc _n this It may be 0 to 10, 0 to 2, or 0.

The Oc _n does not include the number of O atoms and S atoms of each (meth)acrylate compound, or the number of “O” included in the (meth)acrylate.

For example, when the (meth)acrylate compound is dodecanediol dimethacrylate, Oc _n is 0, and when the (meth)acrylate compound is phenylthioethyl acrylate, Oc _n is 1.

Wr _n may be a weight% of each (meth)acrylate compound with respect to the total weight of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound. For example, if the (meth)acrylate compound used is mixed with dodecanediol dimethacrylate 60 kg and phenylthioethyl acrylate 40 kg, Wr _n of dodecanediol dimethacrylate is (60/100 ) X100=60, and Wr _n of phenylthioethylacrylate is (40/100)X100=40.

On the other hand, in Equation 1, the _{ratio of Oc 1} of the monofunctional (meth)acrylate compound and Oc ₂ of the polyfunctional (meth)acrylate compound is 1:0.3 or more and 1:0.9 or less, 1:0.5 or more and 1: It may be 0.9 or less, 1:0.5 or more and 1:0.75 or less, and 1:0.5 or more and 1:0.7 or less.

In addition, in Equation 1, the _{ratio of Mw 1} of the monofunctional (meth)acrylate compound and Mw ₂ of the polyfunctional (meth)acrylate compound is 1: 1.1 or more 1: 1.9 or less, 1: 1.1 or more 1: It may be 1.5 or less, 1: 1.1 or more and 1: 1.4 or less, 1: 1.2 or more and 1: 1.4 or less, and 1: 1.2 or more and 1: 1.3 or less.

2. Dry film photoresist

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

Specifically, the photosensitive resin layer may include a dried product or a cured product of the photosensitive resin composition of the embodiment. The dried product means a material obtained through the drying process of the photosensitive resin composition of the embodiment. The cured product refers to a material obtained through a curing process of the photosensitive resin composition of the embodiment.

Meanwhile, the photosensitive resin layer may have an aromatic ring fraction value calculated by Equation 1 below of -0.015 or more and -0.011 or less.

[Equation 1]

Aromatic ring fraction =

In Equation 1, with respect to the monofunctional (meth)acrylate compound represented by the following Formula 1, and the polyfunctional (meth)acrylate compound represented by the following Formula 2, Pc _n represents each (meth)acrylate compound. Is the number of aromatic rings, Oc _n is the number of O atoms and S atoms of each (meth)acrylate compound, Wr _n is the total weight of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound Is the weight% of each (meth)acrylate compound, Mw _n is the weight average molecular weight of the (meth)acrylate compound,

[Formula 1]

In Formula 1, R ₁ is hydrogen or alkyl having 1 to 10 carbon atoms _{, R 2 is alkylene having 1 to 10 carbon atoms, R 3} is alkyl having 1 to 10 carbon atoms, and n1 is an integer of 1 to 20 ,

[Formula 2]

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

The contents of Equation 1 include all the contents described above in the other embodiment.

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

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

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

The protective film prevents damage to the resist during handling and serves as a protective covering to protect the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface of the photosensitive resin layer on which the base film is not formed. The protective film serves to protect the photosensitive resin layer from the outside, and requires proper releasability and adhesion so that it is easily released when applying a dry film photoresist to a post process, and is not released when stored and distributed.

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

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

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

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

3. Photosensitive element

According to another embodiment of the invention, a polymer substrate; And a photosensitive resin layer formed on the polymer substrate, wherein the photosensitive resin layer has an aromatic ring fraction value calculated by Equation 1 below -0.015 or more and -0.011 or less.

[Equation 1]

Aromatic ring fraction =

In Equation 1, with respect to the monofunctional (meth)acrylate compound represented by the following Formula 1, and the polyfunctional (meth)acrylate compound represented by the following Formula 2, Pc _n represents each (meth)acrylate compound. Is the number of aromatic rings, Oc _n is the number of O atoms and S atoms of each (meth)acrylate compound, Wr _n is the total weight of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound Is the weight% of each (meth)acrylate compound, Mw _n is the weight average molecular weight of the (meth)acrylate compound,

[Formula 1]

In Formula 1, R ₁ is hydrogen or alkyl having 1 to 10 carbon atoms _{, R 2 is alkylene having 1 to 10 carbon atoms, R 3} is alkyl having 1 to 10 carbon atoms, and n1 is an integer of 1 to 20 ,

[Formula 2]

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

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

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

[Formula 1]

In Formula 1, R ₁ is hydrogen or alkyl having 1 to 10 carbon atoms _{, R 2 is alkylene having 1 to 10 carbon atoms, R 3} is alkyl having 1 to 10 carbon atoms, and n1 is an integer of 1 to 20 ,

[Formula 2]

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

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

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

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

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

Such organic particles should be specifically spherical and have a difference in refractive index from the binder resin. Here,'spherical' is defined as the ratio of the minor axis (a) and the major axis (b) of the ellipse is 0.5<a/b <2, and the relationship with the diagonal (d) of the rectangle is d2≦a2+b2. And the relationship between the axis (f) with the longest distance between vertices in the cube and the c axis other than the a and b axes is defined as f2≦c2+a2+b2. The shape of the particles should be spherical, which is preferable in terms of running performance.

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

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

Meanwhile, inorganic particles may be added in addition to the organic particles as described above. In this case, it is not preferable to add an inorganic anti-blocking agent that has been used, and it is preferable to add colloidal silica having a particle size of 100 nm or less. The content is preferably included in an amount of 10 parts by weight or less based on 100 parts by weight of the binder resin. When the particle size and content as described above are satisfied, defects in the sidewall or grooves such as craters may not be generated due to the anti-blocking layer in pattern formation using the dry film photoresist.

As a binder resin that acts as an adhesive for applying such organic particles onto an unstretched polyester film, one having good compatibility with organic particles may be used. Examples of such resins include unsaturated polyester, methyl methacrylate, Acrylic resins such as ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, normal butyl methyl methacrylate, acrylic acid, methacrylic acid copolymer or terpolymer; Urethane resin; Epoxy resin; Or melamine resin etc. are mentioned, Preferably it is an acrylic resin.

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

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

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

Lamination of the photosensitive resin layer is performed on the opposite side of the layer containing organic particles in the polymer substrate. As the photosensitive resin layer is formed on the opposite side of the layer containing organic particles, an anti-blocking agent is included as before. There is no occurrence of a crater-shaped flaw that appears as the base film is laminated. Particles such as silica are not only larger in size than organic particles, but also have a distribution throughout the base film, so that the influence of silica appears insignificantly even at a portion adjacent to the photosensitive resin layer.

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

The photosensitive element may further include a protective film formed on the photosensitive resin layer. The protective film prevents damage to the photosensitive resin layer during handling and serves as a protective covering to protect the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface of the photosensitive resin layer on which the polymer substrate is not formed. The protective film serves to protect the photosensitive resin layer from the outside, and requires proper release properties and adhesion so that the photosensitive element is easily released when applied to a post-process, and is not released when stored and distributed.

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

4. Circuit board, display device

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

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

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

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

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

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

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

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

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

<Production Example: Preparation of alkali developable binder resin>

Manufacturing Example 1

A mechanical stirrer and a reflux device were attached to a four-necked round bottom flask, and then the inside of the flask was purged with nitrogen. 80 g of methyl ethyl ketone (MEK) and 7.5 g of methanol (MeOH) were added to the flask purged with nitrogen, and then 0.45 g of azobisisobutyronitrile (AIBN) was added to completely dissolve. Made it. Here, acrylic acid (AA) 8 g, methacrylic acid (MAA) 15 g, butyl acrylate (BA) 15 g, methyl methacrylate (MMA) 52 g, and styrene ( Styrene, SM) 10 g of a monomer mixture was added, the temperature was raised to 80° C., and then polymerized for 6 hours to prepare an alkali developable binder resin 1.

The alkali developable binder resin 1 was measured to have a weight average molecular weight of 71538 g/mol, a glass transition temperature of 79° C., a solid content of 51.4 wt%, and an acid value of 156.3 mgKOH/g.

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

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

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

Manufacturing Example 2

A mechanical stirrer and a reflux device were attached to a four-necked round bottom flask, and then the inside of the flask was purged with nitrogen. In the flask purged with nitrogen, 235 g of methyl ethyl ketone (MEK) and 19 g of methanol (MeOH) were added, and then 1.9 g of azobisisobutyronitrile (AIBN) was added to completely dissolve it. . Here, a monomer mixture of 63.5 g of methacrylic acid (MAA), 120.6 g of methyl methacrylate (MMA), and 69.8 g of styrene (SM) was added as a monomer, and the temperature was raised to 80 °C. Alkaline developable binder resin 2 (a weight average molecular weight of 37500 g/mol, a glass transition temperature of 128° C., a solid content of 49% by weight, and an acid value of 163 mgKOH/g) was prepared by polymerization for the next 6 hours.

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

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

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

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

The PET film was manufactured through the following process.

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

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

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

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

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

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

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

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

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

1. Fraction of aromatic rings

With respect to the photosensitive resin composition prepared in the above Examples and Comparative Examples, the aromatic ring fraction value was calculated according to Equation 1 below.

[Equation 1]

Aromatic ring fraction =

In Equation 1, for A040 which is a monofunctional (meth)acrylate compound and T063 which is a trifunctional (meth)acrylate compound contained in the photosensitive resin composition, Pc _n represents the aromatic ring of each (meth)acrylate compound. Is the number, Oc _n is the number of O atoms and S atoms of each (meth)acrylate compound, Wr _n is the total weight of the monofunctional (meth)acrylate compound A040 and the trifunctional (meth)acrylate compound T063 It is the weight% of each (meth)acrylate compound with respect to, and Mw _n is the weight average molecular weight of the (meth)acrylate compound.

2. Fine wire adhesion (unit: ㎛)

Preheating the substrate so that the protective film of the dry film photoresist prepared in the above Examples and Comparative Examples is peeled off, and the photosensitive resin layer of the dry film photoresist comes into contact with the copper layer surface of the 1.6 mm thick copper clad laminate subjected to brush polishing treatment. Roll temperature 120 ℃, laminator roll temperature 115 ℃, roll pressure 4.0kgf/㎠ And lamination was performed using HAKUTO MACH 610i under the condition of a roll speed of 2.0 min/m.

Using a photomask for circuit evaluation on the laminate, ultraviolet rays were irradiated for 10 seconds at an exposure amount of ^{16 mJ/cm 2 through ORC's FDi-3, and then allowed to stand for 15 minutes.} After that, the PET film, which is a support for the dry film photoresist, was peeled off, and development was performed for 1 minute under spray pressure of 1.5kgf/cm2 with a 1.0wt% aqueous solution _{of Na 2} CO _{3 at 30±1° C. under the development conditions of a spray method.}

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

3. Resolution (unit: ㎛)

Preheating the substrate so that the protective film of the dry film photoresist prepared in the above Examples and Comparative Examples is peeled off, and the photosensitive resin layer of the dry film photoresist comes into contact with the copper layer surface of the 1.6 mm thick copper clad laminate subjected to brush polishing treatment. Roll temperature 120 ℃, laminator roll temperature 115 ℃, roll pressure 4.0kgf/㎠ Then, a laminate was formed by lamination using a HAKUTO MACH 610i under the condition of a roll speed of 2.0 min/m.

A photomask for circuit evaluation was used so that the width of the circuit line and the space between the circuit lines after development on the laminate were 1:1, and 16mJ/cm ^{2 through ORC's FDi-3} UV rays were irradiated for 10 seconds at the exposure amount of and then left for 15 minutes. After that, the PET film, which is a support for the dry film photoresist, was peeled off, and development was performed for 1 minute under spray pressure of 1.5kgf/cm2 with a 1.0wt% aqueous solution _{of Na 2} CO _{3 at 30±1° C. under the development conditions of a spray method.}

4. Evaluation of anti-contamination for plating

The dry film photoresist prepared in the above Examples and Comparative Examples was cut into a size of 40 cm x 50 cm, the protective film was removed, and the step tablet was exposed at an exposure amount of 20 steps/41 steps, and the PET film was peeled off to obtain a cured film. . This cured film was immersed in 1 L of a plating solution of a copper sulfate/sulfuric acid aqueous solution for 3 days. Electrolytic copper plating was performed on the copper plate with a current of 2A for 10 minutes using a Halcel test bath (produced by Precision Tester Research Institute).

When plating with the plating solution immersed in the cured film as a reference sample using the plating solution not immersed in the cured film, the appearance of the plating is visually observed, and there is an abnormality in the appearance of the plating or changes in gloss. Was judged as.

5. Peeling rate (unit: second)

Preheating the substrate so that the protective film of the dry film photoresist prepared in the above Examples and Comparative Examples is peeled off, and the photosensitive resin layer of the dry film photoresist comes into contact with the copper layer surface of the 1.6 mm thick copper clad laminate subjected to brush polishing treatment. Roll temperature 120 ℃, laminator roll temperature 115 ℃, roll pressure 4.0kgf/㎠ And lamination was performed using HAKUTO MACH 610i under the condition of a roll speed of 2.0 min/m.

Using a photomask for circuit evaluation on the laminate, ultraviolet rays were irradiated for 10 seconds at an exposure amount of ^{16 mJ/cm 2 through ORC's FDi-3, and then allowed to stand for 15 minutes.} After that, peel off the PET film, which is the support of the dry film photoresist, and develop the photocured film with a spray pressure of 1.5kgf/cm2 for 1 minute under the spraying-type development condition with a 1.0wt% _{Na 2} CO _{3 aqueous solution at 30±1℃.} Was prepared.

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

division Aromatic ring fraction Fine wire adhesion
(㎛) resolution
(㎛) Plating amount
Contamination Peeling speed
(second) Example 1 -0.01394 18 17 0 35 Comparative Example 1 -0.01095 17 17 0 50 Comparative Example 2 -0.02 25 22 x 28

As shown in Table 2, the examples show similar levels of session adhesion and resolution as compared to Comparative Example 1 in which the aromatic ring fraction value is more than -0.011, according to the aromatic ring fraction value is -0.015 or more and -0.011 or less. At the same time, it was confirmed that the peeling rate was remarkably excellent. In addition, Examples are, as the aromatic ring fraction value is -0.015 or more and -0.011 or less, compared to Comparative Example 2 in which the aromatic ring fraction value is less than -0.015, remarkably excellent session adhesion, resolution, and contamination prevention for plating It could be confirmed that it was shown.

Claims (24)

Photopolymerizable compounds including trifunctional or higher polyfunctional (meth)acrylate compounds and monofunctional (meth)acrylate compounds; And an alkali developable binder resin,
The monofunctional (meth)acrylate compound includes the compound of Formula 1,
The trifunctional or higher polyfunctional (meth)acrylate compound includes a compound of the following formula (2),
A photosensitive resin layer in which the aromatic ring fraction value calculated by the following equation 1 is -0.015 or more and -0.011 or less:
[Equation 1]
Aromatic ring fraction =

In Equation 1,
Pc _n is the number of aromatic rings of each (meth)acrylate compound,
Oc _n is the number of O atoms and S atoms of each (meth)acrylate compound,
Wr _n is the weight% of each (meth)acrylate compound relative to the total weight of the (meth)acrylate compound,
Mw _n is the weight average molecular weight of the (meth)acrylate compound,
[Formula 1]

In Chemical Formula 1,
R ₁ is hydrogen or alkyl having 1 to 10 carbon atoms,
R ₂ is alkylene having 1 to 10 carbon atoms,
R ₃ is alkyl having 1 to 10 carbon atoms,
n1 is an integer from 1 to 20,
[Formula 2]

In Chemical Formula 2,
R ₄ is hydrogen or alkyl having 1 to 10 carbon atoms,
R ₅ is alkylene having 1 to 10 carbon atoms,
R ₆ is a functional group in which p containing a central group having 1 to 20 carbon atoms,
n2 is an integer from 1 to 20,
p is the _{number of functional groups substituted for R 6} , and is an integer of 3 to 10.
The method of claim 1,
The trifunctional or higher polyfunctional (meth)acrylate compound,
A photosensitive resin layer having a structure in which three or more alkylene oxide groups having 1 to 10 carbon atoms and three or more (meth)acrylate functional groups are each bonded to a central group having 1 to 20 carbon atoms.
delete The method of claim 1,
The trifunctional or higher polyfunctional (meth)acrylate compound is a photosensitive resin layer comprising a compound of Formula 2-1:
[Formula 2-1]

In Formula 2-1,
R ₆ ′ is a trivalent functional group having 1 to 10 carbon atoms,
R ₇ to R ₉ are each independently alkylene having 1 to 10 carbon atoms,
R ₁₀ to R ₁₂ are each independently hydrogen or alkyl having 1 to 10 carbon atoms,
n3 to n5 are each independently an integer of 1 to 3. delete The method of claim 1,
The photopolymerizable compound includes 100 parts by weight or more of the polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound.
The method of claim 1,
The monofunctional (meth)acrylate compound is a photosensitive resin layer comprising a (meth)acrylate containing an alkylene oxide group having 1 to 10 carbon atoms
delete The method of claim 1,
The photopolymerizable compound is a monofunctional (meth)acrylate compound including a (meth)acrylate containing an alkylene oxide group having 1 to 10 carbon atoms; And
Including a trifunctional or higher polyfunctional (meth)acrylate compound having a structure in which three or more (meth)acrylate functional groups are each bonded to a C1 to C20 central group and a C1 to C10 alkylene oxide group.
Photosensitive resin layer.
The method of claim 1,
The alkali developable binder resin has a weight average molecular weight of 20000 g/mol or more and 150000 g/mol or less, a photosensitive resin layer.
The method of claim 1,
In Equation 1 above
The photosensitive resin layer in which the ratio of Oc ₁ of the monofunctional (meth)acrylate compound and Oc ₂ of the polyfunctional (meth)acrylate compound is 1:0.3 or more and 1:0.9 or less.
The method of claim 1,
In Equation 1 above
The photosensitive resin layer, wherein the ratio of Mw ₁ of the monofunctional (meth)acrylate compound and Mw ₂ of the polyfunctional (meth)acrylate compound is 1: 1.1 or more and 1: 1.9 or less.
The method of claim 1,
A photosensitive resin layer comprising 110 parts by weight or more and 500 parts by weight or less of the polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound.
The method of claim 1,
The photopolymerizable compound further comprises a difunctional (meth)acrylate compound, a photosensitive resin layer.
The method of claim 14,
A photosensitive resin layer comprising 500 parts by weight or more and 1500 parts by weight or less based on 100 parts by weight of the monofunctional (meth) acrylate compound.
The method of claim 14,
The photosensitive resin layer comprising 500 parts by weight or more and 1000 parts by weight or less based on 100 parts by weight of the polyfunctional (meth) acrylate compound.
The method of claim 1,
The alkali developable binder resin is
A first alkali phenomenon including a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), a repeating unit represented by the following formula (5), a repeating unit represented by the following formula (6), and a repeating unit represented by the following formula (7) Castle binder resin; And
A photosensitive resin layer comprising: a repeating unit represented by Formula 4 below, a repeating unit represented by Formula 5 below, and a second alkaline developable binder resin including a repeating unit represented by Formula 6 below:
[Formula 3]

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

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

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

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

In Chemical Formula 7,
R ₄ ′ is hydrogen,
R ₅ ′ is alkyl having 1 to 10 carbon atoms.
The method of claim 17,
A photosensitive resin layer comprising 500 parts by weight or more and 1000 parts by weight or less of a second alkali developable binder resin based on 100 parts by weight of the first alkali developable binder resin.
The method of claim 17,
The photosensitive resin layer, wherein a glass transition temperature ratio of the first alkali developable binder resin and the second alkaline developable binder resin is 1:1.5 or more and 1:5 or less.
The method of claim 17,
The photosensitive resin layer, wherein an acid value ratio of the first alkali developable binder resin and the second alkaline developable binder resin is 1:1.01 or more and 1:1.5 or less.
A dry film photoresist comprising the photosensitive resin layer of claim 1.
Polymer substrate; And
A photosensitive element comprising the photosensitive resin layer of claim 1 formed on the polymer substrate.
A circuit board comprising the photosensitive resin layer of claim 1.
A display device comprising the photosensitive resin layer of claim 1.