JP7387900B2 - Photosensitive resin layer, dry film photoresist using the same, and photosensitive element - Google Patents

Description

[Cross reference to related applications]
This application is based on Korean Patent Application No. 10-2019-0179942 dated December 31, 2019, Korean Patent Application No. 10-2019-0179943 dated December 31, 2019, and Korean Patent Application No. 10-2019-0179943 dated December 31, 2019. No. 10-2020-0095384 and Korean Patent Application No. 10-2020-0095385 dated July 30, 2020, and all contents disclosed in the documents of said Korean patent application are Included as part of this specification.
The present invention relates to a photosensitive resin layer, a dry film photoresist using the same, and a photosensitive element.

The sensitive resin composition is a dried film photo resist (Dry Film Photoresist, DFR), a liquid photo resist (Dry Film Photoresist, DFR), which is used for printed circuit boards (Printed Circuit Board; PCB). IQUID PHOTORESIST INK) It is used in the form of
Currently, we are not only manufacturing printed circuit boards (PCBs) and lead frames, but also manufacturing rib barriers for plasma display panels (PDPs), ITO electrodes for other displays, bus address electrodes, and black matrices. ) Dry film photoresists are also widely used in the production of photoresists.

Generally, such dry film photoresists are often used for laminating on copper clad laminates. In this regard, as an example of the manufacturing process of a printed circuit board (PCB), in order to laminate a copper-clad laminate, which is a base plate material of a PCB, a pretreatment process is first performed. The pretreatment process is performed in the order of drilling, deburring, and surface leveling in the outer layer process, and surface leveling or pickling is performed in the inner layer process. The surface preparation process mainly uses bristle brush and jet pumice processes, and the pickling process may include soft etching and 5wt% sulfuric acid pickling.
In order to form a circuit on a copper-clad laminate that has undergone a pretreatment process, a dry film photoresist (hereinafter referred to as DFR) is generally laminated on the copper layer of the copper-clad laminate. In this step, the DFR photoresist layer is laminated onto the copper surface using a laminator while peeling off the DFR protective film. Generally, lamination is carried out at a speed of 0.5 to 3.5 m/min, a temperature of 100 to 130°C, and a heated roll pressure of 10 to 90 psi.
After the printed circuit board that has undergone the lamination process is left for 15 minutes or more to stabilize the board, the DFR photoresist is exposed to light using a photomask on which a desired circuit pattern is formed. In this process, when the photomask is irradiated with ultraviolet rays, the photoresist irradiated with ultraviolet rays starts polymerization at the irradiated areas by the photoinitiator contained therein. First, oxygen in the photoresist is initially consumed, then activated monomers are polymerized to cause a crosslinking reaction, and then a polymerization reaction is performed while a large amount of monomer is consumed. On the other hand, the unexposed region exists in a state where no crosslinking reaction is performed.
Next, a development step is performed to remove the unexposed portions of the photoresist, and in the case of alkaline developable DFR, an aqueous solution of 0.8 to 1.2 wt % potassium carbonate and sodium carbonate is used as the developer. In this step, unexposed areas of the photoresist are washed away in the developer by a saponification reaction between the carboxylic acid of the binder polymer and the developer, leaving the hardened photoresist on the copper surface.

Next, a circuit is formed through different processes depending on the inner layer and outer layer processes. In the inner layer process, a circuit is formed on the substrate through etching and peeling processes, and in the outer layer process, after passing through plating and tenting processes, etching and solder peeling are performed to form a predetermined circuit.
Recently, photosensitive resin compositions have high sensitivity to ultra-high-pressure mercury lamps and laser direct exposure, and their resistance to developing solutions in the development process has increased, making it possible to form high-density circuits. In order to be used as a UV marker for this purpose, there is a need for a photosensitive resin composition that has excellent color development, shortens the peeling time of the cured film, has small peel test pieces, and does not clog filters.

The present invention can realize excellent fine line adhesion and resolution, increase the alignment recognition rate for products during exposure, shorten the production time of final products, reduce the defective rate, and improve reliability. Provide a photosensitive resin layer.
The present invention also provides a dry film photoresist, a photosensitive element, a circuit board, and a display device including the photosensitive resin layer.

In order to solve the above problems, ^the present invention includes a photopolymerizable compound ^containing a trifunctional or higher polyfunctional (meth)acrylate compound; and an alkali-developable binder resin; A photosensitive resin layer in which the time (t) from the time when exposure is started with the exposure amount to the time when the amount of change in the color coordinate b* value calculated by the following formula 1 is 5 minutes or less is 5 minutes or less. I will provide a.
[Formula 1]
Amount of change in color coordinate b ^* value during exposure time (t) (△b ^* ₁ ) = (b ^* ₀ - b ^* ₁ )
In the formula 1,
b ^* ₁ is the color coordinate (b ^* ) value of the photosensitive resin layer after exposure for t minutes at an exposure amount of 10 mJ/cm ² or more and 30 mJ/cm ² or less,
b ^* ₀ is the color coordinate (b ^* ) value of the photosensitive resin layer before exposure.
The present specification also provides a photosensitive resin layer in which the amount of change in the color coordinate b ^* value calculated by Equation 2 below is 0.6 or more and 14.0 or less.
[Formula 2]
Color coordinate b ^* value change amount (△b ^* ₁ ) = (b ^* ₀ - b ^* ₁ ) at 1 minute exposure time
In the formula 2,
b ^* ₁ is the color coordinate (b ^* ) value of the photosensitive resin layer after exposure for 1 minute at an exposure amount of 10 mJ/cm ² or more and 30 mJ/cm ² or less,
b ^* ₀ is the color coordinate (b ^* ) value of the photosensitive resin layer before exposure.
The trifunctional or higher polyfunctional (meth)acrylate compound has 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. obtain.
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 represented by the following chemical formula 2-1. 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 containing an alkylene oxide group having 1 to 10 carbon atoms.
The monofunctional (meth)acrylate compound may include a compound of Formula 1.
The photopolymerizable compound is a monofunctional (meth)acrylate compound containing (meth)acrylate containing an alkylene oxide group having 1 to 10 carbon atoms; and an alkylene oxide group having 1 to 10 carbon atoms in the central group having 1 to 20 carbon atoms. A polyfunctional (meth)acrylate compound having trifunctionality or more and having a structure in which three or more groups and three or more (meth)acrylate functional groups are bonded to each other.

The alkaline developable binder resin may have a weight average molecular weight of 20,000 g/mol or more and 150,000 g/mol or less.
The alkaline developable binder resin has a repeating unit represented by the following chemical formula 3, a repeating unit represented by the following chemical formula 4, a repeating unit represented by the following chemical formula 5, a repeating unit represented by the following chemical formula 6, and the following chemical formula. A first alkali-developable binder resin containing a repeating unit represented by 7; and a repeating unit represented by the following chemical formula 4, a repeating unit represented by the following chemical formula 5, and a repeating unit represented by the following chemical formula 6. A second alkaline developable binder resin may be included. Chemical formulas 3 to 7 are as described below.
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 alkali-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 alkali-developable binder resin may be 1:1.01 or more and 1:1.5 or less.

Also provided herein is a dry film photoresist comprising the photosensitive resin layer.
Also provided herein is a dry film photoresist that includes a photosensitive resin layer.
Also provided herein is a photosensitive element comprising a polymeric substrate; and the photosensitive resin layer formed on the polymeric substrate.
Also provided herein is a photosensitive element that includes a polymeric substrate; and the photosensitive resin layer formed on the polymeric substrate.
Also provided herein are circuit boards and display devices comprising the dry film photoresist.
Also provided herein is a circuit board including the photosensitive resin layer.
Also provided herein is a display device including the photosensitive resin layer.
Hereinafter, a photosensitive resin layer, a dry film photoresist using the same, a photosensitive element, a circuit board, and a display device according to specific embodiments of the invention will be described in more detail.
Unless explicitly mentioned herein, terminology is merely to refer to particular embodiments and is not intended to limit the invention.
As used herein, the singular form includes the plural form as well, unless the wording clearly dictates the contrary.

As used herein, the meaning of "comprising" means to embody a particular characteristic, region, integer, step, act, element and/or component, and to embody a particular characteristic, region, integer, step, act, element and/or component. , the presence or addition of components and/or groups.
In this specification, terms including ordinal numbers such as "first" and "second" are used for the purpose of distinguishing one component from another, and are not limited by the above terms. For example, a first component may be named as a second component, and similarly a second component may also be named as a first component without departing from the scope of the present invention.
In this specification, examples of substituents will be explained below, but the substituents are not limited thereto.
As used herein, the term "substituted" means that another functional group is bonded in place of a hydrogen atom in a compound, and the substituted position is the position where a hydrogen atom is substituted, that is, the substituent is substituted. There are no limitations as long as the positions are possible, and when two or more substituents are substituted, the two or more substituents may be the same or different from each other.

As used herein, 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; ; Sulfonic acid group; Sulfonamide group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkylthioxy group; Arylthioxy group; Alkylsulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an alkoxysilylalkyl group; an arylphosphine group; or a heterocyclic group containing one or more of N, O, and S atoms. It means substituted or unsubstituted with one or more substituents, or substituted or unsubstituted with two or more substituents among the above-mentioned substituents linked together. For example, "a substituent in which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and can also be interpreted as a substituent in which two phenyl groups are linked.

または

は他の置換基に連結される結合を意味し、直接結合は、Ｌで表される部分に別途の原子が存在しない場合を意味する。
本明細書で、（メタ）アクリルは、アクリルおよびメタクリルをすべて含む意味である。例えば、（メタ）アクリレートは、アクリレートおよびメタクリレートを全て含む意味である。
本明細書において、アルキル基はアルカン（ａｌｋａｎｅ）に由来する１価の官能基であり、直鎖または分枝鎖であり得、前記直鎖アルキル基の炭素数は特に限定されないが１～２０であることが好ましい。また、前記分枝鎖アルキル基の炭素数は３～２０である。アルキル基の具体的な例としては、メチル、エチル、プロピル、ｎ－プロピル、イソプロピル、ブチル、ｎ－ブチル、イソブチル、ｔｅｒｔ－ブチル、ｓｅｃ－ブチル、１－メチル－ブチル、１－エチル－ブチル、ペンチル、ｎ－ペンチル、イソペンチル、ネオペンチル、ｔｅｒｔ－ペンチル、ヘキシル、ｎ－ヘキシル、１－メチルペンチル、２－メチルペンチル、４－メチル－２－ペンチル、３，３－ジメチルブチル、２－エチルブチル、ヘプチル、ｎ－ヘプチル、１－メチルヘキシル、オクチル、ｎ－オクチル、ｔｅｒｔ－オクチル、１－メチルヘプチル、２－エチルヘキシル、２－プロピルペンチル、ｎ－ノニル、２，２－ジメチルヘプチル、１－エチル－プロピル、１，１－ジメチル－プロピル、イソヘキシル、２－メチルペンチル、４－メチルヘキシル、５－メチルヘキシル、２，６－ジメチルヘプタン－４－イルなどがあるが、これらに限定されない。前記アルキル基は、置換または非置換され得、置換される場合置換基の例示は上述した通りである。
本明細書において、アリール基は、アレーン（ａｒｅｎｅ）に由来する１価の官能基であり、特に限定されないが炭素数６～２０であることが好ましく、単環式アリール基または多環式アリール基であり得る。前記アリール基が単環式アリール基としては、フェニル基、ビフェニル基、テルフェニル基などであり得るが、これらに限定されるものではない。前記多環式アリール基としては、ナフチル基、アントラセニル基、フェナントリル基、ピレニル基、ペリレニル基、クリセニル基、フルオレニル基などであり得るが、これらに限定されるものではない。前記アリール基は、置換または非置換され得、置換される場合置換基の例示は上述した通りである。 In this specification,

or

means a bond connected to another substituent, and a direct bond means when no other atom is present in the moiety represented by L.
As used herein, (meth)acrylic includes both acrylic and methacrylic. For example, (meth)acrylate includes both acrylate and methacrylate.
In this specification, an alkyl group is a monovalent functional group derived from an alkane, and may be a straight chain or a branched chain, and the number of carbon atoms in the straight chain alkyl group is not particularly limited, but is 1 to 20. It is preferable that there be. Further, the branched alkyl group has 3 to 20 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, Pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl , 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptan-4-yl, and the like. The alkyl group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.
In the present specification, the aryl group is a monovalent functional group derived from arene, and is not particularly limited, but preferably has 6 to 20 carbon atoms, and is a monocyclic aryl group or a polycyclic aryl group. It can be. The monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto. The polycyclic aryl group may include, but is not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like. The aryl group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.

In this specification, an alkylene group is a divalent functional group derived from an alkane, and the above explanation regarding the alkyl group is applicable except that these are divalent functional groups. . For example, it may be linear or branched, and may be a methylene group, ethylene group, propylene group, isobutylene group, sec-butylene group, tert-butylene group, pentylene group, hexylene group, etc. The alkylene group may be substituted or unsubstituted.
In the present specification, a polyvalent functional group is a residue from which multiple hydrogen atoms bonded to an arbitrary compound have been removed, such as a divalent functional group, a trivalent functional group, a tetravalent functional group, etc. The functional groups include: As an example, a tetravalent functional group derived from cyclobutane means a residue in which four arbitrary hydrogen atoms bonded to cyclobutane are removed.
As used herein, a direct bond or a single bond means that no atoms or atomic groups are present at the position and that they are connected by a bond line. Specifically, it means the case where no other atom exists in the moiety represented by R _a or L _b (a and b are each an integer of 1 to 20) in the chemical formula.
In this specification, "(photo)cured product" or "(photo)cured" means that all constituent components having curable or crosslinkable unsaturated groups in their chemical structures are cured, crosslinked, or polymerized. It can also include cases in which a portion thereof is cured, crosslinked, or polymerized.
The present invention will be explained in more detail below.
According to one embodiment of the invention, the photopolymerizable compound includes a trifunctional or more polyfunctional (meth)acrylate compound; and an alkali-developable binder resin; and the exposure amount is 10 mJ/cm ² or more and 30 mJ/cm ² or less. Provided is a photosensitive resin layer in which the time (t) from the time when exposure starts to the time when the amount of change in the color coordinate b* value calculated by the following formula 1 is 5.0 is 5 minutes or less. Ru.

前記化学式３中、Ｒ_３’’は水素であり、

前記化学式４中、Ｒ_３’は炭素数１～１０のアルキルであり、

前記化学式５中、Ｒ_４’’は炭素数１～１０のアルキルであり、Ｒ_５’’は炭素数１～１０のアルキルであり、

前記化学式６中、Ａｒは炭素数６～２０のアリールであり、

The present inventors believe that the photosensitive resin layer of the above embodiment has a time (t) of 5 minutes or less until the amount of change in the color coordinate b* value calculated by the above formula 1 is 5.0. As a result, the circuit properties are the same as existing products, but the contrast change time has been increased for technical reasons to speed up the photocuring speed, thereby speeding up the time for the film to develop color, and increasing the amount of color change. The invention was completed after confirming through experiments that improved developability could be ensured.
(1) Alkali-developable binder resin The photosensitive resin layer of the present invention may contain an alkali-developable binder resin.
Specifically, the alkali-developable binder resin may contain at least two or more kinds of alkali-developable binder resins. At least two or more types of alkali-developable binder resins means a mixture of two or more types of alkali-developable binder resins.
The at least two or more alkaline developable binder resins include a repeating unit represented by the following chemical formula 3, a repeating unit represented by the following chemical formula 4, a repeating unit represented by the following chemical formula 5, and a repeating unit represented by the following chemical formula 6. A first alkali-developable binder resin containing a repeating unit and a repeating unit represented by the following chemical formula 7; and a repeating unit represented by the following chemical formula 4, a repeating unit represented by the following chemical formula 5, and a repeating unit represented by the following chemical formula 6. a second alkali-developable binder resin containing repeating units;

In the chemical formula 3, R ₃ '' is hydrogen,

In the chemical formula 4, R ₃ ' is alkyl having 1 to 10 carbon atoms,

In the chemical formula 5, R ₄ '' is alkyl having 1 to 10 carbon atoms, R ₅ '' is alkyl having 1 to 10 carbon atoms,

In the chemical formula 6, Ar is an aryl having 6 to 20 carbon atoms,

前記化学式３中、Ｒ_３’’は水素であり、

前記化学式４中、Ｒ_３’は炭素数１～１０のアルキルであり、

前記化学式５中、Ｒ_４’’は炭素数１～１０のアルキルであり、Ｒ_５’’は炭素数１～１０のアルキルであり、

前記化学式６中、Ａｒは炭素数６～２０のアリールであり、

前記化学式７中、Ｒ_４’は水素であり、Ｒ_５’は炭素数１～１０のアルキルである。
前記化学式３～７中、前記炭素数１～１０のアルキルの具体的な例としては、メチルが挙げられる。 In the chemical formula 7, R ₄ ' is hydrogen, and R ₅ ' is alkyl having 1 to 10 carbon atoms.
Specifically, the first alkali-developable binder resin includes a repeating unit represented by the following chemical formula 3, a repeating unit represented by the following chemical formula 4, a repeating unit represented by the following chemical formula 5, and a repeating unit represented by the following chemical formula 6. and a random copolymer of a repeating unit represented by the following chemical formula 7.

In the chemical formula 3, R ₃ '' is hydrogen,

In the chemical formula 4, R ₃ ' is alkyl having 1 to 10 carbon atoms,

In the chemical formula 5, R ₄ '' is alkyl having 1 to 10 carbon atoms, R ₅ '' is alkyl having 1 to 10 carbon atoms,

In the chemical formula 6, Ar is an aryl having 6 to 20 carbon atoms,

In the chemical formula 7, R ₄ ' is hydrogen, and R ₅ ' is alkyl having 1 to 10 carbon atoms.
In the chemical formulas 3 to 7, a specific example of the alkyl having 1 to 10 carbon atoms is methyl.

前記化学式４－１中、Ｒ_３’は炭素数１～１０のアルキルである。前記化学式４－１中、Ｒ_３’に関する内容は前記化学式４で上述した内容の通りである。前記化学式４－１で表される単量体の具体的な例として、メタクリル酸（Ｍｅｔｈａｃｒｙｌｉｃ ａｃｉｄ、ＭＡＡ）が挙げられる。
前記化学式５で表される繰り返し単位は、下記化学式５－１で表される単量体に由来する繰り返し単位であり得る。

前記化学式５－１中、Ｒ_４’’は炭素数１～１０のアルキルであり、Ｒ_５’’は炭素数１～１０のアルキルである。前記化学式５－１中、Ｒ_４’’およびＲ_５’’に関する内容は前記化学式５で上述した内容の通りである。前記化学式５－１で表される単量体の具体的な例として、メタクリル酸メチル（Ｍｅｔｈｙｌｍｅｔｈａｃｒｙｌａｔｅ、ＭＭＡ）が挙げられる。 Ar is an aryl having 6 to 20 carbon atoms, and a specific example of the aryl having 6 to 20 carbon atoms is phenyl.
The repeating unit represented by the chemical formula 4 may be a repeating unit derived from a monomer represented by the following chemical formula 4-1.

In the chemical formula 4-1, R ₃ ' is alkyl having 1 to 10 carbon atoms. In the chemical formula 4-1, the content regarding R ₃ ' is as described above for the chemical formula 4. A specific example of the monomer represented by the chemical formula 4-1 is methacrylic acid (MAA).
The repeating unit represented by Chemical Formula 5 may be a repeating unit derived from a monomer represented by Chemical Formula 5-1 below.

In the chemical 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 the chemical formula 5-1, the contents regarding R ₄ '' and R ₅ '' are as described above for the chemical formula 5. A specific example of the monomer represented by the chemical formula 5-1 is methyl methacrylate (MMA).

前記化学式６－１中、Ａｒは炭素数６～２０のアリールである。前記化学式６－１中、Ａｒに関する内容は前記化学式６で上述した内容の通りである。前記化学式６－１で表される単量体の具体的な例として、スチレン（Ｓｔｙｒｅｎｅ、ＳＭ）が挙げられる。
前記第１アルカリ現像性バインダー樹脂は、重量平均分子量が３００００ｇ／ｍｏｌ以上１５００００ｇ／ｍｏｌ以下であり、ガラス転移温度は２０℃以上１５０℃以下であり得る。これにより、ドライフィルムフォトレジストのコーティング性、追従性、および回路形成後のレジスト自体の機械的強度が向上する。また、前記第１アルカリ現像性バインダー樹脂は、酸価が１４０ｍｇＫＯＨ／ｇ以上１６０ｍｇＫＯＨ／ｇ以下であり得る。
また、前記第２アルカリ現像性バインダー樹脂は、重量平均分子量が２００００ｇ／ｍｏｌ以上１３００００ｇ／ｍｏｌ以下であり、ガラス転移温度は３０℃以上１６０℃以下であり得る。これにより、ドライフィルムフォトレジストのコーティング性、追従性、および回路形成後のレジスト自体の機械的強度が向上する。 The repeating unit represented by Chemical Formula 6 may be a repeating unit derived from a monomer represented by Chemical Formula 6-1 below.

In the chemical formula 6-1, Ar is an aryl having 6 to 20 carbon atoms. In the chemical formula 6-1, the content regarding Ar is as described above for the chemical formula 6. A specific example of the monomer represented by the chemical formula 6-1 is styrene (SM).
The first alkaline developable binder resin may have a weight average molecular weight of 30,000 g/mol or more and 150,000 g/mol or less, and a glass transition temperature of 20° C. or more and 150° C. or less. This improves the coating properties and trackability of the dry film photoresist, as well as the mechanical strength of the resist itself after circuit formation. Further, the first alkali-developable binder resin may have an acid value of 140 mgKOH/g or more and 160 mgKOH/g or less.
Further, the second alkali-developable binder resin may have a weight average molecular weight of 20,000 g/mol or more and 130,000 g/mol or less, and a glass transition temperature of 30° C. or more and 160° C. or less. This improves the coating properties and trackability of the dry film photoresist, as well as the mechanical strength of the resist itself after circuit formation.

In this specification, the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, commonly known analytical devices, detection devices such as a differential refractive index detector (Refractive Index Detector), and analytical columns are used. Temperature conditions, solvents, and flow rates can be applied.
As a specific example of the measurement conditions, the alkali-developable binder resin is diluted with tetrahydrofuran at a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on solid content). After filtration using a Syringe Filter with a 0.45 μm pore size, 20 μl was injected into the GPC. Tetrahydrofuran (THF) was used as the GPC mobile phase, and the flow rate was 1.0 mL/min. The column consisted of one Agilent PLgel 5 μm Guard (7.5 x 50 mm) and two Agilent PLgel 5 μm Mixed D (7.5 x 300 mm) connected in series, and the detector was an Agilent 1260 Infinity II system, RI. Using Detector Measured at 40°C.
This was mixed with polystyrene standard samples (STD A, B, C, D) in which polystyrene having various molecular weights as shown below were dissolved at a concentration of 0.1 (w/w)% in tetrahydrofuran. The weight average molecular weight (Mw) of the alkali-developable binder resin was determined using a calibration curve formed by filtration with a Syringe Filter and then injecting it into GPC.
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 determined by comparing the reference and the binder polymer using a DSC (Differential Scanning Calorimeter) (manufactured by Perkin-Elmer, DSC-7). The temperature can be measured by maintaining the temperature at 20°C for 15 minutes and then increasing the temperature to 200°C at a rate of 1°C/min.
The acid value of the alkali-developable binder resin was determined by sampling about 1 g of the alkali-developable binder resin, dissolving it in 50 ml of mixed solvent (MeOH 20%, Acetone 80%), and adding two drops of 1%-phenolphthalein indicator. Afterwards, the acid value was measured by titration with 0.1N-KOH.
The first alkaline developable binder resin may have an acid value of 140 mgKOH/g or more and 160 mgKOH/g or less. Further, the second alkali-developable binder resin may have an acid value of 160 mgKOH/g or more and 200 mgKOH/g or less.
Specifically, the glass transition temperature ratio of the first alkali-developable binder resin and the second alkali-developable binder resin is 1:1.5 or more and 1:5 or less, 1:1.5 or more and 1:3 or less, 1:1.5 or more and 1:2 or less, 1:1.5 or more and 1:1.8 or less, 1:1.5 or more and 1:7.5 or less, or 1:1.6 or more and 1:7 or less. obtain.
Further, the acid value ratio of the first alkali-developable binder resin and the second alkali-developable binder resin is 1:1.01 or more and 1:1.5 or less, 1:1.01 or more and 1:1.25 or less, The ratio may be 1:1.01 or more and 1:1.2 or less, or 1:1.01 or more and 1:1.1 or less.
On the other hand, the first alkali-developable binder resin contained in the photosensitive resin layer of the embodiment contains 1 repeating unit represented by the chemical formula 4 per mol of the repeating unit represented by the chemical formula 3. .2 moles or more and 3 moles or less, 1.2 moles or more and 2 moles or less, 1.5 moles or more and 2 moles or less, or 1.5 moles or more and 1.6 moles or less.
In addition, the first alkali-developable binder resin contained in the photosensitive resin layer of the embodiment contains 2 repeating units represented by the chemical formula 5 per mol of the repeating unit represented by the chemical formula 7. It may be contained in an amount of mol or more and 10 mol or less, 3 mol or more and 10 mol or less, 3 mol or more and 5 mol or less, or 4 mol or more and 5 mol or less.

前記化学式４中、Ｒ_３’は炭素数１～１０のアルキルであり、

前記化学式５中、Ｒ_４’’は炭素数１～１０のアルキルであり、Ｒ_５’’は炭素数１～１０のアルキルであり、

前記化学式６中、Ａｒは炭素数６～２０のアリールである。
前記化学式４で表される繰り返し単位は、下記化学式４－１で表される単量体に由来する繰り返し単位であり得る。

前記化学式４－１中、Ｒ_３’は炭素数１～１０のアルキルである。前記化学式４－１中、Ｒ_３’に関する内容は前記化学式４で上述した内容の通りである。前記化学式４－１で表される単量体の具体的な例として、メタクリル酸（Ｍｅｔｈａｃｒｙｌｉｃ ａｃｉｄ、ＭＡＡ）が挙げられる。 Meanwhile, the second alkali-developable binder resin may include a random copolymer of a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5, and a repeating unit represented by the following Chemical Formula 6. .

In the chemical formula 4, R ₃ ' is alkyl having 1 to 10 carbon atoms,

In the chemical formula 5, R ₄ '' is alkyl having 1 to 10 carbon atoms, R ₅ '' is alkyl having 1 to 10 carbon atoms,

In the chemical formula 6, Ar is aryl having 6 to 20 carbon atoms.
The repeating unit represented by the chemical formula 4 may be a repeating unit derived from a monomer represented by the following chemical formula 4-1.

In the chemical formula 4-1, R ₃ ' is alkyl having 1 to 10 carbon atoms. In the chemical formula 4-1, the contents regarding R ₃ ' are as described above for the chemical formula 4. A specific example of the monomer represented by the chemical formula 4-1 is methacrylic acid (MAA).

前記化学式５－１中、Ｒ_４’’は炭素数１～１０のアルキルであり、Ｒ_５’’は炭素数１～１０のアルキルである。前記化学式５－１中、Ｒ_４’’およびＲ_５’’に関する内容は前記化学式５で上述した内容の通りである。前記化学式５－１で表される単量体の具体的な例として、メタクリル酸メチル（Ｍｅｔｈｙｌｍｅｔｈａｃｒｙｌａｔｅ、ＭＭＡ）が挙げられる。
前記化学式６で表される繰り返し単位は、下記化学式６－１で表される単量体に由来する繰り返し単位であり得る。

前記化学式６－１中、Ａｒは炭素数６～２０のアリールである。前記化学式６－１中、Ａｒに関する内容は前記化学式６で上述した内容の通りである。前記化学式６－１で表される単量体の具体的な例として、スチレン（Ｓｔｙｒｅｎｅ、ＳＭ）が挙げられる。
具体的には、前記第１アルカリ現像性バインダー樹脂は、前記化学式４で表される繰り返し単位：前記化学式５で表される繰り返し単位：前記化学式６で表される繰り返し単位を１：（２以上５以下）：（０．２以上０．９以下）、１：（２以上３以下）：（０．５以上０．９以下）、１：（２．５以上３以下）：（０．６以上０．９以下）または１：（２．７５以上３以下）：（０．６以上０．７５以下）で含み得る。 The repeating unit represented by Chemical Formula 5 may be a repeating unit derived from a monomer represented by Chemical Formula 5-1 below.

In the chemical 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 the chemical formula 5-1, the contents regarding R ₄ '' and R ₅ '' are as described above for the chemical formula 5. A specific example of the monomer represented by the chemical formula 5-1 is methyl methacrylate (MMA).
The repeating unit represented by Chemical Formula 6 may be a repeating unit derived from a monomer represented by Chemical Formula 6-1 below.

In the chemical formula 6-1, Ar is an aryl having 6 to 20 carbon atoms. In the chemical formula 6-1, the content regarding Ar is as described above for the chemical formula 6. A specific example of the monomer represented by the chemical formula 6-1 is styrene (SM).
Specifically, the first alkali-developable binder resin has a repeating unit represented by the chemical formula 4: a repeating unit represented by the chemical formula 5: a repeating unit represented by the chemical formula 6 in a ratio of 1:(2 or more). 5 or less): (0.2 or more and 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 0.9 or more) or 1:(2.75 or more and 3 or less):(0.6 or more and 0.75 or less).

Further, the second alkali-developable binder resin has a repeating unit represented by the chemical formula 4: a repeating unit represented by the chemical formula 5: a repeating unit represented by the chemical formula 6 in a proportion of 1:(1.1 or more and 2 or less): (0.2 or more and 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 layer of one embodiment of the invention includes 500 parts by weight or more and 1000 parts by weight or less, and 600 parts by weight or more of a second alkali-developable binder resin based on 100 parts by weight of the first alkali-developable binder resin. It may be contained in an amount of 800 parts by weight or less, 700 parts by weight or more and 800 parts by weight or less.
As mentioned above, by adding an excess of 500 parts by weight or more of the second alkali-developable binder resin to 100 parts by weight of the first alkali-developable binder resin, a hydrophobic function is imparted to the photosensitive resin and development is achieved. A technical effect of increasing resistance to fluids and improving circuit properties may be achieved.
The alkaline developable binder resin is contained in an amount of 20% by weight or more and 80% by weight or less based on the total weight of the photosensitive resin composition based on the solid content. When the content of the alkali-developable binder resin is within the above range, it is possible to obtain the effect of strengthening fine wire adhesion after circuit formation. The solid content on a weight basis refers to the remaining components after removing the solvent from the photosensitive resin composition for forming a photosensitive resin layer.
The content of the alkali-developable binder resin of the present invention may be 40% by weight or more and 70% by weight or less based on the total weight of the photosensitive resin composition. If the content of the alkali-developable binder resin is less than 40% by weight based on the entire photosensitive resin composition, there is a disadvantage that the developing edge is contaminated and defects such as short circuits occur, and if it exceeds 70% by weight, There is a problem of poor circuit properties such as adhesion and resolution.

(2) Photopolymerization initiator The photopolymerization initiator contained in the photosensitive resin composition of the present invention is a substance that initiates a chain reaction of photopolymerizable monomers by UV and other radiation, and is a substance that initiates a chain reaction of photopolymerizable monomers by UV and other radiation. Plays an important role in hardening.
Compounds that can be used as the photopolymerization initiator include anthraquinone derivatives such as 2-methylanthraquinone and 2-ethylanthraquinone; benzoin such as benzoin methyl ether, benzophenone, phenanthrenequinone, and 4,4'-bis-(dimethylamino)benzophenone; Examples include derivatives.
In addition, 2,2'-bis(2-chlorophenyl)-4,4'-5,5'-tetraphenylbisimidazole, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethane- 1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-[4-morpholinophenyl]butane-1 -one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-[4-(2-hydroxymethoxy)phenyl]-2-hydroxy- 2-methylpropan-1-one, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone, 1-(4-isopropylphenyl)2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'- Methyl dimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzylketone dimethyl acetal, benzylketone β-methoxydiethyl acetal, 1-phenyl-1,2-propyldioxime-o,o'-(2-carbonyl)ethoxyether, methyl o-benzoyl Benzoate, bis[4-dimethylaminophenyl)ketone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, Isobutoxybenzoin, tert-butoxybenzoin, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, α, α A compound selected from -dichloro-4-phenoxyacetophenone and pentyl 4-dimethylaminobenzoate can be used as a photopolymerization initiator, but is not limited thereto.

The content of the photopolymerization initiator is 2% by weight or more and 10% by weight or less based on the total weight of the photosensitive resin composition for forming a photosensitive resin layer, based on the solid content. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity can be obtained. The solid content on a weight basis refers to the remaining components of the photosensitive resin composition after removing the solvent.
If the content of the photopolymerization initiator is less than 2% by weight, the light efficiency is low and a large amount of exposure is required, resulting in a very low production efficiency. If the content exceeds 10% by weight, the film may tear. There are disadvantages such as brittleness and increased contamination of the developer, resulting in defects such as short circuits.

前記化学式２中、Ｒ_４は水素、または炭素数１～１０のアルキルであり、Ｒ_５は炭素数１～１０のアルキレンであり、Ｒ_６は炭素数１～２０の中心グループを含むｐが官能基であり、ｎ２は１～２０の整数であり、ｐは前記Ｒ_６に置換される官能基数であり、３～１０の整数である。
また、前記化学式２中、ｎ２は１～２０の整数、１～１０の整数、または１～５の整数であり、ｐは前記Ｒ_６に置換される官能基数を意味するもので、３～１０の整数、３～５の整数、または３～４の整数である。
すなわち、前記化学式２中、前記Ｒ_６に置換される官能基数を意味するｐが３～１０の整数であるので、前記化学式２で表される多官能（メタ）アクリレート化合物が３官能以上の多官能（メタ）アクリレート化合物であり得る。
具体的には、前記多官能（メタ）アクリレート化合物は、下記化学式２－１で表される。

前記化学式２－１中、Ｒ_７～Ｒ_９はそれぞれ独立して、炭素数１～１０のアルキレンであり、Ｒ_１０～Ｒ_１２はそれぞれ独立して、水素、または炭素数１～１０のアルキルであり、ｎ３～ｎ５はそれぞれ独立して、１～２０の整数である。
前記化学式２－１中、ｎ３～ｎ５は１～２０の整数、１～１０の整数、または１～５の整数である。 (3) Photopolymerizable compound The photopolymerizable compound of the present invention has resistance to a developer after UV exposure and enables pattern formation.
The photopolymerizable compound of the present invention may contain a trifunctional or more polyfunctional (meth)acrylate compound.
Specifically, the trifunctional or higher polyfunctional (meth)acrylate compound has three or more alkylene oxide groups and (meth)acrylate functional groups each having 1 to 10 carbon atoms bonded to a central group having 1 to 20 carbon atoms. It can have a similar structure.
More specifically, the trifunctional or higher polyfunctional (meth)acrylate compound may include a compound represented by the following chemical formula 2.

In the 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, and R ₆ is a group in which p contains 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 on R ₆ , and is an integer of 3 to 10.
Further, in the chemical 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 means the number of functional groups substituted with R ₆ , and 3 to 10. , an integer from 3 to 5, or an integer from 3 to 4.
That is, in the chemical formula 2, since p, which means the number of functional groups substituted with the R ₆ , is an integer of 3 to 10, the polyfunctional (meth)acrylate compound represented by the chemical formula 2 has a trifunctional or higher functionality. It can be a functional (meth)acrylate compound.
Specifically, the polyfunctional (meth)acrylate compound is represented by the following chemical formula 2-1.

In the chemical formula 2-1, R ₇ to R ₉ are each independently alkylene having 1 to 10 carbon atoms, and 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 20.
In the chemical formula 2-1, n3 to n5 are integers of 1 to 20, integers of 1 to 10, or integers of 1 to 5.

前記一実施形態の感光性樹脂層が前記化学式２で表される多官能（メタ）アクリレート化合物を含むことによって、単官能（メタ）アクリレート化合物に比べて前記化学式２で表される多官能（メタ）アクリレート化合物が光硬化時、架橋結合が増加し、反応基が多い技術的原因によって前記化学式２で表される多官能（メタ）アクリレート化合物のみの添加時、問題になる回路の物性低下を防止し、発色変化量を増加させる効果を実現することができる。
一方、前記光重合性化合物は、単官能（メタ）アクリレート化合物をさらに含み得る。
具体的には、前記単官能（メタ）アクリレート化合物は、炭素数１～１０のアルキレンオキシド基を含む（メタ）アクリレートを含み得る。
すなわち、前記光重合性化合物は、炭素数１～１０のアルキレンオキシド基を含む（メタ）アクリレートを含む単官能（メタ）アクリレート化合物；および炭素数１～２０の中心グループに炭素数１～１０のアルキレンオキシド基および（メタ）アクリレート官能基がそれぞれ３個以上結合した構造を有する３官能以上の多官能（メタ）アクリレート化合物；を含み得る。 An example of the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 is not particularly limited, but may be, for example, T063 (Trimethylolpropane [EO] ₆ triacrylate) represented by Chemical Formula B below.

By including the polyfunctional (meth)acrylate compound represented by the chemical formula 2 in the photosensitive resin layer of the above embodiment, the polyfunctional (meth)acrylate compound represented by the chemical formula 2 is more effective than the monofunctional (meth)acrylate compound. ) When the acrylate compound is photocured, cross-linking increases and prevents the deterioration of the physical properties of the circuit, which is a problem when only the polyfunctional (meth)acrylate compound represented by the chemical formula 2 is added due to technical reasons such as a large number of reactive groups. Therefore, it is possible to achieve the effect of increasing the amount of change in color development.
Meanwhile, the photopolymerizable compound may further include a monofunctional (meth)acrylate compound.
Specifically, the monofunctional (meth)acrylate compound may include a (meth)acrylate containing an alkylene oxide group having 1 to 10 carbon atoms.
That is, the photopolymerizable compound is a monofunctional (meth)acrylate compound containing a (meth)acrylate containing an alkylene oxide group having 1 to 10 carbon atoms; It may contain a trifunctional or more polyfunctional (meth)acrylate compound having a structure in which three or more alkylene oxide groups and three or more (meth)acrylate functional groups are bonded to each other.

前記化学式１中、Ｒ_１は水素、または炭素数１～１０のアルキルであり、Ｒ_２は炭素数１～１０のアルキレンであり、Ｒ_３は炭素数１～１０のアルキルであり、ｎ１は１～２０の整数である。
すなわち、本発明の一実施形態による感光性樹脂層は、単官能（メタ）アクリレート化合物、および多官能（メタ）アクリレート化合物の混合物を含み得る。
具体的には、前記化学式１中、ｎ１は１～２０の整数、１～１０の整数、または５～１０の整数である。前記化学式１で表される単官能（メタ）アクリレート化合物の例は特に限定されないが、例えば、下記化学式Ａで表されるＡ０４０（Ｍｅｔｈｏｘｙ ｐｒｏｐｙｌｅｎｅ ｇｌｙｃｏｌ ［４００］ ａｃｒｙｌａｔｅ）であり得る。

前記一実施形態の感光性樹脂層が前記化学式１で表される単官能（メタ）アクリレート化合物を含むことによって、光硬化速度を速くする技術的原因によって露光部分のフィルムの色変化を速く実現する効果を得ることができる。 More specifically, the monofunctional (meth)acrylate compound may include a monofunctional (meth)acrylate compound represented by Chemical Formula 1 below.

In the 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, and n1 is 1 It is an integer between ~20.
That is, the photosensitive resin layer according to one embodiment of the present invention may include a mixture of a monofunctional (meth)acrylate compound and a polyfunctional (meth)acrylate compound.
Specifically, in the chemical formula 1, n1 is an integer of 1 to 20, an integer of 1 to 10, or an integer of 5 to 10. An example of the monofunctional (meth)acrylate compound represented by the chemical formula 1 is not particularly limited, but may be, for example, A040 (methoxy propylene glycol [400] acrylate) represented by the following chemical formula A.

By including the monofunctional (meth)acrylate compound represented by the chemical formula 1 in the photosensitive resin layer of the above embodiment, the color change of the exposed portion of the film is quickly realized due to the technical cause of increasing the photocuring speed. effect can be obtained.

On the other hand, the photosensitive resin layer of the embodiment includes 110 parts by weight or more and 500 parts by weight or less of the trifunctional or higher polyfunctional (meth)acrylate compound, based on 100 parts by weight of the monofunctional (meth)acrylate compound. It may be contained in an amount of 110 parts by weight or more and 300 parts by weight or less, 110 parts by weight or more and 200 parts by weight or less, or 150 parts by weight or more and 200 parts by weight or less.
The photosensitive resin layer of the one embodiment contains the polyfunctional (meth)acrylate compound in excess of the monofunctional (meth)acrylate compound, thereby forming a monofunctional (meth)acrylate compound represented by the chemical formula 1. The effect of increasing the photocuring speed of the acrylate compound to quickly change the color of the film, and increasing the crosslinking during photocuring of the polyfunctional (meth)acrylate compound represented by the chemical formula 2, resulting in only monofunctional substances. It is possible to simultaneously achieve the effects of preventing the deterioration of the physical properties of the circuit that occurs when adding , and increasing the amount of color development due to the increase in the amount of reactive groups, and the change in the color coordinate b * value calculated by the above formula 1. The time (t) until the amount reaches 5.0 can be set to 5 minutes or less, thereby ensuring excellent developability.
In the case where the photosensitive resin layer of the above embodiment contains less than 100 parts by weight of the polyfunctional (meth)acrylate compound relative to 100 parts by weight of the monofunctional (meth)acrylate compound, the circuit deterioration and the amount of color change are reduced. Reduced technical problems may occur.
Meanwhile, the photopolymerizable compound may further include a bifunctional (meth)acrylate compound including an alkylene glycol di(meth)acrylate and a urethane di(meth)acrylate.

That is, the photosensitive resin layer of the embodiment includes a photopolymerizable compound, and the photopolymerizable compound is a monofunctional (meth)acrylate compound, a polyfunctional (meth)acrylate compound, or an alkylene glycol di(meth)acrylate. and difunctional (meth)acrylate compounds including urethane di(meth)acrylates.
Examples of the alkylene glycol di(meth)acrylate include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. Tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate di(meth)acrylate), polypropylene glycol di (meth)acrylate, butylene glycol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate diglycidyl ether di(meth) acrylate), diethylene glycol diglycidyl ether di(meth)acrylate, Miwon Specialty Chemical Co. , Ltd. Products 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), Miwon Specialty Chemical Co. , Ltd. Product Miramer M2100 (BPA (EO) 10DA, Bisphenol A (EO) 10 Diacrylate), Miramer M2200 (BPA (EO) 20DA, Bisphenol A (EO) 20 Diacrylate), Miramer M2101 (Bisphenol A (EO)10 Dimethacrylate) etc. can be used.
Further, as the urethane di(meth)acrylate, KUA-1330h or the like can be used.

The urethane-based di(meth)acrylate has a larger molecular weight than existing simple alkylene oxides and has a linear structure, so it can impart flexibility. This is a cause of improving the tenting properties required for dry film photoresists (DFR) for the outer layer, and the hydrophobicity of polyol, which is one of the constituent elements of urethane acrylate, improves the resistance to plating solutions, which are strong acids. The plating solution is not contaminated.
The urethane di(meth)acrylate is produced 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 then reacting the obtained urethane compound with a hydroxy group and an ethylenic inorganic compound. It is obtained by reacting compounds having all saturated groups.
As the polyether compound having a hydroxy group, glycols such as polytetramethylene glycol, polyoxyethylene, polyoxypropylene, and polyoxytetrahydrofuran are used as polyether glycols, and as the polyester compound having a hydroxy group, adipic acid A condensed compound of 1,4-butadiol, etc. is used.
The diisocyanate compounds include aliphatic diisocyanate compounds having a divalent aliphatic group such as an alkylene group, alicyclic diisocyanate compounds having a divalent alicyclic group such as cycloalkylene, aromatic diisocyanate compounds, and isocyanurates thereof. Examples thereof include chemically modified products, carbodiimidized products, biuret-modified products, and the like.
At this time, examples of the aliphatic diisocyanate compound include hexamethylene isocyanate, trimethylhexamethylene diisocyanate, and the like.
Examples of the alicyclic diisocyanate compound include isophorone diisocyanate, methylenebis(cyclohexyl)diisocyanate, and 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane.
As the aromatic diisocyanate compound, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate or a dimerized polymer of 2,6-toluene diisocyanate, (o, p or m)-xylene Examples include diisocyanate, diphenylmethane diisocyanate, and 1,5-naphthalene diisocyanate.

These may be used alone or in combination of two or more. Further, it may contain an isocyanate compound having two or more isocyanate groups such as triphenylmethane triisocyanate and tris(isocyanate phenyl)thiophosphate. Among them, alicyclic diisocyanate compounds are preferred from the viewpoint of increasing the flexibility and toughness of the photocured product and improving the adhesion to the substrate.
A urethane compound is produced by reacting the polyether compound or polyester compound having a hydroxy group with a diisocyanate compound. In the reaction, the diisocyanate compound is preferably used in a molar ratio of 1.01 to 2.0, preferably 1.1 to 2.0 molar, with respect to 1 mol of the polyether compound or polyester compound having a hydroxy group. More preferred. 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.
Furthermore, in the reaction for synthesizing a urethane compound, it is preferable to add dibutyltin dilaurate as a catalyst.
The reaction temperature is preferably 60 to 120°C. If the temperature 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.
Examples of the compound having both a hydroxy group and an ethylenically unsaturated group to be reacted with the urethane compound produced in this way include a compound having a hydroxy group and a (meth)acryloyl group in the molecule. Such compounds include hydroxy (meth)acrylate, caprolactone adducts or alkylene oxide adducts of hydroxy (meth)acrylate, ester compounds produced by reacting polyhydric alcohols 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 hydroxy (meth)acrylate include hydroxyethyl (meth)acrylate/caprolactone adduct, hydroxypropyl (meth)acrylate/caprolactone adduct, and hydroxybutyl (meth)acrylate/caprolactone adduct; Examples of the alkylene adduct include hydroxyethyl (meth)acrylate/alkylene oxide adduct, hydroxypropyl (meth)acrylate/propylene oxide adduct, and hydroxybutyl (meth)acrylate/butylene oxide adduct.
Examples of the ester compounds include glycerin mono(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane mono(meth)acrylate, and ditrimethylol. Examples include propane tri(meth)acrylate, ethylene oxide adduct di(meth)acrylate of trimethylolpropane, and propylene oxide adduct di(meth)acrylate of trimethylolpropane. These may be used alone or in combination of two or more.
The urethane di(meth)acrylate is a compound derived from an addition reaction between the urethane compound and the compound having all of the hydroxy groups and ethylenically unsaturated groups, and the urethane di(meth)acrylate is a compound derived from the addition reaction of the urethane compound and the compound having all of the hydroxy groups and ethylenically unsaturated groups, and is It is obtained by adding compounds having all sexually unsaturated groups at a molar ratio of 2.0 to 2.4 and carrying out an addition reaction at 60 to 90°C.
The urethane di(meth)acrylate preferably has a weight average molecular weight within the range of 1,000 to 60,000 g/mol. If the weight average molecular weight is less than 1,000 g/mol, it will be difficult to sufficiently increase flexibility and toughness, and the adhesion of the substrate will not be improved; if it exceeds 60,000 g/mol, Problems such as poor developability and slow development time may occur, so the urethane di(meth)acrylate according to the present invention preferably has a weight average molecular weight of 1,000 to 60,000 g/mol.

In the present invention, urethane di(meth)acrylate having a weight average molecular weight of 1,000 to 60,000 g/mol is added to the photosensitive resin composition for forming a photosensitive resin layer in an amount of 1 to 20% by weight, preferably 1.0% by weight. Contains 5 to 15% by weight. If the content of the urethane di(meth)acrylate having a weight average molecular weight of 1,000 to 60,000 g/mol is less than 1% by weight, the effect is small, and if it exceeds 20% by weight, exposure to The disadvantage is that the development time in the post-development step increases rapidly, and a large amount of scum and sludge are generated.
The photosensitive resin layer of the embodiment includes 1 part by weight or more and 50 parts by weight or less, 1 part by weight or more and 30 parts by weight of urethane di(meth)acrylate based on 100 parts by weight of the alkylene glycol di(meth)acrylate. The following may be included in an amount of 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.
By containing the urethane di(meth)acrylate in an amount of 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the alkylene glycol di(meth)acrylate, the photosensitive resin composition of the above embodiment can have a circuit. Technical effects such as a decrease in physical properties or peeling, and a change in development time are realized.
Specifically, the photosensitive resin layer of the embodiment includes 500 parts by weight or more and 1500 parts by weight or less of the difunctional (meth)acrylate compound, and 500 parts by weight, based on 100 parts by weight of the monofunctional (meth)acrylate compound. Parts by weight or more and 1000 parts by weight 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 layer of the one embodiment includes the polyfunctional (meth)acrylate compound in an amount of 110 parts by weight or more based on 100 parts by weight of the monofunctional (meth)acrylate compound, and It may contain an acrylate compound in an amount of 500 parts by weight or more and 1500 parts by weight or less.
In addition, the photosensitive resin layer of the embodiment includes 500 parts by weight or more and 1000 parts by weight or less, and 500 parts by weight or more of the bifunctional (meth)acrylate compound based on 100 parts by weight of the polyfunctional (meth)acrylate compound. It may be contained in an amount of 800 parts by weight or less, 500 parts by weight or more and 750 parts by weight or less, 500 parts by weight or more and 700 parts by weight or less, and 500 parts by weight or more and 600 parts by weight or less.

As described above, by including a monofunctional (meth)acrylate compound, a polyfunctional (meth)acrylate compound, and a difunctional (meth)acrylate compound and at the same time satisfying the above weight range, The photosensitive resin composition is capable of exhibiting appropriate circuit physical properties, and when a light amount of 10 mJ/cm ² or more is applied, a technical effect of rapid color development and color change of the exposed area is realized.
In the present invention, the monofunctional photopolymerizable compound may be contained 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 for forming a photosensitive resin layer.
Further, in the present invention, the polyfunctional photopolymerizable compound may be contained 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 for forming a photosensitive resin layer.
That is, the photosensitive resin layer contains the monofunctional photopolymerizable compound in an amount of 0.1% by weight or more and 2.5% by weight or less based on the entire weight of the photosensitive resin composition for forming the photosensitive resin layer. , the polyfunctional photopolymerizable compound may be contained in an amount of 2.6% by weight or more and 5.0% by weight or less.
The photosensitive resin layer contains less than 0.1% by weight of the monofunctional photopolymerizable compound or 2% by weight of the polyfunctional photopolymerizable compound based on the total weight of the photosensitive resin composition for forming the photosensitive resin layer. If the amount is less than .6% by weight, the effect of adding the compounds represented by chemical formulas 1 and 2 is small, and if the monofunctional photopolymerizable compound exceeds 2.5% by weight or the polyfunctional photopolymerizable compound If it exceeds 5.0% by weight, the hydrophobicity may increase and a problem may arise in which the development time in the post-exposure and development step increases rapidly.

Further, as the photopolymerizable compound of the photosensitive resin layer of the above embodiment, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ylene glycol dimethacrylate), propylene glycol Propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate ylate), neopentyl glycol dimethacrylate, 1,6-hexane glycol dimethacrylate (1, 6-hexane glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, glycerinase glycerin dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate trimethacrylate), dipentaerythritol pentamethacrylate, 2,2-bis(4-methacryloxydiethoxyphenyl)propane (2,2-bis(4-methacryloxydiethoxyphe) nyl)propane), 2,2-bis(4- 2,2-bis(4-methacryloxypolyethoxyphenyl)propane, 2-hydroxy-3-methacryloyloxypropyl methacrylate late), ethylene glycol diglycidyl ether dimethacrylate ( ethylene glycol diglycidyl ether dimethacrylate), diethylene glycol diglycidyl ether dimethacrylate, diglycidyl phthalate Phthalic acid diglycidyl ester dimethacrylate, glycerin polyglycidyl ether polymethacrylate and urethane It may further include a polyfunctional (meth)acrylate containing a group.

The content of the photopolymerizable compound is 10% by weight or more and 70% by weight or less based on the total weight of the photosensitive resin composition for forming a photosensitive resin layer, based on the solid content. When the content of the photopolymerizable compound is within the above range, the effect of enhancing photosensitivity, resolution, adhesion, etc. can be obtained.
The photosensitive resin composition for forming a photosensitive resin layer contains, based on the solid content, an alkali-developable binder resin of 20% to 80% by weight, a photopolymerization initiator of 0.1% to 10% by weight, and It may contain 10% by weight or more and 70% by weight or less of a photopolymerizable compound. The solid content on a weight basis refers to the remaining components of the photosensitive resin composition after removing the solvent.
The photosensitive resin composition may further include a solvent. The solvent is generally selected from methyl ethyl ketone (MEK), methanol, THF, toluene, and acetone, and the solvent is not particularly limited, and the content may vary depending on the photopolymerization initiator, It can be adjusted as appropriate depending on the content of the alkali-developable binder resin and photopolymerizable compound.
Further, the photosensitive resin composition may further contain other additives as necessary, and examples of the other additives include dibutyl phthalate in the form of a phthalate ester, diheptyl phthalate, dioctyl phthalate, diallyl phthalate, etc. as a plasticizer. Phthalates; glycol ester forms of triethylene glycol diacetate and tetraethylene glycol diacetate; acid amide forms of p-toluenesulfonamide, benzenesulfonamide, n-butylbenzenesulfonamide; triphenyl phosphate, and the like can be used.
In the present invention, a leuco dye or a coloring substance may be added to improve the handling properties of the photosensitive resin composition. Examples of the leuco dye include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, and fluoran dye. Among these, it is preferable to use leuco crystal violet because it provides good contrast. When a leuco dye is included, 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 developing contrast, the content is preferably 0.1% by weight or more, and from the viewpoint of maintaining storage stability, the content is preferably 10% by weight or less.

Examples of coloring substances include toluenesulfonic acid monohydrate, fuchsin, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green, Diamond Green, and Basic Blue 20. Can be mentioned. The amount of the coloring substance added may be 0.001% by weight or more and 1% by weight or less based on the photosensitive resin composition. A content of 0.001% by weight or more has the effect of improving handleability, and a content of 1% by weight or less has the effect of maintaining storage stability.
Other additives may further include thermal polymerization inhibitors, dyes, discoloring agents, adhesion promoters, and the like.
On the other hand, in the photosensitive resin layer of the above embodiment, the amount of change in the color coordinate b* value calculated by the following formula 1 from the time when exposure is started at an exposure amount of 10 mJ/cm ² or more and 30 mJ/cm ² or less The time (t) up to the point where the value is 5.0 can be 5 minutes or less, 3 minutes or less, 30 seconds or more and 3 minutes or less, or 30 seconds or more and 2 minutes or less.
[Formula 1]
Amount of change in color coordinate b ^* value during exposure time (t) (△b ^* ₁ ) = (b ^* ₀ - b ^* ₁ )
In the formula 1,
b ^* ₁ is the color coordinate (b ^* ) value of the photosensitive resin layer after exposure for t minutes at an exposure amount of 10 mJ/cm ² or more and 30 mJ/cm ² or less,
b ^* ₀ is the color coordinate (b ^* ) value of the photosensitive resin layer before exposure.
This is realized by the photosensitive resin layer of the embodiment containing the photopolymerizable compound described above.

Specifically, the photosensitive resin layer of the embodiment includes a monofunctional (meth)acrylate compound represented by the chemical formula 1 and a polyfunctional (meth)acrylate compound represented by the chemical formula 2, By including the polyfunctional (meth)acrylate compound in an amount of 100 parts by weight or more with respect to 100 parts by weight of the functional (meth)acrylate compound, the amount of change in the color coordinate b ^* value calculated by the formula 1 is 5.0. The time to a certain point (t) may be 5 minutes or less.
The time (t) from the time when exposure is started with an exposure amount of 10 mJ/cm ² or more and 30 mJ/cm ² or less to the time when the amount of change in the color coordinate b ^* value calculated by the above formula 1 is 5.0 is By setting the time to 5 minutes or less, the reactivity of the photosensitive resin layer of the one embodiment is fast, and the dry film photoresist including the photosensitive resin layer of the one embodiment is excellent in color development time and degree. Therefore, when exposing the dry film photoresist, the alignment recognition rate for the product is increased, which not only shortens production time and reduces the defective rate, but also improves the physical properties of the display device including the dry film photoresist. can be realized.
Meanwhile, in the photosensitive resin layer, the amount of change in the color coordinate b ^* value calculated by Equation 2 below may be 0.6 or more and 14.0 or less.
[Formula 2]
Color coordinate b ^* value change amount (△b ^* ₁ ) = (b ^* ₀ - b ^* ₁ ) at 1 minute exposure time
In the above formula 2, b ^* ₁ is the color coordinate (b*) value of the photosensitive resin layer after exposure for 1 minute at an exposure amount of 10 mJ/cm2 or ^more and 30 mJ/ ^cm2 or less, and b ^* ₀ is the value of the color coordinate (b ^* ) of the photosensitive resin layer after exposure This is the color coordinate (b ^* ) value of the previous photosensitive resin layer.

The present inventors conducted the invention after confirming through experiments that excellent developability can be ensured when the amount of change in the color coordinate b ^* value calculated by the above formula 2 is 0.6 or more and 14.0 or less. completed.
On the other hand, the photosensitive resin layer of the above-mentioned embodiment has a color coordinate b ^* value change amount of 0.6 or more and 14.0 or less, 3.1 or more and 13.5 or less, and 4 or more and 8 or less, or 4.1 or more and 7.5 or less. This is realized by the photosensitive resin layer of the embodiment containing the photopolymerizable compound described above.
[Formula 2]
Color coordinate b ^* value change amount (△b ^* ₁ ) = (b ^* ₀ - b ^* ₁ ) at 1 minute exposure time
In the above formula 2, b ^* ₁ is the color coordinate (b*) value of the photosensitive resin layer after exposure for 1 minute at an exposure amount of 10 mJ/cm2 or ^more and 30 mJ/ ^cm2 or less, and b ^* ₀ is the value of the color coordinate (b ^* ) of the photosensitive resin layer after exposure. This is the color coordinate (b ^* ) value of the previous photosensitive resin layer.
Specifically, the photosensitive resin layer of the embodiment includes a monofunctional (meth)acrylate compound represented by the chemical formula 1 and a polyfunctional (meth)acrylate compound represented by the chemical formula 2, The amount of change in the color coordinate b ^* value calculated by Equation 2 may be greater than or equal to 0.6 and less than or equal to 14.0.
When the amount of change in the color coordinate b* value calculated by the above formula 2 is 0.6 or more and 14.0 or less, the reactivity of the photosensitive resin layer of the above embodiment becomes faster, and Excellent color development time and degree of dry film photoresist containing a photosensitive resin layer. Therefore, when exposing the dry film photoresist, the alignment recognition rate for the product is increased, which not only shortens production time and reduces the defect rate, but also improves the physical properties of the display device including the dry film photoresist. can be realized.

The thickness of the photosensitive resin layer to be measured for the color coordinate (b ^* ) value is 15 μm or more and 50 μm or less, 15 μm or more and 45 μm or less, 15 μm or more and 40 μm or less, or 20 μm or more and 40 μm or less, or 25 μm or more and 40 μm or less. obtain.
Further, the photosensitive resin layer, which is the object of measurement of the color coordinate (b ^* ) value, has an area of a cross section parallel to the ground of 0.10 cm ² or more and 5.00 cm ² or less, or 2.00 cm ² or more and 4.00 cm ² It can be: The thickness and cross-sectional area of the photosensitive resin layer can be measured using an optical microscope.
b ^* ₀ and b ^* ₁ in Equation 2 can be measured using a color difference meter. Specifically, b ^* ₀ and b ^* ₁ mean b ^* values in color coordinates (a, b), which are values of coordinate axes that each indicate a unique color. b ^* has positive (+) and negative (-) values based on 0; a positive number (+) means it will be yellowish; a negative number (-) If so, it means that it has a blue tinge.
b ^* ₀ and b ^* ₁ in Formula 2 can be measured by the ASTM E313 measurement method using CM-2600d manufactured by Konica Minolta.
Specifically, the color coordinates of Equation 2, i.e., b ^* ₀ and b ^* ₁ , are determined by ASTM E313-96 (coefficient: D65/10 degrees) using a color difference meter such as CM-2600d manufactured by Konica Minolta. can be measured based on
In addition, the color coordinates in Equation 2, that is, b ^* ₀ and b ^* ₁ , are determined using a color difference meter such as CM-2600d manufactured by Konica Minolta in SCI (specular component included) mode or It may be measured in SCE (specular component excluded) mode.
The SCI (specular component included) mode means a mode that measures color coordinates for total reflected light including not only diffuse reflected light but also specular reflected light.

Further, the SCE (specular component excluded) mode means a mode in which color coordinates of diffusely reflected light excluding specularly reflected light are measured.
That is, in the above-mentioned embodiment, the amount of change in the color coordinate b ^* value calculated by the above-mentioned formula 2 is calculated using a color difference meter such as CM-2600d manufactured by Konica Minolta. ) mode, or the color coordinate b ^* value measured ⁱⁿ SCE (specular component excluded) mode using a color difference meter such as CM-2600d manufactured by Konica Minolta. It can be one of the amount of change.
In the formula 2, b ^* ₁ is the color coordinate (b *) value of the photosensitive resin layer after exposure for 1 minute at an exposure amount of 10 mJ/cm ² or more and 30 mJ/cm ² or less, and b ^* ₀ is the color coordinate (b *) value of the photosensitive resin layer after exposure. It can be the color coordinate (b*) value of the previous photosensitive resin layer.
Since b ^* ₁ in the above formula 2 is the color coordinate (b ^* ) value of the photosensitive resin layer after exposure for 1 minute at an exposure amount of 10 mJ/cm ² or more and 30 mJ/cm ² or less, it is calculated by the above formula 2. The amount of change in the color coordinate b ^* value (Δb ^* ₁ ) means the amount of change in the initial color coordinate b ^* value after exposure of the photosensitive resin layer of the one embodiment.
That is, since the amount of change in the color coordinate b ^* value calculated by the formula 2 for the photosensitive resin layer of the one embodiment is 0.6 or more and 14.0 or less, the photosensitivity of the one embodiment The amount of change in the initial color coordinate b ^* value of the resin layer after exposure may be 0.6 or more and 14.0 or less.
The fact that the amount of change in the color coordinate b ^* value calculated by the formula 2 is 0.6 or more and 14.0 or less means that the polyfunctional (meth)acrylate compound of the embodiment ) By including an acrylate compound in excess, the photocuring speed of the monofunctional (meth)acrylate compound represented by the chemical formula 1 is increased and the color change of the film is quickly realized. When photocuring a functional (meth)acrylate compound, it increases crosslinking, prevents the deterioration of circuit properties that occurs when only a monofunctional substance is added, and increases the amount of reactive groups, increasing the amount of color change. This is realized by the simultaneous occurrence of the two, thereby ensuring excellent developability.

Meanwhile, for the photosensitive resin layer of the embodiment, the amount of change in the color coordinate b ^* value calculated using Equation 3 below may be 2.2 or more and 14.0 or less.
[Formula 3]
Color coordinate b ^* value change amount (△b ^* ₃ ) = (b ^* ₀ - b ^* ₃ ) at 3 minute exposure time
In the formula 3,
b ^* ₃ is the color coordinate (b*) value of the photosensitive resin layer after exposure for 3 minutes at an exposure amount of 10 mJ/ ^cm2 or more and 30 mJ/cm2 or ^less , and b ^* ₀ is the color coordinate (b ^* ) value of the photosensitive resin layer before exposure. The color coordinate (b ^* ) value of the layer.
The fact that the amount of change in the color coordinate b ^* value calculated by the formula 3 is 2.2 or more and 14.0 or less means that the polyfunctional (meth)acrylate compound of the embodiment ) By including an acrylate compound in excess, the photocuring speed of the monofunctional (meth)acrylate compound represented by the chemical formula 1 is increased and the color change of the film is quickly realized, and the multifunctional acrylate compound represented by the chemical formula 2 is When photocuring a functional (meth)acrylate compound, it increases crosslinking, prevents the deterioration of circuit properties that occurs when only a monofunctional substance is added, and increases the amount of reactive groups, increasing the amount of color change. This is realized by the simultaneous occurrence of the two, thereby ensuring excellent developability.
Further, for the photosensitive resin layer of the above embodiment, the amount of change in the color coordinate b ^* value calculated by the following formula 4 is 4.0 or more and 14.3 or less, or 7.0 or more and 13.0 or less. could be.
[Formula 4]
Color coordinate b ^* value change amount (△b ^* ₅ ) = (b ^* ₀ - b ^* ₅ ) at 5 minutes exposure time
In the above formula 4, b ^* ₅ is the color coordinate (b*) value of the photosensitive resin layer after exposure for 5 minutes at an exposure amount of 10 mJ/cm2 or ^more and 30 mJ/ ^{cm2 or} less, and b ^* ₀ is the value of the color coordinate (b ^* ) of the photosensitive resin layer after exposure. This is the color coordinate (b ^* ) value of the previous photosensitive resin layer.

The fact that the amount of change in the color coordinate b ^* value calculated by the formula 4 for the photosensitive resin layer is 4.0 or more and 14.3 or less means that the polyfunctional (meth)acrylate compound By including an excessive amount of the functional (meth)acrylate compound, the effect of increasing the photocuring speed of the monofunctional (meth)acrylate compound represented by the chemical formula 1 and quickly realizing a color change of the film, and the effect of realizing a rapid color change of the film as represented by the chemical formula 2. When photo-curing polyfunctional (meth)acrylate compounds, cross-linking is increased to prevent deterioration of circuit properties that occurs when only monofunctional substances are added, and the amount of reactive groups is increased to increase the amount of color change. This is realized by the simultaneous occurrence of the effects of oxidation, thereby ensuring excellent developability.

2. Dry Film Photoresist According to another embodiment of the invention, there is provided a dry film photoresist comprising the photosensitive resin layer of the above embodiment. The contents of the photosensitive resin layer include all the contents described above in the embodiment.
Specifically, the photosensitive resin layer may include a dried or cured photosensitive resin composition. The above-mentioned dried material means a substance obtained through a drying process of a photosensitive resin composition. The cured product means a substance obtained through a curing process of a photosensitive resin composition.
The thickness of the dry film photoresist is not particularly limited, but can be adjusted as appropriate within the range of, for example, 0.01 μm to 1 mm. When the thickness of the dry film photoresist increases or decreases by a certain value, the physical properties measured by the dry film photoresist may also change by a certain 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 the production of a 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, such as acrylic film, polyethylene terephthalate (PET) film, triacetyl cellulose (TAC) film, polynorbornene (PNB) film, and cycloolefin polymer (COP) film. , and polycarbonate (PC) film. The thickness of the base film is not particularly limited, but can be adjusted as appropriate within the range of, for example, 0.01 μm to 1 mm.
The protective film serves as a protective cover to prevent damage to the resist during handling and protect the photosensitive resin layer from foreign substances such as dust, and does not form a base film for the photosensitive resin layer. Laminated on the back side. The protective film plays the role of protecting the photosensitive resin layer from the outside, and is designed to easily separate when the dry film photoresist is applied in a subsequent process, and to prevent it from being released from the mold during storage and distribution. Appropriate mold releasability and adhesion are required.

Various plastic films can be used as the protective film, such as acrylic film, polyethylene (PE) film, polyethylene terephthalate (PET) film, triacetyl cellulose (TAC) film, polynorbornene (PNB) film, and cycloolefin. It may include one or more plastic films selected from the group consisting of polymer (COP) films and polycarbonate (PC) films. The thickness of the protective film is not particularly limited, but can be adjusted as appropriate within the range of, for example, 0.01 μm to 1 mm.
Examples of the method for producing the dry film photoresist are not particularly limited. For example, after coating a photosensitive resin composition on a common base film such as polyethylene terephthalate using a common coating method, A dry film can be manufactured by drying and laminating a conventional protective film such as polyethylene on the top surface of the dried photosensitive resin layer.
The method of coating the photosensitive resin composition is not particularly limited, and for example, a method such as a coating bar may be used.
The step of drying the coated photosensitive resin composition can be performed using a heating means such as a hot air oven, a hot plate, a hot air circulation furnace, an infrared oven, etc., and can be performed at a temperature of 50° C. or more and 100° C. or less. .
On the other hand, the dry film photoresist of the above embodiment is calculated by the following formula 1 from the time when exposure to the photosensitive resin layer is started at an exposure amount of 10 mJ/cm ² or more and 30 mJ/cm ^{2 or} less. The time (t) until the amount of change in the color coordinate b ^* value is 5.0 may be 5 minutes or less, 3 minutes or less, 30 seconds or more and 3 minutes or less, or 30 seconds or more and 2 minutes or less.
[Formula 1]
Amount of change in color coordinate b ^* value during exposure time (t) (△b ^* ₁ ) = (b ^* ₀ - b ^* ₁ )
In the formula 1, b ^* ₁ is the color coordinate (b*) value of the photosensitive resin layer after exposure for t minutes at an exposure amount of 10 mJ/cm ² or more and 30 mJ/cm ² or less, and b ^* ₀ is the color coordinate (b ^* ) value of the photosensitive resin layer after exposure. This is the color coordinate (b ^* ) value of the previous photosensitive resin layer.
This is realized by the photosensitive resin layer of the embodiment containing the photopolymerizable compound described above.

Specifically, the photosensitive resin layer of the embodiment includes a monofunctional (meth)acrylate compound represented by the chemical formula 1 and a polyfunctional (meth)acrylate compound represented by the chemical formula 2, By containing the polyfunctional (meth)acrylate compound in an amount of 100 parts by weight or more based on 100 parts by weight of the functional (meth)acrylate compound, the dry film photoresist including the photosensitive resin layer of the above embodiment can have the photosensitive resin layer. From the time when exposure to the resin layer is started at an exposure amount of 10 mJ/cm ² or more and 30 mJ/cm ^{2 or} less until the time when the amount of change in the color coordinate b ^* value calculated by the following formula 1 is 5.0 The time (t) may be 5 minutes or less.
From the time when exposure to the photosensitive resin layer is started at an exposure amount of 10 mJ/cm ² or more and 30 mJ/cm ² or less, the amount of change in the color coordinate b ^* value calculated by the formula 1 is 5.0. When the time (t) to a certain point is 5 minutes or less, the dry film photoresist including the photosensitive resin layer of the above embodiment has excellent color development time and degree. Therefore, when exposing the dry film photoresist, the alignment recognition rate for the product is increased, which not only shortens production time and reduces the defect rate, but also improves the physical properties of the display device including the dry film photoresist. can be realized.
On the other hand, in the dry film photoresist of the embodiment, the amount of change in the color coordinate b ^* value calculated by the following formula 2 for the photosensitive resin layer is 2.2 or more and 14.0 or less, and 3.1 It may be greater than or equal to 13.5, less than or equal to 4, or greater than or equal to 4.1 and less than or equal to 7.5.
[Formula 2]
Color coordinate b ^* value change amount (△b ^* ₁ ) = (b ^* ₀ - b ^* ₁ ) at 1 minute exposure time
In the above formula 2, b ^* ₁ is the color coordinate (b*) value of the photosensitive resin layer after exposure for 1 minute at an exposure amount of 10 mJ/cm2 or ^more and 30 mJ/ ^cm2 or less, and b ^* ₀ is the value of the color coordinate (b ^* ) of the photosensitive resin layer after exposure. It can be the color coordinate (b ^* ) value of the previous photosensitive resin layer. This is realized by the photosensitive resin layer of the embodiment containing the photopolymerizable compound described above.
The content of the amount of change in the color coordinate b ^* value calculated by Equation 1 includes all of the above-mentioned content.

Specifically, the photosensitive resin layer of the embodiment includes a monofunctional (meth)acrylate compound represented by the chemical formula 1 and a polyfunctional (meth)acrylate compound represented by the chemical formula 2, The amount of change in the color coordinate b ^* value calculated by Equation 2 may be greater than or equal to 2.2 and less than or equal to 14.0.
When the amount of change in the color coordinate b* value calculated by Equation 2 is 2.2 or more and 14.0 or less, the dry film photoresist of the embodiment has excellent coloring time and degree, and thereby It is possible to achieve excellent physical properties of a display device including a dry film photoresist.
3. According to still another embodiment of the invention, the photosensitive element includes a polymer base material; and a photosensitive resin layer formed on the polymer base material; ² or more and 30 mJ/cm The time (t) from the time when exposure starts with an exposure amount of ² or less until the time when the amount of change in color coordinate b ^* value is 5.0 calculated by the following formula 1 is 5 minutes or less , 3 minutes or less, 30 seconds or more and 3 minutes or less, 30 seconds or more and 2 minutes or less.
[Formula 1]
Amount of change in color coordinate b ^* value during exposure time (t) (△b ^* ₁ ) = (b ^* ₀ - b ^* ₁ )
In the formula 1, b ^* ₁ is the color coordinate (b*) value of the photosensitive resin layer after exposure for t minutes at an exposure amount of 10 mJ/cm ² or more and 30 mJ/cm ² or less, and b ^* ₀ is the color coordinate (b ^* ) value of the photosensitive resin layer after exposure. This is the color coordinate (b ^* ) value of the previous photosensitive resin layer.
Further, in the photosensitive element of the embodiment, the photosensitive resin layer has a change amount of color coordinate b ^* value of 2.2 to 14.0, and 3.1 to 13.0, calculated by Equation 2 below. 5 or less, 4 or more and 8 or less, or 4.1 or more and 7.5 or less, photosensitive elements are provided.
[Formula 2]
Color coordinate b ^* value change amount (△b ^* ₁ ) = (b ^* ₀ - b ^* ₁ ) at 1 minute exposure time
In the above formula 2, b ^* ₁ is the color coordinate (b*) value of the photosensitive resin layer after exposure for 1 minute at an exposure amount of 10 mJ/cm2 or ^more and 30 mJ/ ^cm2 or less, and b ^* ₀ is the value of the color coordinate (b ^* ) of the photosensitive resin layer after exposure This is the color coordinate (b ^* ) value of the previous photosensitive resin layer.
The content of the amount of change in the color coordinate b ^* value calculated by Equation 2 includes all of the above-mentioned content.

前記化学式１中、Ｒ_１は水素、または炭素数１～１０のアルキルであり、Ｒ_２は炭素数１～１０のアルキレンであり、Ｒ_３は炭素数１～１０のアルキルであり、ｎ１は１～２０の整数であり、

前記化学式２中、Ｒ_４は水素、または炭素数１～１０のアルキルであり、Ｒ_５は炭素数１～１０のアルキレンであり、Ｒ_６は炭素数１～２０の中心グループを含むｐが官能基であり、ｎ２は１～２０の整数であり、ｐは前記Ｒ_６に置換される官能基数であり、３～１０の整数である。
前記感光性樹脂層に対する内容は前記一実施形態と他の実施形態で上述した内容を全て含む。
すなわち、前記感光性樹脂層は、アルカリ現像性バインダー樹脂と光重合性化合物を含み、前記光重合性化合物は、下記化学式１で表される単官能（メタ）アクリレート化合物、および下記化学式２で表される多官能（メタ）アクリレート化合物を含み得る。

前記化学式１中、Ｒ_１は水素、または炭素数１～１０のアルキルであり、Ｒ_２は炭素数１～１０のアルキレンであり、Ｒ_３は炭素数１～１０のアルキルであり、ｎ１は１～２０の整数であり、

前記化学式２中、Ｒ_４は水素、または炭素数１～１０のアルキルであり、Ｒ_５は炭素数１～１０のアルキレンであり、Ｒ_６は炭素数１～２０の中心グループを含むｐが官能基であり、ｎ２は１～２０の整数であり、ｐは前記Ｒ_６に置換される官能基数であり、３～１０の整数である。 Specifically, 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 chemical formula 1, and the following chemical formula It may contain a polyfunctional (meth)acrylate compound represented by 2.

In the 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, and n1 is 1 is an integer of ~20,

In the 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, and R ₆ is a group in which p contains 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 on R ₆ , and is an integer of 3 to 10.
The contents of the photosensitive resin layer include all the contents described above in the one embodiment and the other embodiments.
That is, the photosensitive resin layer includes an alkali-developable binder resin and a photopolymerizable compound, and the photopolymerizable compound is a monofunctional (meth)acrylate compound represented by the following chemical formula 1, and a monofunctional (meth)acrylate compound represented by the following chemical formula 2. may contain polyfunctional (meth)acrylate compounds.

In the 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, and n1 is 1 is an integer of ~20,

In the 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, and R ₆ is a group in which p contains 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 on R ₆ , and is an integer of 3 to 10.

Various plastic films can be used as the polymer base material, such as acrylic film, polyethylene terephthalate (PET) film, triacetyl cellulose (TAC) film, polynorbornene (PNB) film, and cycloolefin polymer (COP). and one or more plastic films selected from the group consisting of polycarbonate (PC) films. The thickness of the polymer base material is not particularly limited, but can be adjusted as appropriate within the range of, for example, 0.01 μm to 1 mm.
As a specific example of the polymer base material, an anti-blocking layer is formed by an in-line coating method in which an unstretched polyester film is uniaxially stretched, a solution containing a binder resin and organic particles is applied to one side, and the remaining uniaxially stretched. Examples include polyester films formed with.
For the polymer base material, an in-line coating method was selected instead of adding an anti-blocking agent, which is usually added in consideration of runnability and winding characteristics during manufacturing, and alternative particles that do not impede transparency were used. It is equipped with an organic particle layer.
Here, examples of organic particles that are used in consideration of runnability and winding characteristics and do not impede transparency include methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, normal butyl methyl methacrylate, acrylic Acrylic particles such as copolymers or terpolymers of acid, methacrylic acid; Olefin particles such as polyethylene, polystyrene, polypropylene; Copolymers of acrylic and olefin; or after forming homopolymer particles, Examples include organic particles such as multilayer multicomponent particles in which different types of monomers are coated on the layers.
Specifically, such organic particles must be spherical and have a refractive index different from that of the binder resin. Here, "spherical" means that in an ellipse, the ratio of the short axis (a) to the long axis (b) is 0.5<a/b<2, and in the case of a rectangle, the relationship with the diagonal (d) is d2≦a2+b2. It is defined as Further, the relationship between the axis (f) with the longest distance between vertices in the hexahedron and the c-axis other than the a and b axes is defined as f2≦c2+a2+b2. If the particle shape is not spherical, it is unfavorable from the viewpoint of runnability.

The organic particles are characterized in that the difference in refractive index between the organic particles and the binder resin is 0.05 or less. If the difference in refractive index is greater than 0.05, haze will increase. This means that there is a lot of scattered light, and when there is a lot of scattered light, the smoothing effect of the sidewall is reduced. This also depends on the size and amount of organic particles. It is preferable that the organic particles have an average particle diameter of about 0.5 μm to 5 μm. If the average particle size is smaller than this, the running characteristics and winding characteristics will deteriorate, and if it is larger than 5 μm, the haze will increase and the occurrence of falling off will be taken into consideration. I don't like it. The content of organic particles is preferably 1 to 10% by weight based on the total amount including the binder resin.
If the content of organic particles is less than 1% by weight based on the total amount with the binder resin, the anti-blocking effect will be insufficient and it will be susceptible to scratches, and the winding characteristics and running characteristics will deteriorate, and if it exceeds 10% by weight, haze will occur. There may be a problem that the transparency characteristics are deteriorated due to an increase in
On the other hand, it is also possible to add inorganic particles in addition to the above-mentioned organic particles, but in this case, it is not preferable to add the commonly used inorganic anti-blocking agent, and the particle size is 100 nm or less. It is preferable to add colloidal silica. The content thereof is preferably 10 parts by weight or less per 100 parts by weight of the binder resin. When the particle size and content described above are met, sidewall defects and crater-like grooves caused by the anti-blocking layer do not occur during pattern formation using a dry film photoresist.
It is preferable to use a binder resin that is compatible with the organic particles as a binder resin that acts as an adhesive for applying such organic particles onto an unstretched polyester film. Examples include unsaturated polyesters, acrylic resins such as methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, normal butyl methyl methacrylate, copolymers or terpolymers of acrylic acid, methacrylic acid; urethane Examples thereof include epoxy resins, melamine resins, and acrylic resins.
Water is preferable as the solvent that can be used in preparing the solution with the binder resin and organic particles.
After uniaxially stretching an unstretched polyester film obtained by melt-extruding PET pellets, a solution containing organic particles in the binder resin is applied onto the uniaxially stretched film. The coating may be performed on at least one side of the uniaxially stretched film, and the thickness thereof is preferably about 30 nm to 200 nm based on the thickness after final drying. If a solution containing organic particles is applied thinner than 30 nm on a uniaxially stretched film, the organic particles will easily fall off and be vulnerable to scratches, resulting in the generation of white powder, and if it is applied thicker than 200 nm, the viscosity of the solution will increase. In in-line coating where the coating speed is high, coating lines are generated in the coating direction.

In this way, the polymer base material obtained by coating with organic particles instead of a general anti-blocking agent by the in-line coating method maintains the winding characteristics and running characteristics due to the particle layer, and is light-resistant. It is a base film with excellent transparency due to the organic particles with excellent transparency.
Lamination of the photosensitive resin layer is performed on the opposite side of the layer containing organic particles in the polymer base material, so by forming the photosensitive resin layer on the opposite side of the layer containing organic particles, There is no occurrence of crater pattern scratches that appear when base films containing anti-blocking agents are laminated. Particles such as silica are not only larger in size than organic particles, but also distributed over the entire base film, so that the influence of silica appears even in areas adjacent to the photosensitive resin layer, even if only slightly.
On the other hand, in the polymer base material 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. Not affected by the physical effects of organic particles. Further, by using organic particles having excellent light transmittance, defects in the sidewall can be reduced and other physical properties of the circuit will not be impaired.
The photosensitive element may further include a protective film formed on the photosensitive resin layer. The protective film serves as a protective cover that prevents damage to the photosensitive resin layer during handling and protects the photosensitive resin layer from foreign substances such as dust. Laminated on the unformed back side. The protective film plays the role of protecting the photosensitive resin layer from the outside, and is easily removed when the photosensitive element is applied in a post-process, and is made of a suitable material so that it does not release from the mold during storage and distribution. Requires releasability and adhesion.

Various plastic films can be used as the protective film, such as acrylic film, polyethylene (PE) film, polyethylene terephthalate (PET) film, triacetyl cellulose (TAC) film, polynorbornene (PNB) film, and cycloolefin. It may include one or more plastic films selected from the group consisting of polymer (COP) films and polycarbonate (PC) films. The thickness of the protective film is not particularly limited, but can be adjusted as appropriate within the range of, for example, 0.01 μm to 1 mm.

4. Circuit board, display device According to yet another embodiment of the invention, there is provided a circuit board or a display device including the photosensitive resin layer of the above embodiment. The contents of the photosensitive resin layer include all the contents described above in the embodiment.
The specific contents regarding the circuit board or the display device are not particularly limited, and various conventionally known technical configurations can be applied without restriction.
The photosensitive resin layer included in the circuit board or display device may be in the form of a film without openings, or may be in the form of a pattern with openings.
An example of a method for forming the photosensitive resin layer in the patterned form is to stack the photosensitive resin layer of the dry film photoresist of the other embodiments on a circuit board or a substrate for display manufacturing equipment, and then expose and One example is a method of performing development. Another method is to stack the photosensitive resin layer of the photosensitive element of the other embodiments on a circuit board or a display manufacturing device substrate, and then perform exposure and development.
When the dry film photoresist or photosensitive element of the other embodiments has a protective film on the photosensitive resin layer, the protective film is removed before the process of laminating the photosensitive resin layer on a circuit board or a substrate for display manufacturing equipment. Further steps can be performed.
In addition, when the dry film photoresist or photosensitive element of the other embodiments has a polymer base material or base film laminated on one surface of the photosensitive resin layer, the polymer base material or base film immediately after the exposure process A further step of removing the film may be performed.
Therefore, the photosensitive resin layer included in the dry film photoresist or photosensitive element of the other embodiments may be included in the circuit board or display device.

According to the present invention, it is possible to achieve excellent fine line adhesion and resolution, increase the alignment recognition rate for products during exposure, shorten the production time of final products, reduce the defective rate, and improve reliability. A photosensitive resin layer can be provided.
Further, according to the present invention, a dry film photoresist, a photosensitive element, a circuit board, and a display device including the photosensitive resin layer can be provided.

The invention will be explained in more detail in the following examples. However, the following examples merely illustrate the present invention, and the content of the present invention is not limited by the following examples.
<Production example: Production of alkaline developable binder resin>
Manufacturing example 1
A 4-neck round bottom flask was equipped with a mechanical stirrer and a reflux device, and then the inside of the flask was purged with nitrogen. Into the flask purged with nitrogen, 80 g of methyl ethyl ketone (MEK) and 7.5 g of methanol (MeOH) were added, and then 0.45 g of azobisisobutyronitrile (AIBN) was added. Completely dissolved. There, 8 g of acrylic acid (AA), 15 g of methacrylic acid (MAA), 15 g of butyl acrylate (BA), 52 g of methyl methacrylate (MMA), and 52 g of methyl methacrylate (MMA) were added as monomers. Ren (Styrene, SM) 10 g of a monomer mixture was added, the temperature was raised to 80° C., and the mixture was polymerized for 6 hours to produce alkali-developable binder resin 1.
The alkaline developable binder resin 1 had a weight average molecular weight of 71,538 g/mol, a glass transition temperature of 79° C., a solid content of 51.4% by weight, and an acid value of 156.3 mgKOH/g.

As a specific example of the conditions for measuring the weight average molecular weight, the alkaline developable binder resin has a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on solid content). After dissolving in tetrahydrofuran so that The column consisted of one Agilent PLgel 5 μm Guard (7.5 x 50 mm) and two Agilent PLgel 5 μm Mixed D (7.5 x 300 mm) connected in series, and the detection device was an Agilent 1260 Infinity. Measurement was performed at 40°C using II system and RI Detector.
The acid value was determined by sampling a little more than 1 g of alkaline-developable binder resin, dissolving it in 50 ml of mixed solvent (MeOH 20%, Acetone 80%), adding two drops of 1%-phenolphthalein indicator, and then adding 0.1N-KOH. The acid value was measured by titration.
The solid content was determined by heating the resin in an oven at 150° C. for 120 minutes based on the weight of the alkali-developable binder resin produced in the above production example, and then measuring the weight percentage of the remaining solid content.
Manufacturing example 2
A 4-neck round bottom flask was equipped with a mechanical stirrer and a reflux device, and then the inside of the flask was purged with nitrogen. Into the flask purged with nitrogen, 110 g of methyl ethyl ketone (MEK) and 10 g of methanol (MeOH) were added, and then 1 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. I let it happen. A monomer mixture of 30 g of methacrylic acid (MAA), 100 g of methyl methacrylate (MMA), and 30 g of styrene (SM) was added thereto, and the temperature was raised to 80°C. Thereafter, the mixture was polymerized for 6 hours to produce alkali-developable binder resin 2 (weight average molecular weight: 49,852 g/mol, glass transition temperature: 125° C., solid content: 48.5% by weight, acid value: 163.17 mgKOH/g).
<Examples and comparative examples: Production of photosensitive resin composition and dry film photoresist>
According to the composition shown in Table 1 below, a photopolymerization initiator is dissolved in methyl ethyl ketone (MEK) as a solvent, and then a photopolymerizable compound and an alkali-developable binder resin are added and mixed using a mechanical stirrer for about 1 hour. A photosensitive resin composition was prepared by mixing for about an hour.
The obtained photosensitive resin composition was coated on a 40 μm PET film using a coating bar. The coated photosensitive resin composition layer is dried using a hot air oven. At this time, the drying temperature is 80°C, the drying time is 5 minutes, and the thickness of the photosensitive resin composition layer after drying is The thickness was 40 μm.
A protective film (polyethylene) was laminated onto the dried photosensitive resin composition layer to produce a dry film photoresist.
The PET film was manufactured by the following steps.

PET was produced by performing transesterification and polycondensation reactions from ethylene glycol and terephthalic acid. After drying the PET pellets under reduced pressure at 120°C for 8 hours, they were fed to an extruder and melted at 280°C. This was wound around a casting drum with a surface temperature of 20° C. using an electrostatic casting method, and cooled and solidified to produce an unstretched film. The thickness of the unstretched film was adjusted to 250 μm by adjusting the discharge rate of the extruder. Thereafter, after stretching the unstretched film 4 times in the longitudinal direction, a solution prepared by mixing 4 g of acrylic resin and 0.1 g of polymethyl methacrylate as organic particles in 95.9 g of water was applied to one side using a gravure machine. After drying, it was applied to a thickness of 50 nm. The polymethyl methacrylate used here has a surface coated with polystyrene, is spherical, and has a refractive index difference of 0.03 from that of the acrylic resin.
A longitudinally uniaxially stretched film coated with a solution containing organic particles was preheated at 120° C. and stretched 4 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 cooled to room temperature to obtain a polyester film having a total thickness of 20 μm and a coating layer thickness of 50 nm.

<Experiment example>
The physical properties of the dry film photoresists produced in the Examples and Comparative Examples were measured using the methods described below, and the results are shown in Tables 2 to 4, respectively.
1. Amount of change in color coordinate b value with respect to exposure time The protective film of the dry film photoresist manufactured in the above Examples and Comparative Examples was peeled off, and the photosensitive resin layer of the dry film photoresist was subjected to brush polishing. The substrate preheating roll temperature was 120°C, the laminator roll temperature was 115°C, the roll pressure was 4.0 kgf/cm ² , and the roll speed was 2.0 min/m so as to contact the surface of the copper layer of a 4 mm thick copper-clad laminate. A laminate was formed by lamination using HAKUTO MACH 610i.
After peeling off the PET film that is the support for the dry film photoresist in the laminate, a sample with a thickness of 29 μm and a cross-sectional area of 3 cm ² was subjected to SCI (specular The respective color coordinates (b ^* ₀ ) were measured in a component included (specularly reflected light included) mode and an SCE (specular component excluded) mode.
After that, a circuit evaluation pattern (openings whose width increases by 1 μm from 4 μm to 50 μm are arranged at 2 μm intervals) was applied to the dry film photoresist from which the PET film was peeled off, and an FDI-3 (LDI exposure device) , manufactured by ORC) at an exposure dose of 19 mJ/cm ² . The exposed sample was measured in SCI (specular component included) mode and SCE using a color difference meter CM-2600d manufactured by Konica Minolta based on ASTM E313-96 measurement method and D65/10 degrees. Each color coordinate (b ^* _n ) was measured in the (specular component excluded) mode.
For the measured values, the amount of change in the color coordinate b ^* value was calculated using the following formula.
[Formula]
Color coordinate b ^* value change amount (△b ^* n) = (b ^* ₀ - b ^* _n ) with n minute exposure time
In the above formula, b ^* _n is the color coordinate (b*) value of the photosensitive resin layer after exposure for n minutes at an exposure dose of 19 mJ/ ^cm2 , and b ^* ₀ is the color coordinate (b ^* ) value of the photosensitive resin layer before exposure. It is a color coordinate (b ^* ) value.

上記表３に示すように、実施例１においては、ＳＣＥモードで測定した１分間色座標ｂ値の変化量が５．４３、３分間色座標ｂ値の変化量が７．８２、５分間色座標ｂ値の変化量が８．５９に現れ、顕著に優れた発色程度を示すことを確認することができた。実施例とは異なり、単官能（メタ）アクリレート化合物を含まない比較例１の場合、本実施例に比べて、ＳＣＥモードで測定した１分間色座標ｂ値の変化量が０．４５、３分間色座標ｂ値の変化量が２．０１、５分間色座標ｂ値の変化量が３．８２に現れ、顕著に劣等な発色程度を示すことを確認することができた。
また、多官能（メタ）アクリレート化合物を含まない比較例２の場合、本実施例に比べて、ＳＣＥモードで測定した１分間色座標ｂ値の変化量が０．３６、３分間色座標ｂ値の変化量が１．９３、５分間色座標ｂ値の変化量が３．５４に現れ、顕著に劣等な発色程度を示すことを確認することができた。 As shown in Table 2 above, in Example 1, the amount of change in color coordinate b value for 1 minute measured in SCI mode was 6.41, the amount of change in color coordinate b value for 3 minutes was 9.13, and the amount of change in color coordinate b value for 5 minutes was 6.41. The amount of change in the coordinate b value appeared at 9.98, and it was confirmed that the degree of color development was significantly excellent.
In the case of Comparative Example 1, which does not contain a monofunctional (meth)acrylate compound, unlike the example, the amount of change in the color coordinate b value per minute measured in SCI mode was 0.54 for 3 minutes compared to this example. It was confirmed that the amount of change in the color coordinate b value was 2.11, and the amount of change in the color coordinate b value after 5 minutes was 3.92, indicating a significantly inferior degree of color development.
In addition, in the case of Comparative Example 2 which does not contain a polyfunctional (meth)acrylate compound, the amount of change in the 1 minute color coordinate b value measured in SCI mode is 0.49, and the 3 minute color coordinate b value is 0.49 compared to this example. The amount of change in color coordinate b value for 5 minutes was 2.05, and the amount of change in b value for 5 minutes was 3.68, and it was confirmed that the degree of color development was significantly inferior.

As shown in Table 3 above, in Example 1, the amount of change in color coordinate b value for 1 minute measured in SCE mode was 5.43, the amount of change in color coordinate b value for 3 minutes was 7.82, and the amount of change in color coordinate b value for 5 minutes was 5.43. The amount of change in the coordinate b value appeared at 8.59, and it was confirmed that the degree of color development was significantly excellent. In the case of Comparative Example 1, which does not contain a monofunctional (meth)acrylate compound, unlike the Example, the amount of change in the color coordinate b value per minute measured in SCE mode was 0.45 for 3 minutes compared to this Example. It was confirmed that the amount of change in the color coordinate b value was 2.01, and the amount of change in the color coordinate b value after 5 minutes was 3.82, indicating a significantly inferior degree of color development.
In addition, in the case of Comparative Example 2 which does not contain a polyfunctional (meth)acrylate compound, the amount of change in the 1 minute color coordinate b value measured in SCE mode is 0.36, and the 3 minute color coordinate b value is 0.36 compared to this example. The amount of change in color coordinate b value for 5 minutes was 1.93, and the amount of change in b value for 5 minutes was 3.54, and it was confirmed that the degree of color development was significantly inferior.

2. Color development time (unit: minutes)
The protective film of the dry film photoresist manufactured in the above Examples and Comparative Examples was peeled off, and the photosensitive resin layer of the dry film photoresist was brush-polished. Lamination was carried out using HAKUTO MACH 610i under the conditions of substrate preheating roll temperature of 120°C, laminator roll temperature of 115°C, roll pressure of 4.0 kgf/cm ² , and roll speed of 2.0 min/m so as to contact the layer surface. formed a body.
In the laminate, a dry film photoresist sample with a thickness of 29 μm and a cross-sectional area of 3 cm ² was measured in SCI (specular component included) mode using a color difference meter CM-2600d manufactured by Konica Minolta. Color coordinates (b ^* ₀ ) were measured.
Thereafter, the dry film photoresist was irradiated with ultraviolet rays at an exposure dose of 19 mJ/cm ² using FDI-3 (LDI exposure device, manufactured by ORC) using a circuit evaluation pattern. After exposure, the sample was color-measured using a color difference meter CM-2600d manufactured by Konica Minolta in SCI (specular component included) mode based on the ASTM E313-96 measurement method and D65/10 degrees. The coordinates (b ^* _n ) were measured.
The time (t) until the amount of change in the color coordinate b ^* value reached 5.0 according to the following mathematical formula was measured for the measured value.
[Formula]
Amount of change in color coordinate b ^* value during exposure time (t) (△b ^* ₁ ) = (b ^* ₀ - b ^* ₁ )
In the above formula, b ^* ₁ is the color coordinate (b*) value of the photosensitive resin layer after exposure for t minutes at an exposure dose of 19 mJ/ ^cm2 , and b ^* ₀ is the color coordinate (b ^* ) value of the photosensitive resin layer before exposure. It is a color coordinate (b ^* ) value.

3. Fine wire adhesion (unit: μm)
The protective film of the dry film photoresist manufactured in the above Examples and Comparative Examples was peeled off, and the photosensitive resin layer of the dry film photoresist was brush-polished. Lamination was carried out using HAKUTO MACH 610i under the conditions of substrate preheating roll temperature of 120°C, laminator roll temperature of 115°C, roll pressure of 4.0 kgf/cm ² , and roll speed of 2.0 min/m so as to contact the layer surface. formed a body.
After irradiating the dry film photoresist in the laminate with ultraviolet rays at an exposure dose of 19 mJ/cm ² using FDI-3 (LDI exposure equipment, manufactured by ORC) using a circuit evaluation pattern, Leave it for a minute. Thereafter, development was carried out for 40 seconds using a 1.0 wt % aqueous solution of Na ₂ CO ₃ at 30±1° C. at a spray pressure of 1.5 kgf/cm ² under spray development conditions.
After the development of the laminate, the minimum line width of the photosensitive resin layer was measured using a ZEISS AXIOPHOT Microscope to evaluate the fine line adhesion. It can be evaluated that the smaller the value, the better the fine wire adhesion.
4. Resolution (unit: μm)
The protective film of the dry film photoresist manufactured in the above Examples and Comparative Examples was peeled off, and the photosensitive resin layer of the dry film photoresist was brush-polished. Lamination was carried out using HAKUTO MACH 610i under the conditions of substrate preheating roll temperature of 120°C, laminator roll temperature of 115°C, roll pressure of 4.0 kgf/cm ² , and roll speed of 2.0 min/m so as to contact the layer surface. formed a body.
The laminate was coated with FDI-3 (LDI) using a photomask for circuit evaluation so that the width of the circuit line after development and the space between the circuit lines was 1:1. After irradiating with ultraviolet rays at an exposure dose of 19 mJ/cm ² using an exposure apparatus (manufactured by ORC), the film was left for 15 minutes. Thereafter, development was carried out for 1 minute using a 1.0 wt % aqueous solution of Na ₂ CO ₃ at 30±1° C. under spraying development conditions at a spray pressure of 1.5 kgf/cm ² .
In the developed laminate, the minimum distance between the photosensitive resin layers was measured using a ZEISS AXIOPHOT Microscope and evaluated at a resolution of 1:1. It can be evaluated that the smaller the value, the better the 1:1 resolution value.
5. Evaluation of contamination prevention properties for plating Cut the dry film photoresists produced in the above Examples and Comparative Examples into pieces of 40 cm x 50 cm, remove the protective film, and evaluate the exposure amount such that the step tablet becomes 20 steps/41 steps. The PET film was exposed to light and the PET film was peeled off to obtain a cured film. The cured film was immersed in 1 L of copper sulfate/sulfuric acid aqueous plating solution for 3 days. Electrolytic copper plating was applied to the copper plate at a current of 2 A for 10 minutes using a Hull Cell testing device (manufactured by Jeongdo Testing Machinery Research Institute, Korea).
When the plating solution in which the cured film is not immersed is used as a standard sample, and the cured film is plated with the plating solution in which the cured film is immersed, the appearance of the plating is observed with the naked eye, and if a poor appearance or a change in the gloss of the plating occurs.X If the sample was the same as the reference sample and there was no abnormality at all, it was judged as O.

上記表４に示すように、実施例１は優れた細線密着力および解像度を示すと同時に、色座標ｂ^＊値の変化量が５．０に達するまでの発色時間が１分以内で速く、顕著に優れた発色時間を示すことを確認することができた。
実施例とは異なり、単官能（メタ）アクリレート化合物を含まない比較例１の場合、本実施例に比べて、色座標ｂ^＊値の変化量が５．０に達するまでの発色時間が顕著に劣ることを確認することができた。
また、多官能（メタ）アクリレート化合物を含まない比較例２の場合、本実施例に比べて、色座標ｂ^＊値の変化量が５．０に達するまでの発色時間が顕著に劣ることを確認することができた。 6. Peeling speed (unit: seconds)
The protective film of the dry film photoresist manufactured in the above Examples and Comparative Examples was peeled off, and the photosensitive resin layer of the dry film photoresist was brush-polished. Lamination was carried out using HAKUTO MACH 610i under the following conditions: a substrate preheating roll temperature of 120° C., a laminator roll temperature of 115° C., a roll pressure of 4.0 kgf/cm ² , and a roll speed of 2.0 min/m so as to contact the layer surface.
The laminate was irradiated with ultraviolet rays at an exposure dose of 19 mJ/cm ² using FDI-3 (LDI exposure device, manufactured by ORC) using a circuit evaluation pattern, and then left for 15 minutes. After that, the PET film that is the support of the dry film photoresist was peeled off, and it was developed with a 1.0 wt% aqueous solution of Na ₂ CO ₃ at 30 ± 1°C for 1 minute under the conditions of spray development at a spray pressure of 1.5 kgf/cm ^2. A photocured film was produced.
Thereafter, peeling was performed using a 3% aqueous sodium hydroxide solution (temperature: 50°C). Peeling speed was evaluated by measuring the time taken for the photocured film to peel off from the copper foil.

As shown in Table 4 above, Example 1 shows excellent fine line adhesion and resolution, and at the same time, the color development time until the amount of change in the color coordinate b ^* value reaches 5.0 is fast, within 1 minute, and is remarkable. It was confirmed that the color development time was excellent.
In the case of Comparative Example 1, which does not contain a monofunctional (meth)acrylate compound, unlike the Examples, the color development time until the amount of change in the color coordinate b ^* value reaches 5.0 is significantly longer than in this Example. I was able to confirm that it was inferior.
In addition, in the case of Comparative Example 2, which does not contain a polyfunctional (meth)acrylate compound, it was confirmed that the color development time until the amount of change in the color coordinate b ^* value reached 5.0 was significantly inferior compared to this example. We were able to.

Claims (16)

A photopolymerizable compound containing a trifunctional or more polyfunctional (meth)acrylate compound; and an alkali-developable binder resin;
The alkaline developable binder resin is
A repeating unit represented by the following chemical formula 3, a repeating unit represented by the following chemical formula 4, a repeating unit represented by the following chemical formula 5, a repeating unit represented by the following chemical formula 6, and a repeating unit represented by the following chemical formula 7. a first alkaline developable binder resin comprising; and
A second alkali-developable binder resin comprising a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5, and a repeating unit represented by the following Chemical Formula 6;
From the time when exposure started with an exposure amount of 19 mJ/cm ² ,
The time (t) until the amount of change in the color coordinate b* value calculated by the following formula 1 is 5.0 is 5 minutes or less,
The color coordinates are measured in SCI (specular component included, specularly reflected light included) mode or SCE (specular component excluded, specularly reflected light) mode using a color difference meter,
The color coordinates are measured based on ASTM E313-96 (coefficient: D65/10 degrees) , photosensitive resin layer:
[Formula 1]
Amount of change in color coordinate b ^* value during exposure time (t) (△b ^* ₁ ) = (b ^* ₀ - b ^* ₁ )
In the formula 1,
b ^* ₁ is the color coordinate (b ^* ) value of the photosensitive resin layer after exposure for t minutes with an exposure amount of 19 mJ/cm2 ^,
b ^* ₀ is the color coordinate (b ^* ) value of the photosensitive resin layer before exposure,
The alkaline developable binder resin is

In the chemical formula 3,
R ₃ '' is hydrogen;

In the chemical formula 4,
R ₃ ' is alkyl having 1 to 10 carbon atoms,

In the chemical formula 5,
R ₄ '' is alkyl having 1 to 10 carbon atoms,
R ₅ '' is alkyl having 1 to 10 carbon atoms,

In the chemical formula 6,
Ar is an aryl having 6 to 20 carbon atoms,

In the chemical formula 7,
R ₄ ' is hydrogen;
R ₅ ' is alkyl having 1 to 10 carbon atoms. The amount of change in color coordinate b ^* value calculated by the following formula 2 is 0.6 or more and 14.0 or less,
The color coordinates are measured in SCI (specular component included, specularly reflected light included) mode or SCE (specular component excluded, specularly reflected light) mode using a color difference meter,
The photosensitive resin layer according to claim 1 , wherein the color coordinates are measured based on ASTM E313-96 (coefficient: D65/10 degrees) :
[Formula 2]
Color coordinate b ^* value change amount (△b ^* ₁ ) = (b ^* ₀ - b ^* ₁ ) at 1 minute exposure time
In the formula 2,
b ^* ₁ is the color coordinate (b ^* ) value of the photosensitive resin layer after exposure for 1 minute at an exposure amount of 19 mJ/cm2 ^,
b ^* ₀ is the color coordinate (b ^* ) value of the photosensitive resin layer before exposure. The trifunctional or higher polyfunctional (meth)acrylate compound is
The photosensitive resin layer according to claim 1, having 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 photosensitive resin layer according to claim 1, wherein the trifunctional or higher polyfunctional (meth)acrylate compound includes a compound represented by the following chemical formula 2:

In the 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 contains 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 on R ₆ , and is an integer of 3 to 10. The photosensitive resin layer according to claim 1, wherein the trifunctional or higher polyfunctional (meth)acrylate compound includes a compound represented by the following chemical formula 2-1:

In the chemical formula 2-1,
R ₆ ' is a trivalent functional group having 1 to 10 carbon atoms,
R ₇ to R ₉ are each independently alkylene having 1 to 10 carbon atoms,
R ₁₀ to R ₁₂ are each independently hydrogen or alkyl having 1 to 10 carbon atoms,
n3 to n5 are each independently an integer of 1 to 3. The photosensitive resin layer according to claim 1, wherein the photopolymerizable compound further includes a monofunctional (meth)acrylate compound. The photosensitive compound according to claim 6, wherein the photopolymerizable compound contains 100 parts by weight or more of the trifunctional or more polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound. resin layer. The photosensitive resin layer according to claim 6, wherein the monofunctional (meth)acrylate compound includes a (meth)acrylate containing an alkylene oxide group having 1 to 10 carbon atoms. The photopolymerizable compound is a monofunctional (meth)acrylate compound containing a (meth)acrylate containing an alkylene oxide group having 1 to 10 carbon atoms; and an alkylene oxide having 1 to 10 carbon atoms in the central group having 1 to 20 carbon atoms. The photosensitive resin layer according to claim 6, comprising a trifunctional or higher-functional polyfunctional (meth)acrylate compound having a structure in which three or more groups and three or more (meth)acrylate functional groups are bonded to each other. The photosensitive resin layer according to claim 1, wherein the alkali-developable binder resin has a weight average molecular weight of 20,000 g/mol or more and 150,000 g/mol or less. The photosensitive resin layer according to claim 1 , comprising 500 parts by weight or more and 1000 parts by weight or less of the second alkali-developable binder resin based on 100 parts by weight of the first alkali-developable binder resin. The photosensitive resin layer according to claim 1, wherein the photosensitive resin layer has a thickness of 15 μm or more and 50 μm or less. The amount of change in color coordinate b ^* value calculated by the following formula 3 is 2.2 or more and 14.0 or less,
The color coordinates are measured in SCI (specular component included, specularly reflected light included) mode or SCE (specular component excluded, specularly reflected light) mode using a color difference meter,
The photosensitive resin layer according to claim 1 , wherein the color coordinates are measured based on ASTM E313-96 (coefficient: D65/10 degrees) :
[Formula 3]
Color coordinate b ^* value change amount (△b ^* ₃ ) = (b ^* ₀ - b ^* ₃ ) at 3 minute exposure time
In the formula 3,
b ^* ₃ is the color coordinate (b ^* ) value of the photosensitive resin layer after exposure for 3 minutes with an exposure amount of 19 mJ/cm2 ^,
b ^* ₀ is the color coordinate (b ^* ) value of the photosensitive resin layer before exposure. The amount of change in color coordinate b ^* value calculated by the following formula 4 is 4.0 or more and 14.3 or less,
The color coordinates are measured in SCI (specular component included, specularly reflected light included) mode or SCE (specular component excluded, specularly reflected light) mode using a color difference meter,
The photosensitive resin layer according to claim 1 , wherein the color coordinates are measured based on ASTM E313-96 (coefficient: D65/10 degrees) :
[Formula 4]
Color coordinate b ^* value change amount (△b ^* ₅ ) = (b ^* ₀ - b ^* ₅ ) at 5 minutes exposure time
In the formula 4,
b ^* ₅ is the color coordinate (b ^* ) value of the photosensitive resin layer after exposure for 5 minutes at an exposure amount of 19 mJ/cm2 ^,
b ^* ₀ is the color coordinate (b ^* ) value of the photosensitive resin layer before exposure. A dry film photoresist comprising the photosensitive resin layer according to claim 1. A photosensitive element comprising a polymeric base material; and a photosensitive resin layer according to claim 1 formed on the polymeric base material.