KR20220141962A - Photosensitive resin composition, and dry film photoresist, photosensitive element, resist pattern, circuit board, display device using the same - Google Patents

Abstract

The present invention relates to: a photosensitive resin composition comprising an alkali developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the photopolymerizable compound includes a urea-based polymer containing at least one (meth)acryloyl group at a terminal thereof; and a dry film photoresist, a photosensitive element, a resist pattern, a circuit board, and a display device using the same.

Description

Photosensitive resin composition and dry film photoresist using same, photosensitive element, resist pattern, circuit board, and display device

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

The photosensitive resin composition is used in the form of Dry Film Photoresist (DFR), Liquid Photoresist Ink, etc. used in Printed Circuit Board (PCB) or Lead Frame. .

Currently, not only manufacturing printed circuit boards (PCB) or lead frames, but also manufacturing rib barriers for plasma display panels (PDP), ITO electrodes for other displays, bus address electrodes, and black matrices. Dry film photoresist is also widely used for the like.

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

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 process, a photoresist layer of DFR is laminated on the copper surface while peeling off the protective film of DFR using a laminator. In general, the lamination speed is 0.5~3.5m/min, the temperature is 100~130℃, and the roller pressure heating roll pressure is 10~90psi.

The printed circuit board that has undergone the lamination process is left for at least 15 minutes to stabilize the board, and then is exposed to the photoresist of the DFR using a photomask on which a desired circuit pattern is formed. In this process, when the photomask is irradiated with ultraviolet rays, polymerization of the photoresist irradiated with ultraviolet rays is initiated by the photoinitiator contained in the irradiated area. First, oxygen in the photoresist is consumed, then the activated monomer is polymerized to cause a crosslinking reaction, and then a large amount of the monomer is consumed and the polymerization reaction proceeds. On the other hand, the unexposed portion exists in a state in which the crosslinking reaction has not proceeded.

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

Then, a circuit is formed through different processes according to the inner layer and outer layer processes. In the inner layer process, a circuit is formed on the substrate through corrosion and peeling processes, and in the outer layer process, plating and tenting processes are performed, followed by etching and solder stripping, and a predetermined circuit is formed.

Copper foil etching is a tenting method, and in particular, the outermost layer of the PCB processes several holes in advance and then forms a circuit. It must not be etched, so high strength and elongation are required.

An object of the present invention is to provide a photosensitive resin composition capable of implementing excellent sandblast resistance and high tenting effect.

Another object of the present invention is to provide a dry film photoresist, a photosensitive element, a resist pattern, a circuit board, and a display device using the photosensitive resin composition.

In order to solve the above problems, in the present specification, an alkali developable binder resin, a photopolymerization initiator, and a photopolymerizable compound are included, and the photopolymerizable compound is a urea-based polymer containing at least one (meth)acryloyl group at the terminal. It provides a photosensitive resin composition comprising a.

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

In the present specification, also, a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, wherein the photosensitive resin layer is provided with a photosensitive element containing the photosensitive resin composition.

In the present specification, there is also provided a resist pattern comprising a photosensitive resin pattern containing the photosensitive resin composition.

The present specification also provides a circuit board and a display device including the resistor pattern or a metal pattern formed by the resistor pattern.

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

Unless explicitly stated herein, terminology is for the purpose of referring to specific embodiments only, and is not intended to limit the present invention.

As used herein, the singular forms also include the plural forms unless the phrases clearly indicate the opposite.

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

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

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

As used herein, the term "substitution" means that another functional group is bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent is substitutable, is not limited, and when two or more substituted , two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amide group; primary amino group; carboxyl group; sulfonic acid group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; alkoxysilylalkyl group; an aryl phosphine group; or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more, or substituted or unsubstituted, in which two or more substituents of the above-exemplified substituents are connected . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.

, 또는

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

, or

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

In the present specification, (meth) acryl is meant to include both acryl and methacryl.

In the present specification, the alkyl group is a monovalent functional group derived from an alkane, and may be linear or branched, and the number of carbon atoms in the straight-chain alkyl group is not particularly limited, but is preferably 1 to 20. In addition, the number of carbon atoms of the branched chain alkyl group is 3 to 20. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl- propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptan-4-yl, and the like. 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 may be a monocyclic aryl group or a polycyclic aryl group. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto. The aryl group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.

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

In the present specification, the arylene group is a divalent functional group derived from arene, and the description of the aryl group described above may be applied, except that these are divalent functional groups. For example, it may be a phenylene group, a biphenylene group, a terphenylene group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, and the like. The arylene group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.

In the present specification, a direct bond or a single bond means that no atom or group of atoms is present at the corresponding position, and thus is connected by a bonding line.

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

1. Photosensitive resin composition

According to one embodiment of the invention, it comprises an alkali developable binder resin, a photopolymerization initiator, and a photopolymerizable compound, wherein the photopolymerizable compound comprises a urea-based polymer containing at least one (meth)acryloyl group at the terminal. A photosensitive resin composition may be provided.

The present inventors have experimented that the photosensitive resin composition of one embodiment is a photopolymerizable compound and includes a urea-based polymer containing at least one (meth)acryloyl group at the end to realize sandblast resistance and high tenting effect. Through confirmation, the invention was completed.

(1) Alkali developable binder resin

The alkali developable binder resin may include a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3), and a repeating unit represented by the following formula (4).

[Formula 1]

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

[Formula 2]

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

[Formula 3]

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

[Formula 4]

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

Specifically, the alkali developable binder resin is a random copolymer of the repeating unit represented by Formula 1, the repeating unit represented by Formula 2, the repeating unit represented by Formula 3, and the repeating unit represented by Formula 4 may include.

By including the repeating unit represented by Formula 1 in the alkali developable binder resin to increase the degree of hydrophobicity of the alkali developable binder resin through the benzene structure included in the repeating unit represented by Formula 1, the photosensitivity In the developing process of dry film photoresist using the resin composition, it suppresses the generation of foam and exhibits excellent developability, and improves substrate adhesion to ensure proper physical properties (resolution, fine wire adhesion, etc.).

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

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

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

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

[Formula 1-1]

In Formula 1-1, R ₁ is hydrogen or alkyl having 1 to 10 carbon atoms, R ₂ is alkylene having 1 to 10 carbon atoms, Ar is aryl having 6 to 20 carbon atoms, and n is an integer from 1 to 20 to be. In Formula 1-1, R ₁ , R ₂ , Ar, and n are the same as described above in Formula 1 above.

Specific examples of the monomer represented by Formula 1-1 include phenoxypolyethyleneoxyacrylate, more specifically 2-phenoxyethylmethacrylate (PHEMA).

The repeating unit represented by Formula 1 is 5 mol% or more and 40 mol% or less, or 5 mol% or more and 30 mol% or less, or 5 mol% or more based on 100 mol% of the total repeating unit molar content contained in the alkali developable binder resin. It may be contained in mol% or more and 25 mol% or less, or 10 mol% or more and 25 mol% or less.

In Formulas 2 to 4, R ₃ and R ₄ are the same as or different from each other, and each independently represents hydrogen or alkyl having 1 to 10 carbon atoms, R ₅ is alkyl having 1 to 10 carbon atoms, and Ar is 6 to 20 carbon atoms. is the aryl of

In Formulas 2 to 4, R ₃ and R ₄ are the same as or different from each other, and each independently may be any one of hydrogen or alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms include carbon atoms. and methyl which is an alkyl of 1.

R ₅ is alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms include methyl, which is alkyl having 1 carbon atoms.

Ar is aryl having 6 to 20 carbon atoms, and specific examples of the aryl having 6 to 20 carbon atoms include phenyl, which is aryl having 6 carbon atoms.

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

[Formula 2-1]

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

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

[Formula 3-1]

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

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

[Formula 4-1]

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

The alkali developable binder resin is 20 mol% or more and 60 mol% or more, or 20 mol% or more of the repeating unit represented by Formula 2, based on 100 mol% of the total repeating unit molar content contained in the alkali developable binder resin. 50 mol% or less, or 30 mol% or more and 40 mol% or less.

In addition, the alkali developable binder resin is based on 100 mol% of the total repeating unit molar content contained in the alkali developable binder resin, 1 mol% or more and 30 mol% or less of the repeating unit represented by Formula 3, or 5 mol % or more and 30 mol% or less, and 30 mol% or more and 60 mol% or less of the repeating unit represented by Formula 4, or 30 mol% or more and 50 mol% or less, or 30 mol% or more and 40 mol% or less.

More specifically, the molar ratio of the repeating unit represented by Formula 3 to 100 moles of the repeating unit represented by Formula 4 is 10 moles or more and 99 moles or less, or 15 moles or more and 95 moles or less, or 20 moles or more and 95 moles or less. may be below.

In addition, the molar ratio of the repeating unit represented by Formula 3 to 100 moles of the repeating unit represented by Formula 1 is 40 mol or less, or 35 mol or less, or 32 mol or less, or 0.1 mol or more and 40 mol or less, or 0.1 moles or more and 35 moles or less, or 0.1 moles or more and 32 moles or less, or 10 moles or more and 40 moles or less, or 10 moles or more and 35 moles or less, or 10 moles or more and 32 moles or less.

As such, as the content of the repeating unit represented by Formula 4, which is hydrophobic, is increased, the degree of hydrophobicity of the alkali developable binder resin is also increased, thereby preventing the generation of bubbles in the developing process of the dry film photoresist using the photosensitive resin composition. can be suppressed

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

In this specification, the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the polystyrene equivalent weight average molecular weight measured by the GPC method, a commonly known analyzer and a detector such as a differential refraction detector and a column for analysis may be used, and the temperature at which it is normally applied Conditions, solvents, and flow rates can be applied.

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

For this, polystyrene standard samples (STD A, B, C, D) obtained by dissolving polystyrene having various molecular weights as follows at a concentration of 0.1 (w/w)% in tetrahydrofuran were filtered with a 0.45㎛ pore size Syringe Filter and then GPC The value of the weight average molecular weight (Mw) of the alkali developable binder resin was calculated using a calibration curve formed by injecting into the .

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

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

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

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

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

The alkali developable binder resin may have an acid value of 120 mgKOH/g or more and 200 mgKOH/g or less, or 140 mgKOH/g or more and 160 mgKOH/g or less. For the acid value, about 1 g of the alkali developable binder resin was sampled, dissolved in 50 ml of a mixed solvent (MeOH 20%, Acetone 80%), two drops of 1%-phenolphthalein indicator were added, and then titrated with 0.1N-KOH to measure the acid value.

The alkali developable binder resin is included in an amount of 20 wt% or more and 80 wt% or less, based on the total weight of the photosensitive resin composition on a solid basis. When the content of the alkali developable binder resin is within the above range, it is possible to obtain an effect of strengthening the fine wire adhesion after circuit formation. The solid content, which is the basis of the weight, refers to the remaining components excluding the solvent in the photosensitive resin composition.

The alkali developable binder resin is included in an amount of 20 wt% or more and 80 wt% or less, based on the total weight of the photosensitive resin composition on a solid basis. When the content of the alkali developable binder resin is within the above range, it is possible to obtain an effect of strengthening the fine wire adhesion after circuit formation. The solid content, which is the basis of the weight, refers to the remaining components excluding the solvent in the photosensitive resin composition.

The content of the alkali developable binder resin of the present invention may be 40% by weight or more and 70% by weight or less based on the total weight of the photosensitive resin composition. When the content of the alkali developable binder resin is less than 40% by weight with respect to the total photosensitive resin composition, there is a disadvantage of causing defects such as short circuit due to contamination of the developing end, and when it exceeds 70% by weight, adhesive strength and resolution, etc. There is a problem in that the circuit properties are poor.

(2) photoinitiator

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

Examples of the compound usable as the photopolymerization initiator include anthraquinone derivatives such as 2-methyl anthraquinone and 2-ethyl anthraquinone; and benzoin derivatives such as benzoin methyl ether, benzophenone, phenanthrene quinone, and 4,4'-bis-(dimethylamino)benzophenone.

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

The photopolymerization initiator is included in an amount of 1 wt% or more and 10 wt% or less, based on the total weight of the photosensitive resin composition based on the solid content. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity may be obtained. The solid content, which is the basis of the weight, refers to the remaining components excluding the solvent in the photosensitive resin composition.

When the content of the photopolymerization initiator is less than 1% by weight, there is a disadvantage that the production efficiency is extremely reduced because the light efficiency is low and a large amount of exposure is required, and when it exceeds 10% by weight, the film is brittle and the developer contamination This increases and there is a problem of causing defects such as short circuit.

(3) photopolymerizable compounds

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

The photopolymerizable compound may include a urea-based polymer containing at least one (meth)acryloyl group at the terminal thereof. As the photosensitive resin composition of one embodiment includes a urea-based polymer containing at least one (meth)acryloyl group at the terminal, an effect of improving sandblast resistance and high tenting properties can be realized.

The urea-based polymer may include an oligomer or polymer (homopolymer or copolymer) containing a urea repeating unit. The urea repeating unit may be represented by the following formula (6).

[Formula 6]

In Formula 6, R ₁₁ is an arylene group having 6 to 20 carbon atoms, and R ₁₂ is an alkylene group having 1 to 10 carbon atoms.

Specifically, the arylene group having 6 to 20 carbon atoms of R ₁₁ may be a functional group represented by the following Chemical Formula 7.

[Formula 7]

In Formula 7, Ar ₁ and Ar ₂ are the same as or different from each other, each independently an arylene group having 6 to 20 carbon atoms, and L ₁ is an alkylene group having 1 to 10 carbon atoms.

More specifically, the arylene group having 6 to 20 carbon atoms of R ₁₁ may be a functional group represented by the following Chemical Formula 7-1.

[Formula 7-1]

.

.

In addition, specific examples of the alkylene group having 1 to 10 carbon atoms in R ₁₂ may include an ethylene group having 2 carbon atoms.

That is, specific examples of the urea repeating unit represented by Chemical Formula 6 may include a repeating unit represented by the following Chemical Formula 6-1.

[Formula 6-1]

Examples of the method for preparing the urea-based polymer are not particularly limited, but for example, a diisocyanate compound having a chemical structure of OCN-R ₁₁ -NCO, and a diamine compound having a chemical structure of H ₂ NR ₁₂ -NH ₂ The urea-based polymer can be prepared through the polymerization reaction of

At least one (meth)acrylate functional group may be contained at the end of the urea-based polymer. The (meth)acryloyl group includes an acryloyl group or a methacryloyl group, and may be freely selected and used as necessary. That is, one (meth)acrylate functional group or two or more (meth)acrylate functional groups may be contained at the end of the urea-based polymer. Preferably, one (meth)acrylate functional group is contained at one end of the urea-based polymer, and one (meth)acrylate functional group is contained at the other end, so that a total of two (meth)acrylate functional groups are contained. can

Specifically, a functional group represented by the following Chemical Formula 8 may be bonded to at least one terminal of the urea-based polymer.

[Formula 8]

In Formula 8, L ₂ is a direct bond or -NH-, R ₁₃ is an alkylene group having 1 to 10 carbon atoms, and R ₁₄ is a (meth)acryloyl group. Specific examples of the alkylene group having 1 to 10 carbon atoms in R ₁₃ include an ethylene group having 2 carbon atoms. Specific examples of the (meth)acryloyl group of R ₁₄ include an acryloyl group.

Specifically, examples of the functional group represented by Chemical Formula 8 include a functional group represented by the following Chemical Formula 8-1 or a functional group represented by Chemical Formula 8-2.

[Formula 8-1]

[Formula 8-2]

As an example of a method of introducing the functional group represented by Formula 8 into at least one terminal of the urea-based polymer, a diisocyanate compound having a chemical structure of OCN-R ₁₁ -NCO and a chemical structure of H ₂ NR ₁₂ -NH _{2 In} the polymerization reaction of _{the diamine} compound having It can be prepared by reacting the compound with the urea-based polymer terminated diisocyanate.

The urea-based polymer containing at least one (meth)acryloyl group at the terminal may have a weight average molecular weight of 1000 g/mol or more and 100000 g/mol or less. In this specification, the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the polystyrene equivalent weight average molecular weight measured by the GPC method, a commonly known analyzer and a detector such as a differential refraction detector and a column for analysis may be used, and the temperature at which it is normally applied Conditions, solvents, and flow rates can be applied.

Meanwhile, the photopolymerizable compound may further include bisphenol-based di(meth)acrylate.

As the bisphenol-based di(meth)acrylate, the bisphenol-based di(meth)acrylate containing ethylene oxide may be used. The bisphenol-based di(meth)acrylate containing the ethylene oxide is a bisphenol-based di(meth)acrylate containing 8 moles or less of ethylene oxide per molecule and more than 8 moles and 16 moles or less of ethylene oxide per molecule. It may include two types of bisphenol-based di(meth)acrylate.

Examples of the bisphenol-based di(meth)acrylate containing 8 mol or less of the ethylene oxide include Miramer M244 (BPA(EO)3DA, Bisphenol A (EO) ₃ Diacrylate) manufactured by Miwon Specialty Chemical Co., Ltd., Miramer M240 (BPA(EO) ₄ DA, Bisphenol A (EO) 4 Diacrylate), Miramer M241 (Bisphenol A (EO) ₄ Dimethacrylate).

Examples of the bisphenol-based di(meth)acrylate containing more than 8 moles and not more than 16 moles of ethylene oxide include Miramer M2100 (BPA(EO) ₁₀ DA, Bisphenol A (EO) ₁₀ manufactured by Miwon Specialty Chemical Co., Ltd.) Diacrylate), Miramer M2200 (BPA(EO) ₂₀ DA, Bisphenol A (EO) ₂₀ Diacrylate), Miramer M2101 (Bisphenol A (EO) ₁₀ Dimethacrylate), etc. can be used.

More specifically, with respect to 100 parts by weight of the bisphenol-based di(meth)acrylate containing more than 8 moles and not more than 16 moles of ethylene oxide per molecule, bisphenol-based di(meth)acryl containing 8 moles or less of ethylene oxide per molecule The rate may be included in an amount of 100 parts by weight or less, 50 parts by weight or less, 1 part by weight or more and 100 parts by weight or less, or 1 part by weight or more and 50 parts by weight or less.

On the other hand, in the photopolymerizable compound, the content of the urea-based polymer containing at least one (meth)acryloyl group at the terminal is 10 parts by weight or more and 80 parts by weight based on 100 parts by weight of the bisphenol-based di(meth)acrylate-based compound. or less, or 30 parts by weight or more and 50 parts by weight or less.

When the content of the urea-based polymer containing at least one (meth)acryloyl group at the terminal is excessively reduced to less than 10 parts by weight, it is difficult to achieve a sufficient level of sandblast resistance and tenting property improvement. In addition, when the content of the urea-based polymer containing at least one (meth)acryloyl group at the terminal is excessively increased to more than 80 parts by weight, photosensitivity and resolution may decrease.

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

(4) photosensitive resin composition

The photosensitive resin composition may include 20 wt% or more and 80 wt% or less of an alkali developable binder resin, 1 wt% or more and 10 wt% or less of a photopolymerization initiator, and 10 wt% or more and 70 wt% or less of a photopolymerizable compound based on the solid content have.

The photosensitive resin composition may further include a solvent. The solvent is generally selected from methyl ethyl ketone (MEK), methanol, THF, toluene, and acetone, and the solvent is not particularly limited. It may be contained by adjusting according to the content.

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

In this invention, in order to improve the handleability of the photosensitive resin composition, you may put a leuco dye and a coloring substance. Examples of the leuco dye include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, and fluoran dye. Especially, when leuco crystal violet is used, the contrast is favorable and it is preferable. In the case of containing the leuco dye, the content may be 0.01% by weight or more and 1% by weight or less in the photosensitive resin composition. From a viewpoint of expression of contrast, 0.01 weight% or more is preferable, and 1 weight% or less is preferable from a viewpoint of maintaining storage stability.

As the coloring material, for example, toluenesulfonic acid monohydrate, fuchsine, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green, Diamond Green, Basic Blue 20, etc. can be heard In the case of containing the coloring material, the added amount may be 0.001% by weight or more and 1% by weight or less in the photosensitive resin composition. At a content of 0.001% by weight or more, there is an effect of improving handling, and at a content of 1% by weight or less, there is an effect of maintaining storage stability.

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

2. Dry Film Photoresist

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

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

The thickness of the dry film photoresist is not particularly limited, but can be freely adjusted 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 specific value, physical properties measured in the dry film photoresist may also change by a predetermined value.

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

As the base film, various plastic films can be used, for example, an acrylic film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a polynorbornene (PNB) film, a cycloolefin polymer (COP) film , and may include at least one plastic film selected from the group consisting of a polycarbonate (PC) film. The thickness of the base film is not particularly limited, but can be freely adjusted within, for example, 0.01 μm to 1 mm.

The protective film prevents damage to the resist during handling and serves as a protective cover for protecting the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface of the photosensitive resin layer on which the base film is not formed. The protective film serves to protect the photosensitive resin layer from the outside, and it is easily detached when the dry film photoresist is applied in a post-process, and requires proper releasability and adhesiveness so as not to be released during storage and distribution.

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

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

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

The drying of the coated photosensitive resin composition may be carried out by a heating means such as a hot air oven, a hot plate, a hot air circulation furnace, an infrared furnace, and may be performed at a temperature of 50 ℃ or more and 120 ℃ or less.

3. Photosensitive element

According to another embodiment of the invention, a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, wherein the photosensitive resin layer contains the photosensitive resin composition of the embodiment, a photosensitive element may be provided.

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

As a specific example of the polymer substrate, an anti-blocking layer is formed by an in-line coating method in which an unstretched polyester film is uniaxially stretched, a crude liquid containing a binder resin and organic particles is applied on one surface of the polymer substrate, and the remainder is uniaxially stretched. film can be mentioned.

In the polymer substrate, an in-line coating method was selected instead of adding an anti-blocking agent, which has been usually added in consideration of running properties and winding characteristics during manufacturing, and an organic particle layer using substitute particles that do not impair transparency. did it

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

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

And, 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, increase the Haze. This means that there is a lot of scattered light, and when there is a lot of such scattered light, the smoothing effect of the sidewall is reduced. It also depends on the size and quantity of organic particles. It is preferable that the organic particles have an average particle diameter of about 0.5 μm to 5 μm, and when it is smaller than this, running characteristics and winding characteristics are deteriorated, and when it is larger than 5 μm, haze is increased, and it is undesirable in consideration of the occurrence of a drop-off problem. The content of the organic particles is preferably 1 to 10% by weight based on the total amount with the binder resin.

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

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

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

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

In this way, a crude liquid containing organic particles in a binder resin is uniaxially stretched on an unstretched polyester film obtained by melt-extrusion of PET pellets, and then is applied on the uniaxially stretched film. The application may be performed on at least one surface of the uniaxially oriented film, and the thickness is preferably about 30 nm to 200 nm based on the thickness after final drying. If the crude liquid containing organic particles is applied thinner than 30 nm on the uniaxially oriented film, the organic particles are easily removed and are vulnerable to scratches, and there is a problem that white powder is generated. Due to this, in-line coating with a fast coating speed, coating streaks occur in the coating direction.

As described above, by the in-line coating method, the polymer substrate obtained by applying organic particles instead of a general anti-blocking agent has excellent transparency due to organic particles having excellent light transmittance while maintaining winding characteristics and running characteristics due to the particle layer. It is a base film.

Lamination of the photosensitive resin layer is performed on the opposite side of the layer containing organic particles in the polymer substrate. There is no crater-shaped flaw that appears as the base film is laminated. Since particles such as silica have a larger size than organic particles and their distribution is throughout the base film, the effect of silica appears in a portion adjacent to the photosensitive resin layer, although insignificant.

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

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

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

4. Register pattern

According to another embodiment of the present invention, a resist pattern including the photosensitive resin pattern containing the photosensitive resin composition of the embodiment may be provided. The content of the photosensitive resin composition includes all of the content described above in the embodiment.

The photosensitive resin pattern may be a photosensitive composition in the form of a pattern having an opening.

An example of the method of forming the photosensitive resin pattern may include a method of laminating the photosensitive resin layer of the dry film photoresist of the other embodiment on a substrate, followed by exposure and development. In addition, after laminating the photosensitive resin layer of the photosensitive element of the other embodiment on a substrate, there is a method of performing exposure and development.

As the substrate, a copper clad laminate, a glass substrate sputtered or deposited with transparent electrodes such as ITO and IZO, the same film substrate, a glass substrate coated with dielectric paste, a silicon wafer, a glass wafer deposited with amorphous silicon, copper, tantalum, molybdenum, etc. A silicon wafer on which a metal thin film is sputtered can be used.

For the exposure process, it is preferable to use a laser direct exposure machine including a light source such as UV, visible light, laser, particularly light having a wavelength of 350 to 410 nm, particularly i-line (365 nm) or h-line (405 nm). When using a laser direct exposure machine, it is possible to work under the conditions of 3 to 15 mJ/cm2 or less of exposure energy, and when using a general lamp exposure machine, it is possible to work under the condition of 20mJ/cm2 or less, so PCB, lead frame, PDP, and other It is useful for producing images of display devices and the like.

The developing process can be carried out by a dipping method, a shower method, a spraying method, a brush method, or the like. As the developer, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines can be used. .

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

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

5. Circuit board, display device

According to another embodiment of the present invention, there may be provided a circuit board or a display device including the resist pattern of the other embodiment or a metal pattern formed by the resistor pattern of the other embodiment. The contents of the register pattern include all the contents described above in the other embodiments.

Specific details regarding the circuit board or the display device are not particularly limited, and various conventionally known technical configurations are applicable without limitation.

The metal pattern may be formed by the above-described resist pattern. Specifically, the metal pattern may be formed by etching or plating through the opening included in the resist pattern. That is, the metal pattern may include a lower metal remaining after etching of the lower metal of the resist pattern through the opening included in the resistor pattern, or a metal plated in the opening included in the resistor pattern.

Specifically, for example, by etching or plating the lower substrate exposed by the above-described resist pattern, a conductor pattern, a printed wiring board, a lead frame, an ITO electrode, a black mattress, a semiconductor bump, and the like can be manufactured. If necessary, after the etching or plating, the resist pattern may be removed by peeling it from the substrate with an aqueous solution having a stronger alkalinity than a developer.

Accordingly, using the dry film photoresist of the present invention, a circuit having a fine line width is formed through a conventional etching/plating process, and a PCB having a fine line width through a known process, in addition to a lead frame, PDP, and other displays Productivity can be maximized in generating images on devices, semiconductor devices, and the like.

According to the present invention, a photosensitive resin composition capable of implementing sandblast resistance and high tenting properties, and a dry film photoresist using the same, a resist pattern, a circuit board, and a display device can be provided.

The invention is described in more detail in the following examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

<Preparation Example 1: Preparation of alkali developable binder resin>

A mechanical stirrer and a reflux device were mounted on the jacket set of the 4-necked reaction flask, and then the inside of the flask was purged with nitrogen. In the flask purged with nitrogen, 90 g of methyl ethyl ketone (Methyl Ethyl Ketone, MEK) and 10 g of methanol (Methanol, MeOH) were added, and then 0.9 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. . Here, 24g (0.28 mol, 33.98 mol% of 100 mol% of total monomer), 6g (0.06 mol, 7.30 of 100 mol% of total monomer) methacrylic acid (MAA) as a monomer mol%), styrene (Styrene, SM) 30g (0.29 mol, 35.09 mol% out of 100 mol% of total monomer), and 40 g (0.19 mol, total monomers) of 2-phenoxyethyl methacrylate (PHEMA) A monomer mixture of 23.63 mol% out of 100 mol%) was added, the temperature was raised to 80 °C, and polymerization was performed for 6 hours to obtain an alkali developable binder resin (weight average molecular weight: 50000 g/mol, solid content 50.0 wt%, acid value 155 mgKOH) /g) was prepared.

As a specific example of the weight average molecular weight measurement condition, the alkali developable binder resin is dissolved in tetrahydrofuran so as to have a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on the solid content) to 0.45 μm Pore After filtration using a Syringe Filter of size, 20 μl was injected into GPC, tetrahydrofuran (THF) was used as the mobile phase of GPC, and was introduced at a flow rate of 1.0 mL/min, and the column was Agilent PLgel 5 μm Guard. One (7.5 x 50 mm) and two Agilent PLgel 5㎛ Mixed D (7.5 x 300 mm) were connected in series, and measurements were made at 40°C using an Agilent 1260 Infinity Ⅱ Detector as a detector.

The acid value was measured by sampling 1 g of the alkali developable binder resin, dissolving it in 50 ml of a mixed solvent (MeOH 20%, Acetone 80%), adding two drops of 1%-phenolphthalein indicator, and then titrating with 0.1N-KOH.

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

<Preparation Example 2: Preparation of photopolymerizable compound>

60 g (1 mol) of ethylene diamine and 0.01 g of BTL as a catalyst were placed in a reaction vessel and mixed. 500 g (2 mol) of 4,4-diphenylmethane diisocyanate was added thereto, stirred and reacted at 80° C. for about 5 hours to prepare a urea polymer having isocyanate groups at both ends. .

Then, 225 g (1 mol) of 2-aminoehtylacrylate was added and stirred. The reaction was stopped where it was reacted for about 2 hours to obtain a urea polymer having acrylate groups at both ends (average molecular weight: 1500 to 18000).

<Comparative Preparation Example 1: Preparation of a photopolymerizable compound>

200 parts by weight of polypropylene glycol (hydroxyl value of 74.8) and 0.01 g of BTL as a catalyst were placed in a reaction vessel and mixed. After adding 27.9 parts by weight of hexamethylene diisocyanate thereto and stirring, the temperature was raised to 40°C to 80°C and reacted as it is for about 5 hours, then 8.5 parts by weight of 2-hydroxyethyl acrylate (molecular weight 116) was added and stirred. did. The reaction was stopped where it was reacted for about 2 hours, and urethane prepolymer A was obtained. The number average molecular weight of the urethane prepolymer A was 10,000.

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

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

The obtained photosensitive resin composition is coated on a PET film of 19 μm using a coating bar to form a photosensitive resin layer, and dried using a hot air oven, wherein the drying temperature is 80° C., and the drying time is 5 min, and the thickness of the photosensitive resin layer after drying was 40 μm.

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

ingredient Trade name (or ingredient name) Content (wt%) Example 1 Comparative Example 1 Comparative Example 2 Alkali developable binder resin Preparation Example 1 57.0 57.0 57.0 photopolymerizable compound M241 3.0 3.0 3.0 M2101 20 20 30.0 Production Example 2 10 0 0 Comparative Preparation Example 1 0 10 0 photopolymerization initiator EAB 0.05 0.05 0.05 BCIM 1.30 1.30 1.30 additive Toluenesulfonic acid monohydrate
(Aldrich Chemical) 0.044 0.044 0.044 N,N-BDA 0.066 0.066 0.066 Ruiko Crystal Violet (Hodogaya Co., Japan) 0.170 0.170 0.170 Diamond Green GH (Japan Hodogaya Co.) 0.015 0.015 0.015 solvent MEK (Methyl Ethyl Ketone) 8.355 8.355 8.355 (1) M241: Bisphenol A (EO) ₄ dimethacrylate (Miwon Specialty Chemical)
(2) M2101: Bisphenol A (EO) ₁₀ dimethacrylate (Miwon Specialty Chemical)
(3) EAB: 4,4'-(Bisdiethylamino)benzophenone (Aldrich Chemical)
(4) BCIM: 2,2'-Bis-(2-chlorophenyl-4,5,4',5'-tetraphenylbisimidazole (Aldrich Chemical)
(5) N,N-BDA: N,N-benzyldimethylamide

<Experimental example>

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

1. Fine wire adhesion (unit: ㎛)

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

After peeling off the support PET film of the dry film photoresist from the laminate, using a photomask for circuit evaluation, UV light at an exposure amount of 80 mJ/cm ² through ORC EXM-1201-F (parallel light exposure machine) for 4 seconds After irradiation, it was left for 15 minutes. After that, development was carried out for 1 minute under the spray pressure of 1.5kgf/cm 2 with a 1.0wt% aqueous solution of Na ₂ CO ₃ at 30±1 ° C.

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

2. 1:1 resolution (unit: μm)

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

After peeling off the support PET film of the dry film photoresist from the laminate, a photomask for circuit evaluation is used so that the width of the circuit line and the space between the circuit lines become 1:1 after development. Therefore, UV light was irradiated for 4 seconds at an exposure amount of 80 mJ/cm ² through ORC EXM-1201-F (parallel light exposure machine), and then left for 15 minutes. After that, development was carried out for 1 minute under the spray pressure of 1.5kgf/cm 2 with a 1.0wt% aqueous solution of Na ₂ CO ₃ at 30±1 ° C.

In the developed laminate, the minimum value of the gap between the photosensitive resin layers was measured with a ZEISS AXIOPHOT Microscope and evaluated at 1:1 resolution. As this value is smaller, it can be evaluated that the 1:1 resolution value is excellent.

3. Peeling speed (unit: seconds)

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

After peeling off the PET film, which is the support for the dry film photoresist, from the laminate, using ORC's EXM-1201 (parallel light exposure machine) using a photomask for circuit evaluation until the exposure amount of 40 mJ/cm ² is reached. After irradiation with ultraviolet light, it was left for 15 minutes. Then, development was carried out for twice the minimum development time under the spray pressure of 1.5 kgf/cm 2 with a 1.0 wt% aqueous solution of Na ₂ CO ₃ at 30±1 ℃.

Then, the photosensitive resin layer was peeled from the copper-clad laminate using a 3% aqueous sodium hydroxide solution (temperature of 50° C.). At this time, the time required for the photosensitive resin layer to fall from the copper-clad laminate was measured.

4. Tentability (Unit: ø)

Laminate dry film photoresist on both the top and bottom of the copper clad laminate with 13Х20 10Х holes in the size of 300Х450 (mm). Each dry film photoresist was exposed to light at 22/41 steps, and then developed at 6 times the minimum development time of each dry film photoresist to check the diameter of the destroyed hole.

division fine wire adhesion 1:1 resolution peel rate tenting Example 1 25 25 40 6ø Comparative Example 1 25 30 40 8ø Comparative Example 2 20 30 55 10ø

As shown in Table 2, it can be seen that the Example has excellent fine wire adhesion, resolution, and tenting property compared to the Comparative Example. In addition, it was found that the peeling process could have a faster peeling rate.

Claims (20)

An alkali developable binder resin, a photoinitiator, and a photopolymerizable compound,
The photopolymerizable compound is a photosensitive resin composition comprising a urea-based polymer containing at least one (meth) acryloyl group at the terminal.
According to claim 1,
The alkali developable binder resin is a photosensitive resin composition comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3), and a repeating unit represented by the following formula (4):
[Formula 1]

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

In the above formula (2),
R ₃ is hydrogen or alkyl having 1 to 10 carbon atoms,
[Formula 3]

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

In the above formula (4),
Ar is aryl having 6 to 20 carbon atoms.
3. The method of claim 2,
The repeating unit represented by Formula 1 is contained in an amount of 5 mol% or more and 40 mol% or less based on 100 mol% of the total repeating unit molar content contained in the alkali developable binder resin.
3. The method of claim 2,
The alkali developable binder resin is based on 100 mol% of the total repeating unit molar content contained in the alkali developable binder resin,
A photosensitive resin composition comprising 20 mol% or more and 60 mol% or less of the repeating unit represented by the formula (2).
3. The method of claim 2,
The alkali developable binder resin is based on 100 mol% of the total repeating unit molar content contained in the alkali developable binder resin,
1 mol% or more and 30 mol% or less of the repeating unit represented by Formula 3, and
A photosensitive resin composition comprising 30 mol% or more and 60 mol% or less of the repeating unit represented by the formula (4).
3. The method of claim 2,
The photosensitive resin composition, wherein the molar ratio of the repeating unit represented by Formula 3 to 100 moles of the repeating unit represented by Formula 4 is 10 mol or more and 99 mol or less.
3. The method of claim 2,
The photosensitive resin composition, wherein the molar ratio of the repeating unit represented by Formula 3 to 100 moles of the repeating unit represented by Formula 1 is 40 mol or less.
According to claim 1,
The urea-based polymer is an oligomer or polymer including a urea repeating unit represented by the following Chemical Formula 6, a photosensitive resin composition:
[Formula 6]

In the formula (6),
R ₁₁ is an arylene group having 6 to 20 carbon atoms,
R ₁₂ is an alkylene group having 1 to 10 carbon atoms.
9. The method of claim 8,
The arylene group having 6 to 20 carbon atoms of R ₁₁ is a functional group represented by the following formula (7), the photosensitive resin composition:
[Formula 7]

In Formula 7,
Ar ₁ and Ar ₂ are the same as or different from each other, and are each independently an arylene group having 6 to 20 carbon atoms,
L ₁ is an alkylene group having 1 to 10 carbon atoms.
9. The method of claim 8,
Wherein R ₁₁ is an arylene group having 6 to 20 carbon atoms is a functional group represented by the following Chemical Formula 7-1, the photosensitive resin composition:
[Formula 7-1]

.
9. The method of claim 8,
A photosensitive resin composition in which a functional group represented by the following formula (8) is bonded to at least one terminal of the urea-based polymer:
[Formula 8]

In the above formula (8),
L ₂ is a direct bond, or -NH-,
R ₁₃ is an alkylene group having 1 to 10 carbon atoms,
R ₁₄ is a (meth)acryloyl group.
According to claim 1,
The photopolymerizable compound further comprises a bisphenol-based di (meth) acrylate, the photosensitive resin composition.
13. The method of claim 12,
In the photopolymerizable compound, the content of the urea-based polymer containing at least one (meth)acryloyl group at the terminal is 10 parts by weight or more and 80 parts by weight or less, based on 100 parts by weight of the bisphenol-based di(meth)acrylate-based compound, A photosensitive resin composition.
13. The method of claim 12,
The photopolymerizable compound includes bisphenol-based di(meth)acrylate containing 8 moles or less of ethylene oxide per molecule, and bisphenol-based di(meth)acrylate containing more than 8 moles and 16 moles or less of ethylene oxide per molecule. which is a photosensitive resin composition.
15. The method of claim 14,
100 parts by weight of bisphenol-based di(meth)acrylate containing more than 8 moles of ethylene oxide and not more than 16 moles per molecule, 100 parts by weight of bisphenol-based di(meth)acrylate containing 8 moles or less of ethylene oxide per molecule A photosensitive resin composition comprising not more than parts by weight.
A dry film photoresist comprising a photosensitive resin layer containing the photosensitive resin composition of claim 1 .
polymer substrate; and a photosensitive resin layer formed on the polymer substrate,
The said photosensitive resin layer contains the photosensitive resin composition of Claim 1, The photosensitive element.
A resist pattern comprising the photosensitive resin pattern containing the photosensitive resin composition of claim 1 .
A circuit board comprising the resist pattern of claim 18, or a metal pattern formed by the resist pattern of claim 18.
A display device comprising the resist pattern of claim 18, or a metal pattern formed by the resist pattern of claim 18.